JP2024513726A - synthetic fiber coated with silk - Google Patents

Abstract

Silk contains a colloidal coating consisting of a filament core protein, silk fibroin, and a nonfilamentous protein, sericin. Silk fibers are lightweight, breathable, and hypoallergenic. Silk is comfortable when worn next to the skin and insulates very well, keeping the wearer warm in low temperatures and cooler than many other fibers in high temperatures. The present disclosure provides novel silk fibroin coated articles and methods for preparing the same. Optional Figure: Figure 1

Description

CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of U.S. Provisional Patent Application No. 63/161,929, filed March 16, 2021, and U.S. Provisional Patent Application No. 63/319,765, filed March 14, 2022, each of which is incorporated by reference in its entirety herein.

The present disclosure is in the field of synthetic fibers coated with silk fibroin proteins and protein fragments.

Silk is a natural polymer produced by various insects and spiders and includes a glue-like coating consisting of a filament core protein, silk fibroin, and a non-filamentary protein, sericin. Silk fibers are lightweight, breathable, and hypoallergenic. Silk is comfortable when worn next to the skin and insulates very well, keeping the wearer warm at low temperatures and cooler than many other fibers at high temperatures.

The present disclosure provides an article comprising a fiber and a coating, the coating comprising a surfactant and/or emulsifier system and silk fibroin fragments of about 1 kDa to about 5 kDa, about 5 kDa to about 10 kDa, about 6 kDa to about 17kDa, about 10kDa to about 15kDa, about 14kDa to about 30kDa, about 15kDa to about 20kDa, about 17kDa to about 39kDa, about 20kDa to about 25kDa, about 25kDa to about 30kDa, about 30kDa to about 35kDa, about 35kDa to about 40kDa, Select from about 39 kDa to about 54 kDa, about 39 kDa to about 80 kDa, about 40 kDa to about 45 kDa, about 45 kDa to about 50 kDa, about 50 kDa to about 55 kDa, about 55 kDa to about 60 kDa, about 60 kDa to about 100 kDa, or about 80 kDa to about 144 kDa. Silk fibroin fragments having an average weight average molecular weight of 1 to about 5, and a polydispersity ranging from 1 to about 5. In some embodiments, the silk fibroin fragments are 1 to about 1.5, about 1.5 to about 2.0, about 2.0 to about 2.5, about 2.5 to about 3.0, about It has a polydispersity of 3.0 to about 3.5, about 3.5 to about 4.0, about 4.0 to about 4.5, or about 4.5 to about 5.0. In some embodiments, the silk fibroin fragments have a polydispersity of about 1.5 to about 3.0. In some embodiments, the silk fibroin fragments include one or more of low molecular weight silk fibroin fragments and medium molecular weight silk fibroin fragments. In some embodiments, the article further comprises about 0.01% (w/w) to about 10% (w/w) sericin relative to the silk fibroin fragment. In some embodiments, the fibers include polyester, polyamide, polyaramid, polytetrafluoroethylene, polyethylene, polypropylene, polyurethane, silicone, blends of polyurethane and polyethylene glycol, ultra-high molecular weight polyethylene, high performance polyethylene, nylon, LYCRA ( polyester-polyurethane copolymers (also known as SPANDEX and elastomers), or mixtures thereof. In some embodiments, the coating further includes one or more of a wetting agent, an antifoaming agent, a softening agent, a wicking agent, and an antimicrobial agent. In some embodiments, the w/w ratio of silk fibroin fragments to surfactant and/or emulsifier system in the coating is about 99:1, about 98:2, about 97:3, about 96:4, about 95:5, about 94:6, about 93:7, about 92:8, about 91:9, about 90:10, about 89:11, about 88:12, about 87:13, about 86:14, about 85:15, approximately 84:16, approximately 83:17, approximately 82:18, approximately 81:19, approximately 80:20, approximately 79:21, approximately 78:22, approximately 77:23, approximately 76:24, approximately 75:25, about 74:26, about 73:27, about 72:28, about 71:29, about 70:30, about 69:31, about 68:32, about 67:33, about 66:34, about 65:35, approximately 64:36, approximately 63:37, approximately 62:38, approximately 61:39, approximately 60:40, approximately 59:41, approximately 58:42, approximately 57:43, approximately 56:44, approximately 55:45, approximately 54:46, approximately 53:47, approximately 52:48, approximately 51:49, approximately 50:50, approximately 49:51, approximately 48:52, approximately 47:53, approximately 46:54, approximately 45:55, about 44:56, about 43:57, about 42:58, about 41:59, about 40:60, about 39:61, about 38:62, about 37:63, about 36:64, about 35:65, approximately 34:66, approximately 33:67, approximately 32:68, approximately 31:69, approximately 30:70, approximately 29:71, approximately 28:72, approximately 27:73, approximately 26:74, approximately 25:75, approximately 24:76, approximately 23:77, approximately 22:78, approximately 21:79, approximately 20:80, approximately 19:81, approximately 18:82, approximately 17:83, approximately 16:84, approximately 15:85, about 14:86, about 13:87, about 12:88, about 11:89, about 10:90, about 9:91, about 8:92, about 7:93, about 6:94, about 5:95, about 4:96, about 3:97, about 2:98, or about 1:99. In some embodiments, the w/w ratio of silk fibroin fragments to surfactant and/or emulsifier in the coating is about 1:1, about 1:2, about 1:4, about 1:8, about 1 :16, or about 1:32. In some embodiments, the w/w ratio of silk fibroin fragments to surfactant and/or emulsifier system in the coating is about 1:1, about 1:2, about 1:3, about 1:4, about 1:5, about 1:6, about 1:7, about 1:8, about 1:9, about 1:10, about 1:11, about 1:12, about 1:13, about 1:14, about 1:15, about 1:16, about 1:17, about 1:18, about 1:19, about 1:20, about 1:21, about 1:22, about 1:23, about 1:24, about 1:25, about 1:26, about 1:27, about 1:28, about 1:29, about 1:30, about 1:31, or about 1:32. In some embodiments, the surfactant and/or emulsifier system is one or more of polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, polyoxyethylene castor oil, and any combinations thereof. including. In some embodiments, the surfactant and/or emulsifier system is polyoxyethylene (10-30) sorbitan monooleate, polyoxyethylene (10-30) sorbitan trioleate, polyoxyethylene (10-50) including one or more of castor oil, and any combination thereof. In some embodiments, the surfactant and/or emulsifier system includes polyoxyethylene (20) sorbitan monooleate, polyoxyethylene (20) sorbitan trioleate, polyoxyethylene (29) castor oil, and the like. Contains one or more of any combination. In some embodiments, the surfactant and/or emulsifier system includes polyoxyethylene (20) sorbitan monolaurate, polyoxyethylene (20) sorbitan monopalmitate, polyoxyethylene (20) sorbitan monostearate, polyoxyethylene (20) sorbitan tristearate, and any combination thereof. In some embodiments, the surfactant and/or emulsifier system includes one or more of sorbitan monofatty acids, sorbitan trifatty acids, castor oil, and any combinations thereof. In some embodiments, the surfactant and/or emulsifier system includes coco glucoside, decyl glucoside, lauryl glucoside, coconut sucrose, caprylic/caprylyl glucoside, caprylyl/capryl glucoside, and any combinations thereof. Contains one or more. In some embodiments, the surfactant and/or emulsifier system has an HLB of about 11 to about 13.50. In some embodiments, the surfactant and/or emulsifier system is about 11 to about 11.50, about 11.50 to about 12, about 12 to about 12.50, about 12.50 to about 13, or It has an HLB of about 13 to about 13.50. In some embodiments, the article has improved moisture management compared to similar articles containing similar fibers but without the coating. In some embodiments, moisture management is evaluated by a water absorption test, a vertical wicking test, or a drying rate test. In some embodiments, the article has improved drapability compared to similar articles containing similar fibers but without the coating. In some embodiments, the article has improved smoothness compared to similar articles containing similar fibers but without the coating. In some embodiments, the article has an improved feel compared to a similar article containing similar fibers but without the coating. In some embodiments, the article has a lower charge density at a given pH value compared to a similar article containing similar fibers but without a coating.

The present disclosure is a method of making silk fibroin coated fibers comprising: applying a solution containing a surfactant and/or emulsifier system to the fibers; applying a silk fibroin fragment solution to the fibers; Drying the fiber. The present disclosure also provides a method of making silk fibroin coated fibers comprising: applying to the fibers a solution comprising a surfactant and/or emulsifier system and silk fibroin fragments; and drying the fibers. A method is provided, including. In some embodiments, the concentration of silk fibroin fragments in the solution ranges from 0.01 g/L to about 100 g/L. In some embodiments, the concentration of surfactant and/or emulsifier system in the solution ranges from 0.01 g/L to about 100 g/L. In some embodiments, the silk fibroin fragments are about 1 kDa to about 5 kDa, about 5 kDa to about 10 kDa, about 6 kDa to about 17 kDa, about 10 kDa to about 15 kDa, about 14 kDa to about 30 kDa, about 15 kDa to about 20 kDa, about 17 kDa. ~about 39kDa, about 20kDa to about 25kDa, about 25kDa to about 30kDa, about 30kDa to about 35kDa, about 35kDa to about 40kDa, about 39kDa to about 54kDa, about 39kDa to about 80kDa, about 40kDa to about 45kDa, about 45kDa to about and a polydispersity in the range of 1 to about 5. In some embodiments, the silk fibroin fragments are 1 to about 1.5, about 1.5 to about 2.0, about 2.0 to about 2.5, about 2.5 to about 3.0, about It has a polydispersity of 3.0 to about 3.5, about 3.5 to about 4.0, about 4.0 to about 4.5, or about 4.5 to about 5.0. In some embodiments, the silk fibroin fragments have a polydispersity of about 1.5 to about 3.0. In some embodiments, the silk fibroin fragments include one or more of low molecular weight silk fibroin fragments and medium molecular weight silk fibroin fragments. In some embodiments, the solution further comprises about 0.01% (w/w) to about 10% (w/w) sericin relative to the silk fibroin fragments. In some embodiments, the fibers include polyester, polyamide, polyaramid, polytetrafluoroethylene, polyethylene, polypropylene, polyurethane, silicone, blends of polyurethane and polyethylene glycol, ultra-high molecular weight polyethylene, high performance polyethylene, nylon, LYCRA ( polyester-polyurethane copolymers (also known as SPANDEX and elastomers), or mixtures thereof. In some embodiments, the solution further includes one or more of a wetting agent, an antifoaming agent, a softening agent, a wicking agent, and an antimicrobial agent. In some embodiments, the w/w ratio of silk fibroin fragments to surfactant and/or emulsifier system is about 99:1, about 98:2, about 97:3, about 96:4, about 95:5. , about 94:6, about 93:7, about 92:8, about 91:9, about 90:10, about 89:11, about 88:12, about 87:13, about 86:14, about 85:15 , about 84:16, about 83:17, about 82:18, about 81:19, about 80:20, about 79:21, about 78:22, about 77:23, about 76:24, about 75:25 , about 74:26, about 73:27, about 72:28, about 71:29, about 70:30, about 69:31, about 68:32, about 67:33, about 66:34, about 65:35 , about 64:36, about 63:37, about 62:38, about 61:39, about 60:40, about 59:41, about 58:42, about 57:43, about 56:44, about 55:45 , about 54:46, about 53:47, about 52:48, about 51:49, about 50:50, about 49:51, about 48:52, about 47:53, about 46:54, about 45:55 , about 44:56, about 43:57, about 42:58, about 41:59, about 40:60, about 39:61, about 38:62, about 37:63, about 36:64, about 35:65 , about 34:66, about 33:67, about 32:68, about 31:69, about 30:70, about 29:71, about 28:72, about 27:73, about 26:74, about 25:75 , about 24:76, about 23:77, about 22:78, about 21:79, about 20:80, about 19:81, about 18:82, about 17:83, about 16:84, about 15:85 , about 14:86, about 13:87, about 12:88, about 11:89, about 10:90, about 9:91, about 8:92, about 7:93, about 6:94, about 5:95 , about 4:96, about 3:97, about 2:98, or about 1:99. In some embodiments, the w/w ratio of silk fibroin fragments to surfactant and/or emulsifier system is about 1:1, about 1:2, about 1:4, about 1:8, about 1:16. , or about 1:32. In some embodiments, the w/w ratio of silk fibroin fragments to surfactant and/or emulsifier system is about 1:1, about 1:2, about 1:3, about 1:4, about 1:5. , about 1:6, about 1:7, about 1:8, about 1:9, about 1:10, about 1:11, about 1:12, about 1:13, about 1:14, about 1:15 , about 1:16, about 1:17, about 1:18, about 1:19, about 1:20, about 1:21, about 1:22, about 1:23, about 1:24, about 1:25 , about 1:26, about 1:27, about 1:28, about 1:29, about 1:30, about 1:31, or about 1:32. In some embodiments, the surfactant and/or emulsifier system is one or more of polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, polyoxyethylene castor oil, and any combinations thereof. including. In some embodiments, the surfactant and/or emulsifier system is polyoxyethylene (10-30) sorbitan monooleate, polyoxyethylene (10-30) sorbitan trioleate, polyoxyethylene (10-50) including one or more of castor oil, and any combination thereof. In some embodiments, the surfactant and/or emulsifier system includes polyoxyethylene (20) sorbitan monooleate, polyoxyethylene (20) sorbitan trioleate, polyoxyethylene (29) castor oil, and the like. Contains one or more of any combination. In some embodiments, the surfactant and/or emulsifier system includes polyoxyethylene (20) sorbitan monolaurate, polyoxyethylene (20) sorbitan monopalmitate, polyoxyethylene (20) sorbitan monostearate, polyoxyethylene (20) sorbitan tristearate, and any combination thereof. In some embodiments, the surfactant and/or emulsifier system includes one or more of sorbitan monofatty acids, sorbitan trifatty acids, castor oil, and any combinations thereof. In some embodiments, the surfactant and/or emulsifier system includes coco glucoside, decyl glucoside, lauryl glucoside, coconut sucrose, caprylic/caprylyl glucoside, caprylyl/capryl glucoside, and any combinations thereof. Contains one or more. In some embodiments, the surfactant and/or emulsifier system has an HLB of about 11 to about 13.50. In some embodiments, the surfactant and/or emulsifier system is about 11 to about 11.50, about 11.50 to about 12, about 12 to about 12.50, about 12.50 to about 13, or It has an HLB of about 13 to about 13.50. In some embodiments, drying includes heating. In some embodiments, the pH of the solution is acidic. In some embodiments, the pH of the solution is about 3.5 to about 4, about 4 to about 4.5, about 4.5 to about 5, about 5 to about 5.5, or about 5.5 to It is about 6.

The present disclosure also provides articles prepared by the methods described herein. According to any one of claims 25 to 49. In some embodiments, the article has improved moisture management compared to a similar article comprising similar fibers but without the coating. In some embodiments, moisture management is evaluated by a water absorption test, a vertical wicking test, or a drying rate test. In some embodiments, the article has improved drapability compared to similar articles containing similar fibers but without the coating. In some embodiments, the article has improved smoothness compared to similar articles containing similar fibers but without the coating. In some embodiments, the article has an improved feel compared to a similar article containing similar fibers but without the coating. In some embodiments, the article has a lower charge density at a given pH value compared to a similar article containing similar fibers but without a coating.

1 is a flowchart illustrating various embodiments for producing silk fibroin protein fragments (SPF) of the present disclosure. 2 is a flowchart showing various parameters that can be modified during the process of producing the silk protein fragment solution of the present disclosure during the extraction and dissolution steps. Figure 2 is a chart showing the absorbency of Activated Silk™ with a caprylic/caprylyl glucoside coating on extensive interlocking nylon fibers, where raw nylon interlock fibers do not absorb water and have poor absorbency. The absorbency of all nylon interlock fibers increases significantly after Activated Silk™ with caprylic/caprylyl glucoside coating. FIG. 2 is a chart showing the absorbency of Activated Silk™ with capryl/caprylyl glucoside coating on various nylon fibers other than interlock structure, where raw nylon fibers do not absorb water or have poor absorbency, and after Activated Silk™ with capryl/caprylyl glucoside coating, the absorbency of all nylon fibers increases significantly. Chart showing no-wash hygroscopicity curves generated by varying the concentration of polyoxyethylene (29) castor oil in the emulsifier mixture (thereby varying the HLB) before addition to the coating solution and the silk concentration in the coating solution is 1 g/L in all samples. FIG. 2 is a chart showing no-wash hand feel ranking curves generated by varying the concentration of polyoxyethylene (29) castor oil (thereby varying the HLB) in the emulsifier mixture prior to addition to the coating solution, all samples having a silk concentration of 1 g/L in the coating solution. The emulsion mixture in the final coating solution (polyoxyethylene (20) sorbitan monooleate, polyoxyethylene (20) sorbitan trioleate, polyoxyethylene (29) castor oil, and water in a ratio of 2:4:8:10) ) is a chart showing no-wash moisture management data generated by varying the concentration of 1 g/L silk in the coating solution for all samples. The emulsion mixture in the final coating solution (polyoxyethylene (20) sorbitan monooleate, polyoxyethylene (20) sorbitan trioleate, polyoxyethylene (29) castor oil, and water in a ratio of 2:4:8:10) ) is a chart showing moisture management data for five washes generated by varying the concentration of 1 g/L silk in the coating solution for all samples. The emulsion mixture in the final coating solution (polyoxyethylene (20) sorbitan monooleate, polyoxyethylene (20) sorbitan trioleate, polyoxyethylene (29) castor oil, and water in a ratio of 2:4:8:10) ) is a chart showing moisture management data for 10 washes generated by varying the concentration of 1 g/L silk in the coating solution for all samples. The emulsion mixture in the final coating solution (polyoxyethylene (20) sorbitan monooleate, polyoxyethylene (20) sorbitan trioleate, polyoxyethylene (29) castor oil, and water in a ratio of 2:4:8:10) ) is a chart showing moisture management data for 25 washes generated by varying the concentration of 1 g/L silk in the coating solution for all samples. The emulsion mixture in the final coating solution (polyoxyethylene (20) sorbitan monooleate, polyoxyethylene (20) sorbitan trioleate, polyoxyethylene (29) castor oil, and water in a ratio of 2:4:8:10) ), with 1 being the highest score and 8 being the lowest hand ranking score, for all samples in solution. The silk concentration of is 1 g/L. The emulsion mixture in the final coating solution (polyoxyethylene (20) sorbitan monooleate, polyoxyethylene (20) sorbitan trioleate, polyoxyethylene (29) castor oil, and water in a ratio of 2:4:8:10) ), where 1 is the highest score and 8 is the lowest hand ranking score, for all samples. The silk concentration in the solution is 1 g/L. The emulsion mixture in the final coating solution (polyoxyethylene (20) sorbitan monooleate, polyoxyethylene (20) sorbitan trioleate, polyoxyethylene (29) castor oil, and water in a ratio of 2:4:8:10) ), where 1 is the highest score and 8 is the lowest hand ranking score, for all samples. The silk concentration in the solution is 1 g/L. The emulsion mixture in the final coating solution (polyoxyethylene (20) sorbitan monooleate, polyoxyethylene (20) sorbitan trioleate, polyoxyethylene (29) castor oil, and water in a ratio of 2:4:8:10) ), where 1 is the highest score and 8 is the lowest hand ranking score, for all samples. The silk concentration in the solution is 1 g/L. FIG. 1 is a chart showing hand feel ranking results from no wash produced by varying the concentration of medium molecular weight silk in the final coating solution, with 1 being the best ranking and 8 being the worst ranking. Figure 2 is a chart showing the hand ranking results from five washes, with 1 being the highest rank and 8 being the lowest rank, generated by varying the concentration of medium molecular weight silk in the final coating solution. Figure 2 is a chart showing the hand ranking results from 10 washes, with 1 being the highest rank and 8 being the lowest rank, generated by varying the concentration of medium molecular weight silk in the final coating solution. Figure 2 is a chart showing the hand ranking results from 25 washes, with 1 being the highest rank and 8 being the lowest rank, generated by varying the concentration of medium molecular weight silk in the final coating solution. FIG. 3 is a chart showing moisture management results from no wash produced by varying the concentration of medium molecular weight silk in the final coating solution. Figure 2 is a chart showing moisture management results from five washes produced by varying the concentration of medium molecular weight silk in the final coating solution. Figure 2 is a chart showing moisture management results from 10 washes produced by varying the concentration of medium molecular weight silk in the final coating solution. Figure 2 is a chart showing moisture management results from 25 washes produced by varying the concentration of medium molecular weight silk in the final coating solution. Figure 2 is a graph showing UV/Vis quantification experiments of low molecular weight activated silk and fibers coated with polyoxyethylene (20) monooleate solution. Graph showing the percentage of silk lost after 5 washes in terms of fiber surface area. Figure 2 is a graph showing UV/Vis quantification experiments of low molecular weight activated silk and fibers coated with polyoxyethylene (20) monooleate solution. Graph showing the quantified mass of silk on the fiber after coating in terms of fiber surface area. Figure 2 is a graph showing UV/Vis quantification experiments of low molecular weight activated silk and fibers coated with polyoxyethylene (20) monooleate solution. Graph showing the percentage of silk lost after 5 washes with respect to fiber type. Figure 2 is a graph showing UV/Vis quantification experiments of low molecular weight activated silk and fibers coated with polyoxyethylene (20) monooleate solution. Graph showing the silk mass quantified in each fiber before and after 5 washes, depending on fiber type. Figure 2 is a chart showing UV/Vis quantification experiments of low molecular weight activated silk and fibers coated with polyoxyethylene (20) monooleate solution. The graph shows the quantified mass of silk on the fiber after coating in terms of fiber mass in grams per cubic meter (GSM). This mass depends on the knit type, fiber content, and filament denier. Includes a series of charts showing potentiometric titration curves with charge density measured at pH 5 for raw weight double knit nylon fibers. The fibers have titration curves obtained without washing (left panel) and with 5 washes (right panel). The change in charge density at pH 5 after washing is shown as ΔC. Includes a series of charts showing potentiometric titration curves where charge density was measured at pH 5 for weight double knit nylon fibers with an activated silk finish. The fibers have titration curves obtained without washing (left panel) and with 5 washes (right panel). The change in charge density at pH 5 after washing is shown as ΔC. Includes a series of charts showing potentiometric titration curves with charge density measured at pH 5 for heavy weight double knit nylon fibers with Archroma RPU wetting agent finish. The fibers have titration curves obtained without washing (left panel) and with 5 washes (right panel). The change in charge density at pH 5 after washing is shown as ΔC.

The present disclosure provides articles that include coated fibers, where the coating includes a surfactant and/or emulsifier system and silk fibroin fragments, and methods of making such articles.

Silk is a natural polymer produced by various insects and spiders. Silk produced by Bombyx mori (silkworm) contains a glue-like coating consisting of filament core proteins, silk fibroin, and sericin, a non-filamentous protein. Silk fibroin is an FDA-approved, edible, non-toxic, and relatively inexpensive protein derived from silkworm cocoons. The structure and content of amino acids in silk fibroin protein are very similar to human body tissues.

Methods for producing silk fibroin protein fragments are known, for example, US Pat. No. 9,187,538, US Pat. No. 9,511,012, US Pat. No. 9,522,108, No. 9,545,369, and No. 10,166,177, all of which are incorporated herein in their entirety. .

Recent advances in silk material technology include the advent of top-down and bottom-up engineering of silk cocoons, particularly the regeneration of cocoons into aqueous silk solutions, and recombination with molecularly defined compositions using genetic engineering. This includes producing silk (Tran et al., A review of the emerging role of silk for the treatment of the eye, Pharm. Res., 2018, vol. 35, pp. 1-16). Recently, it has been reported that silk fibroin protein has found applications in ocular tissue reconstruction, corneal tissue engineering, and ocular surface repair due to its biocompatibility, tunable properties, and transparency. Silk films have been found to support corneal cell growth and express stratified epithelial cell sheets comparable to amniotic stroma (Lawrence et al., Silk film biomaterials for cornea tissue engineering, Biomaterials, 2009; 30 (7):1299-308, Harkin et al., Silk fibroin in ocular tissue reconstruction, Biomaterials, 2011, Chirtla et al., Bombyx mori silk fi Broin membranes as potential substrata for epithelial constructs used in the management of ocular surface disorders.Tissue Engineering Pan A, 2008;14(7):1203-11.). Silk fibroin protein and hydrolyzed peptide fragments have been shown to inhibit transcription and upstream activation of NF-κB protein subunits and inflammatory molecules that are classically under the control of NF-κB (Hayden et al. ., Cell Research, 2011.21(2):223-244, Chon et al., International Journal of Molecular Medicine, 2012.30(5):1203-1210, Kim et al., J. Neurosurg., 2011. 114(2):485-90, J. Microbiol.Biotechnol., 2012.22(4):494-500).

DEFINITIONS [0033] Unless otherwise defined, as used in the above section, and throughout the remainder of the specification, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. All patents and publications mentioned herein are incorporated herein by reference in their entirety.

Unless otherwise specified, all parts, parts, and ratios are based on the total weight of the eye care composition of the present disclosure. All such weights relating to listed ingredients are based on the active level and therefore do not include solvents or by-products that may be included in commercially available materials, unless otherwise specified. The term "percent by weight" may be expressed herein as "% by weight" or % w/w.

As used herein, the terms "a," "an," or "the" are generally intended to encompass both the singular and the plural.

As used herein, the term "about" generally refers to a particular numerical value that is within variation and acceptable error as determined by one of ordinary skill in the art; i.e. it will depend in part on the limitations of the measurement system. For example, "about" can mean zero variation and a range of ±20%, ±10%, or ±5% of a given number.

As used herein, the term "dermatologically acceptable carrier" means a carrier suitable for use in contact with mammalian keratinized tissue without causing any adverse effects, such as, for example, undue toxicity, incompatibility, instability, allergic reaction, etc. Dermatologically acceptable carriers may include, without limitation, water, liquid or solid emollients, humectants, solvents, and the like.

As used herein, the term "hydrophilic-lipophilic balance" (HLB) of a surfactant and/or emulsifier is a measure of its degree of hydrophilicity or hydrophobicity, and the value for different regions of the molecule. is determined by calculating the Griffin method HLB=20×M _h /M, where M _h is the molecular weight of the hydrophilic portion of the surfactant and/or emulsifier, and M is the surfactant is the molecular weight of the entire agent and/or emulsifier molecule, giving results on a scale of 0 to 20. An HLB value of 0 corresponds to a completely lipophilic molecule, and a value of 20 corresponds to a completely hydrophilic molecule. HLB values can be used to predict the surfactant and/or emulsifier properties of a molecule: HLB < 10: lipid soluble (water insoluble), HLB > 10: water soluble (lipid insoluble), HLB = 1-3 : Antifoaming agent, 3-6: W/O (water-in-oil) emulsifier, 7-9: Wetting agent and spreading agent, 8-16: O/W (oil-in-water) emulsifier, 13-16: Surfactant , 16-18: Solubilizers or hydrotropes.

As used herein, "average weight average molecular weight" refers to the average of two or more values of weight average molecular weight of silk fibroin or fragments thereof of the same composition; Determined by separate experimental readings above.

As used herein, the term polymer "polydispersity (PD)" is generally used as a measure of the broadness of a polymer's molecular weight distribution and is represented by the polydispersity formula:

is defined as follows:

As used herein, the term "substantially homogeneous" may refer to silk fibroin-based protein fragments that are normally distributed around an identified molecular weight. As used herein, the term "substantially homogeneous" refers to components or additives, such as silk fibroin fragments, dermatologically acceptable carriers, etc., throughout the compositions of the present disclosure. It can refer to a uniform distribution such as.

As used herein, the terms "silk fibroin peptide," "silk fibroin protein fragment," and "silk fibroin fragment" are used interchangeably. The molecular weight or number of amino acid units is defined when molecular size becomes the parameter of interest.

As used herein, the term "fast-dissolving solid form" refers to fast-dissolving solid forms, including lyophilized forms (cakes, wafers, films), and compressed tablets.

As used herein, the term "peptide" or "protein" refers to a chain of amino acids held together by peptide bonds (also called amide bonds). The basic distinguishing factors for proteins and peptides are size and structure. Peptides are smaller than proteins. Traditionally, peptides are defined as molecules consisting of 2 to 50 amino acids, whereas proteins are composed of 50 or more amino acids. In addition, peptides tend to be less well-defined in structure than proteins and can adopt complex conformations known as secondary, tertiary, and quaternary structures.

As used herein, the term "fibroin" or "silk protein" refers to the type of structural protein produced by certain spider and insect species that produce silk (see definitions provided in WIPO Pearl-WIPO's Multilingual Terminology Portal database, https://wipopearl.wipo.int/en/linguistic). Fibroin can include silkworm fibroin, insect or spider silk proteins (e.g., spidroins), recombinant spider proteins, silk proteins present in other spider silk types, such as tubular gland silk proteins (TuSP), flagellate gland silk proteins, ampullate gland silk proteins, grape-like gland silk proteins, piriform gland silk proteins, condensed gland silk glue, silkworm fibroin produced by genetically modified silkworms, or recombinant silkworm fibroin.

As used herein, the term "silk fibroin" refers to silkworm fibroin, silk fibroin produced by genetically modified silkworms, or genetically recombinant silkworm fibroin (see (1) Narayan Ed., Encyclopedia of Biomedical Engineering, Vol. 2, Elsevier, 2019; (2) Kobayashi et al. Eds., Encyclopedia of Polymeric Nanomaterials, Springer, 2014, https://link.springer.com/referenceworkentry/10.1007%2F978-3-642-36199-9_323-1). In one embodiment, the silk fibroin is obtained from Bombyx mori.

As used herein, the term "solid solution" refers to an active agent that is molecularly dissolved in a solid excipient matrix, such as a hydrophobic polymer, where the active agent is miscible with the polymeric matrix excipient. It is.

As used herein, the term "solid dispersion" refers to an active agent dispersed as crystalline or amorphous particles, where the active agent is dispersed in an amorphous polymer and a polymer matrix carrier. Randomly distributed among the formulations.

As used herein, the term "substantially homogeneous" may refer to silk fibroin-based protein fragments that are normally distributed around an identified molecular weight. As used herein, the term "substantially homogeneous" also refers to components or additives throughout the silk eye care composition, such as silk fibroin-based protein fragments, dermatologically acceptable carriers, etc. It can refer to a uniform distribution such as.

As used herein, the term "surface tension" refers to the tendency of a fluid surface to contract to the smallest possible surface area. At the liquid-air interface, surface tension results from the attraction of liquid molecules toward each other, which is greater than the attraction toward molecules in the air (due to adhesive forces). The net effect is an inward force on its surface that causes the liquid to behave as if it were covered by a stretched elastic membrane. Water has a higher surface tension (72.8 mN/m at 20° C.) than most other liquids due to the relatively high attraction of water molecules to each other through a network of hydrogen bonds.

Definitions and Properties of SPF As used herein, "silk protein fragment" (SPF) includes, without limitation, one or more of the following: "silk fibroin fragment" as defined herein. , "recombinant silk fragment" as defined herein, "spider silk fragment" as defined herein, "silk fibroin-like protein fragment" as defined herein, "silk fibroin-like protein fragment" as defined herein Includes "chemically modified silk fragments" and/or "sericin or sericin fragments" as defined herein. The SPF can have any molecular weight value or range described herein and any polydispersity value or range described herein. As used herein, in some embodiments, the term "silk protein fragment" also refers to each from a natural silk polypeptide or a variation thereof, an amino acid sequence of a natural silk polypeptide, or a combination of both. refers to a silk protein comprising or consisting of at least two identical repeating units, each of which is independently selected.

SPF Molecular Weight and Polydispersity In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 1 to about 5 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 5 to about 10 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 10 to about 15 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 15 to about 20 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 14 to about 30 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 20 to about 25 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 25 to about 30 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 30 to about 35 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 35 to about 40 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 39 to about 54 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 40 to about 45 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 45 to about 50 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 50 to about 55 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 55 to about 60 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 60 to about 65 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 65 to about 70 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 70 to about 75 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 75 to about 80 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 80 to about 85 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 85 to about 90 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 90 to about 95 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 95 to about 100 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 100 to about 105 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 105 to about 110 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 110 to about 115 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 115 to about 120 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 120 to about 125 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 125 to about 130 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 130 to about 135 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 135 to about 140 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 140 to about 145 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 145 to about 150 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 150 to about 155 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 155 to about 160 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 160 to about 165 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 165 to about 170 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 170 to about 175 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 175 to about 180 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 180 to about 185 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 185 to about 190 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 190 to about 195 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 195 to about 200 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 200 to about 205 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 205 to about 210 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 210 to about 215 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 215 to about 220 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 220 to about 225 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 225 to about 230 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 230 to about 235 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 235 to about 240 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 240 to about 245 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 245 to about 250 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 250 to about 255 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 255 to about 260 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 260 to about 265 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 265 to about 270 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 270 to about 275 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 275 to about 280 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 280 to about 285 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 285 to about 290 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 290 to about 295 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 295 to about 300 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 300 to about 305 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 305 to about 310 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 310 to about 315 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 315 to about 320 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 320 to about 325 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 325 to about 330 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 330 to about 335 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 335 to about 340 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 340 to about 345 kDa. In one embodiment, the compositions of the present disclosure include an SPF having an average weight average molecular weight selected from about 345 to about 350 kDa.

In some embodiments, the compositions of the present disclosure include SPF compositions selected from compositions #1001-#2450, having a weight average molecular weight selected from about 1 kDa to about 145 kDa, and having a polydispersity selected from 1 to about 5 (including but not limited to a polydispersity of 1), 1 to about 1.5 (including but not limited to a polydispersity of 1), about 1.5 to about 2, about 1.5 to about 3, about 2 to about 2.5, about 2.5 to about 3, about 3 to about 3.5, about 3.5 to about 4, about 4 to about 4.5, and about 4.5 to about 5:

As used herein, "low molecular weight," "low MW," or "low-MW" SPF refers to a weight average molecular weight, or from about 5 kDa to about 38 kDa, about 14 kDa. and about 30 kDa, or from about 6 kDa to about 17 kDa. In some embodiments, the target low molecular weight for a particular SPF is about 5 kDa, about 6 kDa, about 7 kDa, about 8 kDa, about 9 kDa, about 10 kDa, about 11 kDa, about 12 kDa, about 13 kDa, about 14 kDa, about 15 kDa, about 16kDa, about 17kDa, about 18kDa, about 19kDa, about 20kDa, about 21kDa, about 22kDa, about 23kDa, about 24kDa, about 25kDa, about 26kDa, about 27kDa, about 28kDa, about 29kDa, about 30kDa, about 31kDa, about 32kDa, It can have a weight average molecular weight of about 33 kDa, about 34 kDa, about 35 kDa, about 36 kDa, about 37 kDa, or about 38 kDa.

As used herein, "medium molecular weight," "medium MW," or "mid-MW" SPF refers to a weight average molecular weight, or about 31 kDa to about 55 kDa, or about The SPF may have an average weight average molecular weight selected from 39 kDa to about 54 kDa. In some embodiments, the target intermediate molecular weight for a particular SPF is about 31 kDa, about 32 kDa, about 33 kDa, about 34 kDa, about 35 kDa, about 36 kDa, about 37 kDa, about 38 kDa, about 39 kDa, about 40 kDa, about 41 kDa, It can have a weight average molecular weight of about 42 kDa, about 43 kDa, about 44 kDa, about 45 kDa, about 46 kDa, about 47 kDa, about 48 kDa, about 49 kDa, about 50 kDa, about 51 kDa, about 52 kDa, about 53 kDa, about 54 kDa, or about 55 kDa.

As used herein, "high molecular weight," "high MW," or "high-MW" SPF is a weight average molecular weight, or selected from about 55 kDa to about 150 kDa. may include an SPF having an average weight average molecular weight of In some embodiments, the target macromolecular weight for a particular SPF is about 55 kDa, about 56 kDa, about 57 kDa, about 58 kDa, about 59 kDa, about 60 kDa, about 61 kDa, about 62 kDa, about 63 kDa, about 64 kDa, about 65 kDa, It can be about 66 kDa, about 67 kDa, about 68 kDa, about 69 kDa, about 70 kDa, about 71 kDa, about 72 kDa, about 73 kDa, about 74 kDa, about 75 kDa, about 76 kDa, about 77 kDa, about 78 kDa, about 79 kDa, or about 80 kDa.

In some embodiments, the molecular weights described herein (e.g., low molecular weight silk, medium molecular weight silk, high molecular weight silk) refer to the amino acids included within the respective SPF, as can be understood by those skilled in the art. can be converted to an approximate number of . For example, the average weight of amino acids can be about 110 Daltons (ie, 110 g/mol). Thus, in some embodiments, dividing the molecular weight of a linear protein by 110 Daltons can be used to approximate the number of amino acid residues contained therein.

In one embodiment, the SPF in the compositions of the present disclosure has a polydispersity selected from 1 to about 5.0, including, but not limited to, a polydispersity of 1. In one embodiment, the SPF in the compositions of the present disclosure has a polydispersity selected from about 1.5 to about 3.0. In one embodiment, the SPF in the compositions of the present disclosure has a polydispersity selected from 1 to about 1.5, including, but not limited to, a polydispersity of 1. In one embodiment, the SPF in the compositions of the present disclosure has a polydispersity selected from about 1.5 to about 2.0. In one embodiment, the SPF in the compositions of the present disclosure has a polydispersity selected from about 2.0 to about 2.5. In one embodiment, the SPF in the compositions of the present disclosure has a polydispersity selected from about 2.5 to about 3.0. In one embodiment, the SPF in the compositions of the present disclosure has a polydispersity selected from about 3.0 to about 3.5. In one embodiment, the SPF in the compositions of the present disclosure has a polydispersity selected from about 3.5 to about 4.0. In one embodiment, the SPF in the compositions of the present disclosure has a polydispersity selected from about 4.0 to about 4.5. In one embodiment, the SPF in the compositions of the present disclosure has a polydispersity selected from about 4.5 to about 5.0.

In one embodiment, the SPF in the compositions of the present disclosure has a polydispersity of 1. In one embodiment, the SPF in the compositions of the present disclosure has a polydispersity of about 1.1. In one embodiment, the SPF in the compositions of the present disclosure has a polydispersity of about 1.2. In one embodiment, the SPF in the compositions of the present disclosure has a polydispersity of about 1.3. In one embodiment, the SPF in the compositions of the present disclosure has a polydispersity of about 1.4. In one embodiment, the SPF in the compositions of the present disclosure has a polydispersity of about 1.5. In one embodiment, the SPF in the compositions of the present disclosure has a polydispersity of about 1.6. In one embodiment, the SPF in the compositions of the present disclosure has a polydispersity of about 1.7. In one embodiment, the SPF in the compositions of the present disclosure has a polydispersity of about 1.8. In one embodiment, the SPF in the compositions of the present disclosure has a polydispersity of about 1.9. In one embodiment, the SPF in the compositions of the present disclosure has a polydispersity of about 2.0. In one embodiment, the SPF in the compositions of the present disclosure has a polydispersity of about 2.1. In one embodiment, the SPF in the compositions of the present disclosure has a polydispersity of about 2.2. In one embodiment, the SPF in the compositions of the present disclosure has a polydispersity of about 2.3. In one embodiment, the SPF in the compositions of the present disclosure has a polydispersity of about 2.4. In one embodiment, the SPF in the compositions of the present disclosure has a polydispersity of about 2.5. In one embodiment, the SPF in the compositions of the present disclosure has a polydispersity of about 2.6. In one embodiment, the SPF in the compositions of the present disclosure has a polydispersity of about 2.7. In one embodiment, the SPF in the compositions of the present disclosure has a polydispersity of about 2.8. In one embodiment, the SPF in the compositions of the present disclosure has a polydispersity of about 2.9. In one embodiment, the SPF in the compositions of the present disclosure has a polydispersity of about 3.0. In one embodiment, the SPF in the compositions of the present disclosure has a polydispersity of about 3.1. In one embodiment, the SPF in the compositions of the present disclosure has a polydispersity of about 3.2. In one embodiment, the SPF in the compositions of the present disclosure has a polydispersity of about 3.3. In one embodiment, the SPF in the compositions of the present disclosure has a polydispersity of about 3.4. In one embodiment, the SPF in the compositions of the present disclosure has a polydispersity of about 3.5. In one embodiment, the SPF in the compositions of the present disclosure has a polydispersity of about 3.6. In one embodiment, the SPF in the compositions of the present disclosure has a polydispersity of about 3.7. In one embodiment, the SPF in the compositions of the present disclosure has a polydispersity of about 3.8. In one embodiment, the SPF in the compositions of the present disclosure has a polydispersity of about 3.9. In one embodiment, the SPF in the compositions of the present disclosure has a polydispersity of about 4.0. In one embodiment, the SPF in the compositions of the present disclosure has a polydispersity of about 4.1. In one embodiment, the SPF in the compositions of the present disclosure has a polydispersity of about 4.2. In one embodiment, the SPF in the compositions of the present disclosure has a polydispersity of about 4.3. In one embodiment, the SPF in the compositions of the present disclosure has a polydispersity of about 4.4. In one embodiment, the SPF in the compositions of the present disclosure has a polydispersity of about 4.5. In one embodiment, the SPF in the compositions of the present disclosure has a polydispersity of about 4.6. In one embodiment, the SPF in the compositions of the present disclosure has a polydispersity of about 4.7. In one embodiment, the SPF in the compositions of the present disclosure has a polydispersity of about 4.8. In one embodiment, the SPF in the compositions of the present disclosure has a polydispersity of about 4.9. In one embodiment, the SPF in the compositions of the present disclosure has a polydispersity of about 5.0.

In some embodiments, in compositions described herein having a combination of low, medium, and/or high molecular weight SPF, such low, medium, and/or high molecular weight SPF are the same or They may have different polydispersities.

Silk Fibroin Fragments Methods for making silk fibroin or silk fibroin protein fragments and their applications in various fields are known, for example, U.S. Pat. No. 9,517,191, No. 9,522,107, No. 9,522,108, No. 9,545,369, No. 10,166,177, No. 10,287 , 728 and 10,301,768, all of which are incorporated herein in their entirety. Raw silk from the silkworm Bombyx mori is composed of two major proteins, silk fibroin (approximately 75%) and sericin (approximately 25%). Silk fibroin is a fibrous protein with a semi-crystalline structure that provides stiffness and strength. As used herein, the term "silk fibroin" refers to Bombyx mori cocoon fibers having a weight average molecular weight of approximately 370,000 Da. Crude silkworm fibers consist of double threads of fibroin. The adhesive substance that holds these double fibers together is sericin. Silk fibroin is composed of heavy chains (H chains) with a weight average molecular weight of about 350,000 Da and light chains (L chains) with a weight average molecular weight of about 25,000 Da. Silk fibroin is an amphiphilic polymer with large hydrophobic domains making up the main component of the polymer with high molecular weight. The hydrophobic regions are interrupted by small hydrophilic spacers, and the N- and C-termini of the chain are also highly hydrophilic. The hydrophobic domain of the heavy chain contains a repeating hexapeptide sequence of Gly-Ala-Gly-Ala-Gly-Ser and repeats of Gly-Ala/Ser/Tyr dipeptides, which form stable antiparallel sheet crystallites. be able to. The amino acid sequence of the light chain is non-repetitive, so the light chain is more hydrophilic and relatively elastic. The hydrophilic (Tyr, Ser) and hydrophobic (Gly, Ala) chain segments in the silk fibroin molecule are alternatively arranged to allow self-assembly of the silk fibroin molecule.

Provided herein is a method for producing a pure and highly scalable mixed silk fibroin-protein fragment solution that can be used across multiple industries for a variety of applications. Without wishing to be bound by any particular theory, these methods include, but are not limited to, fragmentation of recombinant silk proteins and silk-like or fibroin-like proteins. It is believed to be equally applicable to any SPF fragmentation.

As used herein, the term "fibroin" includes silkworm fibroin and insect or spider silk proteins. In one embodiment, fibroin is obtained from Bombyx mori. Raw silk from Bombyx mori is composed of two primary proteins: silk fibroin (about 75%) and sericin (about 25%). Silk fibroin is a fibrous protein with a semi-crystalline structure that provides stiffness and strength. As used herein, the term "silk fibroin" refers to Bombyx mori cocoon fibers having a weight average molecular weight of approximately 370,000 Da. Conversion of these insoluble silk fibroin fibers into water-soluble silk fibroin protein fragments requires the addition of concentrated neutral salts (e.g., 8-10 M lithium bromide), which Interfering with ionic as well as hydrogen bonds, they would otherwise render the fibroin protein insoluble in water. Methods for producing silk fibroin protein fragments and/or compositions thereof are known, for example, US Pat. No. 9,187,538, US Pat. No. 9,511,012, and US Pat. , No. 9,522,107, No. 9,522,108, No. 9,545,369, and No. 10,166,177.

Raw silk cocoons from the silkworm Bombyx mori were cut into small pieces. A small piece of silk cocoon was treated in an aqueous solution of Na ₂ CO ₃ at about 100° C. for about 60 minutes to remove sericin (degumming). The volume of water used is equal to about 0.4 times the weight of raw silk, and the amount of Na ₂ CO ₃ is about 0.848 times the weight of raw silk cocoon pieces. The resulting degummed silk cocoon pieces were rinsed three times with deionized water at approximately 60°C (20 minutes/rinse). The volume of rinsing water for each cycle was 0.2 L x the weight of the raw silk cocoon pieces. Excess water from the degummed silk cocoon pieces was removed. After the DI water washing step, the wet, degummed silk cocoon pieces were dried at room temperature. The degummed silk cocoon pieces were mixed with LiBr solution and the mixture was heated to about 100°C. The warmed mixture was placed in a drying oven and heated at about 100° C. for about 60 minutes to achieve complete dissolution of the natural silk proteins. The resulting silk fibroin solution was filtered and dialyzed using tangential flow filtration (TFF) and a 10 kDa membrane against deionized water for 72 hours. The resulting silk fibroin aqueous solution has a concentration of approximately 8.5% by weight. The 8.5% silk solution was then diluted with water resulting in a 1.0% w/v silk solution. TFF can then be used to further concentrate the pure silk solution to a concentration of 20.0% w/w silk in water.

Dialyzing silk through a series of water changes is a manual and time-intensive process that can be accelerated by varying certain parameters, for example by diluting the silk solution before dialysis. can. The dialysis process can be scaled up or down for production by using semi-automatic equipment, such as a tangential flow filtration system.

In some embodiments, the silk solution is prepared under various preparation condition parameters, such as 90°C 30 minutes, 90°C 60 minutes, 100°C 30 minutes, and 100°C 60 minutes. Briefly, 9.3M LiBr was prepared and left at room temperature for at least 30 minutes. 5 mL of LiBr solution was added to 1.25 g of silk and placed in a 60° C. oven. Samples from each set were removed at 4, 6, 8, 12, 24, 168, and 192 hours.

In some embodiments, the silk solution is prepared under various preparation condition parameters, such as 90°C 30 minutes, 90°C 60 minutes, 100°C 30 minutes, and 100°C 60 minutes. Briefly, a 9.3M LiBr solution was heated to one of four temperatures: 60°C, 80°C, 100°C, or boiling. 5 mL of hot LiBr solution was added to 1.25 g of silk and placed in a 60° C. oven. Samples from each set were removed at 1, 4, and 6 hours.

In some embodiments, silk solutions are prepared under various preparation condition parameters. For example: Four different silk extraction combinations were used: 90°C 30 minutes, 90°C 60 minutes, 100°C 30 minutes, and 100°C 60 minutes. Briefly, a 9.3M LiBr solution was heated to one of four temperatures: 60°C, 80°C, 100°C, or boiling. 5 mL of hot LiBr solution was added to 1.25 g of silk and placed in an oven at the same temperature of LiBr. Samples from each set were removed at 1, 4, and 6 hours. 1 mL of each sample was added to 7.5 mL of 9.3 M LiBr and refrigerated for viscosity testing.

In some embodiments, SPF is obtained by dissolving raw, unpolished, partially polished, or polished silkworm fibers with a neutral lithium bromide salt. The raw silkworm silk is treated at selected temperatures and other conditions to remove all sericin and achieve the desired weight average molecular weight ( _Mw ) and polydispersity (PD) of the fragment mixture. be done. The selection of process parameters can be varied to achieve different final silk protein fragment characteristics, depending on the intended use. The resulting final fragment solution contains pure silk fibroin protein fragments and water with undetectable levels of process contaminants, parts per million (ppm) acceptable levels in the pharmaceutical, medical, and consumer eye care markets. It is. The concentration, size, and polydispersity of the SPF can be further varied depending on the desired use and performance requirements.

FIG. 1 is a flowchart showing various embodiments for producing pure silk fibroin protein fragments (SPF) of the present disclosure. It should be understood that not all illustrated steps are necessarily required to make all silk solutions of the present disclosure. As illustrated in FIG. 2, Step A, cocoons (heat treated or non-heat treated), silk fibers, silk powder, spider silk, or recombinant spider silk can be used as the silk source. If starting from raw silk cocoons from Bombyx mori, the cocoons can be cut into small pieces, for example pieces of approximately equal size (step B1). The raw silk is then extracted and rinsed to remove sericin (step C1a). This results in raw silk that is substantially free of sericin. In one embodiment, water is heated to a temperature of 84°C to 100°C (ideally the boiling point) and then Na ₂ CO ₃ (sodium carbonate) is added to the boiling water until the Na ₂ CO ₃ is completely dissolved. Added. Raw silk is added to boiling water/Na ₂ CO ₃ (100° C.) and allowed to soak for about 15-90 minutes; boiling for longer periods of time results in smaller silk protein fragments. In one embodiment, the volume of water is equal to about 0.4 x weight of raw silk and the volume of Na ₂ CO ₃ is equal to about 0.848 x weight of raw silk. In one embodiment, the volume of water is equal to 0.1 x raw silk weight and the volume of Na ₂ CO ₃ is maintained at 2.12 g/L.

The Na ₂ CO ₃ solution dissolved in water is then drained and excess water/Na ₂ CO ₃ is removed from the silk fibroin fibers (e.g., by ringing out the fibroin extract by manual or mechanical dehydration cycles, etc.). (ring out). The resulting silk fibroin extract is rinsed with warm to hot water, typically in the temperature range of about 40°C to about 80°C, with at least one change in water volume (repeated as many times as necessary). , to remove any remaining adsorbed sericin or contaminants. The resulting silk fibroin extract is silk fibroin substantially deficient in sericin. In one embodiment, the resulting silk fibroin extract is rinsed with water at a temperature of about 60°C. In one embodiment, the amount of rinsing water for each cycle is equal to 0.1 L to 0.2 L times the weight of raw silk. To maximize the rinsing effect, it may be advantageous to agitate, rotate or circulate the rinsing water. After rinsing, excess water is removed from the extracted silk fibroin fibers (eg, manually or using a machine to ring out the fibroin extract). Alternatively, methods known to those skilled in the art, such as pressure, temperature, or other reagents, or combinations thereof, can be used for the purpose of sericin extraction. Alternatively, silk glands (100% sericin-free silk protein) can be removed directly from silkworms. This can result in sericin-free liquid silk proteins without any changes in protein structure.

The extracted fibroin fibers are then completely dried. Once dried, the extracted silk fibroin is dissolved using a solvent added to the silk fibroin at between ambient and boiling temperatures (step C1b). In one embodiment, the solvent is a solution of lithium bromide (LiBr) (boiling point for LiBr is 140°C). Alternatively, the extracted fibroin fibers are not dried, but are wet and placed in a solvent, and the solvent concentration can then be varied to achieve a similar concentration as when dry silk is added to the solvent. can. The final concentration of LiBr solvent can range from 0.1M to 9.3M. Complete dissolution of extracted fibroin fibers can be achieved by varying the treatment time and temperature, as well as the concentration of dissolving solvent. Other solvents can be used, including, but not limited to, concentrated aqueous solutions of phosphate phosphoric acid, calcium nitrate, calcium chloride solutions, or other inorganic salts. To ensure complete dissolution, the silk fibers should be fully immersed in the already heated solvent solution and then maintained at a temperature ranging from about 60° C. to about 140° C. for 1 to 168 hours. It is. In one embodiment, the silk fibers should be fully immersed in the solvent solution and then placed in a drying oven at a temperature of about 100° C. for about 1 hour.

The temperature at which the silk fibroin extract is added to the LiBr solution (or vice versa) depends on the time required to completely dissolve the fibroin, as well as on the molecular weight and polydispersity of the resulting final SPF mixture solution. have an effect. In one embodiment, the silk solvent solution concentration is less than or equal to 20% w/v. Stirring may also be used during introduction or dissolution to promote dissolution at varying temperatures and concentrations. The temperature of the LiBr solution provides control over the molecular weight and polydispersity of the silk protein fragment mixture produced. In one embodiment, the higher temperature causes the silk to dissolve more quickly, resulting in enhanced process scalability and mass production of silk solutions. In one embodiment, using a LiBr solution heated to a temperature of 80° C. to 140° C. reduces the time required in the oven to achieve complete dissolution. By varying the time and temperature of the dissolution solvent above 60° C., the MW and polydispersity of the SPF mixture solution formed from the original molecular weight natural silk fibroin protein is varied and controlled.

Alternatively, the whole cocoon can be placed directly into a solvent, such as LiBr, by bypassing the extraction (step B2). This includes methods known in the art for separating hydrophobic and hydrophilic proteins, such as column separation and/or chromatography, ion exchange, salt and/or pH chemical precipitation, and/or enzymatic digestion. and subsequent filtration of silkworm particles from silk and solvent solutions using methods such as filtration or extraction (all methods are general examples for standard protein separation methods, but not limited to) and sericin. Removal is required (Step C2). The non-heat treated cocoons from which the silkworms have been removed may alternatively be placed directly into a solvent, such as LiBr, bypassing the extraction. The method described above can be used for sericin separation, with the advantage that non-heat treated cocoons contain significantly less silkworm debris.

Dialysis can be used to remove the dissolution solvent from the resulting solution of dissolved fibroin protein fragments by dialyzing the solution against a volume of water (step E1). Pre-filtration before dialysis is useful to remove all debris (ie, silkworm remains) from the silk and LiBr solution (Step D). In one example, a 3 μm or 5 μm filter is used at a flow rate of 200-300 mL/min to filter a 0.1%-1.0% silk-LiBr solution prior to dialysis and potential concentration, if desired. . The methods disclosed herein, as described above, utilize a concentration of 9.9% to facilitate filtration and downstream dialysis, particularly when considering creating a scalable process method. Using time and/or temperature to reduce from 3M LiBr to a range of 0.1M to 9.3M. Alternatively, the 9.3M LiBr-silk protein fragment solution may be diluted with water to facilitate filtration and dialysis of debris without the use of additional time or temperature. The result of dissolution upon filtration for the desired time and temperature is a translucent, particle-free, room temperature storage stable silk protein fragment LiBr solution of known MW and polydispersity. It is advantageous to change the dialysis water periodically (eg, change the water after 1 hour, 4 hours, then change the water every 12 hours for a total of 6 times) until the solvent is removed. The total number of water volume exchanges can be varied based on the resulting concentration of solvent used for silk protein solubilization and fragmentation. After dialysis, the final silk solution can be further filtered to remove any remaining debris (ie, silkworm remains).

Alternatively, tangential flow filtration (TFF) is a fast and efficient method for the separation and purification of biomolecules and can be used to remove solvent from the resulting dissolved fibroin solution (step E2 ). TFF provides a highly pure aqueous solution of silk protein fragments and allows scalability of the process to produce large volumes of solution in a controlled and repeatable manner. Solutions of silk and LiBr can be diluted (20% to 0.1% silk in either water or LiBr) before TFF. Prefiltration as described above, prior to TFF treatment, allows filter efficiency to be maintained and eliminates the formation of a silk gel boundary layer on the surface of the filter as a result of the presence of debris particles. to avoid. Prefiltration before TFF also removes any remaining debris (i.e., silkworm remains) from the silk and LiBr solutions that may cause spontaneous or long-term gelation of the resulting water-only solution. (Step D). TFF (circulating or single pass) is used for making a water-silk protein fragment solution of 0.1% to 30.0% silk (more preferably 0.1% to 6.0% silk). be able to. TFF membranes of different cutoff sizes may be required based on the desired concentration, molecular weight, and polydispersity of the silk protein fragment mixture in solution. Membranes in the range of 1 to 100 kDa are required to vary the molecular weight silk solutions made, for example, by varying the length of the extraction boiling time, or the time and temperature in the dissolution solvent (e.g., LiBr). could be. In one embodiment, TFF5 or 10 kDa membranes are used to purify the silk protein fragment mixture solution and provide the final desired silk to water ratio. Additionally, TFF single pass, TFF, and other methods known in the art, such as falling film evaporators, can be used to concentrate the solution after removal of dissolved solvent (e.g., LiBr). (with resulting desired concentrations ranging from 0.1% to 30% silk). This can be used as an alternative to standard HFIP concentration methods known in the art to create water-based solutions. Larger pore membranes can also be utilized to filter out small silk protein fragments and create higher molecular weight silk solutions with and/or without more stringent polydispersity values. .

Assays for LiBr and _{Na2CO3 detection} can be performed using an HPLC system equipped with an evaporative light scattering detector (ELSD). Calculations were performed by linear regression of the resulting peak areas for the analytes plotted against the concentrations. Two or more samples of multiple formulations of the present disclosure were used for sample preparation and analysis. Generally, four samples of different formulations were weighed directly into a 10 mL volumetric flask. The samples were suspended in 5 mL of 20 mM ammonium formate (pH 3.0) and kept at 2-8°C with occasional shaking for 2 hours to extract the analytes from the film. After 2 hours, the solution was diluted with 20 mM ammonium formate (pH 3.0). The sample solution from the volumetric flask was transferred into an HPLC vial and injected into the HPLC-ELSD system for the estimation of sodium carbonate and lithium bromide.

The analytical method developed for the quantification of Na ₂ CO ₃ and LiBr in silk protein formulations was found to be linear in the range of 10-165 μg/mL, but not for sodium carbonate and lithium bromide. The RSD in injection precision was 2% and 1% for area and 0.38% and 0.19% for retention time, respectively. This analytical method can be applied for quantitative determination of sodium carbonate and lithium bromide in silk protein preparations.

FIG. 2 is a flowchart showing various parameters that can be modified during the process of producing the silk protein fragment solution of the present disclosure during the extraction and dissolution steps. The parameters of the selection method can be varied to achieve distinct final solution characteristics, depending on the intended use, eg, molecular weight and polydispersity. It should be understood that not all illustrated steps are necessarily required to make all silk solutions of the present disclosure.

In one embodiment, a silk protein fragment solution useful for a wide range of applications is prepared according to the following steps: forming pieces of silk cocoons from the Bombyx mori silkworm, placing the pieces at about 100° C. in Na ₂ Extraction in an aqueous _CO3 solution for about 60 minutes, wherein the volume of water is equal to about 0.4 times the weight of _the raw silk and the amount of _Na2CO3 is about 0.848 times the weight of the pieces. forming a silk fibroin extract, rinsing the silk fibroin extract three times at about 60° C. for about 20 minutes per rinse in a volume of rinsing water, comprising: , rinsing three times, the rinsing water for each cycle being equal to about 0.2 L times the weight of the pieces; removing excess water from the silk fibroin extract; drying the silk fibroin extract. Dissolving the dried silk fibroin extract in a LiBr solution, wherein the LiBr solution is first heated to about 100° C. to create and maintain a silk and LiBr solution. , in a drying oven at about 100° C. for about 60 minutes to achieve complete dissolution and further fragmentation of the natural silk protein structure into a mixture with the desired molecular weight and polydispersity, and filtering the solution. removing all remaining debris from the silkworm, diluting the solution with water to yield a 1.0 wt% silk solution, and removing the solvent from the solution using tangential flow filtration (TFF). Process. In one embodiment, a 10 kDa membrane is utilized to purify the silk solution to provide the final desired silk to water ratio. TFF can then be used to further concentrate the silk solution to a concentration of 2.0% silk by weight in water.

While not wishing to be bound by any particular theory, varying the extraction (i.e., time and temperature), LiBr (i.e., temperature of the LiBr solution added to the silk fibroin extract or vice versa), and dissolution (i.e., time and temperature) parameters resulted in solvent and silk solutions with different viscosities, uniformities, and colors. Also, while not wishing to be bound by any particular theory, increasing the temperature for extraction, extending the extraction time, using a higher temperature LiBr solution at the onset and over a longer period when dissolving the silk (e.g., in an oven as shown herein, or alternative heat source), and increasing the time at temperature all resulted in lower viscosity, more uniform solvent and silk solutions.

The extraction step can be completed in a larger vessel capable of maintaining temperatures at or between 60° C. and 100° C., such as an industrial washing machine. The rinsing step can also be completed in an industrial cleaning machine, eliminating manual rinsing cycles. Dissolution of silk in LiBr solution can occur in a vessel other than a convection oven, such as a stirred tank reactor. Dialyzing silk through a series of water changes is a manual and time-intensive process that can be accelerated by varying certain parameters, for example by diluting the silk solution before dialysis. can. The dialysis process can be scaled up or down for production by using semi-automatic equipment, such as a tangential flow filtration system.

Varying the extraction (i.e. time and temperature), LiBr (i.e. temperature of the LiBr solution when added to the silk fibroin extract or vice versa), and dissolution (i.e. time and temperature) parameters can result in different A solvent and silk solution with viscosity, uniformity, and color is produced. Increasing the temperature for extraction, prolonging the extraction time, using higher temperature LiBr solutions during appearance and over extended periods of time when dissolving silk, and (e.g., Increasing the time at temperature (in an oven as shown or alternative heat source) all result in a less viscous and more homogeneous solvent and silk solution. While nearly all parameters result in a viable silk solution, methods that allow complete dissolution to be achieved in less than 4-6 hours are preferred for process scalability.

In one embodiment, a solution of silk fibroin protein fragments having a weight average selected from about 6 kDa to about 17 kDa is prepared according to the following steps: Over a processing time of about 30 minutes to about 60 minutes, a silk source is degumming a silk source by adding to a boiling (100° C.) aqueous solution of sodium carbonate, removing sericin from the solution to produce a silk fibroin extract containing undetectable levels of sericin; Draining the solution from the fibroin extract, upon placing the silk fibroin extract in a lithium bromide solution ranging from about 60°C to about 140°C, a solution of lithium bromide having an onset temperature maintaining a solution of silk fibroin-lithium bromide in an oven having a temperature of about 140° C. for up to 1 hour; removing lithium bromide from the silk fibroin extract; producing an aqueous solution of protein fragments, the aqueous solution having a weight average molecular weight selected from about 6 kDa to about 17 kDa, and a polydispersity of 1 to about 5, or about 1.5 to about 3.0. A process of producing, including fragments. The method may further include drying the silk fibroin extract prior to the dissolution step. The aqueous solution of silk fibroin protein fragments may contain less than 300 ppm lithium bromide residue as measured using a high performance liquid chromatography lithium bromide assay. The aqueous solution of silk fibroin protein fragments may contain less than 100 ppm sodium carbonate residue as measured using a high performance liquid chromatography sodium carbonate assay. The aqueous solution of silk fibroin protein fragments may be lyophilized. In some embodiments, the silk fibroin protein fragment solution may be further processed into various forms including gels, powders, and nanofibers.

In one embodiment, a solution of silk fibroin protein fragments having a weight average molecular weight selected from about 17 kDa to about 39 kDa is prepared according to the following steps: treatment for about 30 minutes to about 60 minutes to result in degumming. adding a silk source to a boiling (100° C.) aqueous solution of sodium carbonate over a period of time, removing sericin from this solution to produce a silk fibroin extract containing undetectable levels of sericin, silk fibroin draining the solution from the extract, placing the silk fibroin extract in a solution of lithium bromide having an onset temperature, upon placement of the silk fibroin extract in a lithium bromide solution ranging from about 80°C to about 140°C; maintaining the silk fibroin-lithium bromide solution in a drying oven having a temperature in the range of about 60°C to about 100°C for a period of up to 1 hour. removing lithium bromide and producing an aqueous solution of silk fibroin protein fragments, the aqueous solution of silk fibroin protein fragments comprising from about 10 ppm to about 300 ppm lithium bromide residue; contains from about 10 ppm to about 100 ppm sodium carbonate residue, and the aqueous solution of silk fibroin protein fragments has a weight average molecular weight selected from about 17 kDa to about 39 kDa and from 1 to about 5, or from about 1.5 to about 3.0. producing fragments having a polydispersity of . The method may further include drying the silk fibroin extract prior to the dissolution step. The aqueous solution of silk fibroin protein fragments may contain less than 300 ppm lithium bromide residue as measured using a high performance liquid chromatography lithium bromide assay. The aqueous solution of silk fibroin protein fragments may contain less than 100 ppm sodium carbonate residue as measured using a high performance liquid chromatography sodium carbonate assay.

In some embodiments, a method for preparing an aqueous solution of silk fibroin protein fragments having an average weight average molecular weight selected from about 6 kDa to about 17 kDa comprises providing silk feed over a processing time of about 30 minutes to about 60 minutes. degumming the silk source by adding the source to a boiling (100° C.) aqueous solution of sodium carbonate, removing the sericin from this solution to yield a silk fibroin extract containing undetectable levels of sericin. producing, draining a solution from the silk fibroin extract, the silk fibroin extract having an onset temperature upon placement of the silk fibroin extract in a lithium bromide solution ranging from about 60°C to about 140°C. Dissolving the lithium bromide in a solution of lithium bromide, maintaining the silk fibroin-lithium bromide solution for a period of at least 1 hour in an oven having a temperature of about 140°C. and producing an aqueous solution of silk protein fragments, the aqueous solution having an average weight average molecular weight selected from about 6 kDa to about 17 kDa and from 1 to about 5, or from about 1.5 to about 3. A step of producing a fragment having a polydispersity of zero. The method may further include drying the silk fibroin extract prior to the dissolution step. An aqueous solution of pure silk fibroin protein fragments may contain less than 300 ppm lithium bromide residue as determined using a high performance liquid chromatography lithium bromide assay. An aqueous solution of pure silk fibroin protein fragments may contain less than 100 ppm sodium carbonate residue as determined using a high performance liquid chromatography sodium carbonate assay. The method may further include adding a therapeutic agent to the aqueous solution of pure silk fibroin protein fragments. The method may further include adding a molecule selected from one of an antioxidant or an enzyme to the aqueous solution of pure silk fibroin protein fragments. The method may further include adding vitamins to the aqueous solution of pure silk fibroin protein fragments. This vitamin may be vitamin C or a derivative thereof. Aqueous solutions of pure silk fibroin protein fragments may be lyophilized. The method may further include adding an alpha hydroxy acid to the aqueous solution of pure silk fibroin protein fragments. The alpha hydroxy acid can be selected from the group consisting of glycolic acid, lactic acid, tartaric acid, and citric acid. The method may further include adding hyaluronic acid or a salt form thereof at a concentration of about 0.5% to about 10.0% to the aqueous solution of pure silk fibroin protein fragments. The method may further include adding at least one of zinc oxide or titanium dioxide. Films may be made from aqueous solutions of pure silk fibroin protein fragments produced by this method. The film may contain from about 1.0% to about 50.0% by weight of vitamin C or a derivative thereof. The film can have a water content ranging from about 2.0% to about 20.0% by weight. The film may contain from about 30.0% to about 99.5% by weight pure silk fibroin protein fragments. Gels can be made from aqueous solutions of pure silk fibroin protein fragments produced by this method. The gel may contain from about 0.5% to about 20.0% by weight vitamin C or a derivative thereof. The gel may have a silk content of at least 2% and a vitamin content of at least 20%.

In some embodiments, a method for preparing an aqueous solution of silk fibroin protein fragments having an average weight average molecular weight selected from about 17 kDa to about 39 kDa includes the steps of: Adding the silk source to a boiling (100° C.) aqueous solution of sodium carbonate for a treatment time of 30 minutes to about 60 minutes, removing sericin from this solution to extract silk fibroin containing undetectable levels of sericin. producing a solution from the silk fibroin extract, discharging the silk fibroin extract from the silk fibroin extract at a starting temperature upon placement of the silk fibroin extract in a lithium bromide solution ranging from about 80°C to about 140°C. maintaining the silk fibroin-lithium bromide solution in an oven having a temperature in the range of about 60° C. to about 100° C. for a period of at least 1 hour; Removing lithium bromide from a fibroin extract and producing an aqueous solution of pure silk fibroin protein fragments, the aqueous solution of pure silk fibroin protein fragments containing from about 10 ppm to about 300 ppm lithium bromide residue. wherein the aqueous solution of silk protein fragments comprises from about 10 ppm to about 100 ppm sodium carbonate residue, wherein the aqueous solution of pure silk fibroin protein fragments has an average weight average molecular weight selected from about 17 kDa to about 39 kDa, and from 1 to about 5, or from about 1.5 to about 3.0. The method may further include drying the silk fibroin extract prior to the dissolution step. An aqueous solution of pure silk fibroin protein fragments may contain less than 300 ppm lithium bromide residue as determined using a high performance liquid chromatography lithium bromide assay. An aqueous solution of pure silk fibroin protein fragments may contain less than 100 ppm sodium carbonate residue as determined using a high performance liquid chromatography sodium carbonate assay. The method may further include adding a therapeutic agent to the aqueous solution of pure silk fibroin protein fragments. The method may further include adding a molecule selected from one of an antioxidant or an enzyme to the aqueous solution of pure silk fibroin protein fragments. The method may further include adding vitamins to the aqueous solution of pure silk fibroin protein fragments. This vitamin may be vitamin C or a derivative thereof. Aqueous solutions of pure silk fibroin protein fragments may be lyophilized. The method may further include adding an alpha hydroxy acid to the aqueous solution of pure silk fibroin protein fragments. The alpha hydroxy acid can be selected from the group consisting of glycolic acid, lactic acid, tartaric acid, and citric acid. The method may further include adding hyaluronic acid or a salt form thereof at a concentration of about 0.5% to about 10.0% to the aqueous solution of pure silk fibroin protein fragments. The method may further include adding at least one of zinc oxide or titanium dioxide. Films may be made from aqueous solutions of pure silk fibroin protein fragments produced by this method. The film may contain from about 1.0% to about 50.0% by weight of vitamin C or a derivative thereof. The film may have a water content ranging from about 2.0% to about 20.0% by weight. The film may contain from about 30.0% to about 99.5% by weight pure silk fibroin protein fragments. Gels can be made from aqueous solutions of pure silk fibroin protein fragments produced by this method. The gel may contain from about 0.5% to about 20.0% by weight vitamin C or a derivative thereof. The gel may have a silk content of at least 2% and a vitamin content of at least 20%.

In one embodiment, a solution of silk fibroin protein fragments having a weight average molecular weight selected from about 39 kDa to about 80 kDa is prepared according to the following steps: adding a source to a boiling (100° C.) aqueous solution of sodium carbonate; removing sericin from the solution to produce a silk fibroin extract containing undetectable levels of sericin; Draining the solution, dissolving the silk fibroin extract in a solution of lithium bromide having an onset temperature upon placement of the silk fibroin extract in the lithium bromide solution in the range of about 80°C to about 140°C. maintaining a silk fibroin-lithium bromide solution in a drying oven having a temperature in the range of about 60°C to about 100°C for a period of up to 1 hour; and producing an aqueous solution of silk fibroin protein fragments, wherein the aqueous solution of silk fibroin protein fragments contains about 10 ppm to about 300 ppm lithium bromide residue, about 10 ppm to about 100 ppm sodium carbonate residue, producing a fragment having a weight average molecular weight selected from about 39 kDa to about 80 kDa and a polydispersity of 1 to about 5, or about 1.5 to about 3.0. The method may further include drying the silk fibroin extract prior to the dissolution step. The aqueous solution of silk fibroin protein fragments may contain less than 300 ppm lithium bromide residue as measured using a high performance liquid chromatography lithium bromide assay. The aqueous solution of silk fibroin protein fragments may contain less than 100 ppm sodium carbonate residue as measured using a high performance liquid chromatography sodium carbonate assay. In some embodiments, the method can further include adding an active agent (eg, a therapeutic agent) to the aqueous solution of pure silk fibroin protein fragments. The method may further include adding an active agent selected from one of an antioxidant or an enzyme to the aqueous solution of pure silk fibroin protein fragments. The method may further include adding vitamins to the aqueous solution of pure silk fibroin protein fragments. This vitamin may be vitamin C or a derivative thereof. Aqueous solutions of pure silk fibroin protein fragments may be lyophilized. The method may further include adding an alpha-hydroxy acid to the aqueous solution of pure silk fibroin protein fragments. The alpha hydroxy acid can be selected from the group consisting of glycolic acid, lactic acid, tartaric acid, and citric acid. The method may further include adding hyaluronic acid or a salt form thereof at a concentration of about 0.5% to about 10.0% to the aqueous solution of pure silk fibroin protein fragments. Films may be made from aqueous solutions of pure silk fibroin protein fragments produced by this method. The film may contain from about 1.0% to about 50.0% by weight of vitamin C or a derivative thereof. The film may have a water content ranging from about 2.0% to about 20.0% by weight. The film may contain from about 30.0% to about 99.5% by weight pure silk fibroin protein fragments. Gels can be made from aqueous solutions of pure silk fibroin protein fragments produced by this method. The gel may contain from about 0.5% to about 20.0% by weight vitamin C or a derivative thereof. The gel may have a silk content of at least 2% by weight and a vitamin content of at least 20% by weight.

The molecular weight of silk protein fragments depends on the specific parameters utilized during the extraction process, including extraction time and temperature, the LiBr temperature at the time of immersion of the silk in lithium bromide and whether the solution is maintained at a specific temperature. control can be based on the specific parameters utilized during the lysis step, including the time for filtration, as well as the specific parameters utilized during the filtration step. Silk fibroin with a polydispersity equal to or lower than 2.5 at various different molecular weights selected from 5 kDa to 200 kDa, or 10 kDa to 80 kDa by controlling process parameters using the methods of the present disclosure. It is possible to create a protein fragment solution. Target a range of fragment mixture end products with desired polydispersities equal to or lower than 2.5 based on desired performance requirements by changing process parameters to achieve silk solutions with different molecular weights. It can be done. For example, high molecular weight silk films containing ophthalmic drugs may have controlled and sustained release rates compared to lower molecular weight films, making them ideal for delivery vehicles in eye care products. . Additionally, silk fibroin protein fragment solutions with polydispersities greater than 2.5 can be achieved. Additionally, two solutions with different average molecular weights and polydispersities can be mixed to create a combination solution. Alternatively, liquid silk gland (100% sericin-free silk protein) removed directly from silkworms can be used in combination with any of the silk fibroin protein fragment solutions of the present disclosure. The molecular weight of pure silk fibroin protein fragment compositions was determined using high pressure liquid chromatography (HPLC) with refractive index detector (RID). Polydispersity was calculated using Cirrus GPC online GPC/SEC software version 3.3 (Agilent).

Differences in processing parameters can result in regenerated silk fibroin varying in molecular weight and peptide chain size distribution (polydispersity, PD). This, in turn, affects the performance of regenerated silk fibroin, including mechanical strength, water solubility, etc.

Parameters were varied during the processing of raw silk cocoons into silk solution. Varying these parameters affected the MW of the resulting silk solution. The parameters manipulated included (i) extraction time and temperature, (ii) LiBr temperature, (iii) dissolution oven temperature, and (iv) dissolution time. Experiments were conducted to determine the effect of varying the extraction time. The results are summarized in Tables A-G. The summary is as follows:
-Sericin extraction time of 30 minutes resulted in a higher molecular weight than sericin extraction time of 60 minutes.
- The molecular weight decreases over time in the oven.
-140°C LiBr and oven yielded a lower limit of the confidence interval below a molecular weight of 9500 Da.
- 30 min extraction at 1st and 4th hour has undigested silk.
- A 30 minute extraction at the 1st hour resulted in a significantly higher molecular weight, with the lower limit of the confidence interval being 35,000 Da.
The molecular weight range in which the upper limit of the confidence interval was reached was 18,000-216,000 Da (important to provide a solution with a specific upper limit).

Experiments were conducted to determine the effect of varying the extraction temperature. Table G summarizes the results. Here is the summary:
- Sericin extraction at 90°C resulted in higher MW than sericin extraction at 100°C.
- Both 90°C and 100°C show a decrease in MW over time in the oven.

Experiments were performed to determine the effect of varying lithium bromide (LiBr) temperature when added to silk. The results are summarized in Tables H-I. The summary is as follows:
- No effect on molecular weight or confidence intervals (all CI approx. 10500-6500 Da).
- Tests demonstrate that when LiBr is added and dissolution begins, the temperature of the LiBr-silk melt drops rapidly below the original LiBr temperature due to the majority of its mass being silk at room temperature.

Experiments were conducted to determine the effect of oven/melting temperature. The results are summarized in Tables J to N. Here is the summary:
- Oven temperature has less effect on silk extracted for 60 minutes than on silk extracted for 30 minutes. Without wishing to be bound by theory, 30 min silk does not decompose as much during extraction and therefore oven temperature has more effect for larger MW and less decomposition of silk. The portions are considered smaller.
- For 60°C vs. 140°C ovens, silk extracted for 30 minutes showed a highly significant effect of lower MW at higher oven temperature, while silk extracted for 60 minutes had no effect But it was much less.
-140°C oven resulted in an adjustment in the confidence interval at ~6000 Da.

Raw silk cocoons from the silkworm Bombyx mori were cut into small pieces. Pieces of raw silk cocoons were boiled in an aqueous solution of Na ₂ CO ₃ (about 100° C.) for a period of between about 30 minutes and about 60 minutes to remove sericin (degumming). The volume of water used is equal to about 0.4 times the weight of raw silk, and the amount of Na ₂ CO ₃ is about 0.848 times the weight of raw silk cocoon pieces. The resulting degummed silk cocoon pieces were rinsed three times with deionized water at approximately 60°C (20 minutes/rinse). The volume of rinsing water for each cycle was 0.2 L x the weight of the raw silk cocoon pieces. Excess water from the degummed silk cocoon pieces was removed. After the DI water washing step, the wet, degummed silk cocoon pieces were dried at room temperature. The degummed silk cocoon pieces were mixed with LiBr solution and the mixture was heated to about 100°C. The warmed mixture was placed in a drying oven and heated at a temperature ranging from about 60° C. to about 140° C. for about 60 minutes to achieve complete dissolution of the natural silk proteins. The resulting solution was cooled to room temperature and then dialyzed to remove LiBr salts using a 3,500 Da MWCO membrane. Multiple exchanges were performed in Di water until the Br ⁻ ions were below 1 ppm, as determined in the hydrolyzed fibroin solution lead on an octone bromide (Br ⁻ ) double-junction ion-selective electrode.

The resulting aqueous silk fibroin solution has an average weight average molecular weight selected from about 6 kDa to about 16 kDa, about 17 kDa to about 39 kDa, and about 39 kDa to about 80 kDa and a polydispersity of about 1.5 to about 3.0. Contains pure silk fibroin protein fragments with a concentration of approximately 8.0% w/v. Dilute 8.0% w/v with DI water, 1.0% w/v, 2.0% w/v, 3.0% w/v, 4.0% w/v, 5.0% A w/v coating solution was provided.

Various percent silk concentrations have been produced through the use of tangential flow filtration (TFF). In all cases, 1% silk solution was used as input feed. A range of 750-18,000 mL of 1% silk solution was used as the starting volume. Diafilter the solution in TFF to remove lithium bromide. Once below a specified level of residual LiBr, the solution is subjected to ultrafiltration to increase concentration through water removal. See example below.

Six silk solutions were utilized in standard silk construction with the following results:
Solution #1 has a silk concentration of 5.9% by weight, an average MW of 19.8 kDa, and 2.2 PDI (made with boiling extraction for 60 minutes, LiBr dissolution at 100° C. for 1 hour).
Solution #2 has a silk concentration of 6.4% by weight (made with boiling extraction for 30 minutes, LiBr dissolution at 60° C. for 4 hours).
Solution #3 has a silk concentration of 6.17% by weight (made with boiling extraction for 30 minutes, LiBr dissolution at 100° C. for 1 hour).
Solution #4 has a silk concentration of 7.30% by weight. A 7.30% silk solution was produced from a 30 minute extraction batch of 100 g silk cocoons per batch. The extracted silk fibers were then dissolved using 9.3M LiBr at 100°C for 1 hour in a 100°C oven. 100 g of silk fibers were dissolved per batch to make 20% silk in LiBr. The silk dissolved in LiBr was then diluted to 1% silk and filtered through a 5 μm filter to remove large debris. 15,500 mL of 1% filtered silk solution was used as the starting volume of TFF/diafiltration volume. Once the LiBr was removed, the solution was ultrafiltered to a volume of around 1300 mL. 1262 mL of 7.30% silk was then collected. Water was added to the feed to help remove residual solution and 547 mL of 3.91% silk was then collected.
Solution #5 has a silk concentration of 6.44% by weight. A 6.44% by weight silk solution was produced starting with 60 minute extraction batches of a mixture of 25, 33, 50, 75, and 100 g of silk cocoons per batch. The extracted silk fibers were then dissolved using 9.3M LiBr at 100°C for 1 hour in a 100°C oven. 35, 42, 50, and 71 g per batch of silk fibers were dissolved to make 20% silk in LiBr and combined. The dissolved silk in LiBr was then diluted to 1% silk and filtered through a 5 μm filter to remove large debris. 17,000 mL of 1% filtered silk solution was used as the starting volume for TFF/diafiltration volume. Once the LiBr was removed, the solution was ultrafiltered to a volume of around 3000 mL. 1490 mL of 6.44% silk was then collected. Water was added to the feed to help remove residual solution and 1454 mL of 4.88% silk was then collected.
Solution #6 has a silk concentration of 2.70% by weight. A 2.70% silk solution was produced from a 60 minute extraction batch of 25 g silk cocoons per batch. The extracted silk fibers were then dissolved using 9.3M LiBr at 100°C for 1 hour in a 100°C oven. 35.48 g of silk fibers were dissolved per batch to make 20% silk in LiBr. The silk dissolved in LiBr was then diluted to 1% silk and filtered through a 5 μm filter to remove large debris. 1000 mL of 1% filtered silk solution was used as the starting volume of TFF/diafiltration volume. Once the LiBr was removed, the solution was ultrafiltered to a volume of around 300 mL. 312 mL of 2.7% silk was then collected.

The preparation of silk fibroin solutions with high molecular weights is given in Table O.

Silk aqueous coating compositions for application to fibers are provided in Tables P and Q below.

Three silk solutions were utilized in film production with the following results:
Solution #1 has a silk concentration of 5.9%, average MW of 19.8 kDa, and 2.2 PD (made with boiling extraction for 60 minutes, LiBr dissolution at 100° C. for 1 hour).
Solution #2 is 6.4% silk concentration (made with boiling extraction for 30 minutes, LiBr dissolution at 60° C. for 4 hours).
Solution #3 is 6.17% silk concentration (made with boiling extraction for 30 minutes, 100° C. LiBr dissolution over 1 hour).

The film was produced by Rockwood et al. (Nature Protocols, Vol. 6; No. 10; published on-line Sep. 22, 2011; doi: 10.1038/nprot. 2011.379). Add 4 mL of 1% or 2% (wt/vol) silk aqueous solution into a 100 mm Petri dish (silk volume can vary for thicker or thinner films and is not critical) and cover with It was left to dry overnight. The bottom of the vacuum dessicator was filled with water. The dried film was placed in a desiccator and vacuum was applied to water anneal the film for 4 hours before removal from the dish. Films cast from solution #1 did not result in structurally continuous films. The film was broken into several pieces. These film pieces dissolved in water despite the water annealing treatment.

Silk solutions of various molecular weights and/or combinations of molecular weights can be optimized for gel applications. The following provides an example of the process, but it is not intended to be limiting in application or formulation. Three silk solutions were utilized in gel preparation with the following results:
Solution #1 has a silk concentration of 5.9%, average MW of 19.8 kDa, and 2.2 PD (made with boiling extraction for 60 minutes, LiBr dissolution at 100° C. for 1 hour).
Solution #2 is 6.4% silk concentration (made with boiling extraction for 30 minutes, LiBr dissolution at 60° C. for 4 hours).
Solution #3 is 6.17% silk concentration (made with boiling extraction for 30 minutes, 100° C. LiBr dissolution over 1 hour).

"Egel" is a song by Rockwood of al. The electrogelation process as described in . Briefly, 10 ml of silk aqueous solution was added to a 50 ml conical tube and a pair of platinum wire electrodes were immersed into the silk solution. A potential of 20 volts was applied to the platinum electrode for 5 minutes, the power was turned off and the gel was collected. Solution #1 did not form EGEL over 5 minutes of applied current.

Solutions #2 and #3 were gelled according to published horseradish peroxidase (HRP) protocols. The behavior appeared to be typical of published solutions.

Materials and Methods: The following equipment and materials are used in the determination of silk molecular weight: chemstation software ver. Agilent 1100 with 10.01, refractive index detector (RID), analytical balance, volumetric flasks (1000 mL, 10 mL, and 5 mL), HPLC grade water, ACS grade sodium chloride, ACS grade sodium phosphate dibasic 7 Hydrate, phosphoric acid, dextran MW standards - nominal molecular weights 5 kDa, 11.6 kDa, 23.8 kDa, 48.6 kDa, and 148 kDa, 50 mL PET or polypropylene disposable centrifuge tubes, graduated pipettes, amber glass with Teflon caps HPLC vial, Phenomenex PolySep GFC P-4000 column (size: 7.8 mm x 300 mm).

Steps:
A) Preparation of 1 L mobile phase (0.1 M sodium chloride solution in 0.0125 M sodium phosphate buffer).
Take a 250 mL clean dry beaker, place it on the balance and tare it. Approximately 3.3509 g of sodium phosphate dibasic heptahydrate is added to the beaker. Note the exact weight of the sodium phosphate dibasic. Dissolve the weighed sodium phosphate by adding 100 mL of HPLC water into the beaker. Be careful not to spill the contents of the beaker. Carefully transfer the solution into a clean, dry 1000 mL volumetric flask. Rinse the beaker and transfer the rinse solution into the volumetric flask. Repeat rinsing 4 to 5 times. In a separate clean, dry 250 mL beaker, accurately weigh approximately 5.8440 g of sodium chloride. Dissolve the weighed amount of sodium chloride in 50 mL of water and transfer the solution to the sodium phosphate solution in a volumetric flask. Rinse the beaker and transfer the rinse solution into the volumetric flask. Adjust the pH of the solution to 7.0±0.2 using phosphoric acid. Bring up the volume in the volumetric flask to 1000 mL with HPLC water and stir vigorously to mix the solution uniformly. The solution is filtered through a 0.45 μm polyamide membrane filter. Transfer this solution to a clean, dry solvent bottle and label the bottle. The volume of this solution can be varied to the requirements by correspondingly varying the amounts of sodium phosphate dibasic heptahydrate and sodium chloride.

B) Preparation of Dextran Molecular Weight Standards At least five different molecular weight standards are used for each batch of samples run such that the expected value of the sample being tested is sandwiched by the value of the standard used. Six 20 mL scintillation glass vials are each labeled for a molecular weight standard. Accurately weigh approximately 5 mg of each dextran molecular weight standard and record the weight. Dissolve the dextran molecular weight standard in 5 mL of mobile phase to make a 1 mg/mL standard solution.

C) Preparation of the Sample Solution When preparing the sample solution, if there is a limit to the amount of sample available, the preparation may be adjusted as long as the proportions are maintained. Depending on the sample type and silk protein content in the sample, weigh enough sample in a 50 mL disposable centrifuge tube with an analytical balance to make a 1 mg/mL sample solution for analysis. Dissolve the sample in an equal volume of mobile phase to make a 1 mg/mL solution. Cap the tube tightly and mix the sample (in solution). Leave the sample solution at room temperature for 30 minutes. The sample solution is mixed gently again for 1 minute and centrifuged at 4000 RPM for 10 minutes.

D) HPLC Analysis of Samples Transfer 1.0 mL of all standards and sample solutions into individual HPLC vials. Molecular weight standards (one injection of each) and two injections of each sample are made. Analyze all standards and sample solutions using the following HPLC conditions:

Data Analysis and Calculations - Average Molecular Weight Calculations Using Cirrus Software Upload the chromatography data files of the standards and analytical samples into the Cirrus SEC data acquisition and molecular weight analysis software. Calculate the weight average molecular weight (M _w ), number average molecular weight (M _n ), peak average molecular weight (M _p ), and polydispersity for each injection of the sample.

Spider Silk Fragments Spider silk is a natural polymer consisting of three domains: a repetitive intermediate core domain that dominates the protein chain, and a unique N-terminal and C-terminal domain. The large core domain is organized in a block copolymer-like configuration in which two basic sequences, crystalline [poly(A) or poly(GA)] and less crystalline (GGX or GPGXX (SEQ ID NO:6) )) Polypeptides appear alternately. Dragline silk is a protein complex composed of major gland drugline silk protein 1 (MaSp1) and major gland drugline silk protein 2 (MaSp2). Both silks are approximately 3500 amino acids long. MaSp1 can be found in the fiber core and periphery, whereas MaSp2 forms clusters in specific core regions. The large central domains of MaSp1 and MaSp2 are organized in a block copolymer-like configuration in which two basic sequences, crystalline [poly(A) or poly(GA)] and less crystalline (GGX or GPGXX (SEQ ID NO: 6)) polypeptides alternate in the core domain. Specific secondary structures have been assigned to the poly(A)/(GA), GGX, and GPGXX (SEQ ID NO: 6) motifs, including β-sheets, β-helices, and β-spirals, respectively. The primary sequence, composition, and secondary structure elements of the repetitive core domain are involved in the mechanical properties of spider silk, whereas the non-repetitive N- and C-terminal domains are responsible for the doping of liquid silk in the lumen. is essential for the preservation of and fibril formation in the spinning duct.

The main difference between MaSp1 and MaSp2 is the presence of a proline (P) residue, which accounts for 15% of the total amino acid content in MaSp2, whereas MaSp1 is proline-free. N. By calculating the number of proline residues in the clavipes dragline silk, it is possible to estimate the presence of two proteins in the fibers, 81% MaSp1 and 19% MaSp2. Different spiders have different ratios of MaSp1 and MaSp2. For example, dragline silk fibers from the orb weaver Argiope aurantia contain 41% MaSp1 and 59% MaSp2. Such changes in the proportion of major glandular silk can influence the performance of silk fibers.

At least seven different types of silk proteins are known for one orbweaver species of spider. Silks differ in primary arrangement, physical properties and function. For example, dragline silk used to construct frames, radii, and lifelines is known for its outstanding mechanical properties, including strength, toughness, and elasticity. On an equal weight basis, spider silk has higher toughness than steel and Kevlar. The flagellated gland silk found in the entrapment spiral has an extensibility of up to 500%. Flabular gland silk is found in the auxiliary spirals and predation of orb webs, and has high toughness and strength almost similar to macroflagal silk, but does not supercontract in water.

Spider silks are known for their high tensile strength and toughness. Recombinant silk proteins also impart advantageous properties to cosmetic or dermatological compositions, such as being able to improve moisturizing or softening effects, good film-forming properties, and low surface density, among others. . Diverse and unique biomechanical properties, together with biocompatibility and slow degradation rates, make spider silk a biomaterial for tissue engineering, guided tissue repair, and drug delivery, as well as for beauty products (e.g., nail and hair enhancement). agents, skin care products), and industrial materials (e.g. nanowires, nanofibers, surface coatings).

In one embodiment, silk proteins may include polypeptides derived from natural spider silk proteins. The polypeptide is not particularly limited as long as it is derived from a natural spider silk protein; examples of polypeptides include natural spider silk proteins and recombinant spider silk proteins, such as variants, analogs of natural spider silk proteins. , derivatives, or the like. For superior tenacity, the polypeptide can be derived from the major drug line silk protein produced in the macroflaccal gland of spiders. Examples of major drug line silk proteins include the major spidroins MaSp1 and MaSp2 from Nephila clavipes, and ADF3 and ADF4 from Araneus diadematus. Examples of polypeptides derived from major dragline silk proteins include variants, analogs, derivatives, or the like of major dragline silk proteins. Additionally, the polypeptide may be derived from flagellated silk protein produced in the flagellated gland of spiders. Examples of flagellated gland silk proteins include flagellated gland silk proteins derived from Nephila clavipes and the like.

An example of a polypeptide derived from a major drug line silk protein is a polypeptide comprising two or more units of the amino acid sequence represented by formula 1: REP1-REP2 (1), preferably five or more units thereof. polypeptides, and more preferably polypeptides comprising 10 or more units thereof. Alternatively, a polypeptide derived from a major drug line silk protein may be a polypeptide comprising a unit of the amino acid sequence represented by formula 1: REP1-REP2 (1), which at the C-terminus has the entire reference Amino acid sequences represented by any of SEQ ID NOs: 52-54 of U.S. Pat. No. 9,051,453, incorporated by reference, or as illustrated in U.S. Pat. No. 9,051,453, also incorporated by reference in its entirety. It has an amino acid sequence that has 90% or more homology with the amino acid sequence represented by any of SEQ ID NOs: 52 to 54. In polypeptides derived from major drug line silk proteins, the amino acid sequence units represented by formula 1: REP1-REP2 (1) may be the same or different from each other. When producing a recombinant protein using a microorganism such as E. coli as a host, the molecular weight of the polypeptide derived from the main drug line silk protein is 500 kDa or less, or 300 kDa or less, or 200 kDa from the viewpoint of productivity. It is as follows.

In formula (1), REP1 represents polyalanine. In REP1, the number of consecutively arranged alanine residues is preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, and particularly preferably 5 or more. Further, in REP1, the number of consecutively arranged alanine residues is preferably 20 or less, more preferably 16 or less, even more preferably 12 or less, and particularly preferably 10 or less. In formula (1), REP2 is an amino acid sequence composed of 10 to 200 amino acid residues. The total number of glycine, serine, glutamine, and alanine residues contained in the amino acid sequence is 40% or more, preferably 60% or more, and more preferably 70% or more of the total number of amino acid residues contained therein. It is.

In major dragline silk, REP1 corresponds to crystalline regions in the fibers where crystalline β-sheets are formed, and REP2 corresponds to crystalline regions in the fibers where the majority of the parts lack regular organization and have greater flexibility. Corresponds to the amorphous region. Furthermore, [REP1-REP2] corresponds to a repetitive region (repetitive sequence) composed of a crystalline region and an amorphous region, which is a characteristic sequence of drug line silk protein.

Recombinant silk fragments In some embodiments, recombinant silk protein refers to a recombinant spider silk polypeptide, a recombinant insect silk polypeptide, or a recombinant mussel silk polypeptide. In some embodiments, the recombinant silk protein fragments disclosed herein comprise a recombinant spider silk polypeptide of Araneidae or Araneoid, or a recombinant insect silk polypeptide of Bombyx mori. In some embodiments, the recombinant silk protein fragments disclosed herein comprise a recombinant spider silk polypeptide of Araneidae or Araneoid. In some embodiments, the recombinant silk protein fragments disclosed herein comprise a block copolymer with a repeat unit derived from a natural spider silk polypeptide of Araneidae or Araneoid. In some embodiments, the recombinant silk protein fragments disclosed herein comprise a block copolymer with a synthetic repeat unit derived from a spider silk polypeptide of Araneidae or Araneoid, and a non-repeating unit derived from a natural repeat unit of a spider silk polypeptide of Araneidae or Araneoid.

Recent advances in genetic engineering have provided routes for producing various types of recombinant silk proteins. Recombinant DNA technology is being used to provide a more practical source of silk protein. As used herein, "recombinant silk protein" refers to a synthetic protein that is produced heterologously in a prokaryotic or eukaryotic expression system using genetic engineering methods.

Various methods for synthesizing recombinant silk peptides are known and are described by Ausubel et al. , Current Protocols in Molecular Biology §8 (John Wiley & Sons 1987, (1990)), which is incorporated herein by reference. E., a gram-negative rod-shaped bacterium. E. coli is a well-established host for industrial scale production of proteins. Therefore, most of the recombinant silk is E. It has been produced in E.coli. E. Easy to operate. E. coli has a short generation time, is relatively low cost, and can be scaled up for large quantity protein production.

Recombinant silk proteins can be produced by transformed prokaryotic or eukaryotic systems that contain cDNA encoding a silk protein, a fragment of this protein, or an analog of such a protein. Recombinant DNA approaches enable the production of recombinant silk with programmed sequence, secondary structure, structure, and precise molecular weight. There are four main steps in this process: (i) design and assembly of the synthetic silk-like gene into a gene "cassette", (ii) insertion of this segment into a DNA recombinant vector, (iii) host cells. (iv) expression and purification of selected clones.

The term "recombinant vector" as used herein includes any vector known to those skilled in the art, including plasmid vectors, cosmid vectors, phage vectors, such as lambda phage, viral vectors, such as adenovirus or baculovirus vectors, or artificial chromosome vectors, such as bacterial artificial chromosomes (BAC), yeast artificial chromosomes (YAC), or P1 artificial chromosomes (PAC). Such vectors include expression vectors as well as cloning vectors. Expression vectors include plasmids as well as viral vectors, and generally contain a desired coding sequence and suitable DNA sequences necessary for expression of an operably linked coding sequence in a particular host organism (e.g., bacteria, yeast, or plants) or in an in vitro expression system. Cloning vectors are generally used to manipulate and amplify a particular desired DNA fragment and may lack functional sequences necessary for expression of the desired DNA fragment.

Prokaryotic systems include Gram-negative or Gram-positive bacteria. Prokaryotic expression vectors contain an origin of replication that can be recognized by a host organism, a homologous or heterologous promoter that is functional in that host, a DNA sequence encoding a spider silk protein, a fragment of this protein, or a similar protein. can include. Non-limiting examples of prokaryotic expression organisms include Escherichia coli, Bacillus subtilis, Bacillus megaterium, Corynebacterium glutamicum, Anabaena, Caulobacter, Gluconobacterium Acter, Rhodobacter, Pseudomonas, Para coccus, Bacillus (e.g. Bacillus subtilis) Brevibacterium, Corynebacterium, Rhizobium ( Sinorhizobium), Flavobacterium, Klebsiella, Enterobacter, Lactobacillus, Lactococcus, Methylobacterium, Propionibacterium, Staphy lococcus or Streptomyces cells.

Eukaryotic systems include yeast and insect, mammalian or plant cells. In this case, the expression vector may contain a yeast plasmid origin of replication or an autonomously replicating sequence, a promoter, a DNA sequence coding for the spider silk protein, for a fragment or for a similar protein, a polyadenylation sequence, a transcription termination site and finally a selection gene. Non-limiting examples of eukaryotic expression organisms include yeasts, such as Saccharomyces cerevisiae, Pichia pastoris, basidiosporogenous, ascosporogenous, filamentous fungi, such as Aspergillus niger, Aspergillus oryzae, Aspergillus nidulans, Trichoderma reesei, Acremonium chrysogenum, Candida, Hansenula, Kluyveromyces, Saccharomyces (e.g., Saccharomyces cerevisiae), Schizosaccharomyces, Pichia (e.g., Pichia pastoris) or Yarrowia cells, mammalian cells such as HeLa cells, COS cells, CHO cells, insect cells such as Sf9 cells, MEL cells, "insect host cells" such as Spodoptera frugiperda or Trichoplusia ni cells. SF9 cells, SF-21 cells, or High-Five cells, where SF-9 and SF-21 are ovary cells from Spodoptera frugiperda and High-Five cells are Trichoplusia ni., "plant host cells" such as egg cells from tobacco, potato, or pea cells.

Various heterologous host systems have been explored to produce different types of recombinant silk. Recombinant partial spidroins as well as engineered silks have been cloned and tested in bacteria (Escherichia coli), yeast (Pichia pastoris), insects (silkworm larvae), plants (tobacco, soybean, potato, Arabidopsis), and mammalian cell lines (BHT). /hamster) and transgenic animals (mice, goats). The majority of silk proteins are produced with an N-terminal or C-terminal His tag to simplify purification and produce sufficient amounts of protein.

In some embodiments, suitable hosts for expressing recombinant spider silk proteins using heterologous systems can include transgenic animals and plants. In some embodiments, suitable hosts for expressing recombinant spider silk proteins using heterologous systems include bacteria, yeast, and mammalian cell lines. In some embodiments, a suitable host for expressing recombinant spider silk proteins using a heterologous system is E. Contains coli. In some embodiments, suitable hosts for expressing recombinant spider silk proteins using a heterologous system include transgenic B. Including mori.

Recombinant silk proteins in this disclosure include synthetic proteins based on repeat units of natural silk proteins. Besides synthetic repetitive silk protein sequences, these can additionally include one or more natural non-repetitive silk protein sequences.

In some embodiments, "recombinant silk protein" refers to recombinant silkworm silk protein or fragments thereof. Recombinant production of silk fibroin and silk sericin has been reported. A variety of hosts have been used for production, including E. coli, mori, Sacchromyces cerevisiae, Pseudomonas sp., Rhodopseudomonas sp., Bacillus sp., and Strepomyces. See EP 0230702, which is incorporated herein by reference in its entirety.

In this specification, B. Design and biology of silk fibroin protein-like multiblock polymers containing GAGAGX (SEQ ID NO: 1) hexapeptide (X is A, Y, V, or S) derived from the repeat domain of the mori silk heavy chain (H chain) A scientific synthesis is provided.

In some embodiments, the present disclosure provides a B. Silk protein-like multiblock polymers derived from the repeat domains of mori silk heavy chains (H chains) are provided. GAGAGS (SEQ ID NO: 2) hexapeptide is the core unit of the heavy chain and plays an important role in the formation of crystalline domains. Silk protein-like multiblock polymers containing GAGAGS (SEQ ID NO: 2) hexapeptide repeat units spontaneously aggregate into β-sheet structures, similar to natural silk fibroin proteins, where the silk protein-like multiblock polymers in the silk protein-like multiblock polymer may have any weight average molecular weight as described herein.

In some embodiments, the present disclosure provides the B. GAGAGS (SEQ ID NO: 2) hexapeptide repeat fragment derived from the H chain of silk heavy chain of E. mori and E. mori. A silk peptide-like multiblock copolymer is provided that is composed of the mammalian elastin VPGVG (SEQ ID NO: 3) motif produced by E. coli. In some embodiments, the present disclosure provides the B. GAGAGS (SEQ ID NO: 2) hexapeptide repeat fragment derived from the H chain of silk heavy chain of E. mori and E. mori. The present invention provides fused silk fibroin proteins composed of GVGVP (SEQ ID NO: 4) produced by E. coli in a silk protein-like multiblock polymer having any weight average molecular weight as described herein.

In some embodiments, _the present disclosure provides a B.A. mori silkworm recombinant protein is provided. In some embodiments, the present disclosure relates to E. (GAGAGS) ₁₆ (SEQ ID NO: 55) repetitive fragment and non-repetitive (GAGAGS) ₁₆ -F-COOH (SEQ ID NO: 56), (GAGAGS) ₁₆ -F-F-COOH (SEQ ID NO: 57), produced by E. coli. (GAGAGS) ₁₆ -F-F-F-COOH (SEQ ID NO: 58), (GAGAGS) ₁₆ -FF-F-F-COOH (SEQ ID NO: 59), (GAGAGS) ₁₆ -FF-F-F -F-F-F-F-COOH (SEQ ID NO: 60), (GAGAGS) ₁₆ -FF-F-FF-FF-FF-FF-FF-F-F-COOH (SEQ ID NO: 61 ), where F is the following amino acid sequence SGFGPVANGGSGEASSESDFGSSGFGPVANASSGEASSESDFAG (SEQ ID NO: 5), the silk protein-like multiblock polymer having any weight average molecular weight as described herein.

In some embodiments, "recombinant silk protein" refers to a recombinant spider silk protein or fragment thereof. Production of recombinant spider silk proteins based on partial cDNA clones has been reported. The recombinant spider silk protein produced as such contains a portion of the repeat sequences derived from the drug line spider silk protein, Spidroin 1, from the spider Nephila clavipes. Xu et al. (See Proc. Natl. Acad. Sci. U.S.A., 87:7120-7124 (1990). The encoding cDNA clones and their recombinant synthesis are described in J. Biol. Chem., 1992, volume 267, pp. 19320-19324. Recombinant synthesis of spider silk proteins, including, is described in U.S. Pat. No. 5,733,771 and US Pat. No. 5,756,677. A cDNA clone encoding the flagellate silk protein from an orb-web spinning spider has been disclosed in US Pat. No. 5,994,099. No. 6,268,169 is derived from repetitive peptide sequences found in the natural spider drug line of Nephila clavipes by E. coli, Bacillus subtilis, and Pichia pastoris recombinant expression systems. WO 03/020916 describes the recombinant synthesis of spider silk-like proteins. e aurantia, Argiope trifasciata, Gasteracantha mammosa, and Latrodectus geometricus, Argiope trifasciata. A cDNA clone and its recombinant production encoding a spider silk protein with repeat sequences derived from the flagellated gland, the jarred gland of Dolomedes tenebrosus, two sets of silk glands from Plectreurys tristis, and the silk gland of the mygalomorph Euagrus chisoseus are described. Each of the above references is incorporated herein by reference in its entirety.

In some embodiments, the recombinant spider silk protein is a hybrid protein of spider silk protein and insect silk protein, spider silk protein and collagen, spider silk protein and resilin, or spider silk protein and keratin. The spider silk repeating unit is a natural macropharyngeal gland polypeptide, such as a drugline macrovellate spider silk polypeptide, a microvelar gland polypeptide, a flagellated gland polypeptide, an aggregated gland spider silk polypeptide, a vine-like gland spider silk polypeptide, or a pear-like gland spider silk polypeptide. The amino acid sequence comprises or consists of a region comprising or consisting of at least one peptide motif that occurs repeatedly within a spider silk polypeptide or the like.

In some embodiments, the recombinant spider silk proteins of the present disclosure are synthetic spider silks derived from repeat units of natural spider silk proteins, consensus sequences, and, optionally, one or more natural non-repetitive spider silk protein sequences. Contains protein. The repeating unit of a naturally occurring spider silk polypeptide may include an Araneidae or Araneoid drug line spider silk polypeptide or a flagellated spider silk polypeptide.

As used herein, a spider silk "repeat unit" refers to a naturally occurring macropharyngeal gland polypeptide, such as drug line spider silk polypeptide, microvesicular gland polypeptide, flagellated gland polypeptide, aggregated gland spider silk polypeptide. , a grapevine spider silk polypeptide, or a pyriform spider silk polypeptide, or the like. A "repeat unit" is at least one peptide that occurs repeatedly in amino acid sequence within a naturally occurring silk polypeptide (e.g., MaSpI, ADF-3, ADF-4, or Flag) (i.e., identical amino acid sequence). A region corresponding to a region comprising or consisting of a motif (e.g., AAAAAA (SEQ ID NO: 20)) or GPGQQ (SEQ ID NO: 15)) or an amino acid sequence substantially similar thereto (i.e., a variant amino acid sequence) refers to A "repeat unit" having an amino acid sequence that is "substantially similar" to a corresponding amino acid sequence within a native silk polypeptide (i.e., a wild-type repeat unit) is also similar with respect to its properties, e.g. Silk proteins that contain "substantially similar repeat units" remain insoluble and retain their insolubility. For example, a "repeat unit" having an amino acid sequence that is "identical" to the amino acid sequence of a natural silk polypeptide may include MaSpI (SEQ ID NO: 48), MaSpII (SEQ ID NO: 49), ADF-3 (SEQ ID NO: 50), and/or or a portion of a silk polypeptide that corresponds to one or more peptide motifs of ADF-4 (SEQ ID NO: 51). For example, "repeat units" having amino acid sequences "substantially similar" to the amino acid sequences of natural silk polypeptides include MaSpI (SEQ ID NO: 48), MaSpII (SEQ ID NO: 49), ADF-3 (SEQ ID NO: 50). ), and/or ADF-4 (SEQ ID NO: 51), but may be a portion of a silk polypeptide that has one or more amino acid substitutions at specific amino acid positions. .

As used herein, the term "consensus peptide sequence" refers to an amino acid sequence that includes an amino acid that occurs frequently at a particular position (e.g., G), where other amino acids not yet determined are replaced by the placeholder "X." In some embodiments, the consensus sequence is at least one of: (i) GPGXX (SEQ ID NO: 6), where X is an amino acid selected from A, S, G, Y, P, and Q; (ii) GGX, where X is an amino acid selected from Y, P, R, S, A, T, N, and Q, preferably Y, P, and Q; (iii) A _x , where x is an integer from 5 to 10.

The consensus peptide sequences GPGXX (SEQ ID NO: 6) and GGX, a glycine-rich motif, provide flexibility to silk polypeptides and thus to sutures formed from silk proteins containing the motifs. In particular, the repeated GPGXX (SEQ ID NO: 6) motif forms a turned helical structure and confers elasticity to the silk polypeptide. Both the major gland and flagellated gland silks have the GPGXX (SEQ ID NO: 6) motif. The repeated GGX motif is associated with a helical structure with three amino acids per turn and is found in most spider silks. The GGX motif may provide additional elastic properties to silk. Repeated polyalanine Ax (peptide) motifs form crystalline β-sheet structures that provide strength to silk polypeptides, as described, for example, in WO 03/057727.

In some embodiments, the recombinant spider silk protein of the present disclosure comprises two identical repeating units, each from the group consisting of GGRPSDTYG (SEQ ID NO: 7) and GGRPSSSYG (SEQ ID NO: 8) derived from resilin. at least one, preferably one, selected amino acid sequence. Resilin is an elastomeric protein found in most arthropods that provides low stiffness and high strength.

As used herein, "unrepeat unit" means within a naturally occurring drug line polypeptide (i.e., a wild type non-repeat (carboxy-terminal) unit), preferably the entirety of which is herein incorporated by reference. ADF-3 (SEQ ID NO: 50), ADF-4 (SEQ ID NO: 51), NR3 (SEQ ID NO: 62), NR4 (SEQ ID NO: 63) of the spider Araneus diadematus, also described in incorporated US Pat. No. 9,217,017. ), the C16 peptide (spider silk protein eADF4, molecular weight of 47.7 kDa, AMSilk), comprising 16 repeats of the corresponding non-repetitive (carboxy-terminal) amino acid sequence, sequence GSSAAAAAASGPGGYGPENQGPSGPGGYGPGGP (SEQ ID NO: 9), A. refers to an amino acid sequence that is "substantially similar" to the amino acid sequence adapted from the natural sequence of ADF4 from P. diadematus. Non-repetitive ADF-4 and its variants exhibit efficient assembly behavior.

Among the synthetic spider silk proteins, the recombinant silk proteins in this disclosure include, in some embodiments, the polypeptides described in U.S. Patent No. 8,288,512, which is also incorporated herein by reference in its entirety. Contains the C16 protein having the peptide sequence SEQ ID NO: 64. In addition to the polypeptide sequence shown in SEQ ID NO: 64, also included are functional equivalents, functional derivatives, and salts of this sequence, among others.

As used herein, "functional equivalent" refers to a variant having an amino acid other than the specifically mentioned amino acid in at least one sequence position of the above amino acid sequence.

In some embodiments, the recombinant spider silk proteins of the present disclosure are administered in an effective amount by Xu et al. , PNAS, USA, 87, 7120, (1990). Biol. Chem. , 267, 19320, (1922), U.S. Patent Application No. 2016/0222174, and U.S. Pat. 089, 8,173,772, 8,642,734, 8,367,803, 8,097,583, 8,030,024, 7,754,851, 7,148,039, 7,060,260, or alternatively minor as described in patent application no. WO 95/25165. At least one natural silk protein or recombinant silk protein, including a spider silk protein, corresponding to Spidroins. Each of the references cited above is incorporated herein by reference in its entirety. Additional recombinant spider silk proteins suitable for the recombinant RSPF of the present disclosure include ADF3 and ADF4 from the "flagular" gland of Araneus diadematus.

Recombinant silk has also been described in other patents and patent applications, which are incorporated herein by reference: US2004/590196, US7,754,851, US2007/654470, US7,951,908, US2010/ 785960, US8,034,897, US2009/0263430, US2008/226854, US2009/0123967, US2005/712095, US2007/991037, US2009/0162896, US2008/85266, US8, 372,436, US2007/989907, US2009/267596, US2010/319542, US2009/265344, US2012/684607, US2004/583227, US8,030,024, US2006/643569, US7,868,146, US2007/991916, US8,097,583, US2 006/643200, US8,729, 238, US8,877,903, US2019/0062557, US2016/0280960, US2011/0201783, US2008/991916, US2011/986662, US2012/697729, US2015/0328363, US9,0 34,816, US2013/0172478, US9,217, 017, US2017/0202995, US8,721,991, US2008/227498, US9,233,067, US8,288,512, US2008/161364, US7,148,039, US1999/247806, US2001/861597, US2004/887100, US9,481,719, US8,765,688, US2008/80705, US2010/809102, US8,367,803, US2010/664902, US7,569,660, US1999/138833, US2000/591632, US2012 /0065126,US2010/ U S2005/0227322 and US2004/4418.

Recombinant silk has also been described in other patents and patent applications, incorporated herein by reference: US2019/0062557, US2015/0284565, US2013/0225476, US2013/0172478, US2013/0136779, US2013/ 0109762, US2012/0252294, US2011/0230911, US2011/0201783, US2010/0298877, US10,478,520, US10,253,213, US10,072,152, US9,233,067, US9, 217,017, US9, 034,816, US8,877,903, US8,729,238, US8,721,991, US8,097,583, US8,034,897, US8,030,024, US7,951,908, US7,868, 146, and US 7,754,851.

In some embodiments, the recombinant spider silk proteins of the present disclosure comprise or consist of 2 to 80 repeating units, each of which is defined herein as GPGXX (SEQ ID NO: 6). , GGX, and _Ax .

In some embodiments, the recombinant spider silk proteins of the present disclosure include GPGAS (SEQ ID NO: 10), GPGSG (SEQ ID NO: 11), GPGGY (SEQ ID NO: 11), as described in U.S. Patent No. 8,877,903. No. 12), GPGGP (SEQ ID NO: 13), GPGGA (SEQ ID NO: 14), GPGQQ (SEQ ID NO: 15), GPGGG (SEQ ID NO: 16), GPGQG (SEQ ID NO: 17), GPGGS (SEQ ID NO: 18), GGY, GGP, GGA, GGR, GGS, GGT, GGN, GGQ, AAAAAA (SEQ ID NO: 19), AAAAAA (SEQ ID NO: 20), AAAAAAA (SEQ ID NO: 21), AAAAAAAAA (SEQ ID NO: 22), AAAAAAAAA (SEQ ID NO: 23), AAAAAAAAAA (SEQ ID NO: 23) No. 24), GGRPSDTYG (SEQ ID No. 7), and GGRPSSSYG (SEQ ID No. 8), (i) GPYGPGASAAAAAAGGYGPGSGQQ (SEQ ID No. 25), (ii) GSSAAAAAASGPGGYGPENQGPSGPGGYGPGGP (SEQ ID No. 9), (iii) GPG QQGPGQQGPGQQGPGQQ (SEQ ID NO: 26), ( iv) GPGGAGGPYGPGGAGGPYGPGGAGGPY (SEQ ID NO: 27), (v) GGTTIIEDLDITIDGADGPITISEELTI (SEQ ID NO: 28), (vi) PGSSAAAAAAASGPGQGQGQGQGQGGRPSDTYG (SEQ ID NO: 29), (vi i) SAAAAAAAAAAGPGGGNGGRPSDTYGAPGGGNGGRPSSSYG (SEQ ID NO: 30), (viii) GGAGGAGGAGGSGGAGGS (SEQ ID NO: 31), ( ix) GPGGAGPGGYGPGGSGPGGYGPGGSGPGGY (SEQ ID NO: 32), (x) GPYGPGASAAAAAAGGYGPGCGQQ (SEQ ID NO: 33), (xi) GPYGPGASAAAAAAAGGYGPGKGQQ (SEQ ID NO: 34), (xii) GSSAAAAAA AASGPGGYGPENQGPCGPGGYGPGGP (SEQ ID NO: 35), (xiii)GSSAAAAAAASGPGGYGPKNQGPSGPGGYGPGGP (SEQ ID NO: 36), ( xiv) GSSAAAAAAASGPGGYGPKNQGPCGPGGYGPGGP (SEQ ID NO: 37), or a variant thereof, for example, the sequence order of GPGAS (SEQ ID NO: 10), GGY, GPGSG (SEQ ID NO: 11) in the peptide chain, or AAAAAAAAAA (SEQ ID NO: 22) in the peptide chain, selected from the group consisting of synthetic spider peptides having the sequence order GPGGY (SEQ ID NO: 12), GPGGP (SEQ ID NO: 13), and the sequence sequence AAAAAAAAAA (SEQ ID NO: 22), GPGQG (SEQ ID NO: 17), GGR in the peptide chain. comprising or consisting of repeating units each independently selected from

In some embodiments, the present disclosure provides silk protein-like multimodules that mimic repeating units of amino acids derived from natural spider silk proteins, such as spidroin major 1 domain, spidroin major 2 domain, or spidroin minor 1 domain. Provides a profile of variation between block peptides and repeat units without modification of three-dimensional conformation, where these silk protein-like multiblock peptides have the following sequences (I), (II), (III). , and/or (IV).

[(XGG) _w (XGA) (GXG) _x (AGA) _y (G) _z AG] _p (SEQ ID NO: 38) Formula (I), where X corresponds to tyrosine or glutamine, and w is 2 or is an integer equal to 3, x is an integer from 1 to 3, y is an integer from 5 to 7, z is an integer equal to 1 or 2, and p is an integer; having any weight average molecular weight as described, and/or [(GPG ₂ YGPGQ ₂ ) _a (X') ₂ S(A) _b ] _p (SEQ ID NO: 39) formula (II), where X' corresponds to the amino acid sequence GPS or GPG, a is equal to 2 or 3, b is an integer from 7 to 10, and p is an integer and has any weight average molecular weight as described herein. and/or [(GR)(GA) _l (A) _m (GGX) _n (GA) _n (A) _m ] _p (SEQ ID NO: 40) Formula (III) and/or [(GGX") _n ( GA) _m (A) _l ] _p (SEQ ID NO: 41) Formula (IV), where X'' corresponds to tyrosine, glutamine, or alanine, l is an integer from 1 to 6, and m is 0 to 4 n is an integer from 1 to 4, and p is an integer.

In some embodiments, a recombinant spider silk protein or an analog of a spider silk protein comprising an amino acid repeat unit of sequence (V):
[ ₍ Xaa Gly Gly) _{w (} Xaa Gly _Ala ) (Gly or an integer equal to 3, x is an integer from 1 to 3, y is an integer from 5 to 7, z is an integer equal to 1 or 2, and p is an integer.

In some embodiments, the recombinant spider silk proteins of this disclosure are ADF-3 or a variant thereof, ADF-4 or a variant thereof, as described in U.S. Patent No. 9,217,017. , MaSpI or a variant thereof, MaSpII or a variant thereof.

In some embodiments, the present disclosure provides water-soluble recombinant spider silk proteins produced in mammalian cells. The solubility of spider silk proteins produced in mammalian cells is due to the presence of a COOH terminus in these proteins, which makes them more hydrophilic. These COOH-terminal amino acids are not present in spider silk proteins expressed in microbial hosts.

In some embodiments, the recombinant spider silk proteins of the present disclosure include GCGGGGGGG (SEQ ID NO: 42), GKGGGGGG (SEQ ID NO: 43), GCGGSGGGGSGGGG (SEQ ID NO: 44), GKGGGGGGSGGGGG (SEQ ID NO: 45), and GCGGGGGGSGGGG (SEQ ID NO: 45). 46), a water-soluble recombinant spider silk protein C16 modified at the amino or carboxyl terminus. In some embodiments, the recombinant spider silk proteins of the present disclosure include _C16NR4 , _C32NR4 , C16, C32, _NR4C16 , such that the molecular weight of the protein is in the ranges described herein. NR4, NR4C ₃₂ NR4, NR3C ₁₆ NR3, or NR3C ₃₂ NR3.

In some embodiments, the recombinant spider silk proteins of the present disclosure are derived from A. The present invention includes a recombinant spider silk protein having a synthetic repeat peptide segment and amino acid sequence adapted from the natural sequence of ADF4 from P. diadematus. In some embodiments, the RSPF of the present disclosure comprises a recombinant spider silk protein having repeat peptide units derived from a natural spider silk protein, such as a Spidroin major 1 domain, a Spidroin major 2 domain, or a Spidroin minor 1 domain; The peptide sequence is GSSAAAAAAAAASGPGQGQGQGQGQGGRPSDTYG (SEQ ID NO: 47) or SAAAAAAAAGPGGGNGGRPSDTYGAPGGGNGGRPSSSYG (SEQ ID NO: 30), as described in U.S. Patent No. 8,367,803, herein incorporated by reference in its entirety. .

In some embodiments, the present disclosure provides a recombinant spider protein composed of GPGGAGPGGYGPGGSGPGGYGPGGSGPGGY (SEQ ID NO: 32) repeat fragment and having a molecular weight described herein.

As used herein, the term "recombinant silk" refers to recombinant spider and/or silkworm silk proteins or fragments thereof. In one embodiment, the spider silk proteins include band silk (graptic gland silk), egg sac silk (columnar gland silk), egg case silk (tubular gland silk), non-adhesive dragline silk (macro gland silk), adherent selected from the group consisting of thread silk (pyriform gland silk), sticky silk core fibers (flagellate gland silk), and sticky outer silk fibers (agglomerated gland silk). For example, recombinant spider silk proteins are described in US Patent Application No. 2016/0222174 and US Pat. , 689,089, 8,173,772, and 8,642,734.

Some organisms produce multiple silk fibers with unique arrangements, structural elements, and mechanical properties. For example, orb-weaving spiders have six unique types of glands that produce different silk polypeptide sequences polymerized into fibers tailored to suit the environment or life cycle niche. Fibers are named after the gland from which they are derived, and polypeptides are labeled with the glandular abbreviation (eg, "Ma") and "Sp" for spidroin (abbreviation for spider fibroin). In orb weavers, these types are macroflactal glands (MaSp, also called draglines), miraculous glands (MiSp), flagellar glands (Flag), grapelike glands (AcSp), tubular glands (TuSp), and piriform glands (TuSp). Contains the PySp. This combination of polypeptide sequences spanning fiber types, domains, and variation between different genera and species leads to a wide range of potential properties that can be exploited by commercial production of recombinant fibers. To date, most of the research using recombinant silk has focused on malocular gland spidroin (MaSp).

Acute glandular (AcSp) silks tend to have high toughness as a result of a combination of moderately high strength and moderately high extensibility. AcSp silks are characterized by large block (“ensemble repeat”) sizes that often incorporate polyserine and GPX motifs. Tubular (TuSp or cylindrical) silks tend to have large diameters, with moderate strength and high extensibility. TuSp silks are characterized by their polyserine and polythreonine content and short tubes of polyalanine. MaSp silks tend to have high strength and moderate extensibility. MaSp silks can be one of two subtypes, MaSp1 and MaSp2. MaSp1 silk is generally less extensible than MaSp2 silk and is characterized by polyalanine, GX, and GGX motifs. MaSp2 silk is characterized by polyalanine, GGX, and GPX motifs. Milial gland (MiSp) silk tends to have moderate strength and moderate extensibility. MiSp silk is characterized by GGX, GA, and polyA motifs and often contains a spacer element of about 100 amino acids. Flag silk tends to have very high extensibility and moderate strength. Flag silk is typically characterized by GPG, GGX, and short spacer motifs.

Silk polypeptides are characteristically composed of repetitive domains (REPs) flanked by non-repetitive regions (eg, a C-terminal domain and an N-terminal domain). In one embodiment, both the C-terminal domain and the N-terminal domain are 75-350 amino acids long. Repetitive domains exhibit hierarchical structure. A repeating domain includes a series of blocks (also called repeating units). The blocks are repeated throughout the silk repeat domain, sometimes completely and sometimes incompletely (forming quasi-repeat domains). Block length and composition vary between and across different silk types. Table 1 of U.S. Published Application No. 2016/0222174, incorporated herein in its entirety, lists examples of block sequences from selected species and silk types, and further examples are provided by Rising, A. et al. , Spider silk proteins: recent advances in recombinant production, structure-function relationships and biomedical application s, Cell Mol. Life Sci. , 68:2, pg169-184 (2011), and Gatesy, J. et al. , Extreme diversity, conservation, and convergence of spider silk fibroin sequences, Science, 291:5513, pg. 2603-2605 (2001). In some cases, the blocks are arranged in a regular pattern to form larger macrorepeats that appear multiple times (usually 2-8) in the repeat domain of the silk sequence. Repeat blocks within a repeat domain or macrorepeat, and repeat macrorepeats within a repeat domain, may be separated by spacing elements.

Structures of certain spider silk block copolymer polypeptides from block and/or macrorepeat domains according to certain embodiments of the present disclosure are illustrated in US Patent Application Publication No. 2016/0222174.

Recombinant block copolymer polypeptides based on spider silk sequences produced by gene expression in recombinant prokaryotic or eukaryotic systems can be purified according to methods known in the art. In preferred embodiments, commercially available expression/secretion systems can be used whereby the recombinant polypeptide is expressed and subsequently secreted from the host cell and easily purified from the surrounding medium. . If an expression/secretion vector is not used, an alternative approach is to recombine the polypeptide from a cell lysate (the remainder of the cell after disruption of cell integrity) derived from the prokaryotic or eukaryotic cell in which it was expressed. and purifying the block copolymer polypeptide. Methods for the production of such cell lysates are known to those skilled in the art. In some embodiments, recombinant block copolymer polypeptides are isolated from cell culture supernatants.

Recombinant block copolymer polypeptides can be isolated by affinity separation, e.g., for the isolation of recombinant polypeptides tagged with 6 to 8 histidine residues at their N- or C-terminus. or may be purified by immunological interaction with an antibody that specifically binds to a nickel column; alternative tags may include FLAG epitopes or hemagglutinin epitopes. Such methods are commonly used by those skilled in the art.

Solutions of such polypeptides (ie, recombinant silk proteins) may then be prepared and used as described herein.

In another embodiment, recombinant silk proteins may be prepared according to the methods described in U.S. Patent No. 8,642,734, incorporated herein in its entirety and described herein. used as such.

In one embodiment, recombinant spider silk proteins are provided. Spider silk proteins typically have 170-760 amino acid residues, such as 170-600 amino acid residues, preferably 280-600 amino acid residues, such as 300-400 amino acid residues, more preferably 340-380 amino acid residues. Consists of amino acid residues. Small size is advantageous. This is because longer spider silk proteins tend to form amorphous aggregates, which require the use of harsh solvents for solubilization and polymerization. The recombinant spider silk protein may contain more than 760 residues, particularly if the spider silk protein contains three or more fragments derived from the N-terminal portion of the spider silk protein, and the spider silk protein It comprises an N-terminal fragment consisting of at least one fragment (NT) derived from a corresponding part of a silk protein and a repeat fragment (REP) derived from a corresponding internal fragment of a spider silk protein. Optionally, the spider silk protein comprises a C-terminal fragment (CT) derived from a corresponding fragment of a spider silk protein. Spider silk proteins typically include a single fragment (NT) derived from the N-terminal portion of a spider silk protein; however, in preferred embodiments, the N-terminal fragments include at least two, e.g. including two fragments (NT) derived from the N-terminal portion of Thus, a spidroin can be represented schematically by the formula NT _m -REP, and alternatively NT _m -REP-CT, where m is 1 or more, such as 2 or more, preferably 1 to 2, 1 -4, 1-6, 2-4, or an integer within the range of 2-6. Preferred spidroins can be represented schematically by the formula NT ₂ -REP or NT-REP, and alternatively NT ₂ -REP-CT or NT-REP-CT. Protein fragments are typically covalently linked via peptide bonds. In one embodiment, the spider silk protein is comprised of a NT fragment attached to a REP fragment, which is optionally attached to a CT fragment.

In one embodiment, the first step of the method of producing a polymer of isolated spider silk proteins comprises expression of a polynucleic acid molecule encoding a spider silk protein in a suitable host, such as E. coli. The protein thus obtained is isolated using standard procedures. Optionally, lipopolysaccharides and other pyrogens are actively removed at this stage.

In the second step of the method of producing a polymer of isolated spider silk proteins, a solution of spider silk proteins in a liquid medium is provided. The terms "soluble" and "in solution" mean that the protein does not visibly aggregate or precipitate out of the solvent at 60,000 x g. The liquid medium can be any suitable medium, such as an aqueous medium, preferably a physiological medium, typically a buffered aqueous medium, such as a 10-50 mM Tris-HCl buffer or a phosphate buffer. can. The liquid medium has a pH of 6.4 or higher and/or an ionic composition that prevents polymerization of spider silk proteins. That is, the liquid medium has either a pH of 6.4 or higher, or an ionic composition that prevents polymerization of spider silk proteins, or both.

Ionic compositions that prevent polymerization of spider silk proteins can be readily prepared by those skilled in the art using the methods disclosed herein. A preferred ionic composition that prevents polymerization of spider silk proteins has an ionic strength of greater than 300 mM. Particular examples of ionic compositions that prevent the polymerization of spider silk proteins include greater than 300 mM NaCl, 100 mM phosphate, and combinations of these ions that have the desired preventive effect on the polymerization of spider silk proteins, e.g. of phosphate and 300mM NaCl.

The presence of NT fragments improves solution stability and prevents polymer formation under these conditions. This may be advantageous when immediate polymerization may not be desirable, for example during protein purification, during large batch preparation, or when other conditions need to be optimized. The pH of the liquid medium may be adjusted to 6.7 or higher, such as 7.0 or higher, or even 8.0 or higher, such as up to 10.5, to achieve high solubility of spider silk proteins. preferable. It may also be advantageous for the pH of the liquid medium to be adjusted to a range of 6.4-6.8, thereby providing sufficient solubility of spider silk proteins, but after pH adjustment is promoted to below 6.3.

In the third step, the properties of the liquid medium are adjusted to a pH below 6.3 and an ionic composition that allows polymerization. That is, if the liquid medium in which the spider silk protein is dissolved has a pH of 6.4 or higher, the pH is reduced to 6.3 or lower. Those skilled in the art will be well aware of various ways to accomplish this, typically including the addition of strong or weak acids. If the liquid medium in which spider silk proteins are dissolved has an ionic composition that prevents polymerization, the ionic composition changes to allow polymerization. Those skilled in the art are well aware of various ways to accomplish this, such as dilution, dialysis, or gel filtration. If necessary, this step includes reducing the pH of the liquid medium to below 6.3 and changing the ionic composition to enable polymerization. The pH of the liquid medium is preferably adjusted to 6.2 or less, for example 6.0 or less. In particular, it is practical to limit the pH drop from 6.4 or 6.4-6.8 in the previous step to 6.3 or 6.0-6.3, e.g. 6.2, in this step. This can be advantageous from a certain point of view. In a preferred embodiment, the pH of the liquid medium of this step is greater than or equal to 3, such as greater than or equal to 4.2. The resulting pH range, for example 4.2 to 6.3, promotes rapid polymerization.

In the fourth step, spider silk proteins can be polymerized in a liquid medium with a pH of 6.3 or less and an ionic composition that allows polymerization of spider silk proteins. The presence of NT fragments improves the solubility of spider silk proteins at pHs above 6.4 and/or the ionic composition that prevents polymerization of spider silk proteins, since the ionic composition accelerates polymer formation at pH below 6.3. The resulting polymers are preferably solid and macroscopic; they are formed in a liquid medium with a pH below 6.3 and an ionic composition that allows polymerization of spider silk proteins. In a preferred embodiment, the pH of the liquid medium of this step is greater than or equal to 3, such as greater than or equal to 4.2. The resulting pH range, e.g., 4.2 to 6.3, promotes rapid polymerization, and the resulting polymers are provided at the molecular weights described herein and are suitable for article coating. It may also be prepared as a solution form which can be used as required.

Ionic compositions that enable polymerization of spider silk proteins can be readily prepared by those skilled in the art using the methods disclosed herein. Preferred ionic compositions that allow polymerization of spider silk proteins have an ionic strength of less than 300 mM. Specific examples of ionic compositions that enable the polymerization of spider silk proteins include 150 mM NaCl, 10 mM phosphate, 20 mM phosphate, and those ions that lack a preventive effect on the polymerization of spider silk proteins. combinations, such as 10 mM phosphate or a combination of 20 mM phosphate and 150 mM NaCl. The ionic strength of this liquid medium is preferably adjusted to a range of 1 to 250 mM.

Without wishing to be limited to any particular theory, NT fragments have oppositely charged poles, and environmental changes in pH affect the charge balance on the surface of the protein, leading to polymerization and other It is assumed that salt inhibits the same event.

At neutral pH, polymerization would be expected to be prevented by the energetic cost of burying the excess negative charge at the acidic pole. However, as the dimer approaches its isoelectric point at lower pH, attractive electrostatic forces eventually dominate, explaining the observed salt- and pH-dependent polymerization behavior of NTs and NT-containing minispidroins. In some embodiments, it is proposed that the pH-induced NT polymerization and increased efficiency of NT-minispidroin fibril assembly are due to changes in surface electrostatic potential, and that clustering of acidic residues at one pole of the NTs shifts their charge balance, causing a polymerization transition at pH values below 6.3.

In a fifth step, the resulting, preferably solid, spider silk protein polymer is isolated from the liquid medium. Optionally, this step includes actively removing lipopolysaccharides and other pyrogens from the spidroin polymer.

Without wishing to be limited to any particular theory, it has been observed that the formation of spidroin polymers proceeds through the formation of water-soluble spidroin dimers. The present disclosure thus also provides a method of producing an isolated spider silk protein dimer, the first two method steps being as described above. Spider silk proteins exist as dimers in liquid media at a pH of 6.4 or higher and/or ionic compositions that prevent polymerization of the spider silk proteins. The third step involves isolating the dimer obtained in the second step, optionally including removal of lipopolysaccharides and other pyrogens. In preferred embodiments, the spider silk protein polymers of the present disclosure consist of polymerized protein dimers. The present disclosure thus provides novel uses of spider silk proteins, preferably those disclosed herein, to produce dimers of spider silk proteins.

According to another aspect, the present disclosure provides a polymer of the spider silk protein disclosed herein. In one embodiment, the polymer of the protein is obtainable by any one of the methods according to the present disclosure. Thus, the present disclosure provides various uses of recombinant spider silk proteins, preferably those disclosed herein, for producing polymers of spider silk proteins as recombinant silk-based coatings. According to one embodiment, the present disclosure provides a novel use of dimers of spider silk proteins, preferably those disclosed herein, for producing polymers of isolated spider silk proteins as recombinant silk-based coatings. In these uses, the polymer is preferably produced in a liquid medium having a pH of 6.3 or less and an ionic composition that allows polymerization of the spider silk protein. In one embodiment, the pH of the liquid medium is 3 or more, such as 4.2 or more. The resulting pH range, for example 4.2 to 6.3, promotes rapid polymerization,

Using the methods of the present disclosure, it is possible to control the polymerization process, which allows optimization of parameters to obtain silk polymers with desired properties and shapes.

In one embodiment, the recombinant silk proteins described herein include those described in US Pat. No. 8,642,734, which is incorporated by reference in its entirety.

In another embodiment, the recombinant silk proteins described herein may be prepared according to the methods described in U.S. Patent No. 9,051,453, herein incorporated by reference in its entirety. Incorporated.

The amino acid sequence represented by SEQ ID NO: 52, which is also explained in US Pat. Accession number: AAC47010, GI: 1263287). The amino acid sequence represented by SEQ ID NO: 53, also described in U.S. Pat. No. 9,051,453, is also described in U.S. Pat. No. 9,051,453, with 20 residues removed from the C-terminus. The amino acid sequence is identical to the amino acid sequence represented by SEQ ID NO: 52. The amino acid sequence represented by SEQ ID NO: 54, which is also described in U.S. Patent No. 9,051,453, is identical to the amino acid sequence represented by SEQ ID NO: 52, with 29 residues removed from the C-terminus. .

Formula 1: Contains an amino acid sequence unit represented by REP1-REP2 (1), and has an amino acid sequence represented by any of SEQ ID NOs: 52 to 54 at the C-terminus or also described in US Patent No. 9,051,453 Examples of polypeptides having an amino acid sequence having 90% or more homology with any of SEQ ID NOs: 52-54 include US Pat. It is a polypeptide having the amino acid sequence represented by SEQ ID NO: 65, which is also described in No. 051,453. A polypeptide having the amino acid sequence represented by SEQ ID NO: 65, which is also described in US Pat. No. 9,051,453, is obtained by the following mutation: The amino acid sequence consists of a start codon, a His10 tag, and an HRV3C protease (human rhinovirus 3C protease) recognition site at its N-terminus (SEQ ID NO: also described in US Pat. No. 9,051,453). 66) is added, the 1st to 13th repeat region is approximately doubled, and translation ends at the 1154th amino acid residue. In the polypeptide having the amino acid sequence represented by SEQ ID NO: 65, which is also described in US Pat. No. 9,051,453, the C-terminal sequence is identical to the amino acid sequence represented by SEQ ID NO: 54.

Furthermore, it contains a unit of the amino acid sequence represented by formula 1: REP1-REP2 (1), and at the C-terminus, a unit represented by any of SEQ ID NOs: 52 to 54, which is also described in US Pat. No. 9,051,453. A polypeptide having an amino acid sequence having 90% or more homology with the amino acid sequence represented by the amino acid sequence represented by , having the amino acid sequence represented by SEQ ID NO: 65, also described in U.S. Patent No. 9,051,453, in which one or more amino acids have been substituted, deleted, inserted, and/or added; And it can be a protein having a repeating region composed of a crystalline region and an amorphous region.

Additionally, examples of polypeptides containing two or more units of the amino acid sequence represented by Formula 1: REP1-REP2 (1) are found in U.S. Pat. No. 9,051,453, which is incorporated herein by reference in its entirety. A recombinant protein derived from ADF4 having the amino acid sequence represented by SEQ ID NO: 67, which is also described in the following. The amino acid sequence represented by SEQ ID NO: 67, which is also explained in US Patent No. 9,051,453, is the N By adding to the end an amino acid sequence (SEQ ID NO: 66, which is also explained in U.S. Patent No. 9,051,453) consisting of a start codon, a His10 tag, and an HRV3C protease (human rhinovirus 3C protease) recognition site. This is the obtained amino acid sequence. Furthermore, a polypeptide containing two or more units of the amino acid sequence represented by Formula 1: REP1-REP2 (1) has one or more amino acids substituted, deleted, inserted, and/or added. A polypeptide having the amino acid sequence represented by SEQ ID NO: 67, which is also described in U.S. Pat. obtain. Additionally, examples of polypeptides containing two or more units of the amino acid sequence represented by Formula 1: REP1-REP2 (1) are found in U.S. Pat. No. 9,051,453, which is incorporated herein by reference in its entirety. A recombinant protein derived from MaSp2 having the amino acid sequence represented by SEQ ID NO: 68, which is also described in the following. The amino acid sequence represented by SEQ ID NO: 68, which is also described in U.S. Patent No. 9,051,453, is the N By adding to the end an amino acid sequence (SEQ ID NO: 66, which is also explained in U.S. Patent No. 9,051,453) consisting of a start codon, a His10 tag, and an HRV3C protease (human rhinovirus 3C protease) recognition site. This is the obtained amino acid sequence. Furthermore, a polypeptide containing two or more units of the amino acid sequence represented by Formula 1: REP1-REP2 (1) has one or more amino acids substituted, deleted, inserted, and/or added. , U.S. Pat. No. 9,051,453, and has a repeat region consisting of a crystalline region and an amorphous region.

Examples of polypeptides derived from flagellated gland silk proteins include polypeptides comprising 10 or more units of the amino acid sequence represented by formula 2: REP3 (2), preferably 20 or more units thereof, and More preferably, it includes a polypeptide containing 30 or more units thereof. When producing a recombinant protein using a microorganism such as Escherichia coli as a host, the molecular weight of the polypeptide derived from the flagellated gland silk protein is preferably 500 kDa or less, more preferably 300 kDa, from the viewpoint of productivity. It is more preferably 200 kDa or less.

In formula (2), REP3 represents an amino acid sequence consisting of Gly-Pro-Gly-Gly-X (SEQ ID NO: 69), where X is selected from the group consisting of Ala, Ser, Tyr, and Val. Indicates amino acids.

The main feature of spider silk is that flagellated silk does not have crystalline regions, but has repeating regions composed of amorphous regions. Because primary dragline silks and the like have repeating regions composed of crystalline and amorphous regions, they are expected to have both high stress and stretchability. On the other hand, for flagellated gland silk, the stress is lower than that of major dragline silk, but its elasticity is high. The reason for this is believed to be that the majority of the flagellated gland silk is composed of amorphous regions.

Examples of polypeptides comprising 10 or more units of the amino acid sequence represented by Formula 2: REP3(2) are also described in U.S. Pat. No. 9,051,453, which is incorporated herein by reference in its entirety. It is a recombinant protein derived from flagellated gland silk protein having the amino acid sequence represented by SEQ ID NO:70. The amino acid sequence represented by SEQ ID NO: 70, which is also described in US Pat. Partial sequences of the protein, specifically its amino acid sequence from the 1220th residue to the 1659th residue from the N-terminus (referred to as the PR1 sequence) corresponding to repeats and motifs, are stored in the NCBI database (NCBI Access Session number: AAC38847, GI: 2833649) partial sequence of the flagellated gland silk protein of Nephila clavipes, specifically the C-terminal amino acid sequence from the 816th residue to the 907th residue from the C-terminus. N of the combined sequence, followed by an amino acid sequence consisting of a start codon, a His10 tag, and an HRV3C protease recognition site (SEQ ID NO: 66, also described in U.S. Pat. No. 9,051,453). This is the amino acid sequence obtained by adding it to the end. Furthermore, a polypeptide comprising 10 or more units of the amino acid sequence represented by formula 2: REP3 (2) is a polypeptide in which one or more amino acids have been substituted, deleted, inserted, and/or added. It may be a polypeptide having the amino acid sequence represented by SEQ ID NO: 70, which is also explained in Patent No. 9,051,453, and having a repetitive region composed of amorphous regions.

Polypeptides can be produced using a host transformed with an expression vector containing a gene encoding the polypeptide. Methods for producing the gene include, but are not limited to, amplifying the gene encoding the natural spider silk protein from cells derived from spiders, such as polymerase chain reaction (PCR), and cloning it. or may be chemically synthesized. In addition, the method of chemically synthesizing the gene is not particularly limited, but it can be synthesized, for example, as follows: Based on information on the amino acid sequence of natural spider silk protein obtained from the NCBI web database etc. Then, oligonucleotides automatically synthesized using AKTA Oligo Pilot Plus 10/100 (GE Healthcare Japan Corporation) are ligated by PCR or the like. At this point, in order to facilitate purification and observation of the protein, a gene encoding a protein having the above amino acid sequence is synthesized at the N-terminus with an amino acid sequence consisting of a start codon and a His10 tag. It is possible to do so.

Examples of expression vectors include plasmids, phages, viruses, and the like that can express proteins based on DNA sequences. The plasmid type expression vector is not particularly limited as long as it allows the target gene to be expressed in the host cell and can itself be amplified. For example, when using E. coli Rosetta (DE3) as a host, pET22b(+) plasmid vectors, pCold plasmid vectors, and the like can be used. Among these, in terms of protein productivity, it is preferable to use the pET22b(+) plasmid vector. Examples of hosts include animal cells, plant cells, microorganisms, and the like.

The polypeptide used in this disclosure is preferably a polypeptide derived from ADF3, which is one of the two major drug line silk proteins of Araneus diadematus. This polypeptide essentially has high strength-extensibility and toughness and has the advantage of being easily synthesized.

Accordingly, recombinant silk proteins (e.g., recombinant spider silk-based proteins) used in accordance with the embodiments, articles, and/or methods described herein may be described above or described in U.S. Pat. No. 8,173,772, No. 8,278,416, No. 8,618,255, No. 8,642,734, No. 8,691,581, No. 8,729,235 No. 9,115,204, No. 9,157,070, No. 9,309,299, No. 9,644,012, No. 9,708,376, No. 9 , 051,453, 9,617,315, 9,968,682, 9,689,089, 9,732,125, 9,856,308 , No. 9,926,348, No. 10,065,997, No. 10,316,069, and No. 10,329,332, and U.S. Patent Publication No. 2009/0226969, No. 2011/0281273, 2012/0041177, 2013/0065278, 2013/0115698, 2013/0316376, 2014/0058066, 2014/0079674, 2014 /0245923, 2015/0087046, 2015/0119554, 2015/0141618, 2015/0291673, 2015/0291674, 2015/0239587, 2015/ 0344542, 2015/0361144, 2015/0374833, 2015/0376247, 2016/0024464, 2017/0066804, 2017/0066805, 2015/0293076 No. 2016/0222174, No. 2017/0283474, No. 2017/0088675, No. 2019/0135880, No. 2015/0329587, No. 2019/0040109, No. 2019/0135881 , 2019/0177363, 2019/0225646, 2019/0233481, 2019/0031842, 2018/0355120, 2019/0186050, 2019/0002644, 2020/0031887, 2018/0273590, 20191/094403, 2019/0031843, 2018/0251501, 2017/0066805, 2018/0127553, No. 2019/0329526, No. 2020/0031886, No. 2018/0080147, No. 2019/0352349, No. 2020/0043085, No. 2019/0144819, No. 2019/0228449, No. 2019/0340666, 2020/0000091, 2019/0194710, 2019/0151505, 2018/0265555, 2019/0352330, 2019/0248847, and 2019/0378191, herein incorporated by reference in its entirety.

Silk Fibroin-Like Protein Fragments Recombinant silk proteins in the present disclosure include synthetic proteins based on repeating units of natural silk proteins. Besides synthetic repetitive silk protein sequences, these can additionally include one or more natural non-repetitive silk protein sequences. As used herein, "silk fibroin-like protein fragment" refers to the molecular weight and polydispersity as defined herein, and natural silk protein, fibroin heavy chain, fibroin light chain, or one or more Refers to a protein fragment having some degree of homology with a protein selected from any protein containing multiple GAGAGS (SEQ ID NO: 2) hexaamino acid repeat units. In some embodiments, the degree of homology is about 99%, about 98%, about 97%, about 96%, about 95%, about 94%, about 93%, about 92%, about 91%, about 90%, about 89%, about 88%, about 87%, about 86%, about 85%, about 84%, about 83%, about 82%, about 81%, about 80%, about 79%, about 78% , about 77%, about 76%, about 75%, or less than 75%.

As described herein, a protein, such as a natural silk protein, a fibroin heavy chain, a fibroin light chain, or any protein containing one or more GAGAGS (SEQ ID NO: 2) hexaamino acid repeat units, between about 9% and about 45% glycine, or about 9% glycine, or about 10% glycine, about 43% glycine, about 44% glycine, about 45% glycine, or about 46% glycine. including. As described herein, a protein, such as a natural silk protein, a fibroin heavy chain, a fibroin light chain, or any protein containing one or more GAGAGS (SEQ ID NO: 2) hexaamino acid repeat units, may be about comprising between 13% and about 30% alanine, or about 13% alanine, or about 28% alanine, or about 29% alanine, or about 30% alanine, or about 31% alanine. As described herein, the protein, such as natural silk protein, fibroin heavy chain, fibroin light chain, or any protein containing one or more GAGAGS (SEQ ID NO: 2) hexaamino acid repeat units, can be % to about 12% serine, or about 9% serine, or about 10% serine, or about 11% serine, or about 12% serine.

In some embodiments, the silk fibroin-like proteins described herein are about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 11%, about 12% %, about 13%, about 14%, about 15%, about 16%, about 17%, about 18%, about 19%, about 20%, about 21%, about 22%, about 23%, about 24%, About 25%, about 26%, about 27%, about 28%, about 29%, about 30%, about 31%, about 32%, about 33%, about 34%, about 35%, about 36%, about 37 %, about 38%, about 39%, about 40%, about 41%, about 42%, about 43%, about 44%, about 45%, about 46%, about 47%, about 48%, about 49%, Contains about 50%, about 51%, about 52%, about 53%, about 54%, or about 55% glycine. In some embodiments, the silk fibroin-like proteins described herein are about 13%, about 14%, about 15%, about 16%, about 17%, about 18%, about 19%, about 20% %, about 21%, about 22%, about 23%, about 24%, about 25%, about 26%, about 27%, about 28%, about 29%, about 30%, about 31%, about 32%, Contains about 33%, about 34%, about 35%, about 36%, about 37%, about 38%, or about 39% alanine. In some embodiments, the silk fibroin-like protein described herein is about 2%, about 3%, about 4%, about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 11%, about 12%, about 13%, about 14%, about 15%, about 16%, about 17%, about 18%, about 19%, about 20%, about 21% , or about 22% serine. In some embodiments, the silk fibroin-like proteins described herein may independently include any amino acid known to be included in natural fibroin. In some embodiments, the silk fibroin-like proteins described herein may independently exclude any amino acids known to be included in natural fibroin. In some embodiments, an average of 2 out of 6 amino acids, 3 out of 6 amino acids, or 4 out of 6 amino acids in the silk fibroin-like proteins described herein are glycine. In some embodiments, an average of 1 out of 6 amino acids, 2 out of 6 amino acids, or 3 out of 6 amino acids in the silk fibroin-like proteins described herein are alanine. In some embodiments, an average of 0 out of 6 amino acids, 1 out of 6 amino acids, or 2 out of 6 amino acids in the silk fibroin-like proteins described herein are serine.

Sericin or Sericin Fragments The body of raw silk is silk fibroin fibers, which are coated with the adhesive silk sericin. Sericin is a colloidal silk protein that coats the surface of silk threads and is composed of bulky amino acids that are rich in chemical reactions, such as serine, threonine, and aspartic acid, in addition to glycine and alanine. In various processes to produce silk from raw silk, sericin is important in controlling silk solubility and producing high quality silk. Furthermore, it plays a very important role as an adhesive functional protein. When silk fibers are used as clothing materials, most of the silk sericin covering the silk threads is removed and discarded, so sericin is a valuable unused resource.

In some embodiments, the silk protein fragments described herein include sericin or sericin fragments. Methods for preparing sericin or sericin fragments and their uses in various fields are known and described herein and also in, for example, U.S. Pat. Nos. 7,115,388, 7,157,273, and 9,187,538, all of which are incorporated herein by reference in their entireties.

In some embodiments, sericin removed from raw silk cocoons, such as during a degumming process, can be collected and used in the methods described herein. Sericin can also be reconstituted from powder and used within the compositions and methods of the present disclosure.

Other Properties of PF Compositions of the present disclosure are or exhibit "biocompatible" meaning that the compositions are non-toxic, non-toxic, non-physiologically reactive, and resistant to immune rejection. By not causing any damage, it is meant to be compatible with living tissues or systems. Such biocompatibility can be demonstrated by having participants apply the compositions of the disclosure topically on their skin for an extended period of time. In one embodiment, the extension period is about 3 days. In one embodiment, the extension period is about 7 days. In one embodiment, the extension period is about 14 days. In one embodiment, the extension period is about 21 days. In one embodiment, the extension period is about 30 days. In one embodiment, the extension period is about 1 month, about 2 months, about 3 months, about 4 months, about 5 months, about 6 months, about 7 months, about 8 months, about selected from the group consisting of 9 months, about 10 months, about 11 months, about 12 months, and indefinitely. For example, in some embodiments, the coatings described herein are biocompatible coatings.

In some embodiments, the compositions described herein can be biocompatible compositions (e.g., biocompatible coatings comprising silk) and have been evaluated to be recognized in the "Biological evaluation of medical devices". - Part 1: Evaluation and testing with a risk management process”. In some embodiments, the compositions described herein may be biocompatible compositions that are cytotoxic, sensitizing, hemocompatible, pyrogenic, transplantable, genotoxic, May be evaluated under ISO 106993-1 for one or more of carcinogenicity, reproductive and developmental toxicity, and degradation.

The compositions of the present disclosure are "hypoallergenic," meaning that they have a relatively low potential for causing allergic reactions. Such hypoallergenicity can be demonstrated by participants applying the compositions of the present disclosure topically on their skin for an extended period of time. In one embodiment, the extension period is about 3 days. In one embodiment, the extension period is about 7 days. In one embodiment, the extension period is about 14 days. In one embodiment, the extension period is about 21 days. In one embodiment, the extension period is about 30 days. In one embodiment, the extension period is about 1 month, about 2 months, about 3 months, about 4 months, about 5 months, about 6 months, about 7 months, about 8 months, about selected from the group consisting of 9 months, about 10 months, about 11 months, about 12 months, and indefinitely.

In one embodiment, the stability of the compositions of the present disclosure is about 1 day. In one embodiment, the stability of the compositions of the present disclosure is about 2 days. In one embodiment, the stability of the compositions of the present disclosure is about 3 days. In one embodiment, the stability of the compositions of the present disclosure is about 4 days. In one embodiment, the stability of the compositions of the present disclosure is about 5 days. In one embodiment, the stability of the compositions of the present disclosure is about 6 days. In one embodiment, the stability of the compositions of the present disclosure is about 7 days. In one embodiment, the stability of the compositions of the present disclosure is about 8 days. In one embodiment, the stability of the compositions of the present disclosure is about 9 days. In one embodiment, the stability of the compositions of the present disclosure is about 10 days.

In one embodiment, the stability of the compositions of the present disclosure is about 11 days, about 12 days, about 13 days, about 14 days, about 15 days, about 16 days, about 17 days, about 18 days, about 19 days. , about 20 days, about 21 days, about 22 days, about 23 days, about 24 days, about 25 days, about 26 days, about 27 days, about 28 days, about 29 days, or about 30 days.

In one embodiment, the stability of the compositions of the present disclosure is between 10 days and 6 months. In one embodiment, the stability of the compositions of the present disclosure is from 6 months to 12 months. In one embodiment, the stability of the compositions of the present disclosure is from 12 months to 18 months. In one embodiment, the stability of the compositions of the present disclosure is between 18 and 24 months. In one embodiment, the stability of the compositions of the present disclosure is between 24 months and 30 months. In one embodiment, the stability of the compositions of the present disclosure is between 30 months and 36 months. In one embodiment, the stability of the compositions of the present disclosure is between 36 months and 48 months. In one embodiment, the stability of the compositions of the present disclosure is between 48 months and 60 months.

In one embodiment, the SPF compositions of the present disclosure are not soluble in aqueous solutions due to the crystalline nature of the protein. In one embodiment, the SPF compositions of the present disclosure are soluble in aqueous solution. In one embodiment, the SPF of the compositions of the present disclosure includes about two-thirds crystalline portion and about one-third amorphous region. In one embodiment, the SPF of the compositions of the present disclosure includes about half a crystalline portion and about half an amorphous region. In one embodiment, the SPF of the compositions of the present disclosure includes 99% crystalline portion and 1% amorphous region. In one embodiment, the SPF of the compositions of the present disclosure includes 95% crystalline portion and 5% amorphous region. In one embodiment, the SPF of the composition of the present disclosure includes 90% crystalline portion and 10% amorphous region. In one embodiment, the SPF of the composition of the present disclosure includes 85% crystalline portion and 15% amorphous region. In one embodiment, the SPF of the composition of the present disclosure includes 80% crystalline portion and 20% amorphous region. In one embodiment, the SPF of the composition of the present disclosure includes 75% crystalline portion and 25% amorphous region. In one embodiment, the SPF of the composition of the present disclosure includes 70% crystalline portion and 30% amorphous region. In one embodiment, the SPF of the composition of the present disclosure includes 65% crystalline portion and 35% amorphous region. In one embodiment, the SPF of the composition of the present disclosure includes 60% crystalline portion and 40% amorphous region. In one embodiment, the SPF of the composition of the present disclosure includes 50% crystalline portion and 50% amorphous region. In one embodiment, the SPF of the composition of the present disclosure includes 40% crystalline portion and 60% amorphous region. In one embodiment, the SPF of the composition of the present disclosure includes 35% crystalline portion and 65% amorphous area. In one embodiment, the SPF of the composition of the present disclosure includes 30% crystalline portion and 70% amorphous region. In one embodiment, the SPF of the composition of the present disclosure includes 25% crystalline portion and 75% amorphous area. In one embodiment, the SPF of the composition of the present disclosure includes 20% crystalline portion and 80% amorphous region. In one embodiment, the SPF of the composition of the present disclosure includes 15% crystalline portion and 85% amorphous area. In one embodiment, the SPF of the compositions of the present disclosure includes 10% crystalline portion and 90% amorphous region. In one embodiment, the SPF of the compositions of the present disclosure includes 5% crystalline portion and 90% amorphous area. In one embodiment, the SPF of the compositions of the present disclosure includes 1% crystalline portion and 99% amorphous area.

As used herein, the term "substantially free of inorganic residues" means that the composition exhibits 0.1% (w/w) or less of residues. In one embodiment, "substantially free of inorganic residues" refers to a composition exhibiting 0.05% (w/w) or less of residues. In one embodiment, "substantially free of inorganic residues" refers to a composition exhibiting 0.01% (w/w) or less of residues. In one embodiment, the amount of inorganic residue is between 0 ppm ("not detectable" or "ND") and 1000 ppm. In one embodiment, the amount of inorganic residue is from ND to about 500 ppm. In one embodiment, the amount of inorganic residue is from ND to about 400 ppm. In one embodiment, the amount of inorganic residue is from ND to about 300 ppm. In one embodiment, the amount of inorganic residue is from ND to about 200 ppm. In one embodiment, the amount of inorganic residue is from ND to about 100 ppm. In one embodiment, the amount of inorganic residue is between 10 ppm and 1000 ppm.

As used herein, the term "substantially free of organic residues" means that the composition exhibits 0.1% (w/w) or less of residues, and in one embodiment: "Substantially free of organic residues" refers to compositions that exhibit 0.05% (w/w) or less of residues. In one embodiment, "substantially free of organic residues" refers to a composition exhibiting 0.01% (w/w) or less of residues. In one embodiment, the amount of organic residue is between 0 ppm ("not detectable" or "ND") and 1000 ppm. In one embodiment, the amount of organic residue is from ND to about 500 ppm. In one embodiment, the amount of organic residue is from ND to about 400 ppm. In one embodiment, the amount of organic residue is from ND to about 300 ppm. In one embodiment, the amount of organic residue is from ND to about 200 ppm. In one embodiment, the amount of organic residue is from ND to about 100 ppm. In one embodiment, the amount of organic residue is between 10 ppm and 1000 ppm.

The compositions of the present disclosure exhibit "biocompatibility," meaning that the compositions are compatible with living tissues or systems by not being toxic, toxic, or physiologically reactive, and not causing immune rejection. It means to do. Such biocompatibility can be demonstrated by having participants apply the compositions of the disclosure topically on their skin for an extended period of time. In one embodiment, the extension period is about 3 days. In one embodiment, the extension period is about 7 days, in one embodiment, the extension period is about 14 days, and in one embodiment, the extension period is about 21 days. In one embodiment, the extension period is about 30 days. In one embodiment, the extension period is about 1 month, about 2 months, about 3 months, about 4 months, about 5 months, about 6 months, about 7 months, about 8 months, about selected from the group consisting of 9 months, about 10 months, about 11 months, about 12 months, and indefinitely.

The compositions of the present disclosure are "hypoallergenic," meaning that they have a relatively low potential for causing allergic reactions. Such hypoallergenicity can be demonstrated by participants applying the compositions of the present disclosure topically on their skin for an extended period of time. In one embodiment, the extension period is about 3 days. In one embodiment, the extension period is about 7 days. In one embodiment, the extension period is about 14 days. In one embodiment, the extension period is about 21 days. In one embodiment, the extension period is about 30 days. In one embodiment, the extension period is about 1 month, about 2 months, about 3 months, about 4 months, about 5 months, about 6 months, about 7 months, about 8 months, about selected from the group consisting of 9 months, about 10 months, about 11 months, about 12 months, and indefinitely.

The following are non-limiting examples of suitable ranges for various parameters in and for the preparation of silk solutions of the present disclosure. Silk solutions of the present disclosure may include one or more, but not necessarily all, of these parameters, but may be prepared using various combinations of ranges of such parameters.

In one embodiment, the SPF (%) in the solution is less than 30.0% by weight. In one embodiment, the SPF (%) in the solution is less than 25.0% by weight. In one embodiment, the SPF (%) in the solution is less than 20.0% by weight. In one embodiment, the SPF (%) in the solution is less than 19.0% by weight. In one embodiment, the SPF (%) in the solution is less than 18.0% by weight. In one embodiment, the SPF (%) in the solution is less than 17.0% by weight. In one embodiment, the SPF (%) in the solution is less than 16.0% by weight. In one embodiment, the SPF (%) in the solution is less than 15.0% by weight. In one embodiment, the SPF (%) in the solution is less than 14.0% by weight. In one embodiment, the SPF (%) in the solution is less than 13.0% by weight. In one embodiment, the SPF (%) in the solution is less than 12.0% by weight. In one embodiment, the SPF (%) in the solution is less than 11.0% by weight. In one embodiment, the SPF (%) in the solution is less than 10.0% by weight. In one embodiment, the SPF (%) in the solution is less than 9.0% by weight. In one embodiment, the SPF (%) in the solution is less than 8.0% by weight. In one embodiment, the SPF (%) in the solution is less than 7.0% by weight. In one embodiment, the SPF (%) in the solution is less than 6.0% by weight. In one embodiment, the SPF (%) in the solution is less than 5.0% by weight. In one embodiment, the SPF (%) in the solution is less than 4.0% by weight. In one embodiment, the SPF (%) in the solution is less than 3.0% by weight. In one embodiment, the SPF (%) in the solution is less than 2.0% by weight. In one embodiment, the SPF (%) in the solution is less than 1.0% by weight. In one embodiment, the SPF (%) in the solution is less than 0.9% by weight. In one embodiment, the SPF (%) in the solution is less than 0.8% by weight. In one embodiment, the SPF (%) in the solution is less than 0.7% by weight. In one embodiment, the SPF (%) in the solution is less than 0.6% by weight. In one embodiment, the SPF (%) in the solution is less than 0.5% by weight. In one embodiment, the SPF (%) in the solution is less than 0.4% by weight. In one embodiment, the SPF (%) in the solution is less than 0.3% by weight. In one embodiment, the SPF (%) in the solution is less than 0.2% by weight. In one embodiment, the SPF (%) in the solution is less than 0.1% by weight.

In one embodiment, the SPF (%) in the solution is greater than 0.1% by weight. In one embodiment, the SPF (%) in the solution is greater than 0.2% by weight. In one embodiment, the SPF (%) in the solution is greater than 0.3% by weight. In one embodiment, the SPF (%) in the solution is greater than 0.4% by weight. In one embodiment, the SPF (%) in the solution is greater than 0.5% by weight. In one embodiment, the SPF (%) in the solution is greater than 0.6% by weight. In one embodiment, the SPF (%) in the solution is greater than 0.7% by weight. In one embodiment, the SPF (%) in the solution is greater than 0.8% by weight. In one embodiment, the SPF (%) in the solution is greater than 0.9% by weight. In one embodiment, the SPF (%) in the solution is greater than 1.0% by weight. In one embodiment, the % SPF in the solution is greater than 2.0% by weight. In one embodiment, the SPF (%) in the solution is greater than 3.0% by weight. In one embodiment, the SPF (%) in the solution is greater than 4.0% by weight. In one embodiment, the SPF (%) in the solution is greater than 5.0% by weight. In one embodiment, the SPF (%) in the solution is greater than 6.0% by weight. In one embodiment, the SPF (%) in the solution is greater than 7.0% by weight. In one embodiment, the SPF (%) in the solution is greater than 8.0% by weight. In one embodiment, the SPF (%) in the solution is greater than 9.0% by weight. In one embodiment, the SPF (%) in the solution is greater than 10.0% by weight. In one embodiment, the SPF (%) in the solution is greater than 11.0% by weight. In one embodiment, the SPF (%) in the solution is greater than 12.0% by weight. In one embodiment, the SPF (%) in the solution is greater than 13.0% by weight. In one embodiment, the SPF (%) in the solution is greater than 14.0% by weight. In one embodiment, the SPF (%) in the solution is greater than 15.0% by weight. In one embodiment, the SPF (%) in the solution is greater than 16.0% by weight. In one embodiment, the SPF (%) in the solution is greater than 17.0% by weight. In one embodiment, the SPF (%) in the solution is greater than 18.0% by weight. In one embodiment, the SPF (%) in the solution is greater than 19.0% by weight. In one embodiment, the SPF (%) in the solution is greater than 20.0% by weight. In one embodiment, the SPF (%) in the solution is greater than 25.0% by weight.

In one embodiment, the SPF (%) in the solution ranges from about 0.1% to about 30.0% by weight. In one embodiment, the % SPF in the solution ranges from about 0.1% to about 25.0% by weight. In one embodiment, the SPF (%) in the solution ranges from about 0.1% to about 20.0% by weight. In one embodiment, the SPF (%) in the solution ranges from about 0.1% to about 15.0% by weight. In one embodiment, the SPF (%) in the solution ranges from about 0.1% to about 10.0% by weight. In one embodiment, the SPF (%) in the solution ranges from about 0.1% to about 9.0% by weight. In one embodiment, the SPF (%) in the solution ranges from about 0.1% to about 8.0% by weight. In one embodiment, the SPF (%) in the solution ranges from about 0.1% to about 7.0% by weight. In one embodiment, the SPF (%) in the solution ranges from about 0.1% to about 6.5% by weight. In one embodiment, the SPF (%) in the solution ranges from about 0.1% to about 6.0% by weight. In one embodiment, the SPF (%) in the solution ranges from about 0.1% to about 5.5% by weight. In one embodiment, the SPF (%) in the solution ranges from about 0.1% to about 5.0% by weight. In one embodiment, the SPF (%) in the solution ranges from about 0.1% to about 4.5% by weight. In one embodiment, the SPF (%) in the solution ranges from about 0.1% to about 4.0% by weight. In one embodiment, the SPF (%) in the solution ranges from about 0.1% to about 3.5% by weight. In one embodiment, the SPF (%) in the solution ranges from about 0.1% to about 3.0% by weight. In one embodiment, the SPF (%) in the solution ranges from about 0.1% to about 2.5% by weight. In one embodiment, the SPF (%) in the solution ranges from about 0.1% to about 2.0% by weight. In one embodiment, the SPF (%) in the solution ranges from about 0.1% to about 2.4% by weight. In one embodiment, the SPF (%) in the solution ranges from about 0.5% to about 5.0% by weight. In one embodiment, the SPF (%) in the solution ranges from about 0.5% to about 4.5% by weight. In one embodiment, the SPF (%) in the solution ranges from about 0.5% to about 4.0% by weight. In one embodiment, the SPF (%) in the solution ranges from about 0.5% to about 3.5% by weight. In one embodiment, the SPF (%) in the solution ranges from about 0.5% to about 3.0% by weight. In one embodiment, the SPF (%) in the solution ranges from about 0.5% to about 2.5% by weight. In one embodiment, the SPF (%) in the solution ranges from about 1.0% to about 4.0% by weight. In one embodiment, the SPF (%) in the solution ranges from about 1.0% to about 3.5% by weight. In one embodiment, the SPF (%) in the solution ranges from about 1.0% to about 3.0% by weight. In one embodiment, the SPF (%) in the solution ranges from about 1.0% to about 2.5% by weight. In one embodiment, the SPF (%) in the solution ranges from about 1.0% to about 2.4% by weight. In one embodiment, the SPF (%) in the solution ranges from about 1.0% to about 2.0% by weight.

In one embodiment, the SPF (%) in the solution ranges from about 20.0% to about 30.0% by weight. In one embodiment, the SPF (%) in the solution ranges from about 0.1% to about 10.0% by weight. In one embodiment, the SPF (%) in the solution ranges from about 1.0% to about 10.0% by weight. In one embodiment, the % SPF in the solution ranges from about 2% to about 10.0% by weight. In one embodiment, the SPF (%) in the solution ranges from about 0.1% to about 6.0% by weight. In one embodiment, the SPF (%) in the solution ranges from about 6.0% to about 10.0% by weight. In one embodiment, the SPF (%) in the solution ranges from about 6.0% to about 8.0% by weight. In one embodiment, the SPF (%) in the solution ranges from about 6.0% to about 9.0% by weight. In one embodiment, the % SPF in the solution ranges from about 10.0% to about 20.0% by weight. In one embodiment, the SPF (%) in the solution ranges from about 11.0% to about 19.0% by weight. In one embodiment, the SPF (%) in the solution ranges from about 12.0% to about 18.0% by weight. In one embodiment, the SPF (%) in the solution ranges from about 13.0% to about 17.0% by weight. In one embodiment, the SPF (%) in the solution ranges from about 14.0% to about 16.0% by weight. In one embodiment, the SPF (%) in the solution is about 1.0% by weight. In one embodiment, the SPF (%) in the solution is about 0.5% by weight. In one embodiment, the SPF (%) in the solution is about 1.5% by weight. In one embodiment, the SPF (%) in the solution is about 2.0% by weight. In one embodiment, the SPF (%) in the solution is about 2.4% by weight. In one embodiment, the SPF (%) in the solution is 3.0% by weight. In one embodiment, the SPF (%) in the solution is 3.5% by weight. In one embodiment, the SPF (%) in the solution is about 4.0% by weight. In one embodiment, the SPF (%) in the solution is about 4.5% by weight. In one embodiment, the SPF (%) in the solution is about 5.0% by weight. In one embodiment, the SPF (%) in the solution is about 5.5% by weight. In one embodiment, the SPF (%) in the solution is about 6.0% by weight. In one embodiment, the SPF (%) in the solution is about 6.5% by weight. In one embodiment, the SPF (%) in the solution is about 7.0% by weight. In one embodiment, the SPF (%) in the solution is about 7.5% by weight. In one embodiment, the SPF (%) in the solution is about 8.0% by weight. In one embodiment, the SPF (%) in the solution is about 8.5% by weight. In one embodiment, the SPF (%) in the solution is about 9.0% by weight. In one embodiment, the SPF (%) in the solution is about 9.5% by weight. In one embodiment, the SPF (%) in the solution is about 10.0% by weight.

In one embodiment, the % sericin in the solution is between undetectable and 25.0% by weight. In one embodiment, the % sericin in the solution is from undetectable to 5.0% by weight. In one embodiment, the % sericin in the solution is 1.0% by weight. In one embodiment, the % sericin in the solution is 2.0% by weight. In one embodiment, the % sericin in the solution is 3.0% by weight. In one embodiment, the % sericin in the solution is 4.0% by weight. In one embodiment, the % sericin in the solution is 5.0% by weight. In one embodiment, the % sericin in the solution is 10.0% by weight. In one embodiment, the % sericin in the solution is 25.0% by weight.

In some embodiments, the SPF solution compositions of the present disclosure have a storage stability of 10 days to 3 years, depending on storage conditions, percentage of SPF, and number of shipments and shipping conditions; There is no slow or spontaneous gelling when stored in aqueous solution, no aggregation of fragments, and therefore no increase in molecular weight over time). In addition, the pH can be varied to prevent premature folding and agglomeration of the silk, thereby extending shelf life and/or aiding shipping conditions. In one embodiment, the stability of the LiBr-silk fragment solution is between 0 and 1 year. In one embodiment, the stability of the LiBr-silk fragment solution is between 0 and 2 years. In one embodiment, the stability of the LiBr-silk fragment solution is 0-3 years. In one embodiment, the stability of the LiBr-silk fragment solution is between 0 and 4 years. In one embodiment, the stability of the LiBr-silk fragment solution is 0-5 years. In one embodiment, the stability of the LiBr-silk fragment solution is 1-2 years. In one embodiment, the stability of the LiBr-silk fragment solution is 1-3 years. In one embodiment, the stability of the LiBr-silk fragment solution is 1-4 years. In one embodiment, the stability of the LiBr-silk fragment solution is 1-5 years. In one embodiment, the stability of the LiBr-silk fragment solution is 2-3 years. In one embodiment, the stability of the LiBr-silk fragment solution is 2-4 years. In one embodiment, the stability of the LiBr-silk fragment solution is 2-5 years. In one embodiment, the stability of the LiBr-silk fragment solution is 3-4 years. In one embodiment, the stability of the LiBr-silk fragment solution is 3-5 years. In one embodiment, the stability of the LiBr-silk fragment solution is 4-5 years.

In one embodiment, the stability of the compositions of the present disclosure is between 10 days and 6 months. In one embodiment, the stability of the compositions of the present disclosure is from 6 months to 12 months. In one embodiment, the stability of the compositions of the present disclosure is between 12 months and 18 months. In one embodiment, the stability of the compositions of the present disclosure is between 18 and 24 months. In one embodiment, the stability of the compositions of the present disclosure is from 24 months to 30 months. In one embodiment, the stability of the compositions of the present disclosure is between 30 months and 36 months. In one embodiment, the stability of the compositions of the present disclosure is between 36 months and 48 months. In one embodiment, the stability of the compositions of the present disclosure is between 48 months and 60 months.

In one embodiment, a composition of the present disclosure with SPF has undetectable levels of LiBr residue. In one embodiment, the amount of LiBr residue in the compositions of the present disclosure is between 10 ppm and 1000 ppm. In one embodiment, the amount of LiBr residue in the compositions of the present disclosure is between 10 ppm and 300 ppm. In one embodiment, the amount of LiBr residue in the compositions of the present disclosure is less than 25 ppm. In one embodiment, the amount of Li Br residue in the compositions of the present disclosure is less than 50 ppm. In one embodiment, the amount of LiBr residue in the compositions of the present disclosure is less than 75 ppm. In one embodiment, the amount of LiBr residue in the compositions of the present disclosure is less than 100 ppm. In one embodiment, the amount of LiBr residue in the compositions of the present disclosure is less than 200 ppm. In one embodiment, the amount of LiBr residue in the compositions of the present disclosure is less than 300 ppm. In one embodiment, the amount of LiBr residue in the compositions of the present disclosure is less than 400 ppm. In one embodiment, the amount of LiBr residue in the compositions of the present disclosure is less than 500 ppm. In one embodiment, the amount of LiBr residue in the compositions of the present disclosure is less than 600 ppm. In one embodiment, the amount of LiBr residue in the compositions of the present disclosure is less than 700 ppm. In one embodiment, the amount of LiBr residue in the compositions of the present disclosure is less than 800 ppm. In one embodiment, the amount of LiBr residue in the compositions of the present disclosure is less than 900 ppm. In one embodiment, the amount of LiBr residue in the compositions of the present disclosure is less than 1000 ppm. In one embodiment, the amount of LiBr residue in the compositions of the present disclosure is from undetectable to 500 ppm. In one embodiment, the amount of LiBr residue in the compositions of the present disclosure is from undetectable to 450 ppm. In one embodiment, the amount of LiBr residues in the compositions of the present disclosure is from undetectable to 400 ppm. In one embodiment, the amount of LiBr residue in the compositions of the present disclosure is from undetectable to 350 ppm. In one embodiment, the amount of LiBr residue in the compositions of the present disclosure is from undetectable to 300 ppm. In one embodiment, the amount of LiBr residue in the compositions of the present disclosure is from undetectable to 250 ppm. In one embodiment, the amount of LiBr residue in the compositions of the present disclosure is from undetectable to 200 ppm. In one embodiment, the amount of LiBr residue in the compositions of the present disclosure is from undetectable to 150 ppm. In one embodiment, the amount of LiBr residue in the compositions of the present disclosure is from undetectable to 100 ppm. In one embodiment, the amount of LiBr residue in the compositions of the present disclosure is between 100 ppm and 200 ppm. In one embodiment, the amount of LiBr residue in the compositions of the present disclosure is between 200 ppm and 300 ppm. In one embodiment, the amount of LiBr residue in the composition of the present disclosure is between 300 ppm and 400 ppm. In one embodiment, the amount of LiBr residue in the compositions of the present disclosure is between 400 ppm and 500 ppm.

In one embodiment, a composition of the present disclosure with SPF has undetectable levels of Na ₂ CO ₃ residue. In one embodiment, the amount of Na ₂ CO ₃ residue in the compositions of the present disclosure is less than 100 ppm. In one embodiment, the amount of Na ₂ CO ₃ residue in the composition of the present disclosure is less than 200 ppm. In one embodiment, the amount of Na ₂ CO ₃ residue in the composition of the present disclosure is less than 300 ppm. In one embodiment, the amount of Na ₂ CO ₃ residue in the composition of the present disclosure is less than 400 ppm. In one embodiment, the amount of Na ₂ CO ₃ residue in the composition of the present disclosure is less than 500 ppm. In one embodiment, the amount of Na ₂ CO ₃ residue in the composition of the present disclosure is less than 600 ppm. In one embodiment, the amount of Na ₂ CO ₃ residue in the composition of the present disclosure is less than 700 ppm. In one embodiment, the amount of Na ₂ CO ₃ residue in the composition of the present disclosure is less than 800 ppm. In one embodiment, the amount of Na ₂ CO ₃ residue in the composition of the present disclosure is less than 900 ppm. In one embodiment, the amount of Na ₂ CO ₃ residue in the composition of the present disclosure is less than 1000 ppm. In one embodiment, the amount of Na ₂ CO ₃ residue in the compositions of the present disclosure is from undetectable to 500 ppm. In one embodiment, the amount of Na ₂ CO ₃ residue in the compositions of the present disclosure is from undetectable to 450 ppm. In one embodiment, the amount of Na ₂ CO ₃ residue in the compositions of the present disclosure is from undetectable to 400 ppm. In one embodiment, the amount of Na ₂ CO ₃ residue in the compositions of the present disclosure is from undetectable to 350 ppm. In one embodiment, the amount of Na ₂ CO ₃ residue in the compositions of the present disclosure is from undetectable to 300 ppm. In one embodiment, the amount of Na ₂ CO ₃ residue in the compositions of the present disclosure is from undetectable to 250 ppm. In one embodiment, the amount of Na ₂ CO ₃ residue in the compositions of the present disclosure is from undetectable to 200 ppm. In one embodiment, the amount of Na ₂ CO ₃ residue in the compositions of the present disclosure is from undetectable to 150 ppm. In one embodiment, the amount of Na ₂ CO ₃ residue in the compositions of the present disclosure is from undetectable to 100 ppm. In one embodiment, the amount of Na ₂ CO ₃ residue in the composition of the present disclosure is between 100 ppm and 200 ppm. In one embodiment, the amount of Na ₂ CO ₃ residue in the composition of the present disclosure is between 200 ppm and 300 ppm. In one embodiment, the amount of Na ₂ CO ₃ residue in the composition of the present disclosure is between 300 ppm and 400 ppm. In one embodiment, the amount of Na ₂ CO ₃ residue in the composition of the present disclosure is between 400 ppm and 500 ppm.

A unique feature of the SPF solution compositions of the present disclosure is their storage stability from 10 days to 3 years, depending on storage conditions, silk percentage, and number of shipments and shipping conditions (they are There is no slow or spontaneous gelling when stored, no aggregation of fragments, and therefore no increase in molecular weight over time). In addition, the pH can be varied to prevent premature folding and agglomeration of the silk, thereby extending shelf life and/or aiding shipping conditions. In one embodiment, the SPF solution compositions of the present disclosure have storage stability at room temperature (RT) for up to two weeks. In one embodiment, the SPF solution compositions of the present disclosure have storage stability at RT for up to 4 weeks. In one embodiment, the SPF solution compositions of the present disclosure have storage stability at RT for up to 6 weeks. In one embodiment, the SPF solution compositions of the present disclosure have storage stability at RT for up to 8 weeks. In one embodiment, the SPF solution composition of the present disclosure has storage stability at RT for up to 10 weeks. In one embodiment, the SPF solution compositions of the present disclosure have storage stability at RT for up to 12 weeks. In one embodiment, the SPF solution compositions of the present disclosure have storage stability at RT ranging from about 4 weeks to about 52 weeks.

Table R below shows storage stability test results for embodiments of the SPF compositions of the present disclosure.

In some embodiments, the water solubility of silk films derived from the silk fibroin protein fragments described herein is modified by solvent annealing (water or methanol annealing), chemical cross-linking, enzymatic cross-linking, and heat treatment. be able to.

In some embodiments, the annealing process may include inducing beta-sheet formation in a silk fibroin protein fragment solution used as a coating material. Techniques have been described that promote annealing (eg, increased crystallinity) or otherwise "molecular packing" of silk fibroin protein-based fragments. In some embodiments, the amorphous silk film is annealed to introduce beta sheets in the presence of water or a solvent selected from the group of organic solvents. In some embodiments, the amorphous silk film is annealed to introduce beta sheets in the presence of water (water annealing process). In some embodiments, the amorphous silk fibroin protein fragment film is annealed to introduce beta sheets in the presence of methanol. In some embodiments, annealing (eg, beta sheet formation) is induced by addition of an organic solvent. Suitable organic solvents include, but are not limited to, methanol, ethanol, acetone, isopropanol, or combinations thereof.

In some embodiments, annealing is performed by so-called "water annealing" or "steam annealing," in which water vapor is used as an intermediate plasticizer or catalyst to promote packing of the beta sheets. In some embodiments, the water annealing process may be performed under vacuum. A suitable such method is described by Jin H-J et al. (2005), Water-stable Silk Films with Reduced Beta-Sheet Content, Advanced Functional Materials, 15:1241-1247, Xiao H. et al. (2011), Regulation of Silk Material Structure by Temperature-Controlled Water Vapor Annealing, Biomacromolecules, 12(5): 1686-16 96.

An important feature of the water annealing process is to drive the formation of crystalline beta sheets in the silk fibroin protein fragment peptide chains, causing silk fibroin to self-assemble into a continuous film. In some embodiments, the crystallinity of silk fibroin protein fragment films is controlled by controlling the temperature of the water vapor and the duration of annealing. In some embodiments, annealing is performed at a temperature ranging from about 65°C to about 110°C. In some embodiments, the water temperature is maintained at about 80°C. In some embodiments, annealing is performed at about 65°C, about 70°C, about 75°C, about 80°C, about 85°C, about 90°C, about 95°C, about 100°C, about 105°C, and about 110°C. carried out at a temperature selected from the group of.

In some embodiments, the annealing process is performed for about 1 minute to about 40 minutes, about 1 minute to about 50 minutes, about 1 minute to about 60 minutes, about 1 minute to about 70 minutes, about 1 minute to about 80 minutes. , about 1 minute to about 90 minutes, about 1 minute to about 100 minutes, about 1 minute to about 110 minutes, about 1 minute to about 120 minutes, about 1 minute to about 130 minutes, about 5 minutes to about 40 minutes, about 5 minutes to about 50 minutes, about 5 minutes to about 60 minutes, about 5 minutes to about 70 minutes, about 5 minutes to about 80 minutes, about 5 minutes to about 90 minutes, about 5 minutes to about 100 minutes, about 5 minutes ~110 minutes, approximately 5 minutes to approximately 120 minutes, approximately 5 minutes to approximately 130 minutes, approximately 10 minutes to approximately 40 minutes, approximately 10 minutes to approximately 50 minutes, approximately 10 minutes to approximately 60 minutes, approximately 10 minutes to approximately 70 minutes, about 10 minutes to about 80 minutes, about 10 minutes to about 90 minutes, about 10 minutes to about 100 minutes, about 10 minutes to about 110 minutes, about 10 minutes to about 120 minutes, about 10 minutes to about 130 minutes , about 15 minutes to about 40 minutes, about 15 minutes to about 50 minutes, about 15 minutes to about 60 minutes, about 15 minutes to about 70 minutes, about 15 minutes to about 80 minutes, about 15 minutes to about 90 minutes, about 15 minutes to about 100 minutes, about 15 minutes to about 110 minutes, about 15 minutes to about 120 minutes, about 15 minutes to about 130 minutes, about 20 minutes to about 40 minutes, about 20 minutes to about 50 minutes, about 20 minutes ~60 minutes, approximately 20 minutes to approximately 70 minutes, approximately 20 minutes to approximately 80 minutes, approximately 20 minutes to approximately 90 minutes, approximately 20 minutes to approximately 100 minutes, approximately 20 minutes to approximately 110 minutes, approximately 20 minutes to approximately 120 minutes, about 20 minutes to about 130 minutes, about 25 minutes to about 40 minutes, about 25 minutes to about 50 minutes, about 25 minutes to about 60 minutes, about 25 minutes to about 70 minutes, about 25 minutes to about 80 minutes , about 25 minutes to about 90 minutes, about 25 minutes to about 100 minutes, about 25 minutes to about 110 minutes, about 25 minutes to about 120 minutes, about 25 minutes to about 130 minutes, about 30 minutes to about 40 minutes, about 30 minutes to about 50 minutes, about 30 minutes to about 60 minutes, about 30 minutes to about 70 minutes, about 30 minutes to about 80 minutes, about 30 minutes to about 90 minutes, about 30 minutes to about 100 minutes, about 30 minutes ~110 minutes, approximately 30 minutes to approximately 120 minutes, approximately 30 minutes to approximately 130 minutes, approximately 35 minutes to approximately 40 minutes, approximately 35 minutes to approximately 50 minutes, approximately 35 minutes to approximately 60 minutes, approximately 35 minutes to approximately 70 minutes, about 35 minutes to about 80 minutes, about 35 minutes to about 90 minutes, about 35 minutes to about 100 minutes, about 35 minutes to about 110 minutes, about 35 minutes to about 120 minutes, about 35 minutes to about 130 minutes , about 40 minutes to about 50 minutes, about 40 minutes to about 60 minutes, about 40 minutes to about 70 minutes, about 40 minutes to about 80 minutes, about 40 minutes to about 90 minutes, about 40 minutes to about 100 minutes, about 40 minutes to about 110 minutes, about 40 minutes to about 120 minutes, about 40 minutes to about 130 minutes, about 45 minutes to about 50 minutes, about 45 minutes to about 60 minutes, about 45 minutes to about 70 minutes, about 45 minutes ~80 minutes, approximately 45 minutes to approximately 90 minutes, approximately 45 minutes to approximately 100 minutes, approximately 45 minutes to approximately 110 minutes, approximately 45 minutes to approximately 120 minutes, and approximately 45 minutes to approximately 130 minutes. Lasts for a period of time. In some embodiments, the annealing process lasts for a period ranging from about 1 minute to about 60 minutes. In some embodiments, the annealing process lasts for a period ranging from about 45 minutes to about 60 minutes. Longer water annealing after treatment corresponded to increased crystallinity of silk fibroin protein fragments.

In some embodiments, with an annealed silk fibroin protein fragment membrane, a wet silk fibroin protein fragment membrane is soaked in 100% methanol for 60 minutes at room temperature. Methanol annealing changed the composition of the silk fibroin protein fragment membrane from a predominantly amorphous random coil to a crystalline antiparallel beta-sheet structure.

In some embodiments, the SPF solutions described herein can be used to prepare SPF microparticles by precipitation with methanol. Alternative flash drying, fluid bed drying, spray drying, or vacuum drying can be applied to remove water from the silk solution. The SPF powder can then be stored and handled without refrigeration or other special handling procedures. In some embodiments, the SPF powder comprises low molecular weight silk fibroin protein fragments. In some embodiments, the SPF powder comprises medium molecular weight silk fibroin protein fragments. In some embodiments, the SPF powder comprises a mixture of low molecular weight silk fibroin protein fragments and medium molecular weight silk fibroin protein fragments.

As used herein, the terms "substantially free of sericin" or "substantially devoid of sericin" refer to silk fibers from which the majority of sericin protein has been removed. In one embodiment, silk fibroin substantially devoid of sericin refers to silk fibroin having from about 0.01% to about 10.0% sericin by weight. In one embodiment, silk fibroin substantially devoid of sericin refers to silk fibroin having from about 0.01% to about 9.0% sericin by weight. In one embodiment, silk fibroin substantially devoid of sericin refers to silk fibroin having from about 0.01% to about 8.0% sericin by weight. In one embodiment, silk fibroin substantially devoid of sericin refers to silk fibroin having from about 0.01% to about 7.0% sericin by weight. In one embodiment, silk fibroin substantially devoid of sericin refers to silk fibroin having from about 0.01% to about 6.0% sericin by weight. In one embodiment, silk fibroin substantially devoid of sericin refers to silk fibroin having from about 0.01% to about 5.0% sericin by weight. In one embodiment, silk fibroin substantially devoid of sericin refers to silk fibroin having from about 0% to about 4.0% sericin by weight. In one embodiment, silk fibroin substantially devoid of sericin refers to silk fibroin having from about 0.05% to about 4.0% sericin by weight. In one embodiment, silk fibroin substantially devoid of sericin refers to silk fibroin having from about 0.1% to about 4.0% sericin by weight. In one embodiment, silk fibroin substantially devoid of sericin refers to silk fibroin having from about 0.5% to about 4.0% by weight sericin. In one embodiment, silk fibroin substantially devoid of sericin refers to silk fibroin having from about 1.0% to about 4.0% by weight sericin. In one embodiment, silk fibroin substantially devoid of sericin refers to silk fibroin having from about 1.5% to about 4.0% sericin by weight. In one embodiment, silk fibroin substantially devoid of sericin refers to silk fibroin having from about 2.0% to about 4.0% sericin by weight. In one embodiment, silk fibroin substantially devoid of sericin refers to silk fibroin having about 2.5% to about 4.0% sericin by weight. In one embodiment, silk fibroin substantially devoid of sericin refers to silk fibroin having a sericin content of about 0.01% to about 0.1% by weight. In one embodiment, silk fibroin substantially devoid of sericin refers to silk fibroin having a sericin content of less than about 0.1% by weight. In one embodiment, silk fibroin substantially devoid of sericin refers to silk fibroin having a sericin content of less than about 0.05% by weight. In one embodiment, from about 26.0% to about 31% by weight when the silk source is added to a boiling (100° C.) aqueous solution of sodium carbonate over a treatment time of from about 30 minutes to about 60 minutes. A degumming loss of .0% by weight is obtained.

The following are non-limiting examples of suitable ranges for various parameters in and for the preparation of silk solutions of the present disclosure. Silk solutions of the present disclosure may include one or more, but not necessarily all, of these parameters, but may be prepared using various combinations of ranges of such parameters.

In one embodiment, the SPF (%) in the solution is less than 30.0% by weight. In one embodiment, the SPF (%) in the solution is less than 25.0% by weight. In one embodiment, the SPF (%) in the solution is less than 20.0% by weight. In one embodiment, the SPF (%) in the solution is less than 19.0% by weight. In one embodiment, the SPF (%) in the solution is less than 18.0% by weight. In one embodiment, the SPF (%) in the solution is less than 17.0% by weight. In one embodiment, the SPF (%) in the solution is less than 16.0% by weight. In one embodiment, the SPF (%) in the solution is less than 15.0% by weight. In one embodiment, the SPF (%) in the solution is less than 14.0% by weight. In one embodiment, the SPF (%) in the solution is less than 13.0% by weight. In one embodiment, the SPF (%) in the solution is less than 12.0% by weight. In one embodiment, the SPF (%) in the solution is less than 11.0% by weight. In one embodiment, the SPF (%) in the solution is less than 10.0% by weight. In one embodiment, the SPF (%) in the solution is less than 9.0% by weight. In one embodiment, the SPF (%) in the solution is less than 8.0% by weight. In one embodiment, the SPF (%) in the solution is less than 7.0% by weight. In one embodiment, the SPF (%) in the solution is less than 6.0% by weight. In one embodiment, the SPF (%) in the solution is less than 5.0% by weight. In one embodiment, the SPF (%) in the solution is less than 4.0% by weight. In one embodiment, the SPF (%) in the solution is less than 3.0% by weight. In one embodiment, the SPF (%) in the solution is less than 2.0% by weight. In one embodiment, the SPF (%) in the solution is less than 1.0% by weight. In one embodiment, the SPF (%) in the solution is less than 0.9% by weight. In one embodiment, the SPF (%) in the solution is less than 0.8% by weight. In one embodiment, the SPF (%) in the solution is less than 0.7% by weight. In one embodiment, the SPF (%) in the solution is less than 0.6% by weight. In one embodiment, the SPF (%) in the solution is less than 0.5% by weight. In one embodiment, the SPF (%) in the solution is less than 0.4% by weight. In one embodiment, the SPF (%) in the solution is less than 0.3% by weight. In one embodiment, the SPF (%) in the solution is less than 0.2% by weight. In one embodiment, the SPF (%) in the solution is less than 0.1% by weight.

In one embodiment, the SPF (%) in the solution is greater than 0.1% by weight. In one embodiment, the SPF (%) in the solution is greater than 0.2% by weight. In one embodiment, the SPF (%) in the solution is greater than 0.3% by weight. In one embodiment, the SPF (%) in the solution is greater than 0.4% by weight. In one embodiment, the SPF (%) in the solution is greater than 0.5% by weight. In one embodiment, the SPF (%) in the solution is greater than 0.6% by weight. In one embodiment, the SPF (%) in the solution is greater than 0.7% by weight. In one embodiment, the SPF (%) in the solution is greater than 0.8% by weight. In one embodiment, the SPF (%) in the solution is greater than 0.9% by weight. In one embodiment, the SPF (%) in the solution is greater than 1.0% by weight. In one embodiment, the % SPF in the solution is greater than 2.0% by weight. In one embodiment, the SPF (%) in the solution is greater than 3.0% by weight. In one embodiment, the SPF (%) in the solution is greater than 4.0% by weight. In one embodiment, the SPF (%) in the solution is greater than 5.0% by weight. In one embodiment, the SPF (%) in the solution is greater than 6.0% by weight. In one embodiment, the SPF (%) in the solution is greater than 7.0% by weight. In one embodiment, the SPF (%) in the solution is greater than 8.0% by weight. In one embodiment, the SPF (%) in the solution is greater than 9.0% by weight. In one embodiment, the SPF (%) in the solution is greater than 10.0% by weight. In one embodiment, the SPF (%) in the solution is greater than 11.0% by weight. In one embodiment, the SPF (%) in the solution is greater than 12.0% by weight. In one embodiment, the SPF (%) in the solution is greater than 13.0% by weight. In one embodiment, the SPF (%) in the solution is greater than 14.0% by weight. In one embodiment, the SPF (%) in the solution is greater than 15.0% by weight. In one embodiment, the SPF (%) in the solution is greater than 16.0% by weight. In one embodiment, the SPF (%) in the solution is greater than 17.0% by weight. In one embodiment, the SPF (%) in the solution is greater than 18.0% by weight. In one embodiment, the SPF (%) in the solution is greater than 19.0% by weight. In one embodiment, the SPF (%) in the solution is greater than 20.0% by weight. In one embodiment, the SPF (%) in the solution is greater than 25.0% by weight.

In one embodiment, the SPF (%) in the solution ranges from about 0.1% to about 30.0% by weight. In one embodiment, the SPF (%) in the solution ranges from about 0.1% to about 25.0% by weight. In one embodiment, the SPF (%) in the solution ranges from about 0.1% to about 20.0% by weight. In one embodiment, the SPF (%) in the solution ranges from about 0.1% to about 15.0% by weight. In one embodiment, the SPF (%) in the solution ranges from about 0.1% to about 10.0% by weight. In one embodiment, the SPF (%) in the solution ranges from about 0.1% to about 9.0% by weight. In one embodiment, the SPF (%) in the solution ranges from about 0.1% to about 8.0% by weight. In one embodiment, the SPF (%) in the solution ranges from about 0.1% to about 7.0% by weight. In one embodiment, the SPF (%) in the solution ranges from about 0.1% to about 6.5% by weight. In one embodiment, the SPF (%) in the solution ranges from about 0.1% to about 6.0% by weight. In one embodiment, the SPF (%) in the solution ranges from about 0.1% to about 5.5% by weight. In one embodiment, the SPF (%) in the solution ranges from about 0.1% to about 5.0% by weight. In one embodiment, the SPF (%) in the solution ranges from about 0.1% to about 4.5% by weight. In one embodiment, the SPF (%) in the solution ranges from about 0.1% to about 4.0% by weight. In one embodiment, the SPF (%) in the solution ranges from about 0.1% to about 3.5% by weight. In one embodiment, the SPF (%) in the solution ranges from about 0.1% to about 3.0% by weight. In one embodiment, the SPF (%) in the solution ranges from about 0.1% to about 2.5% by weight. In one embodiment, the SPF (%) in the solution ranges from about 0.1% to about 2.0% by weight. In one embodiment, the SPF (%) in the solution ranges from about 0.1% to about 2.4% by weight. In one embodiment, the SPF (%) in the solution ranges from about 0.5% to about 5.0% by weight. In one embodiment, the SPF (%) in the solution ranges from about 0.5% to about 4.5% by weight. In one embodiment, the SPF (%) in the solution ranges from about 0.5% to about 4.0% by weight. In one embodiment, the SPF (%) in the solution ranges from about 0.5% to about 3.5% by weight. In one embodiment, the SPF (%) in the solution ranges from about 0.5% to about 3.0% by weight. In one embodiment, the SPF (%) in the solution ranges from about 0.5% to about 2.5% by weight. In one embodiment, the SPF (%) in the solution ranges from about 1.0% to about 4.0% by weight. In one embodiment, the SPF (%) in the solution ranges from about 1.0% to about 3.5% by weight. In one embodiment, the SPF (%) in the solution ranges from about 1.0% to about 3.0% by weight. In one embodiment, the SPF (%) in the solution ranges from about 1.0% to about 2.5% by weight. In one embodiment, the SPF (%) in the solution ranges from about 1.0% to about 2.4% by weight. In one embodiment, the SPF (%) in the solution ranges from about 1.0% to about 2.0% by weight.

In one embodiment, the SPF (%) in the solution ranges from about 20.0% to about 30.0% by weight. In one embodiment, the SPF (%) in the solution ranges from about 0.1% to about 10.0% by weight. In one embodiment, the SPF (%) in the solution ranges from about 1.0% to about 10.0% by weight. In one embodiment, the SPF (%) in the solution ranges from about 2% to about 10.0% by weight. In one embodiment, the SPF (%) in the solution ranges from about 0.1% to about 6.0% by weight. In one embodiment, the SPF (%) in the solution ranges from about 6.0% to about 10.0% by weight. In one embodiment, the SPF (%) in the solution ranges from about 6.0% to about 8.0% by weight. In one embodiment, the SPF (%) in the solution ranges from about 6.0% to about 9.0% by weight. In one embodiment, the % SPF in the solution ranges from about 10.0% to about 20.0% by weight. In one embodiment, the SPF (%) in the solution ranges from about 11.0% to about 19.0% by weight. In one embodiment, the SPF (%) in the solution ranges from about 12.0% to about 18.0% by weight. In one embodiment, the SPF (%) in the solution ranges from about 13.0% to about 17.0% by weight. In one embodiment, the SPF (%) in the solution ranges from about 14.0% to about 16.0% by weight. In one embodiment, the % SPF in the solution is about 1.0% by weight. In one embodiment, the SPF (%) in the solution is about 1.5% by weight. In one embodiment, the SPF (%) in the solution is about 2.0% by weight. In one embodiment, the SPF (%) in the solution is about 2.4% by weight. In one embodiment, the SPF (%) in the solution is 3.0% by weight. In one embodiment, the SPF (%) in the solution is 3.5% by weight. In one embodiment, the SPF (%) in the solution is about 4.0% by weight. In one embodiment, the SPF (%) in the solution is about 4.5% by weight. In one embodiment, the SPF (%) in the solution is about 5.0% by weight. In one embodiment, the SPF (%) in the solution is about 5.5% by weight. In one embodiment, the SPF (%) in the solution is about 6.0% by weight. In one embodiment, the SPF (%) in the solution is about 6.5% by weight. In one embodiment, the SPF (%) in the solution is about 7.0% by weight. In one embodiment, the SPF (%) in the solution is about 7.5% by weight. In one embodiment, the SPF (%) in the solution is about 8.0% by weight. In one embodiment, the SPF (%) in the solution is about 8.5% by weight. In one embodiment, the SPF (%) in the solution is about 9.0% by weight. In one embodiment, the SPF (%) in the solution is about 9.5% by weight. In one embodiment, the SPF (%) in the solution is about 10.0% by weight.

In one embodiment, the % sericin in the solution is between undetectable and 25.0% by weight. In one embodiment, the % sericin in the solution is from undetectable to 5.0% by weight. In one embodiment, the % sericin in the solution is 1.0% by weight. In one embodiment, the % sericin in the solution is 2.0% by weight. In one embodiment, the % sericin in the solution is 3.0% by weight. In one embodiment, the % sericin in the solution is 4.0% by weight. In one embodiment, the % sericin in the solution is 5.0% by weight. In one embodiment, the % sericin in the solution is 10.0% by weight. In one embodiment, the % sericin in the solution is 25.0% by weight.

In some embodiments, the silk fibroin-based protein fragments of the present disclosure have storage stability of 10 days to 3 years, depending on storage conditions, percent SPF, and number of shipments and shipping conditions. does not gel slowly or spontaneously when stored in aqueous solution, there is no aggregation of fragments, and therefore no increase in molecular weight over time). In addition, the pH can be varied to prevent premature folding and agglomeration of the silk, thereby extending shelf life and/or aiding shipping conditions. In one embodiment, the stability of the LiBr-silk fragment solution is between 0 and 1 year. In one embodiment, the stability of the LiBr-silk fragment solution is between 0 and 2 years. In one embodiment, the stability of the LiBr-silk fragment solution is 0-3 years. In one embodiment, the stability of the LiBr-silk fragment solution is between 0 and 4 years. In one embodiment, the stability of the LiBr-silk fragment solution is 0-5 years. In one embodiment, the stability of the LiBr-silk fragment solution is 1-2 years. In one embodiment, the stability of the LiBr-silk fragment solution is 1-3 years. In one embodiment, the stability of the LiBr-silk fragment solution is 1-4 years. In one embodiment, the stability of the LiBr-silk fragment solution is 1-5 years. In one embodiment, the stability of the LiBr-silk fragment solution is 2-3 years. In one embodiment, the stability of the LiBr-silk fragment solution is 2-4 years. In one embodiment, the stability of the LiBr-silk fragment solution is 2-5 years. In one embodiment, the stability of the LiBr-silk fragment solution is 3-4 years. In one embodiment, the stability of the LiBr-silk fragment solution is 3-5 years. In one embodiment, the stability of the LiBr-silk fragment solution is 4-5 years.

In one embodiment, the stability of the compositions of the present disclosure is between 10 days and 6 months. In one embodiment, the stability of the compositions of the present disclosure is from 6 months to 12 months. In one embodiment, the stability of the compositions of the present disclosure is from 12 months to 18 months. In one embodiment, the stability of the compositions of the present disclosure is between 18 and 24 months. In one embodiment, the stability of the compositions of the present disclosure is between 24 months and 30 months. In one embodiment, the stability of the compositions of the present disclosure is between 30 months and 36 months. In one embodiment, the stability of the compositions of the present disclosure is between 36 months and 48 months. In one embodiment, the stability of the compositions of the present disclosure is between 48 months and 60 months.

In one embodiment, selected properties of the SPF coated article that may be enhanced compared to uncoated articles include dimensional stability to laundering, dimensional stability to dry cleaning, post-wash appearance, Appearance after cleaning, color fastness to washing, color fastness to dry cleaning, color fastness to non-chlorine bleach, seam torque/spirality (on knitted fabrics), color fastness to crocking, color fastness to abrasion , color fastness to water, color fastness to light, color fastness to sweat, color fastness to chlorinated pool water, color fastness to seawater, tensile strength, seam slippage, tear strength, seam breaking strength , abrasion resistance, anti-pilling, stretch recovery, bursting strength, color fastness to die transfer during storage (label), color fastness to ozone, pile retention, curvature and skew, color fastness to saliva, resistance to Snagging properties, wrinkle resistance (e.g. garment appearance, fabric fold retention, fabric smooth appearance), water repellency, waterproofness, stain resistance (e.g. water repellency, oil repellency, water/alcohol repellency) , vertical wicking, water absorption, drying speed, ease of soil removal, breathability, wicking, antibacterial properties, UV protection, resistance to torque, odor resistance, biocompatibility, wetting time, absorption rate, diffusion rate, One or more of the following may be mentioned: directional moisture transfer index, flame retardancy, color properties, fiber softening properties, pH adjusting properties, anti-felting properties, as well as overall moisture management ability.

In any of the above embodiments, at least one property of the article is improved, the improved property is dimensional stability to washing, and the property is at least 5%, at least 10%, at least 15%, at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, at least 50%, at least 55%, at least 60%, at least 65%, at least 70% , at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 100%, at least 125%, at least 150%, at least 200%, at least 300%, at least 400%, and from at least 500% improved by an amount selected from the group .

In any of the above embodiments, at least one property of the article is improved, the improved property is size retention on laundering, and the property is at least 5%, at least 10% greater than the uncoated article. %, at least 15%, at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, consisting of at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 100%, at least 125%, at least 150%, at least 200%, at least 300%, at least 400%, and at least 500% improved by the amount selected from the group.

In any of the above embodiments, at least one property of the article is improved, the improved property is resistance to shrinkage, and the property is improved by at least 5%, at least 10% relative to the uncoated article. , at least 15%, at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least The group consisting of 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 100%, at least 125%, at least 150%, at least 200%, at least 300%, at least 400%, and at least 500%. improved by the amount selected from.

Compositions and Processes Comprising Silk Protein Fragment Coatings In one embodiment, the present disclosure may include textiles, such as fibers, threads, fibers, or other materials, and combinations thereof, as described herein. The article may be coated with an SPF mixture solution (i.e., silk fibroin solution (SFS)) to produce a coated article. In one embodiment, the coated articles described herein may be treated with additional chemicals that may enhance the properties of the coated article. In one embodiment, the SFS may include one or more chemicals that may enhance the properties of the coated article.

In one embodiment, the fabric may be a flexible material (woven or non-woven), including a web of natural and/or artificial fibers, threads, threads, or combinations thereof. SFS can be applied at any stage of textile processing from individual fibers, threads, fibers, threads, or combinations thereof.

In one embodiment, the fibers may be natural fibers, which may include a natural fiber cellulose base, including (1) basting, such as flax, hemp, kenaf, jute, linen, and/or ramie; (2) leaves such as flax, hemp, sisal, abaca, banana, hemp, ramie, sunhemp, and/or coir; and (3) seed hairs such as cotton and/or kapok. In one embodiment, the fibers may be natural fibers that may include a natural fiber protein base, such as (1) alpaca, camel, cashmere, llama, mohair, and/or vicuna hair, (2) ) wool, such as sheep; (3) filaments, such as silk. In one embodiment, the fibers may be natural fibers, which may include a natural fiber mineral base, including asbestos. In one embodiment, the fibers can be man-made fibers, which can include man-made fiber organic natural polymer bases, such as (1) cellulose bases, such as bamboo, rayon, lyocell, acetate, and/or triacetate; 2) a protein base such as azulon; (3) alginic acid; and (4) gum. In one embodiment, the fibers can be man-made fibers, which can include man-made fiber organic synthetic bases, such as acrylics, anidex, aramids, fluorocarbons, modacrylics, novoloids, nylons, nyltriles, olefins, PBI, polycarbonates, polyesters, It may include one or more of rubber, saran, spandex, vinyl boning. In one embodiment, the fibers can be artificial fibers, which can include an artificial fiber inorganic base, which can include one or more of glass materials, metallic materials, and carbon materials.

In one embodiment, the yarn may include natural fibers, which may include a natural fiber cellulose base, including (1) basting, such as flax, hemp, kenaf, jute, linen, and/or ramie; ) leaves such as flax, hemp, sisal, abaca, banana, hemp, ramie, sunhemp, and/or coir; or (3) seeds such as cotton and/or kapok. In one embodiment, the yarn may include natural fibers, which may include a natural fiber protein base, such as (1) alpaca, camel, cashmere, llama, mohair, and/or vicuna hair, (2) ) wool, such as sheep, or (3) filaments, such as silk. In one embodiment, the yarn may include natural fibers, which may include a natural fiber mineral base, including asbestos. In one embodiment, the yarn may include an artificial fiber, which may include an artificial fiber organic natural polymer base, which may include (1) a cellulose base, such as bamboo, rayon, lyocell, acetate, and/or triacetate; 2) a protein base such as azulon, (3) alginic acid, or (4) gum. In one embodiment, the yarn can be a man-made fiber, which can include a man-made fiber organic synthetic base, such as acrylic, anidex, aramid, fluorocarbon, modacrylic, novoloid, nylon, nyltrile, olefin, PBI, polycarbonate, polyester, May include rubber, saran, spandex, and/or vinyl bong. In one embodiment, the thread may include artificial fibers, which may include an artificial fiber inorganic base, which may include glass materials, metallic materials, carbon materials, and/or specialty materials.

In one embodiment, the fibers may include natural fibers and/or yarns that may include a natural fiber cellulose base, such as (1) flax, hemp, kenaf, jute, linen, and/or ramie. basting, (2) leaves such as flax, hemp, sisal, abaca, banana, hemken, ramie, sunhemp, and/or coil; or (3) seed wool such as cotton and/or kapok. In one embodiment, the fibers may include natural fibers and/or yarns that may include a natural fiber protein base, such as (1) alpaca, camel, cashmere, llama, mohair, and/or vicuna. It may be from filaments such as hair, (2) wool, such as sheep, or (3) silk. In one embodiment, the fibers may include natural fibers and/or threads, which may include a natural fiber mineral base, including asbestos. In one embodiment, the fibers may include artificial fibers and/or yarns that may include an artificial fiber organic natural polymer base, such as (1) bamboo, rayon, lyocell, acetate, and/or triacetate. It may include a cellulose base, (2) a protein base such as azulon, (3) alginic acid, or (4) a gum. In one embodiment, the fibers can be man-made fibers and/or yarns that can include man-made fiber organic synthetic bases, such as acrylics, anidex, aramids, fluorocarbons, modacrylics, novoloids, nylons, nyltrils, olefins, PBI, May include polycarbonate, polyester, rubber, saran, spandex, and/or vinylbond. In one embodiment, the fibers may include artificial fibers and/or threads, which may include an artificial fiber inorganic base, which may include glass materials, metallic materials, carbon materials, and/or specialty materials.

In some embodiments, the fibers include alpaca fiber, alpaca fleece, alpaca wool, llama fiber, llama fleece, llama wool, cotton, sheep fleece, sheep wool, linen, cyangora, quibute, yak, rabbit, lambswool, mohair wool, Tibetan wool, lopi, camel hair, pashmina, angora wool, silkworm silk, spider silk, abaca fiber, coir fiber, flax fiber, jute fiber, kapok fiber, kenaf fiber, raffia fiber, bamboo fiber, hemp, modal fiber, pina , ramie, sisal, soy protein fiber, polyester, polyamide, polyaramid, polytetrafluoroethylene, polyethylene, polypropylene, polyurethane, silicone, mixture of polyurethane and polyethylene glycol, ultra-high molecular weight polyethylene, high performance polyethylene, nylon, LYCRA (polyester- polyurethane copolymers (also known as SPANDEX and elastomers), or mixtures thereof. In some embodiments, the fiber comprises wool. In some embodiments, the fibers include polyester, polyamide, polyaramid, polytetrafluoroethylene, polyethylene, polypropylene, polyurethane, silicone, blends of polyurethane and polyethylene glycol, ultra-high molecular weight polyethylene, high performance polyethylene, nylon, LYCRA ( Inert synthetic materials such as polyester-polyurethane copolymers (also known as SPANDEX and elastomers), or mixtures thereof.

In some embodiments, the fibers include one or more selected from the group consisting of cotton, silk, alpaca fleece, alpaca wool, llama fleece, llama wool, cotton, cashmere, sheep fleece, sheep wool, and combinations thereof. include. In some embodiments, the fiber is one or more of natural wool, synthetic wool, alpaca fleece, alpaca wool, llama fleece, llama wool, cashmere, sheep fleece, sheep wool, mohair wool, camel hair, or angora wool. including.

In some embodiments, the articles described herein can include synthetic fiber components in an amount of 100% by weight (w/w) of the article. In some embodiments, the articles described herein are 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8% by weight (w/w) of the article. , 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25 %, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58% , 59%, 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75 %, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, The synthetic fiber component may include an amount of greater than 92%, 93%, 94%, 95%, 96%, 97%, 98%, or 99%, with the remainder of the article being, by weight (w/w), as described herein. It is a non-synthetic fiber component as described in the book. In some embodiments, the articles described herein are 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8% by weight (w/w) of the article. , 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25 %, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58% , 59%, 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75 %, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91%, The synthetic fiber component may include an amount of less than 92%, 93%, 94%, 95%, 96%, 97%, 98%, or 99%, with the remainder of the article being, by weight (w/w), It is a non-synthetic fiber component as described in the book. In some embodiments, the articles described herein are about 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8% by weight (w/w) of the article. %, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41% , 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58 %, 59%, 60%, 61%, 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88%, 89%, 90%, 91% , 92%, 93%, 94%, 95%, 96%, 97%, 98%, or 99% of the synthetic fiber component, with the remainder of the article, by weight (w/w), as described herein. It is a non-synthetic fiber component as described in the book.

In some embodiments, the coating further includes a crosslinker. In some embodiments, any SPF described herein, including silk fibroin or silk fibroin-based protein fragments, is chemically modified with a precursor linker that includes a cross-linking agent to form a silk conjugate. . In some embodiments, the fibers are covalently bonded to a crosslinking agent. In some embodiments, the crosslinker is covalently bonded to the surfactant and/or emulsifier. In some embodiments, the crosslinking agent is covalently bonded to the fiber and the surfactant and/or emulsifier. In some embodiments, the crosslinking agent is covalently bonded to the fiber and the SPF.

The precursor linker may be selected from any of the following natural crosslinkers, caffeic acid, tannic acid, genipin, proanthocyanidins, and the like. Precursor crosslinks include the following enzyme crosslinks, transglutaminase transferase crosslinks, hydrolase crosslinks, peptidase crosslinks (e.g. sortase SrtA from Staphylococcus aureus), oxidoreductase crosslinks, tyrosinase crosslinks, laccase crosslinks, peroxidase crosslinks (e.g. horseradish peroxidase) , lysyl oxidase cross-linking, peptide ligase (eg, butelase 1, peptigase, subtiligase, etc.), and the like.

In some embodiments, silk fibroin or silk fibroin-based protein fragments are chemically modified with precursor linkers such as N-hydroxysuccinimide ester crosslinkers, imidoester crosslinkers, sulfosuccinimidylaminobenzoates, Methacrylate, silane, silicate, alkyne compound, azide compound, aldehyde, carbodiimide crosslinker, dicyclohexylcarbodiimide activator, dicyclohexylcarbodiimide crosslinker, maleimide crosslinker, haloacetyl crosslinker, pyridyl disulfide crosslinker, hydrazide crosslinker, alkoxyamine Crosslinkers, reductive amination crosslinkers, arylazide crosslinkers, diazirine crosslinkers, azide-phosphine crosslinkers, transferase crosslinkers, hydrolase crosslinkers, transglutaminase crosslinkers, peptidase crosslinkers, oxidoreductase crosslinkers, tyrosinase crosslinkers , laccase crosslinkers, peroxidase crosslinkers, lysyl oxidase crosslinkers, and any combinations thereof. Some chemically modified silk fibroins are described in J Mater Chem. 2009, June 23, 19(36), 6443-6450, and includes cyanuric chloride-activated coupling, carbodiimide coupling, arginine masking, chlorosulfonic acid reaction, diazonium coupling, tyrosinase-catalyzed grafting, and poly(methacrylate) ) including transplants.

In some embodiments, the article further includes a crosslinking agent. In some embodiments, the crosslinking agent is a polyphenol compound containing 12 phenolic hydroxyl groups having a molecular weight of about 500-4000 Da and exhibiting about 5-7 aromatic rings per 1000 Da. In some embodiments, the crosslinking agent is curcumin, desmethoxycurcumin, bis-desmethoxycurcumin, restorelatol, caffeic acid, tannin, gallotanin, procyanidin, hydrolyzable tannin, phlorotanine, gallic acid, chlorogenic acid, carnosol, Capsaicin, 6-shogaol, 6-gingerol, flavonoids, flavanols, neoflavonoids, arbutin, cynarin, apigenin, isocatterrarin, luteolin, nobiletin, tangaretin, tectochrysin, galangin, kaempferol, myricetin, quercetin, rutin, citrin, selected from the group consisting of curcocitrin, eriodithiol, hesperidin, narginine, naringin, pinocembrin, quercitrin, biochanin A, chrysin, daidzein, equol, formononetin, distein, glycetein, ipriflavone, lactoin, pycnogenol, silymarin, lignin, and combinations thereof It is a polyphenol compound.

In one embodiment, the coating is applied to the fiber-containing article at the thread level. In one embodiment, the coating is applied at the fiber level. In one embodiment, the coating is of the group consisting of about 5 nm, about 10 nm, about 15 nm, about 20 nm, about 25 nm, about 50 nm, about 100 nm, about 200 nm, about 500 nm, about 1 μm, about 5 μm, about 10 μm, and about 20 μm. having a thickness selected from. In one embodiment, the coating is about 5 nm to about 100 nm, about 100 nm to about 200 nm, about 200 nm to about 500 nm, about 1 μm to about 2 μm, about 2 μm to about 5 μm, about 5 μm to about 10 μm, and about 10 μm to about 20 μm. having a thickness range selected from the group consisting of:

In one embodiment, the fibers include polyglycolide (PGA), polyethylene glycol, copolymers of glycolide, glycolide/L-lactide copolymers (PGA/PLLA), glycolide/trimethylene carbonate copolymers (PGA/TMC), polylactide (PLA), stereocopolymer of PLA, poly-L-lactide (PLLA), poly-DL-lactide (PDLLA), L-lactide/DL-lactide copolymer, copolymer of PLA, lactide/tetramethyl glycolide copolymer, lactide/trimethylene carbonate copolymer, Lactide/δ-valerolactone copolymer, lactide/ε-caprolactone copolymer, polydepsipeptide, PLA/polyethylene oxide copolymer, asymmetric 3,6-substituted poly-1,4-dioxane-2,5-dione, poly-β-hydroxy butyrate (PHBA), PHBA/β-hydroxyvaleric acid copolymer (PHBA/HVA), poly-β-hydroxypropionate (PHPA), poly-p-dioxanone (PDS), poly-δ-valerolactone, poly- ε-caprolactone, methyl methacrylate-N-vinylpyrrolidine copolymer, polyester amide, polyester of oxalic acid, polydihydropyran, polyalkyl-2-cyanoacrylate, polyurethane (PU), polyvinyl alcohol (PVA), polypeptide, poly-β - Malic acid (PMLA), poly-β-alkanoic acid, polyvinyl alcohol (PVA), polyethylene oxide (PEO), chitin polymer, polyethylene, polypropylene, polyacetal, polyamide, polyester, polysulfone, polyether ether ketone, polyethylene terephthalate, polycarbonate , polyaryletherketone, and polyetherketoneketone.

In one embodiment, the textile may be manufactured via one or more of the following processes: weaving, knitting, and nonwoven processes. In one embodiment, the weaving process may include plain weave, twill, and/or satin weave. In one embodiment, the knitting process may include weft knitting (e.g., circular, flat bed, and/or fully fashioned) and/or warp knitting (e.g., tricot, raschel, and/or crochet). In one embodiment, the nonwoven process may include staple fiber (e.g., dry-laid and/or wet-laid) and/or continuous filament (e.g., spun and/or meltblown).

In one embodiment, the present disclosure provides an article comprising fibers coated with silk protein fragments. In one embodiment, the present disclosure provides an article comprising fibers coated with silk protein fragments, where the fibers are fibers used in human clothing, including performance apparel and/or athletic clothing. In one embodiment, the present disclosure provides articles comprising fibers coated with silk protein fragments, the fibers exhibiting improved moisture management properties and/or resistance to microbial growth. In one embodiment, the present disclosure provides an article comprising a fiber coated with silk protein fragments, the fiber being a fiber used for home interior decoration. In one embodiment, the present disclosure provides an article comprising fibers coated with silk protein fragments, the fibers being used in automobile interiors. In one embodiment, the present disclosure provides an article comprising fibers coated with silk protein fragments, the fibers being used in aircraft interiors. In one embodiment, the present disclosure provides an article comprising fibers coated with silk protein fragments, wherein the fibers are used in transportation vehicles for public, commercial, military, or other uses, including buses and trains. Used for interior decoration. In one embodiment, the present disclosure provides an article comprising fibers coated with silk protein fragments, the fibers being used for interior decoration of products requiring a high degree of abrasion resistance compared to regular upholstery. used.

In one embodiment, the present disclosure provides an article comprising a fiber coated with silk protein fragments, the fiber being a fiber that is fabricated as a decoration for an automobile interior. In one embodiment, the present disclosure provides an article comprising a fiber coated with silk protein fragments, the article being a textile that is fabricated as a steering wheel. In one embodiment, the present disclosure provides an article comprising a fiber coated with silk protein fragments, the fiber being a textile that is fabricated as a headrest. In one embodiment, the present disclosure provides an article comprising a fiber coated with silk protein fragments, the fiber being a textile that is fabricated as an armrest. In one embodiment, the present disclosure provides an article comprising a fiber coated with silk protein fragments, the fiber being a textile that is fabricated as an automobile floor mat. In one embodiment, the present disclosure provides an article comprising a fiber coated with silk protein fragments, the fiber being a textile that is fabricated as a carpet for an automobile or vehicle. In one embodiment, the present disclosure provides an article comprising a fiber coated with silk protein fragments, the fiber being a textile that is fabricated as a decoration for an automobile. In one embodiment, the present disclosure provides an article comprising a fiber coated with silk protein fragments, the fiber being a textile that is fabricated as a child seat. In one embodiment, the present disclosure provides an article comprising a fiber coated with silk protein fragments, the fiber being a textile fabricated as a seat belt or safety gear. In one embodiment, the present disclosure provides an article comprising a fiber coated with silk protein fragments, the fiber being a textile fabricated as a dashboard. In one embodiment, the present disclosure provides an article comprising a fiber coated with silk protein fragments, the fiber being a textile fabricated as a sheet. In one embodiment, the present disclosure provides an article comprising a fiber coated with silk protein fragments, the fiber being a textile fabricated as a seat panel. In one embodiment, the present disclosure provides an article comprising a fiber coated with silk protein fragments, the fiber being a textile fabricated as an interior panel. In one embodiment, the present disclosure provides an article comprising a fiber coated with silk protein fragments, the fiber being a textile fabricated as an airbag cover. In one embodiment, the present disclosure provides an article comprising a fiber coated with silk protein fragments, the fiber being a textile fabricated as an airbag. In one embodiment, the present disclosure provides an article comprising a fiber coated with silk protein fragments, the fiber being a textile fabricated as a sun visor. In one embodiment, the present disclosure provides an article comprising a fiber coated with silk protein fragments, the fiber being a textile product fabricated as a wire harness. In one embodiment, the present disclosure provides an article comprising a fiber coated with silk protein fragments, the article being a cushion. In one embodiment, the present disclosure provides an article coated with silk protein fragments, the product being an automobile, aircraft, or vehicle insulation. In some embodiments, the coating comprises an article coated with silk protein fragments having a weight average molecular weight range of about 1 kDa to about 350 kDa, wherein the silk protein fragments have an average weight average molecular weight range selected from the group consisting of about 5 to about 10 kDa, about 6 kDa to about 17 kDa, about 17 kDa to about 39 kDa, about 39 kDa to about 80 kDa, about 60 to about 100 kDa, and about 80 kDa to about 144 kDa, and wherein the silk protein fragments have a polydispersity of about 1.5 to about 3.0, or about 1.0 to about 5.0, and optionally, the protein or protein fragments prior to coating the fiber do not spontaneously or gradually gel and do not visibly change in color or turbidity when in solution for at least 10 days. The coating comprises silk protein fragments having a weight average molecular weight range of about 5 kDa to about 144 kDa, the silk protein fragments having an average weight average molecular weight range selected from the group consisting of about 5 to about 10 kDa, about 6 kDa to about 17 kDa, about 17 kDa to about 39 kDa, about 39 kDa to about 80 kDa, about 60 to about 100 kDa, and about 80 kDa to about 144 kDa, the silk protein fragments having a polydispersity of about 1.5 to about 3.0, and optionally, the protein or protein fragments prior to coating the fiber do not spontaneously or gradually gel and do not visibly change in color or turbidity when in solution for at least 10 days.

In one embodiment, the present disclosure provides an article comprising fibers coated with silk protein fragments. In one embodiment, the articles are fabrics used in the manufacture of tents, sleeping bags, ponchos, and soft coolers. In one embodiment, the fibers are those used in the manufacture of athletic equipment. In one embodiment, the fibers are those used in the manufacture of outdoor equipment. In one embodiment, the fibers are those used in the manufacture of hiking equipment such as harnesses and backpacks. In one embodiment, the fiber is a fiber used in the manufacture of mountaineering equipment. In one embodiment, the fiber is canvas fabric. In one embodiment, the fibers are those used in the manufacture of hats. In one embodiment, the fibers are those used in the manufacture of umbrellas. In one embodiment, the fibers are those used in the manufacture of tents. In one embodiment, the fibers are those used in the manufacture of infant sleepers, infant blankets, or infant pajamas. In one embodiment, the fibers are those used in the manufacture of gloves, such as driving gloves or athletic gloves. In one embodiment, the fibers are those used in the manufacture of athletic pants, such as sweatpants, jogging pants, yoga pants, or pants for use in competitive sports. In one embodiment, the fibers are those used in the manufacture of athletic shirts, such as sweatshirts, jogging shirts, yoga shirts, or shirts for use in competitive sports. In one embodiment, the fibers are fabrics used in the manufacture of beach equipment, such as beach umbrellas, beach chairs, beach blankets, and beach towels. In one embodiment, the fibers are those used in the manufacture of jackets or overcoats. In one embodiment, the fibers are used in surgical drapes, surgical gowns, surgical sleeves, laboratory sleeves, laboratory coats, wound dressings, sterile wraps, surgical face masks, retention bandages, support devices, compression A fiber used to make medical clothing such as bandages, shoe covers, and surgical blankets. The coating includes silk-based proteins or fragments thereof having a weight average molecular weight range of about 5 kDa to about 144 kDa.

In one embodiment, the present disclosure provides an article comprising a fabric coated with silk fibroin-based proteins or fragments thereof. In one embodiment, the fabric is a fabric used in the manufacture of tents, sleeping bags, ponchos, and soft coolers. In one embodiment, the fabric is a fabric used in the manufacture of athletic equipment. In one embodiment, the fabric is a fabric used in the manufacture of outdoor equipment. In one embodiment, the fabric is a fabric used in the manufacture of hiking gear such as harnesses and shirts. In one embodiment, the fabric is a fabric used in the manufacture of mountaineering equipment. In one embodiment, the fabric is a canvas fabric. In one embodiment, the fabric is a fabric used in the manufacture of hats. In one embodiment, the fabric is a fabric used in the manufacture of umbrellas. In one embodiment, the fabric is a fabric used in the manufacture of tents. In one embodiment, the fabric is a fabric used in the manufacture of infant sleepers, infant blankets, or infant pajamas. In one embodiment, the fabric is a fabric used in the manufacture of gloves, such as driving gloves or athletic gloves. In one embodiment, the fabric is a fabric used to make athletic pants, such as sweatpants, jogging pants, yoga pants, or pants for use in competitive sports. In one embodiment, the fabric is a fabric used in the manufacture of athletic shirts, such as sweatshirts, jogging shirts, yoga shirts, or shirts for use in competitive sports. In one embodiment, the fabric is a fabric used in the manufacture of beach equipment, such as beach umbrellas, beach chairs, beach blankets, and beach towels. In one embodiment, the fabric is a fabric used in the manufacture of jackets or overcoats. In one embodiment, the fabric is used for surgical drapes, surgical gowns, surgical sleeves, laboratory sleeves, laboratory coats, wound dressings, sterile wraps, surgical face masks, retention bandages, support devices, compression A textile used in the manufacture of medical clothing such as bandages, shoe covers, and surgical blankets. The coating includes silk-based proteins or fragments thereof having a weight average molecular weight range of about 1 kDa to about 350 kDa, wherein the silk-based proteins or protein fragments thereof have a weight average molecular weight range of about 5 to about 10 kDa, about 6 kDa to about 17 kDa, about having an average weight average molecular weight range selected from the group consisting of 17 kDa to about 39 kDa, about 39 kDa to about 80 kDa, about 60 to about 100 kDa, and about 80 kDa to about 144 kDa; 1.0 to about 5.0, and optionally, the protein or protein fragment prior to coating the fibers does not gel spontaneously or gradually and remains in solution for at least 10 days. No visible change in color or turbidity at any time.

In one embodiment, the present disclosure provides shoes coated with silk fibroin-based proteins or fragments thereof. In one embodiment, the present disclosure provides shoes coated with silk fibroin-based proteins or fragments thereof, wherein the shoes exhibit improved properties compared to uncoated shoes. In one embodiment, the present disclosure provides a shoe coated with silk fibroin-based proteins or fragments thereof, wherein the shoe exhibits improved properties compared to an uncoated shoe, and the shoe exhibits improved properties. is stain resistant. In one embodiment, the present disclosure provides a shoe coated with silk fibroin-based proteins or fragments thereof, wherein the shoe exhibits improved properties compared to an uncoated shoe, and where the shoe exhibits improved properties compared to an uncoated shoe; Made from leather or synthetic leather. The coating comprises silk-based proteins or fragments thereof having a weight average molecular weight range of about 1 kDa to about 350 kDa or about 5 kDa to about 144 kDa, wherein the silk-based proteins or protein fragments thereof have a weight average molecular weight range of about 5 to about 10 kDa, about silk-based protein or The fragments have a polydispersity of about 1.0 to about 5.0 or about 1.5 to about 3.0, and optionally, the protein or protein fragments before coating the fiber are does not gel visibly or gradually and does not change visibly in color or turbidity when in solution for at least 10 days.

In one aspect, the present disclosure provides methods of making silk coated fibers and/or articles using the silk protein fragments of the present disclosure. In some embodiments, the silk coated fibers are silk fibroin coated fibers. In some embodiments, the silk coated article is a silk fibroin coated article. In some embodiments, the present disclosure also includes articles prepared by the methods of the present disclosure. In some embodiments, the present disclosure also includes articles comprising coated fibers prepared by the methods of the present disclosure. In some embodiments, the present disclosure also includes coated fibers prepared by the methods of the present disclosure.

In some embodiments, the present disclosure includes a method of making a fiber coated with silk fibroin, the method comprising: applying a solution including a reducing agent to the fiber; and applying a silk fibroin solution to the fiber. and drying the fibers.

In some embodiments, the present disclosure includes a method of improving size retention for laundering of fibers, the method comprising: applying a solution including a reducing agent to the fibers; and applying a silk fibroin solution to the fibers. , drying the fibers.

In one aspect, the present disclosure includes a method for improving size retention of fibers upon laundering, the method comprising: coating the surface of the fiber with a solution containing a reducing agent; and preparing a silk fibroin solution containing silk protein fibroin fragments. coating the surface of the fiber with a silk fibroin solution; and drying the surface of the fiber coated with the silk fibroin solution, so that during washing, the coated fiber is removed from its initial state before washing. substantially retains size.

Any surfactant and/or emulsifier is contemplated by this disclosure. In a non-limiting example, surfactants and/or emulsifiers are used to treat the fibers when mixed with the silk fibroin solution. In a non-limiting example, surfactants and/or emulsifiers are used to pre-treat the surface of the fibers to improve the surface affinity between the silk protein fragments and the fibers. In some embodiments, the surfactant and/or emulsifier is a natural surfactant and/or emulsifier. In some embodiments, the surfactant and/or emulsifier is selected from coco glucoside, decyl glucoside, lauryl glucoside, coconut sucrose, capryl/caprylyl glucoside, and caprylyl/capryl glucoside. In some embodiments, the surfactant and/or emulsifier is selected from polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, and polyoxyethylene castor oil. In some embodiments, the surfactants and/or emulsifiers include polyoxyethylene (10-30) sorbitan monooleate, polyoxyethylene (10-30) sorbitan trioleate, and polyoxyethylene (10-50) sorbitan monooleate. Selected from castor oil. In some embodiments, the surfactant and/or emulsifier is selected from polyoxyethylene (20) sorbitan monooleate, polyoxyethylene (20) sorbitan trioleate, and polyoxyethylene (29) castor oil. . In some embodiments, the surfactant and/or emulsifier is polyoxyethylene (20) sorbitan monooleate. In some embodiments, the surfactant and/or emulsifier is polyoxyethylene (20) sorbitan monolaurate. In some embodiments, the surfactant and/or emulsifier is polyoxyethylene (20) sorbitan monopalmitate. In some embodiments, the surfactant and/or emulsifier is polyoxyethylene (20) sorbitan monostearate. In some embodiments, the surfactant and/or emulsifier is polyoxyethylene (20) sorbitan trioleate. In some embodiments, the surfactant and/or emulsifier is polyoxyethylene (20) sorbitan tristearate. In some embodiments, the surfactant and/or emulsifier is polyoxyethylene (29) castor oil. In some embodiments, the surfactant and/or emulsifier comprises sorbitan monofatty acid. In some embodiments, the surfactant and/or emulsifier comprises a sorbitan trifatty acid. In some embodiments, the surfactant and/or emulsifier includes castor oil. In some embodiments, the surfactant and/or emulsifier has a degree of ethoxylation that can be adjusted to provide a particular HLB value.

In some embodiments, the concentration of surfactant and/or emulsifier in the solution ranges from 0.01 g/L to about 100 g/L. In some embodiments, the concentration of surfactant and/or emulsifier in the solution ranges from 0.1 g/L to about 50 g/L. In some embodiments, the concentration of surfactant and/or emulsifier in the solution ranges from 0.5 g/L to about 25 g/L. In some embodiments, the concentration of surfactant and/or emulsifier in the solution ranges from 1 g/L to about 20 g/L. In some embodiments, the concentration of surfactant and/or emulsifier in the solution ranges from about 20 g/L to about 50 g/L. In some embodiments, the concentration of surfactant and/or emulsifier is about 1 g/L. In some embodiments, the concentration of surfactant and/or emulsifier is about 2 g/L. In some embodiments, the concentration of surfactant and/or emulsifier is about 3 g/L. In some embodiments, the concentration of surfactant and/or emulsifier is about 4 g/L. In some embodiments, the concentration of surfactant and/or emulsifier is about 5 g/L. In some embodiments, the concentration of surfactant and/or emulsifier is about 6 g/L. In some embodiments, the concentration of surfactant and/or emulsifier is about 7 g/L. In some embodiments, the concentration of surfactant and/or emulsifier is about 8 g/L. In some embodiments, the concentration of surfactant and/or emulsifier is about 9 g/L. In some embodiments, the concentration of surfactant and/or emulsifier is about 10 g/L. In some embodiments, the concentration of surfactant and/or emulsifier is about 11 g/L. In some embodiments, the concentration of surfactant and/or emulsifier is about 12 g/L. In some embodiments, the concentration of surfactant and/or emulsifier is about 13 g/L. In some embodiments, the concentration of surfactant and/or emulsifier is about 14 g/L. In some embodiments, the concentration of surfactant and/or emulsifier is about 15 g/L. In some embodiments, the concentration of surfactant and/or emulsifier is about 16 g/L. In some embodiments, the concentration of surfactant and/or emulsifier is about 17 g/L. In some embodiments, the concentration of surfactant and/or emulsifier is about 18 g/L. In some embodiments, the concentration of surfactant and/or emulsifier is about 19 g/L. In some embodiments, the concentration of surfactant and/or emulsifier is about 20 g/L. In some embodiments, the concentration of surfactant and/or emulsifier is about 21 g/L. In some embodiments, the concentration of surfactant and/or emulsifier is about 22 g/L. In some embodiments, the concentration of surfactant and/or emulsifier is about 23 g/L. In some embodiments, the concentration of surfactant and/or emulsifier is about 24 g/L. In some embodiments, the concentration of surfactant and/or emulsifier is about 25 g/L. In some embodiments, the concentration of surfactant and/or emulsifier is about 26 g/L. In some embodiments, the concentration of surfactant and/or emulsifier is about 27 g/L. In some embodiments, the concentration of surfactant and/or emulsifier is about 28 g/L. In some embodiments, the concentration of surfactant and/or emulsifier is about 29 g/L. In some embodiments, the concentration of surfactant and/or emulsifier is about 30 g/L. In some embodiments, the concentration of surfactant and/or emulsifier is about 31 g/L. In some embodiments, the concentration of surfactant and/or emulsifier is about 32 g/L. In some embodiments, the concentration of surfactant and/or emulsifier is about 33 g/L. In some embodiments, the concentration of surfactant and/or emulsifier is about 34 g/L. In some embodiments, the concentration of surfactant and/or emulsifier is about 35 g/L. In some embodiments, the concentration of surfactant and/or emulsifier is about 36 g/L. In some embodiments, the concentration of surfactant and/or emulsifier is about 37 g/L. In some embodiments, the concentration of surfactant and/or emulsifier is about 38 g/L. In some embodiments, the concentration of surfactant and/or emulsifier is about 39 g/L. In some embodiments, the concentration of surfactant and/or emulsifier is about 40 g/L. In some embodiments, the concentration of surfactant and/or emulsifier is about 41 g/L. In some embodiments, the concentration of surfactant and/or emulsifier is about 42 g/L. In some embodiments, the concentration of surfactant and/or emulsifier is about 43 g/L. In some embodiments, the concentration of surfactant and/or emulsifier is about 44 g/L. In some embodiments, the concentration of surfactant and/or emulsifier is about 45 g/L. In some embodiments, the concentration of surfactant and/or emulsifier is about 46 g/L. In some embodiments, the concentration of surfactant and/or emulsifier is about 47 g/L. In some embodiments, the concentration of surfactant and/or emulsifier is about 48 g/L. In some embodiments, the concentration of surfactant and/or emulsifier is about 49 g/L. In some embodiments, the concentration of surfactant and/or emulsifier is about 50 g/L.

In some embodiments, the concentration of silk fibroin fragments in solution ranges from 0.01 g/L to about 100 g/L. In some embodiments, the concentration of silk fibroin fragments in solution ranges from 0.1 g/L to about 50 g/L. In some embodiments, the concentration of silk fibroin fragments in the solution ranges from 0.5 g/L to about 25 g/L. In some embodiments, the concentration of silk fibroin fragments in solution ranges from 1 g/L to about 20 g/L. In some embodiments, the concentration of silk fibroin fragments in the solution ranges from about 20 g/L to about 50 g/L. In some embodiments, the concentration of silk fibroin fragments is about 1 g/L. In some embodiments, the concentration of silk fibroin fragments is about 2 g/L. In some embodiments, the concentration of silk fibroin fragments is about 3 g/L. In some embodiments, the concentration of silk fibroin fragments is about 4 g/L. In some embodiments, the concentration of silk fibroin fragments is about 5 g/L. In some embodiments, the concentration of silk fibroin fragments is about 6 g/L. In some embodiments, the concentration of silk fibroin fragments is about 7 g/L. In some embodiments, the concentration of silk fibroin fragments is about 8 g/L. In some embodiments, the concentration of silk fibroin fragments is about 9 g/L. In some embodiments, the concentration of silk fibroin fragments is about 10 g/L. In some embodiments, the concentration of silk fibroin fragments is about 11 g/L. In some embodiments, the concentration of silk fibroin fragments is about 12 g/L. In some embodiments, the concentration of silk fibroin fragments is about 13 g/L. In some embodiments, the concentration of silk fibroin fragments is about 14 g/L. In some embodiments, the concentration of silk fibroin fragments is about 15 g/L. In some embodiments, the concentration of silk fibroin fragments is about 16 g/L. In some embodiments, the concentration of silk fibroin fragments is about 17 g/L. In some embodiments, the concentration of silk fibroin fragments is about 18 g/L. In some embodiments, the concentration of silk fibroin fragments is about 19 g/L. In some embodiments, the concentration of silk fibroin fragments is about 20 g/L. In some embodiments, the concentration of silk fibroin fragments is about 21 g/L. In some embodiments, the concentration of silk fibroin fragments is about 22 g/L. In some embodiments, the concentration of silk fibroin fragments is about 23 g/L. In some embodiments, the concentration of silk fibroin fragments is about 24 g/L. In some embodiments, the concentration of silk fibroin fragments is about 25 g/L. In some embodiments, the concentration of silk fibroin fragments is about 26 g/L. In some embodiments, the concentration of silk fibroin fragments is about 27 g/L. In some embodiments, the concentration of silk fibroin fragments is about 28 g/L. In some embodiments, the concentration of silk fibroin fragments is about 29 g/L. In some embodiments, the concentration of silk fibroin fragments is about 30 g/L. In some embodiments, the concentration of silk fibroin fragments is about 31 g/L. In some embodiments, the concentration of silk fibroin fragments is about 32 g/L. In some embodiments, the concentration of silk fibroin fragments is about 33 g/L. In some embodiments, the concentration of silk fibroin fragments is about 34 g/L. In some embodiments, the concentration of silk fibroin fragments is about 35 g/L. In some embodiments, the concentration of silk fibroin fragments is about 36 g/L. In some embodiments, the concentration of silk fibroin fragments is about 37 g/L. In some embodiments, the concentration of silk fibroin fragments is about 38 g/L. In some embodiments, the concentration of silk fibroin fragments is about 39 g/L. In some embodiments, the concentration of silk fibroin fragments is about 40 g/L. In some embodiments, the concentration of silk fibroin fragments is about 41 g/L. In some embodiments, the concentration of silk fibroin fragments is about 42 g/L. In some embodiments, the concentration of silk fibroin fragments is about 43 g/L. In some embodiments, the concentration of silk fibroin fragments is about 44 g/L. In some embodiments, the concentration of silk fibroin fragments is about 45 g/L. In some embodiments, the concentration of silk fibroin fragments is about 46 g/L. In some embodiments, the concentration of silk fibroin fragments is about 47 g/L. In some embodiments, the concentration of silk fibroin fragments is about 48 g/L. In some embodiments, the concentration of silk fibroin fragments is about 49 g/L. In some embodiments, the concentration of silk fibroin fragments is about 50 g/L.

In some embodiments, the w/w ratio of silk fibroin fragments to surfactant and/or emulsifier in solution is about 99:1, about 98:2, about 97:3, about 96:4, about 95 :5, about 94:6, about 93:7, about 92:8, about 91:9, about 90:10, about 89:11, about 88:12, about 87:13, about 86:14, about 85 :15, about 84:16, about 83:17, about 82:18, about 81:19, about 80:20, about 79:21, about 78:22, about 77:23, about 76:24, about 75 :25, about 74:26, about 73:27, about 72:28, about 71:29, about 70:30, about 69:31, about 68:32, about 67:33, about 66:34, about 65 :35, about 64:36, about 63:37, about 62:38, about 61:39, about 60:40, about 59:41, about 58:42, about 57:43, about 56:44, about 55 :45, about 54:46, about 53:47, about 52:48, about 51:49, about 50:50, about 49:51, about 48:52, about 47:53, about 46:54, about 45 :55, about 44:56, about 43:57, about 42:58, about 41:59, about 40:60, about 39:61, about 38:62, about 37:63, about 36:64, about 35 :65, about 34:66, about 33:67, about 32:68, about 31:69, about 30:70, about 29:71, about 28:72, about 27:73, about 26:74, about 25 :75, about 24:76, about 23:77, about 22:78, about 21:79, about 20:80, about 19:81, about 18:82, about 17:83, about 16:84, about 15 :85, about 14:86, about 13:87, about 12:88, about 11:89, about 10:90, about 9:91, about 8:92, about 7:93, about 6:94, about 5 :95, about 4:96, about 3:97, about 2:98, or about 1:99. In some embodiments, the w/w ratio of silk fibroin fragments to surfactant and/or emulsifier in the solution is about 1:1.

In some embodiments, the w/w ratio of silk fibroin fragments to surfactant and/or emulsifier in the article is about 99:1, about 98:2, about 97:3, about 96:4, about 95 :5, about 94:6, about 93:7, about 92:8, about 91:9, about 90:10, about 89:11, about 88:12, about 87:13, about 86:14, about 85 :15, about 84:16, about 83:17, about 82:18, about 81:19, about 80:20, about 79:21, about 78:22, about 77:23, about 76:24, about 75 :25, about 74:26, about 73:27, about 72:28, about 71:29, about 70:30, about 69:31, about 68:32, about 67:33, about 66:34, about 65 :35, about 64:36, about 63:37, about 62:38, about 61:39, about 60:40, about 59:41, about 58:42, about 57:43, about 56:44, about 55 :45, about 54:46, about 53:47, about 52:48, about 51:49, about 50:50, about 49:51, about 48:52, about 47:53, about 46:54, about 45 :55, about 44:56, about 43:57, about 42:58, about 41:59, about 40:60, about 39:61, about 38:62, about 37:63, about 36:64, about 35 :65, about 34:66, about 33:67, about 32:68, about 31:69, about 30:70, about 29:71, about 28:72, about 27:73, about 26:74, about 25 :75, about 24:76, about 23:77, about 22:78, about 21:79, about 20:80, about 19:81, about 18:82, about 17:83, about 16:84, about 15 :85, about 14:86, about 13:87, about 12:88, about 11:89, about 10:90, about 9:91, about 8:92, about 7:93, about 6:94, about 5 :95, about 4:96, about 3:97, about 2:98, or about 1:99. In some embodiments, the w/w ratio of silk fibroin fragments to surfactant and/or emulsifier in the article is about 1:1.

In some embodiments, the silk fibroin solution comprises low molecular weight silk fibroin-based protein fragments, medium molecular weight silk fibroin-based protein fragments, and/or high molecular weight silk fibroin-based protein fragments. In some embodiments, the silk fibroin solution comprises low molecular weight silk fibroin-based protein fragments. In some embodiments, the silk fibroin solution comprises medium molecular weight silk fibroin-based protein fragments.

In some embodiments, drying the surface of the fiber includes heating the surface of the fiber without substantially altering silk fibroin coating performance.

In some embodiments, the method includes an additional step of drying the surface of the fiber. In some embodiments, an additional drying step is performed after coating the surface of the fiber with a solution containing a reducing agent. In some embodiments, an additional drying step is performed before coating the surface with silk fibroin solution.

In some embodiments, upon laundering, the fiber substantially retains its initial size prior to laundering. In some embodiments, upon laundering, the fibers are substantially smaller than their initial size prior to laundering compared to similar fibers that have not been similarly treated with a surfactant and/or emulsifier and a silk fibroin solution. Retain high fraction.

In any of the above embodiments, at least one property of the article is improved, the improved property is dimensional stability to washing, and the property is at least 5%, at least 10%, at least 15%, at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, at least 50%, at least 55%, at least 60%, at least 65%, at least 70% , at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 100%, at least 125%, at least 150%, at least 200%, at least 300%, at least 400%, and from at least 500% improved by an amount selected from the group .

In any of the above embodiments, at least one property of the article is improved, and the improved property is moisture management. In some embodiments, moisture management is improved compared to similar articles containing similar fibers but without a coating. Moisture management can be assessed by any method known in the art, such as, without limitation, water absorption testing, vertical wicking testing, or drying rate testing. Moisture management is at least 5%, at least 10%, at least 15%, at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, at least 50%, at least 55%, at least 60% %, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 100%, at least 125%, at least 150%, at least 200%, at least 300%, The improvement may be at least 400%, or at least 500%.

In any of the above embodiments, at least one property of the article is improved, the improved property is size retention on laundering, and the property is at least 5%, at least 10% greater than the uncoated article. %, at least 15%, at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, consisting of at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 100%, at least 125%, at least 150%, at least 200%, at least 300%, at least 400%, and at least 500% improved by the amount selected from the group.

In any of the above embodiments, at least one property of the article is improved, the improved property is resistance to shrinkage, and the property is improved by at least 5%, at least 10% relative to the uncoated article. , at least 15%, at least 20%, at least 25%, at least 30%, at least 35%, at least 40%, at least 45%, at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least The group consisting of 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 100%, at least 125%, at least 150%, at least 200%, at least 300%, at least 400%, and at least 500%. improved by the amount selected from.

In one embodiment, the improved properties described above, or any other improved properties described herein, include 0 cycles, 1 cycle, 2 cycles, 3 cycles, 4 cycles, 5 cycles, 6 cycles. , 7 cycles, 8 cycles, 9 cycles, 10 cycles, 11 cycles, 12 cycles, 13 cycles, 14 cycles, 15 cycles, 20 cycles, 25 cycles, 30 cycles, 35 cycles, 40 cycles, 45 cycles, and 50 cycles determined after a period of machine cleaning (e.g., by washing a domestic washing machine) cycle selected from the group consisting of:

In one embodiment, the concentration of silk fibroin solution is less than 30.0% w/v. In one embodiment, the concentration of silk fibroin solution is less than 25.0% w/v. In one embodiment, the concentration of silk fibroin solution is less than 20.0% w/v. In one embodiment, the concentration of the silk fibroin solution is less than 19.0% w/v. In one embodiment, the concentration of the silk fibroin solution is less than 18.0% w/v. In one embodiment, the concentration of the silk fibroin solution is less than 17.0% w/v. In one embodiment, the concentration of the silk fibroin solution is less than 16.0% w/v. In one embodiment, the concentration of silk fibroin solution is less than 15.0% w/v. In one embodiment, the concentration of the silk fibroin solution is less than 14.0% w/v. In one embodiment, the concentration of the silk fibroin solution is less than 13.0% w/v. In one embodiment, the concentration of silk fibroin solution is less than 12.0% w/v. In one embodiment, the concentration of the silk fibroin solution is less than 11.0% w/v. In one embodiment, the concentration of silk fibroin solution is less than 10.0% w/v. In one embodiment, the concentration of the silk fibroin solution is less than 9.0% w/v. In one embodiment, the concentration of the silk fibroin solution is less than 8.0% w/v. In one embodiment, the concentration of the silk fibroin solution is less than 7.0% w/v. In one embodiment, the concentration of the silk fibroin solution is less than 6.0% w/v. In one embodiment, the concentration of silk fibroin solution is less than 5.0% w/v. In one embodiment, the concentration of the silk fibroin solution is less than 4.0% w/v. In one embodiment, the concentration of silk fibroin solution is less than 3.0% w/v. In one embodiment, the concentration of the silk fibroin solution is less than 2.0% w/v. In one embodiment, the concentration of silk fibroin solution is less than 1.0% w/v. In one embodiment, the concentration of silk fibroin solution is less than 0.9% w/v. In one embodiment, the concentration of silk fibroin solution is less than 0.8% w/v. In one embodiment, the concentration of silk fibroin solution is less than 0.7% w/v. In one embodiment, the concentration of silk fibroin solution is less than 0.6% w/v. In one embodiment, the concentration of silk fibroin solution is less than 0.5% w/v. In one embodiment, the concentration of silk fibroin solution is less than 0.4% w/v. In one embodiment, the concentration of silk fibroin solution is less than 0.3% w/v. In one embodiment, the concentration of the silk fibroin solution is less than 0.2% w/v. In one embodiment, the concentration of silk fibroin solution is less than 0.1% w/v.

In one embodiment, the concentration of silk fibroin solution is greater than 0.1% w/v. In one embodiment, the concentration of silk fibroin solution is greater than 0.2% w/v. In one embodiment, the concentration of silk fibroin solution is greater than 0.3% w/v. In one embodiment, the concentration of silk fibroin solution is greater than 0.4% w/v. In one embodiment, the concentration of silk fibroin solution is greater than 0.5% w/v. In one embodiment, the concentration of silk fibroin solution is greater than 0.6% w/v. In one embodiment, the concentration of silk fibroin solution is greater than 0.7% w/v. In one embodiment, the concentration of silk fibroin solution is greater than 0.8% w/v. In one embodiment, the concentration of silk fibroin solution is greater than 0.9% w/v. In one embodiment, the concentration of silk fibroin solution is greater than 1.0% w/v. In one embodiment, the concentration of silk fibroin solution is greater than 2.0% w/v. In one embodiment, the concentration of silk fibroin solution is greater than 3.0% w/v. In one embodiment, the concentration of silk fibroin solution is greater than 4.0% w/v. In one embodiment, the concentration of silk fibroin solution is greater than 5.0% w/v. In one embodiment, the concentration of silk fibroin solution is greater than 6.0% w/v. In one embodiment, the concentration of silk fibroin solution is greater than 7.0% w/v. In one embodiment, the concentration of silk fibroin solution is greater than 8.0% w/v. In one embodiment, the concentration of silk fibroin solution is greater than 9.0% w/v. In one embodiment, the concentration of silk fibroin solution is greater than 10.0% w/v. In one embodiment, the concentration of silk fibroin solution is greater than 11.0% w/v. In one embodiment, the concentration of silk fibroin solution is greater than 12.0% w/v. In one embodiment, the concentration of the silk fibroin solution is greater than 13.0% w/v. In one embodiment, the concentration of silk fibroin solution is greater than 14.0% w/v. In one embodiment, the concentration of silk fibroin solution is greater than 15.0% w/v. In one embodiment, the concentration of silk fibroin solution is greater than 16.0% w/v. In one embodiment, the concentration of silk fibroin solution is greater than 17.0% w/v. In one embodiment, the concentration of silk fibroin solution is greater than 18.0% w/v. In one embodiment, the concentration of silk fibroin solution is greater than 19.0% w/v. In one embodiment, the concentration of silk fibroin solution is greater than 20.0% w/v. In one embodiment, the concentration of silk fibroin solution is greater than 25.0% w/v.

In one embodiment, the concentration of the silk fibroin solution ranges from about 0.1% w/v to about 30.0% w/v. In one embodiment, the concentration of the silk fibroin solution ranges from about 0.1% w/v to about 25.0% w/v. In one embodiment, the concentration of the silk fibroin solution ranges from about 0.1% w/v to about 20.0% w/v. In one embodiment, the concentration of the silk fibroin solution ranges from about 0.1% w/v to about 15.0% w/v. In one embodiment, the concentration of the silk fibroin solution ranges from about 0.1% w/v to about 10.0% w/v. In one embodiment, the concentration of the silk fibroin solution ranges from about 0.1% w/v to about 9.0% w/v. In one embodiment, the concentration of the silk fibroin solution ranges from about 0.1% w/v to about 8.0% w/v. In one embodiment, the concentration of the silk fibroin solution ranges from about 0.1% w/v to about 7.0% w/v. In one embodiment, the concentration of the silk fibroin solution ranges from about 0.1% w/v to about 6.5% w/v. In one embodiment, the concentration of the silk fibroin solution ranges from about 0.1% w/v to about 6.0% w/v. In one embodiment, the concentration of the silk fibroin solution ranges from about 0.1% w/v to about 5.5% w/v. In one embodiment, the concentration of the silk fibroin solution ranges from about 0.1% w/v to about 5.0% w/v. In one embodiment, the concentration of the silk fibroin solution ranges from about 0.1% w/v to about 4.5% w/v. In one embodiment, the concentration of the silk fibroin solution ranges from about 0.1% w/v to about 4.0% w/v. In one embodiment, the concentration of the silk fibroin solution ranges from about 0.1% w/v to about 3.5% w/v. In one embodiment, the concentration of the silk fibroin solution ranges from about 0.1% w/v to about 3.0% w/v. In one embodiment, the concentration of the silk fibroin solution ranges from about 0.1% w/v to about 2.5% w/v. In one embodiment, the concentration of the silk fibroin solution ranges from about 0.1% w/v to about 2.0% w/v. In one embodiment, the concentration of the silk fibroin solution ranges from about 0.1% w/v to about 2.4% w/v. In one embodiment, the concentration of the silk fibroin solution ranges from about 0.5% w/v to about 5.0% w/v. In one embodiment, the concentration of the silk fibroin solution ranges from about 0.5% w/v to about 4.5% w/v. In one embodiment, the concentration of the silk fibroin solution ranges from about 0.5% w/v to about 4.0% w/v. In one embodiment, the concentration of the silk fibroin solution ranges from about 0.5% w/v to about 3.5% w/v. In one embodiment, the concentration of the silk fibroin solution ranges from about 0.5% w/v to about 3.0% w/v. In one embodiment, the concentration of the silk fibroin solution ranges from about 0.5% w/v to about 2.5% w/v. In one embodiment, the concentration of the silk fibroin solution ranges from about 1.0% w/v to about 4.0% w/v. In one embodiment, the concentration of the silk fibroin solution ranges from about 1.0% w/v to about 3.5% w/v. In one embodiment, the concentration of the silk fibroin solution ranges from about 1.0% w/v to about 3.0% w/v. In one embodiment, the concentration of the silk fibroin solution ranges from about 1.0% w/v to about 2.5% w/v. In one embodiment, the concentration of the silk fibroin solution ranges from about 1.0% w/v to about 2.4% w/v. In one embodiment, the concentration of the silk fibroin solution ranges from about 1.0% w/v to about 2.0% w/v.

In one embodiment, the concentration of the silk fibroin solution ranges from about 20.0% w/v to about 30.0% w/v. In one embodiment, the concentration of the silk fibroin solution ranges from about 0.1% w/v to about 10.0% w/v. In one embodiment, the concentration of the silk fibroin solution ranges from about 1.0% w/v to about 10.0% w/v. In one embodiment, the concentration of the silk fibroin solution ranges from about 2% w/v to about 10.0% w/v. In one embodiment, the concentration of the silk fibroin solution ranges from about 0.1% w/v to about 6.0% w/v. In one embodiment, the concentration of the silk fibroin solution ranges from about 6.0% w/v to about 10.0% w/v. In one embodiment, the concentration of the silk fibroin solution ranges from about 6.0% w/v to about 8.0% w/v. In one embodiment, the concentration of the silk fibroin solution ranges from about 6.0% w/v to about 9.0% w/v. In one embodiment, the concentration of the silk fibroin solution ranges from about 10.0% w/v to about 20.0% w/v. In one embodiment, the concentration of the silk fibroin solution ranges from about 11.0% w/v to about 19.0% w/v. In one embodiment, the concentration of the silk fibroin solution ranges from about 12.0% w/v to about 18.0% w/v. In one embodiment, the concentration of the silk fibroin solution ranges from about 13.0% w/v to about 17.0% w/v. In one embodiment, the concentration of the silk fibroin solution ranges from about 14.0% w/v to about 16.0% w/v. In one embodiment, the concentration of silk fibroin solution is about 1.0% w/v. In one embodiment, the concentration of silk fibroin solution is about 0.5% w/v. In one embodiment, the concentration of silk fibroin solution is about 1.5% w/v. In one embodiment, the concentration of the silk fibroin solution is about 2.0% by weight. In one embodiment, the concentration of silk fibroin solution is about 2.4% w/v. In one embodiment, the concentration of silk fibroin solution is 3.0% w/v. In one embodiment, the concentration of silk fibroin solution is 3.5% w/v. In one embodiment, the concentration of silk fibroin solution is about 4.0% w/v. In one embodiment, the concentration of silk fibroin solution is about 4.5% w/v. In one embodiment, the concentration of silk fibroin solution is about 5.0% w/v. In one embodiment, the concentration of silk fibroin solution is about 5.5% w/v. In one embodiment, the concentration of silk fibroin solution is about 6.0% w/v. In one embodiment, the concentration of silk fibroin solution is about 6.5% w/v. In one embodiment, the concentration of silk fibroin solution is about 7.0% w/v. In one embodiment, the concentration of silk fibroin solution is about 7.5% w/v. In one embodiment, the concentration of silk fibroin solution is about 8.0% w/v. In one embodiment, the concentration of silk fibroin solution is about 8.5% w/v. In one embodiment, the concentration of silk fibroin solution is about 9.0% w/v. In one embodiment, the concentration of silk fibroin solution is about 9.5% w/v. In one embodiment, the concentration of silk fibroin solution is about 10.0% w/v.

In some embodiments, the SFS includes an acidic agent. In some embodiments, the acidic agent is a Bronsted acid. In one embodiment, the acidic agent includes one or more of citric acid and acetic acid. In one embodiment, the acidic agent aids in the deposition and coating of the SPF mixture (i.e., SFS coating) on the coated fabric compared to the absence of such acidic agent. In one embodiment, the acidic agent improves crystallization of the SPF mixture in the coated fabric.

In one embodiment, the acidic agent is greater than about 0.001%, or greater than about 0.002%, or greater than about 0.003%, or greater than about 0.004%, or greater than about 0.005%, or about More than 0.006%, or more than about 0.007%, or more than about 0.008%, or more than about 0.009%, or more than about 0.01%, or more than about 0.02%, or about 0. 03%, or about 0.04%, or about 0.05%, or about 0.06%, or about 0.07%, or about 0.08%, or about 0.09% or more than about 0.1%, or more than about 0.2%, or more than about 0.3%, or more than about 0.4%, or more than about 0.5%, or more than about 0.6%, or more than about 0.7%, or more than about 0.8%, or more than about 0.9%, or more than about 1.0%, or more than about 2.0%, or more than about 3.0%, or about It is added at a concentration by weight (%w/w or %w/v) or volume (v/v) of greater than 4.0%, or greater than about 5.0%.

In one embodiment, the acidic agent is less than about 0.001%, or less than about 0.002%, or less than about 0.003%, or less than about 0.004%, or less than about 0.005%, or about less than 0.006%, or less than about 0.007%, or less than about 0.008%, or less than about 0.009%, or less than about 0.01%, or less than about 0.02%, or about 0. 0.03%, or less than about 0.04%, or less than about 0.05%, or less than about 0.06%, or less than about 0.07%, or less than about 0.08%, or about 0.09% or less than about 0.1%, or less than about 0.2%, or less than about 0.3%, or less than about 0.4%, or less than about 0.5%, or less than about 0.6%, or less than about 0.7%, or less than about 0.8%, or less than about 0.9%, or less than about 1.0%, or less than about 2.0%, or less than about 3.0%, or about It is added at a concentration by weight (%w/w or %w/v) or volume (v/v) of less than 4.0%, or less than about 5.0%.

In some embodiments, the SFS may have a pH of less than about 9, or less than about 8.5, or less than about 8, or less than about 7.5, or less than about 7, or less than about 6.5, or less than about 6, or less than about 5.5, or less than about 5, or less than about 4.5, or less than about 4, or less than about 3.5, or greater than about 4, or greater than about 4.5, or greater than about 5, or greater than about 5.5, or greater than about 6, or greater than about 6.5, or greater than about 7, or greater than about 7.5, or greater than about 8, or greater than about 8.5.

In some embodiments, the SFS may include an acidic agent and is less than about 9, or less than about 8.5, or less than about 8, or less than about 7.5, or less than about 7, or less than about 6.5. or less than about 6, or less than about 5.5, or less than about 5, or less than about 4.5, or less than about 4, or less than about 3.5, or more than about 4, or more than about 4.5, or having a pH of greater than about 5, or greater than about 5.5, or greater than about 6, or greater than about 6.5, or greater than about 7, or greater than about 7.5, or greater than about 8, or greater than about 8.5. It is possible.

In some embodiments, the SFS with or without surfactants and/or emulsifiers has a pH in the range of about 3-5. In some embodiments, the SFS with or without surfactants and/or emulsifiers has a pH of about 4. In some embodiments, the SFS with or without surfactants and/or emulsifiers has a pH of about 4.5. In some embodiments, the SFS with or without surfactants and/or emulsifiers has a pH of about 4 to about 4.5.

In some embodiments, the SFS is less than about 100 nm, or less than about 200 nm, or less than about 300 nm, or less than about 400 nm, or less than about 500 nm, or less than about 600 nm, or less than about 700 nm, or less than about 800 nm, or less than about 900 nm, or less than about 1000 nm, or less than about 2 μm, or less than about 5 μm, or less than about 10 μm, or less than about 20 μm, or less than about 30 μm, or less than about 40 μm, or less than about 50 μm, or less than about 60 μm, or less than about 70 μm, or less than about 80 μm, or less than about 90 μm, or less than about 100 μm, or less than about 200 μm, or less than about 300 μm, or less than about 400 μm, or less than about 500 μm, or less than about 600 μm, or less than about 700 μm, or less than about 800 μm, or less than about 900 μm, or less than about 1000 μm, or less than about 2 mm, or less than about 3 mm, or less than about 4 mm, or less than about 5 mm, or less than about 6 mm, or less than about 7 mm, or less than about 8 mm, or less than about 9 mm, or less than about 10 mm, or less than about 20 mm, or less than about 30 mm, or less than about 40 mm, or less than about 50 mm, or less than about 60 mm, or less than about 70 mm, or less than about 80 mm, or less than about 90 mm, or A diameter of less than about 100 mm, or less than about 200 mm, or less than about 300 mm, or less than about 400 mm, or less than about 500 mm, or less than about 600 mm, or less than about 700 mm, or less than about 800 mm, or less than about 900 mm, or less than about 1000 mm. can be applied to fibers and/or threads with

In some embodiments, the SFS is greater than about 100 nm, or greater than about 200 nm, or greater than about 300 nm, or greater than about 400 nm, or greater than about 500 nm, or greater than about 600 nm, or greater than about 700 nm, or greater than about 800 nm, or greater than about 900 nm, or greater than about 1000 nm, or greater than about 2 μm, or greater than about 5 μm, or greater than about 10 μm, or greater than about 20 μm, or greater than about 30 μm, or greater than about 40 μm, or greater than about 50 μm, or greater than about 60 μm, or more than about 70 μm, or more than about 80 μm, or more than about 90 μm, or more than about 100 μm, or more than about 200 μm, or more than about 300 μm, or more than about 500 μm, or more than about 600 μm, or more than about 700 μm, or more than about 800 μm, or more than about 900 μm, or more than about 1000 μm, or more than about 2 mm, or more than about 3 mm, or more than about 4 mm, or more than about 5 mm, or more than about 6 mm, or more than about 7 mm, or more than about 8 mm, or more than about 9 mm, or more than about 10 mm, or more than about 20 mm, or more than about 30 mm, or more than about 40 mm, or more than about 50 mm, or more than about 60 mm, or more than about 70 mm, or more than about 80 mm, or more than about 90 mm, or A diameter of more than about 100 mm, or more than about 200 mm, or more than about 300 mm, or more than about 400 mm, or more than about 500 mm, or more than about 600 mm, or more than about 700 mm, or more than about 800 mm, or more than about 900 mm, or more than about 1000 mm. can be applied to fibers and/or threads with

In some embodiments, the SFS is less than about 100 nm, or less than about 200 nm, or less than about 300 nm, or less than about 400 nm, or less than about 500 nm, or less than about 600 nm, or less than about 700 nm, or less than about 800 nm, or less than about 900 nm, or less than about 1000 nm, or less than about 2 μm, or less than about 5 μm, or less than about 10 μm, or less than about 20 μm, or less than about 30 μm, or less than about 40 μm, or less than about 50 μm, or less than about 60 μm, or less than about 70 μm, or less than about 80 μm, or less than about 90 μm, or less than about 100 μm, or less than about 200 μm, or less than about 300 μm, or less than about 400 μm, or less than about 500 μm, or less than about 600 μm, or less than about 700 μm, or less than about 800 μm, or less than about 900 μm, or less than about 1000 μm, or less than about 2 mm, or less than about 3 mm, or less than about 4 mm, or less than about 5 mm, or less than about 6 mm, or less than about 7 mm, or less than about 8 mm, or less than about 9 mm, or less than about 10 mm, or less than about 20 mm, or less than about 30 mm, or less than about 40 mm, or less than about 50 mm, or less than about 60 mm, or less than about 70 mm, or less than about 80 mm, or less than about 90 mm, or A length of less than about 100 mm, or less than about 200 mm, or less than about 300 mm, or less than about 400 mm, or less than about 500 mm, or less than about 600 mm, or less than about 700 mm, or less than about 800 mm, or less than about 900 mm, or less than about 1000 mm. It can be applied to fibers and/or threads that have a stiffness.

In some embodiments, the SFS is greater than about 100 nm, or greater than about 200 nm, or greater than about 300 nm, or greater than about 400 nm, or greater than about 500 nm, or greater than about 600 nm, or greater than about 700 nm, or greater than about 800 nm, or greater than about 900 nm, or greater than about 1000 nm, or greater than about 2 μm, or greater than about 5 μm, or greater than about 10 μm, or greater than about 20 μm, or greater than about 30 μm, or greater than about 40 μm, or greater than about 50 μm, or greater than about 60 μm, or more than about 70 μm, or more than about 80 μm, or more than about 90 μm, or more than about 100 μm, or more than about 200 μm, or more than about 300 μm, or more than about 500 μm, or more than about 600 μm, or more than about 700 μm, or more than about 800 μm, or more than about 900 μm, or more than about 1000 μm, or more than about 2 mm, or more than about 3 mm, or more than about 4 mm, or more than about 5 mm, or more than about 6 mm, or more than about 7 mm, or more than about 8 mm, or more than about 9 mm, or more than about 10 mm, or more than about 20 mm, or more than about 30 mm, or more than about 40 mm, or more than about 50 mm, or more than about 60 mm, or more than about 70 mm, or more than about 80 mm, or more than about 90 mm, or A length of more than about 100 mm, or more than about 200 mm, or more than about 300 mm, or more than about 400 mm, or more than about 500 mm, or more than about 600 mm, or more than about 700 mm, or more than about 800 mm, or more than about 900 mm, or more than about 1000 mm. It can be applied to fibers and/or threads that have a stiffness.

In some embodiments, the SFS is less than about 1 g/m ² , or less than about 2 g/m ² , or less than about 3 g/m ² , or less than about 4 g/m ² , or less than about 5 g/m ² , or Less than about 6 g/m ² , or less than about 7 g/m ² , or less than about 8 g/m ² , or less than about 9 g/m ² , or less than about 10 g/m ² , or less than about 20 g/m ² , or about 30 g /m ² , or less than about 40 g/m ² , or less than about 50 g/m ² , or less than about 60 g/m ² , or less than about 70 g/m ² , or less than about 80 g/m ² , or about 90 g/m 2 Weight (g/m ² ) of less than ² , or less than about 100 g/m ² , or less than about 200 g/m ² , or less than about 300 g/m ² , or less than about 400 g/m ² , or less than about 500 g/m ² can be applied to fibers and/or threads with

In some embodiments, the SFS is greater than about 1 g/ ^m2 , or greater than about 2 g/ ^m2 , or greater than about 3 g/ ^m2 , or greater than about 4 g/ ^m2 , or greater than about 5 g/ ^m2 , or greater than about 6 g/ ^m2 , or greater than about 7 g/ ^m2 , or greater than about 8 g/ ^m2 , or greater than about 9 g/ ^m2 , or greater than about 10 g/ ^m2 , or greater than about 20 g/ ^m2 , or greater than about 30 g/ ^m2 , or greater than about 40 g/ ^m2 , or greater than about 50 g/ ^m2 , or greater than about 60 g/ ^m2 , or greater than about 70 g/ ^m2 , or greater than about 80 g/ ^m2 , or greater than about 90 g/ ^m2 , or greater than about 100 g/ ^m2 , or greater than about 200 g/ ^m2 , or greater than about 300 g/ ^m2 , or greater than about 400 g/m2. It may be applied to fibres and/or yarns having a weight (g/m ² ) of more than ² , or more than about 500 g/m ² .

In some embodiments, the SFS is less than about 100 nm, or less than about 200 nm, or less than about 300 nm, or less than about 400 nm, or less than about 500 nm, or less than about 600 nm, or less than about 700 nm, or less than about 800 nm, or less than about 900 nm, or less than about 1000 nm, or less than about 2 μm, or less than about 5 μm, or less than about 10 μm, or less than about 20 μm, or less than about 30 μm, or less than about 40 μm, or less than about 50 μm, or less than about 60 μm, or less than about 70 μm, or less than about 80 μm, or less than about 90 μm, or less than about 100 μm, or less than about 200 μm, or less than about 300 μm, or less than about 400 μm, or less than about 500 μm, or less than about 600 μm, or less than about 700 μm, or less than about 800 μm, or less than about 900 μm, or less than about 1000 μm, or less than about 2 mm, or less than about 3 mm, or less than about 4 mm, or less than about 5 mm, or less than about 6 mm, or less than about 7 mm, or less than about 8 mm, or It can be applied to fibers having a thickness of less than about 9 mm, or less than about 10 mm.

In some embodiments, the SFS is greater than about 100 nm, or greater than about 200 nm, or greater than about 300 nm, or greater than about 400 nm, or greater than about 500 nm, or greater than about 600 nm, or greater than about 700 nm, or greater than about 800 nm, or greater than about 900 nm, or greater than about 1000 nm, or greater than about 2 μm, or greater than about 5 μm, or greater than about 10 μm, or greater than about 20 μm, or greater than about 30 μm, or greater than about 40 μm, or greater than about 50 μm, or greater than about 60 μm, or more than about 70 μm, or more than about 80 μm, or more than about 90 μm, or more than about 100 μm, or more than about 200 μm, or more than about 300 μm, or more than about 500 μm, or more than about 600 μm, or more than about 700 μm, or more than about 800 μm, or more than about 900 μm, or more than about 1000 μm, or more than about 2 mm, or more than about 3 mm, or more than about 4 mm, or more than about 5 mm, or more than about 6 mm, or more than about 7 mm, or more than about 8 mm, or It can be applied to fibers having a thickness of greater than about 9 mm, or greater than about 10 mm.

In some embodiments, the SFS is less than about 100 nm, or less than about 200 nm, or less than about 300 nm, or less than about 400 nm, or less than about 500 nm, or less than about 600 nm, or less than about 700 nm, or less than about 800 nm, or less than about 900 nm, or less than about 1000 nm, or less than about 2 μm, or less than about 5 μm, or less than about 10 μm, or less than about 20 μm, or less than about 30 μm, or less than about 40 μm, or less than about 50 μm, or less than about 60 μm, or less than about 70 μm, or less than about 80 μm, or less than about 90 μm, or less than about 100 μm, or less than about 200 μm, or less than about 300 μm, or less than about 400 μm, or less than about 500 μm, or less than about 600 μm, or less than about 700 μm, or less than about 800 μm, or less than about 900 μm, or less than about 1000 μm, or less than about 2 mm, or less than about 3 mm, or less than about 4 mm, or less than about 5 mm, or less than about 6 mm, or less than about 7 mm, or less than about 8 mm, or less than about 9 mm, or less than about 10 mm, or less than about 20 mm, or less than about 30 mm, or less than about 40 mm, or less than about 50 mm, or less than about 60 mm, or less than about 70 mm, or less than about 80 mm, or less than about 90 mm, or less than about 100 mm, or less than about 200 mm, or less than about 300 mm, or less than about 400 mm, or less than about 500 mm, or less than about 600 mm, or less than about 700 mm, or less than about 800 mm, or less than about 900 mm, or less than about 1000 mm, or It may be applied to fibers having a width of less than about 2 m, or less than about 3 m, or less than about 4 m, or less than about 5 m.

In some embodiments, the SFS is greater than about 100 nm, or greater than about 200 nm, or greater than about 300 nm, or greater than about 400 nm, or greater than about 500 nm, or greater than about 600 nm, or greater than about 700 nm, or greater than about 800 nm, or greater than about 900 nm, or greater than about 1000 nm, or greater than about 2 μm, or greater than about 5 μm, or greater than about 10 μm, or greater than about 20 μm, or greater than about 30 μm, or greater than about 40 μm, or greater than about 50 μm, or greater than about 60 μm, or more than about 70 μm, or more than about 80 μm, or more than about 90 μm, or more than about 100 μm, or more than about 200 μm, or more than about 300 μm, or more than about 500 μm, or more than about 600 μm, or more than about 700 μm, or more than about 800 μm, or more than about 900 μm, or more than about 1000 μm, or more than about 2 mm, or more than about 3 mm, or more than about 4 mm, or more than about 5 mm, or more than about 6 mm, or more than about 7 mm, or more than about 8 mm, or more than about 9 mm, or more than about 10 mm, or more than about 20 mm, or more than about 30 mm, or more than about 40 mm, or more than about 50 mm, or more than about 60 mm, or more than about 70 mm, or more than about 80 mm, or more than about 90 mm, or More than about 100 mm, or more than about 200 mm, or more than about 300 mm, or more than about 400 mm, or more than about 500 mm, or more than about 600 mm, or more than about 700 mm, or more than about 800 mm, or more than about 900 mm, or more than about 1000 mm, or It can be applied to fibers having a width of more than about 2 m, or about 3 m, or about 4 m, or about 5 m.

In some embodiments, the SFS is less than about 100 nm, or less than about 200 nm, or less than about 300 nm, or less than about 400 nm, or less than about 500 nm, or less than about 600 nm, or less than about 700 nm, or less than about 800 nm, or less than about 900 nm, or less than about 1000 nm, or less than about 2 μm, or less than about 5 μm, or less than about 10 μm, or less than about 20 μm, or less than about 30 μm, or less than about 40 μm, or less than about 50 μm, or less than about 60 μm, or less than about 70 μm, or less than about 80 μm, or less than about 90 μm, or less than about 100 μm, or less than about 200 μm, or less than about 300 μm, or less than about 400 μm, or less than about 500 μm, or less than about 600 μm, or less than about 700 μm, or less than about 800 μm, or less than about 900 μm, or less than about 1000 μm, or less than about 2 mm, or less than about 3 mm, or less than about 4 mm, or less than about 5 mm, or less than about, or less than about 6 mm, or less than about 7 mm, or about less than 8 mm, or less than about 9 mm, or less than about 10 mm, or less than about 20 mm, or less than about 30 mm, or less than about 40 mm, or less than about 50 mm, or less than about 60 mm, or less than about 70 mm, or less than about 80 mm, or about less than 90 mm, or less than about 100 mm, or less than about 200 mm, or less than about 300 mm, or less than about 400 mm, or less than about 500 mm, or less than about 600 mm, or less than about 700 mm, or less than about 800 mm, or less than about 900 mm, or about It can be applied to fibers with a length of less than 1000 mm.

In some embodiments, the SFS is greater than about 100 nm, or greater than about 200 nm, or greater than about 300 nm, or greater than about 400 nm, or greater than about 500 nm, or greater than about 600 nm, or greater than about 700 nm, or greater than about 800 nm, or greater than about 900 nm, or greater than about 1000 nm, or greater than about 2 μm, or greater than about 5 μm, or greater than about 10 μm, or greater than about 20 μm, or greater than about 30 μm, or greater than about 40 μm, or greater than about 50 μm, or greater than about 60 μm, or more than about 70 μm, or more than about 80 μm, or more than about 90 μm, or more than about 100 μm, or more than about 200 μm, or more than about 300 μm, or more than about 500 μm, or more than about 600 μm, or more than about 700 μm, or more than about 800 μm, or more than about 900 μm, or more than about 1000 μm, or more than about 2 mm, or more than about 3 mm, or more than about 4 mm, or more than about 5 mm, or more than about 6 mm, or more than about 7 mm, or more than about 8 mm, or more than about 9 mm, or more than about 10 mm, or more than about 20 mm, or more than about 30 mm, or more than about 40 mm, or more than about 50 mm, or more than about 60 mm, or more than about 70 mm, or more than about 80 mm, or more than about 90 mm, or A length of more than about 100 mm, or more than about 200 mm, or more than about 300 mm, or more than about 400 mm, or more than about 500 mm, or more than about 600 mm, or more than about 700 mm, or more than about 800 mm, or more than about 900 mm, or more than about 1000 mm. It can be applied to fibers with a

In some embodiments, the SFS is less than about 1%, or less than about 2%, or less than about 3%, or less than about 4%, or less than about 5%, or less than about 6%, or less than about 7%. or less than about 8%, or less than about 9%, or less than about 10%, or less than about 20%, or less than about 30%, or less than about 40%, or less than about 50%, or less than about 60%, or less than about 70%, or less than about 80%, or less than about 90%, or less than about 100, or less than about 110%, or less than about 120%, or less than about 130%, or less than about 140%, or about 150% or less than about 160%, or less than about 170%, or less than about 180%, or less than about 190%, or less than about 200%. The stretch rate is, for a fiber with an unstretched width, stretching the fiber to the stretched width, then subtracting the unstretched width from the stretched width to get the net stretched width, then dividing the net stretched width, It can be determined to multiply the quotient by 100 to find the stretch rate (%).

In some embodiments, the SFS is greater than about 1%, or greater than about 2%, or greater than about 3%, or greater than about 4%, or greater than about 5%, or greater than about 6%, or greater than about 7%. or more than about 8%, or more than about 9%, or more than about 10%, or more than about 20%, or more than about 30%, or more than about 40%, or more than about 50%, or more than about 60%, or More than about 70%, or more than about 80%, or more than about 90%, or more than about 100, or more than about 110%, or more than about 120%, or more than about 130%, or more than about 140%, or about 150% or greater than about 160%, or greater than about 170%, or greater than about 180%, or greater than about 190%, or greater than about 200%.

In some embodiments, the SFS is less than about 1 cN/cm ² , or less than about 2 cN/cm ² , or less than about 3 cN/cm ² , or less than about 4 cN/cm ² , or less than about 5 cN/cm ² , or less than about 5 cN/ ^cm2 , or less than about 6 cN/ ^cm2 , or less than about 7 cN/ ^cm2 , or less than about 8 cN/ ^cm2 , or less than about 9 cN/ ^cm2 , or less than about 10 cN/ ^cm2 , or about 20 cN / ^cm2 , or less than about 30 cN/ ^cm2 , or less than about 40 cN/ ^cm2 , or less than about 50 cN/ ^cm2 , or less than about 60 cN/ ^cm2 , or less than about 70 cN/ ^cm2 , or about 80 cN/cm2. less than ² , or less than about 90 cN/cm ² , or less than about 100 cN/cm ² , or less than about 2 N/cm ² , or less than about 3 N/cm ² , or less than about 4 N/cm ² , or less than about 5 N/cm ² , or less than about 6 N/cm ² , or less than about 7 N/cm ² , or less than about 8 N/cm ² , or less than about 9 N/cm ² , or less than about 10 N/cm ² , or less than about 20 N/cm ² , or Less than about 30 N/cm ² , or less than about 40 N/cm ² , or less than about 50 N/cm ² , or less than about 60 N/cm ² , or less than about 70 N/cm ² , or less than about 80 N/cm ² , or about 90 N or less than about 100 ^N / ^{cm 2 ,} or less than about 150 N/cm ² , or less than about 200 N/cm ² .

In some embodiments, the SFS is greater than about 1 cN/ ^cm2 , or greater than about 2 cN/ ^cm2 , or greater than about 3 cN/ ^cm2 , or greater than about 4 cN/ ^cm2 , or greater than about 5 cN/ ^cm2 , or greater than about 5 cN/ ^cm2 , or greater than about 6 cN/ ^cm2 , or greater than about 7 cN/ ^cm2 , or greater than about 8 cN/ ^cm2 , or greater than about 9 cN/ ^cm2 , or greater than about 10 cN/ ^cm2 , or greater than about 20 cN/ ^cm2 , or greater than about 30 cN/ ^cm2 , or greater than about 40 cN/ ^cm2 , or greater than about 50 cN/ ^cm2 , or greater than about 60 cN/ ^cm2 , or greater than about 70 cN/ ^cm2 , or greater than about 80 cN/ ^cm2 , or greater than about 90 cN/ ^cm2 , or greater than about 100 cN/ ^cm2 , or greater than about 2 N/cm2. In ^some embodiments, the ^coating may be applied to fibers having a tensile energy (N/cm ² ) of greater than about 2, or greater than about 3 N/cm ² , or greater than about 4 N/cm ² , or greater than about 5 N/cm ² , or greater than about 6 N/cm ² , or greater than about 7 N/cm ² , or greater than about 8 N/cm ² , or greater than about 9 N/cm ² , or greater than about 10 N/cm ² , or greater than about 20 N/cm 2, or ^greater than about 30 N/cm ² , or greater than about 40 N/cm ² , or greater than about 50 N/cm ² , or greater than about 60 N/cm ² , or greater than about 70 N/cm 2, or greater than about 80 N/cm ² , or greater than about 90 N/cm ² , or greater than about 100 N/cm ² , or greater than about 150 N/cm ² , or greater than about 200 N/cm ² .

In some embodiments, the SFS is less than about 1 cN/cm degrees, or less than about 2 cN/cm degrees, or less than about 3 cN/cm degrees, or less than about 4 cN/cm degrees, or less than about 5 cN/cm degrees, or less than about 5 cN/cm degrees, or less than about 6 cN/cm degrees, or less than about 7 cN/cm degrees, or less than about 8 cN/cm degrees, or less than about 9 cN/cm degrees, or less than about 10 cN/cm degrees, or about 20 cN /cm degrees, or less than about 30 cN/cm degrees, or less than about 40 cN/cm degrees, or less than about 50 cN/cm degrees, or less than about 60 cN/cm degrees, or less than about 70 cN/cm degrees, or about 80 cN/cm degrees. or less than about 90 cN/cm degrees, or less than about 100 cN/cm degrees, or less than about 2 N/cm degrees, or less than about 3 N/cm degrees, or less than about 4 N/cm degrees, or less than about 5 N/cm degrees. or less than about 6 N/cm degrees, or less than about 7 N/cm degrees, or less than about 8 N/cm degrees, or less than about 9 N/cm degrees, or less than about 10 N/cm degrees, or less than about 20 N/cm degrees, or less than about 30 N/cm degrees, or less than about 40 N/cm degrees, or less than about 50 N/cm degrees, or less than about 60 N/cm degrees, or less than about 70 N/cm degrees, or less than about 80 N/cm degrees, or about 90 N /cm degrees, or less than about 100 N/cm degrees, or less than about 150 N/cm degrees, or less than about 200 N/cm degrees.

In some embodiments, the SFS is greater than about 1 cN/cm degrees, or greater than about 2 cN/cm degrees, or greater than about 3 cN/cm degrees, or greater than about 4 cN/cm degrees, or greater than about 5 cN/cm degrees, or greater than about 5 cN/cm degrees, or greater than about 6 cN/cm degrees, or greater than about 7 cN/cm degrees, or greater than about 8 cN/cm degrees, or greater than about 9 cN/cm degrees, or greater than about 10 cN/cm degrees, or greater than about 20 cN/cm degrees, or greater than about 30 cN/cm degrees, or greater than about 40 cN/cm degrees, or greater than about 50 cN/cm degrees, or greater than about 60 cN/cm degrees, or greater than about 70 cN/cm degrees, or greater than about 80 cN/cm degrees, or greater than about 90 cN/cm degrees, or greater than about 100 cN/cm degrees. It may be applied to fibers having a shear stiffness (N/cm) of greater than about 2 N/cm, greater than about 3 N/cm, greater than about 4 N/cm, greater than about 5 N/cm, greater than about 6 N/cm, greater than about 7 N/cm, greater than about 8 N/cm, greater than about 9 N/cm, greater than about 10 N/cm, greater than about 20 N/cm, greater than about 30 N/cm, greater than about 40 N/cm, greater than about 50 N/cm, greater than about 60 N/cm, greater than about 70 N/cm, greater than about 80 N/cm, greater than about 90 N/cm, greater than about 100 N/cm, greater than about 150 N/cm, or greater than about 200 N/cm.

In some embodiments, the SFS is less than about 1 cN·cm ² /cm, or less than about 2 cN·cm ² /cm, or less than about 3 cN·cm ² /cm, or less than about 4 cN·cm ² /cm, or less than about 5 cN·cm ² /cm, or less than about 5 cN·cm ² /cm, or less than about 6 cN·cm ² /cm, or less than about 7 cN·cm ² /cm, or less than about 8 cN·cm ² /cm, or less than about 9 cN·cm ² /cm, or less than about 10 cN·cm ² /cm, or less than about 20 cN·cm ² /cm, or less than about 30 cN·cm ² /cm, or less than about 40 cN·cm ² /cm, or less than about 50 cN·cm 2 /cm, or less than about 60 cN·cm ² /cm, or less than about 70 cN·cm ² /cm ^. /cm, or less than about 80 cN.cm ² /cm, or less than about 90 cN.cm ² /cm, or less than about 100 cN.cm ² /cm, or less than about 2 N.cm ² /cm, or less than about 3 N.cm ² /cm, or less than about 4 N.cm ² /cm, or less than about 5 N.cm ² /cm, or less than about 6 N.cm ² /cm, or less than about 7 N.cm ² /cm, or less than about 8 N.cm ² /cm, or less than about 9 N.cm ² /cm, or less than about 10 N.cm ² /cm, or less than about 20 N.cm ² /cm, or less than about 30 N.cm ² /cm, or less than about 40 N.cm ² /cm, or less than about 50 N.cm ² /cm, or less than about 60 N.cm ² /cm, or less than about 70 N.cm ² /cm, or less than about 80 N·cm ² /cm, or less than about 90 N·cm ² /cm, or less than about 100 N ^{·cm 2 /cm, or less than about 150 N·cm 2 /cm, or less than about 200 N·cm 2 / cm .}

In some embodiments, the SFS is greater than about 1 cN·cm ² /cm, or greater than about 2 cN·cm ² /cm, or greater than about 3 cN·cm ² /cm, or greater than about 4 cN·cm ² /cm, or greater than about 5 cN·cm ² /cm, or greater than about 5 cN·cm ² /cm, or greater than about 6 cN·cm ² /cm, or greater than about 7 cN·cm ² /cm, or greater than about 8 cN·cm ² /cm, or greater than about 9 cN·cm ² /cm, or greater than about 10 cN·cm ² /cm, or greater than about 20 cN·cm ² /cm, or greater than about 30 cN·cm ² /cm, or greater than about 40 cN·cm ² /cm, or greater than about 50 cN·cm 2 /cm, or greater than about 60 cN·cm ² /cm, or greater than about 70 cN·cm ² /cm ^. /cm, or greater than about 80 cN.cm ² /cm, or greater than about 90 cN.cm ² /cm, or greater than about 100 cN.cm ² /cm, or greater than about 2 N.cm ² /cm, or greater than about 3 N.cm ² /cm, or greater than about 4 N.cm ² /cm, or greater than about 5 N.cm ² /cm, or greater than about 6 N.cm ² /cm, or greater than about 7 N.cm ² /cm, or greater than about 8 N.cm ² /cm, or greater than about 9 N.cm ² /cm, or greater than about 10 N.cm ² /cm, or greater than about 20 N.cm ² /cm, or greater than about 30 N.cm ² /cm, or greater than about 40 N.cm ² /cm, or greater than about 50 N.cm ² /cm, or greater than about 60 N.cm ² /cm, or greater than about 70 N.cm ² /cm, or greater than about 80 N·cm ² /cm, or greater than about 90 N·cm ² /cm, or greater than about 100 N·cm ² /cm, or greater than about 150 N·cm ² /cm, or greater than about 200 N·cm ^{2 /} cm.

In some embodiments, the SFS is less than about 1 cN-cm/ ^cm2 , or less than about 2 cN-cm/ ^cm2 , or less than about 3 cN-cm/ ^cm2 , or less than about 4 cN-cm/ ^cm2 , or less than about 5 cN-cm/ ^cm2 , or less than about 5 cN-cm/ ^cm2 , or less than about 6 cN-cm/ ^cm2 , or less than about 7 cN-cm/ ^cm2 , or less than about 8 cN-cm/ ^cm2 , or less than about 9 cN-cm/ ^cm2 , or less than about 10 cN-cm/cm2, or less than about 20 cN-cm/ ^cm2 , or less than about 30 cN-cm/ ^cm2 , or less than about 40 cN-cm/ ^cm2 , or less than about 50 cN-cm/ ^cm2 , or less than about 60 cN-cm/ ^cm2 , or less than about 70 cN-cm/ ^cm2 , or less than about 80 cN-cm/ ^cm2 . ² , or less than about 90 ^cN.cm/cm2 , or less than about 100 cN.cm/cm2, or less than about ^{2 N.cm/cm2} , or less than about 3 ^N.cm/cm2 , or less than about ⁴ N.cm/cm2, or less than about 5 ^N.cm/cm2 , or less than about ⁶ N.cm/cm2, or less than about 7 ^N.cm/cm2 , or less than about 8 ^N.cm/cm2 , or less than about 9 ^N.cm/cm2 , or less than about 10 ^N.cm/cm2 , or less than about 20 ^N.cm/cm2 , or less than about 30 ^N.cm/cm2 , or less than about 40 ^N.cm/cm2 , or less than about 50 ^N.cm/cm2 , or less than about 60 ^N.cm/cm2 , or less than about 70 N.cm/cm2, or less than about 80 ^N.cm/cm2 , or less than about ⁹⁰ N.cm/cm2 In ^some embodiments, the compressive energy (N·cm/cm 2 ) may be less than about ^{2, or less than about 100 N·cm/cm 2 ,} or less than about 150 N·cm/cm ² , or less than about 200 N·cm/cm ² .

In some embodiments, the SFS is greater than about 1 cN cm/cm ² , or greater than about 2 cN cm/cm ² , or greater than about 3 cN cm/cm ² , or greater than about 4 cN cm/cm ² , or More than about 5 cN cm/cm ² , or more than about 5 cN cm/cm ² , or more than about 6 cN cm/cm ² , or more than about 7 cN cm/cm ² , or more than about 8 cN cm/cm ² , or More than about 9 cN cm/cm ² , or more than about 10 cN cm/cm ² , or more than about 20 cN cm/cm ² , or more than about 30 cN cm/cm ² , or more than about 40 cN cm/cm ² , or More than about 50 cN cm/cm ² , or more than about 60 cN cm/cm ² , or more than about 70 cN cm/cm ² , or more than about 80 cN cm/cm ² , or more than about 90 cN cm/cm ² , or More than about 100 cN・cm/cm ² , or more than about 2 N・cm/cm ² , or more than about 3 N・cm/cm ² , or more than about 4 N・cm/cm ² , or more than about 5 N・cm/cm ² , or More than about 6 ^N.cm/cm2 , or more than about 7 ^N.cm/cm2 , or more than about 8 ^N.cm/cm2 , or more than about 9 ^N.cm/cm2 , or more than about 10 ^N.cm/cm2 , or More than about 20 N.cm/cm ² , or more than about 30 N.cm/cm ² , or more than about 40 N.cm/cm ² , or more than about 50 N.cm/cm ² , or more than about 60 N.cm/cm ² , or More than about 70 ^N.cm/cm2 , or more than about 80 ^N.cm/cm2 , or more than about 90 ^N.cm/cm2 , or more than about 100 ^N.cm/cm2 , or more than about ¹⁵⁰ N.cm/cm2, or It can be applied to fibers with compressive energy (N·cm/cm ² ) greater than about 200 N·cm/cm ² .

In one embodiment, the SFS is less than about 0.04, or less than about 0.05, or less than about 0.06, or less than about 0.07, or less than about 0.08, or less than about 0.09, or less than about 0.10, or less than about 0.10, or less than about 0.15, or less than about 0.20, or less than about 0.25, or less than about 0.30, or less than about 0.35, or about less than 0.40, or less than about 0.45, or less than about 0.50, or less than about 0.55, or less than about 0.60, or less than about 0.65, or less than about 0.70, or about 0 having a coefficient of friction of less than .75, or less than about 0.80, or less than about 0.85, or less than about 0.90, or less than about 0.95, or less than about 1.00, or less than about 1.05. Can be applied to fibers.

In one embodiment, the SFS is greater than about 0.04, or greater than about 0.05, or greater than about 0.06, or greater than about 0.07, or greater than about 0.08, or greater than about 0.09, or greater than about 0.10, or greater than about 0.10, or greater than about 0.15, or greater than about 0.20, or greater than about 0.25, or greater than about 0.30, or greater than about 0.35, or about greater than 0.40, or greater than about 0.45, or greater than about 0.50, or greater than about 0.55, or greater than about 0.60, or greater than about 0.65, or greater than about 0.70, or about 0 having a coefficient of friction of greater than .75, or greater than about 0.80, or greater than about 0.85, or greater than about 0.90, or greater than about 0.95, or greater than about 1.00, or greater than about 1.05. Can be applied to fibers.

In some embodiments, a chemical finish may be applied to textiles before or after such textiles are coated with SFS. In one embodiment, chemical finishing is intended as the application of chemicals and/or SFS to fibers, yarns, and fabrics comprising fibers, or to garments prepared by such fibers, yarns, and fibers. can modify the properties of the original fabric or garment to achieve fabric or garment properties that would not otherwise exist. In chemical finishes, textiles treated with such chemical finishes may act as a surface treatment and/or the treatment may alter the elemental analysis of the treated textile base polymer.

In one embodiment, a type of chemical finishing may include applying certain silk fibroin-based solutions to the fabric. For example, SFS may be applied to the fibers after they have been dyed, but the application of SFS may be applied during processing, during dyeing, or after the garment has been assembled from the selected fabric or fibers, threads, or threads. There are some scenarios where this may be necessary. In some embodiments, after its application, the SFS may be dried by the use of heat. The SFS can then be fixed to the surface of the fabric in a processing step called curing.

In some embodiments, SFS may be supplied in concentrated form suspended in water. In some embodiments, the SFS is less than about 50%, or less than about 45%, or less than about 40%, or about 35% by weight (%w/w or %w/v) or volume (v/v). %, or less than about 30%, or less than about 25%, or less than about 20%, or less than about 15%, or less than about 10%, or less than about 5%, or less than about 4%, or less than about 3% or less than about 2%, or less than about 1%, or less than about 0.1%, or less than about 0.01%, or less than about 0.001%, or less than about 0.0001%, or about 0.00001 %. In some embodiments, the SFS is greater than about 50%, or greater than about 45%, or greater than about 40%, or about 35% by weight (%w/w or %w/v) or volume (v/v). %, or about 30%, or about 25%, or about 20%, or about 15%, or about 10%, or about 5%, or about 4%, or about 3% , or more than about 2%, or more than about 1%, or more than about 0.1%, or more than about 0.01%, or more than about 0.001%, or more than about 0.0001%, or about 0.00001 %.

In some embodiments, the solution concentration and wet-picking of the material determines the amount of silk fibroin solution (SFS) that can be fixed or otherwise adhered to the fabric being coated. May include silk-based proteins or fragments thereof. Wet pickup can be expressed by the following equation.

The total amount of SFS added to the textile material can be expressed by the following formula:

Regarding methods for applying SFS to textiles more broadly, SFS can be applied to textiles through on-process pad or roller application, saturation and removal processes, and/or topical application processes. Additionally, methods of silk application (ie, SFS application or coating) may include bath coating, kiss rolling, spray coating, and/or double-sided rolling. In some embodiments, coating processes (e.g., bath coating, kiss rolling, spray coating, double-sided rolling, roller application, saturation and removal application, and/or topical application), drying processes, and curing processes are described herein. may be changed to modify one or more selected textile (e.g., fiber) properties of the resulting coated fabric, such properties including, but not limited to: includes wetting time, absorption rate, diffusion rate, unidirectional moisture transfer index, and/or overall moisture management capacity. In some embodiments, the selected properties described above may be enhanced by changing one or more of the coating, drying, and curing processes described herein.

In one embodiment, padding may be used on dry or wet fabrics. For example, it can be applied onto textiles after the dyeing process. The fabric may be fed into a water bath solution and saturation may be reached. The fibers to be coated may then be passed through a set of rollers that over-extract the bath solution to the desired % wet pick-up based on multiple variables. Variables that affect % wet pickup are roller pressure and material, fiber composition and structure, and SFS viscosity.

In one embodiment, padding the wet fabric may be used to reduce the cost of drying the fabric after dyeing. The fibers exiting the pad rollers may maintain a higher weight percent than the incoming fibers to maintain SFS deposits on the fibers, and the SFS solution is less concentrated due to the water present on the incoming fibers. Any dilution that occurs may need to be taken into account.

In one embodiment, saturation and removal application is a low wet pickup method that may solve some of the problems associated with removing large amounts of water during the drying process, for example. As the fibers may dry in the oven from the outside surface to the inside, water can migrate from the inside to the outside, resulting in a higher coating concentration on the outside surface. Low water content may reduce migration due to higher viscosity in the solution. However, reduced wet pickup can result in non-uniform solution deposition.

In one embodiment, vacuum extraction may be used as a method for low wet pickup. The saturated fiber may be subjected to a vacuum, drawing the solution from the fiber and returning it to the application loop. Air jet evacuation may be a method to provide low wet pickup. The saturated fiber may be subjected to high pressure steam to remove the solution from the fiber and return it to the application loop.

In one embodiment, a porous bowl method may be used for low wet pickup. Solid pad rollers may be replaced with rubber coated fibrous rollers. Saturated fibers may be subjected to roller pressure because the porosity of the rollers may allow more solution to be squeezed out of the fibers.

In one embodiment, a transfer padding method may be used for low wet pickup. The saturated fibers may be passed through two consecutive dry nonwovens and pressed at low pressure. Nonwovens can extract excess solution from the fibers being treated.

In one embodiment, topical application may be used as a low wet pickup application method to deposit the desired amount of SFS onto the fibers without removing any excess material. Although the method described above can be used for single-sided coating application, there are variations that can allow double-sided coating.

In one embodiment, kiss rolling may be used as a topical application method to transfer the SFS from a roller (ie, a kiss roller) to one side of the fiber. Solution viscosity, roller surface finish, roller speed, fiber speed, contact angle of the fiber on the roller, and fiber properties are parameters that control the amount of solution deposited on the fiber.

In one embodiment, a variation on the kiss roller technology could be the Triatex MA system, which uses two moisture content sensors to determine solution pickup at the kiss roller and adjusts controllable variables of the kiss roller to maintain consistent solution deposition on the fibers.

In one embodiment, loop transfer application may be used as a topical application method to transfer SFS from saturated loop fibers to fibers that are coated between low pressure pad rollers. There are two roller versions that may allow minimal contact with the fibers and three roller versions that may allow greater contact with the fibers.

In one embodiment, engraved roller application can be used as a topical application method that can transfer metered amounts of SFS onto the fibers. This can be achieved by carving a pattern onto the surface of the roller with a precise depth and design containing a controlled amount of SFS. A blade may be used to remove any solution deposited on the surface of the roller to maintain consistent transfer of solution to the fibers being coated.

In one embodiment, rotary screen printing can be used as a topical application method in which SFS can be deposited onto the fibers by leaching the solution through a roller screen. The solution may be contained in the screen printing roller core at a set level, while the blades remove any excess solution from the inner roller wall and provide a clean surface for the next rotation of the screen printer roller. can be used to

In one embodiment, magnetic roller coating can be used as a topical application method that can deposit SFS onto the coated fibers from a kissing roller. The kissing roller is semi-immersed in the bath solution, while the magnetic field created within the fiber drive roller determines the amount of pressure applied by the kissing roller and controls the pick-up speed of the solution.

In one embodiment, spraying may be used as a topical application method to transfer the SFS to the fibers by spraying the solution. Spray patterns can be controlled by nozzle pattern, size, and airflow. Spray application can also be used for single-sided or double-sided applications.

In one embodiment, foam application can be used as a topical application method that can transfer SFS onto the fibers. Foams can be made by replacing some of the water in the solution with air, thus reducing the amount of water applied to the fibers. Foam application can be used for one-sided or double-sided applications, where the same foam can be deposited through a squeeze roller, or different foam solutions can be provided through a transfer roll or through a slot applicator.

In one embodiment, the application of SFS may be done after the garment has been assembled. In one embodiment, the process may be performed in a washing and dyeing machine or a spray booth. For example, the washing and dyeing machine may be similar in shape to a domestic front loader washing machine, which allows the process to be carried out at exhaustion after dyeing or in an independent treatment cycle. In one embodiment, the spray booth machine may include a manual or fully automated process. For example, the garment may be held by a mannequin while an operator or humanoid robot sprays the solution onto the fabric.

In one embodiment, the SFS may be an aqueous solution that may require thermal vaporization to infuse the SFS onto the fabric after its application to the fabric. Thermal vaporization can be applied by heat transfer through radiation by devices such as infrared or high frequency dryers.

In one embodiment, thermal vaporization can be applied to the required temperature by convection through heated air circulating in an oven, while the fibers are clamped and transported by a conveyor. This allows complete control over fiber width dimensions.

In one embodiment, thermal vaporization may be applied by conduction through contacting the fabric with a heating or calendaring cylinder. Since the fibers are not clamped, control over fiber width is minimal.

In one embodiment, the curing of the SFS on the fabric can be completed in the same equipment used for thermal vaporization in a continuous or separate cycle.

In one embodiment, the cure time temperature may depend on the textile polymer content and the method of bonding SFS with the particular polymer. The curing process may not begin until thermal vaporization is complete.

In some embodiments, sensors may be used to monitor the SFS deposition on the fabric as well as the drying and curing process.

In some embodiments, non-contact sensors such as those provided by the Pleva model AF120 based on microwave absorption of water may be used to monitor SFS deposition. Measurement of material moisture can be based on microwave absorption by water. A semiconductor oscillator transmits microwave energy through the web. The unabsorbed portion of the energy can be received on the other side by a microwave receiver. Absorption is a measurement of absolute water content. Microwave sensors can detect and measure water content from a minimum of 0 to a maximum of 2000 gH ₂ O/m ² .

In some embodiments, for wide fiber processing, multiple sensors may be paired side-by-side, with data analysis and centralized control that can add more solution to areas of low fibers. Deliver to system loop.

In some embodiments, another sensor based on microwave technology may be used, such as Aqualot by Mahlo. The sensor may evaluate the shift of the resonant frequencies of the two standing waves with respect to each other, rather than the attenuation of the microwaves due to the amount of water molecules in the measurement gap.

In some embodiments, another non-contact sensor for SFS may be the IR-3000 by MoistTech, which is based on near-infrared sensing technology. The sensor measures the amount of near-infrared energy reflected at a given wavelength, which is inversely proportional to the amount of absorbing molecules within the fiber.

In some embodiments, residual moisture at the end of the curing process can be measured to further confirm the drying and curing process. In addition to the sensors described above, contact sensors such as the Textometer RMS by Mahlo can be used to measure moisture through conductivity.

In some embodiments, monitoring the end of the drying process step may be accomplished by measuring fiber temperature using a non-contact temperature sensor. When wet products enter the dryer, they are first heated to the cooling limit temperature. In some embodiments, when the moisture content drops to the residual moisture level, the product temperature may begin to increase again. The closer the product temperature is to the circulating air temperature in the dryer, the slower the temperature will continue to rise. In some embodiments, at a certain temperature threshold (referred to as a fixed temperature), the required temperature for processing, fixation, or condensation is reached.

In some embodiments, the surface temperature of the product is measured without contact at several locations in the dryer using a high temperature resistant infrared pyrometer to determine the residence time for the desired product temperature. obtain. The Mahlo Permaset VMT is an infrared pyrometer that can be assembled in multiple units to monitor temperature throughout the dryer. Setex is another manufacturer that offers textile temperature sensors for use in dryers and ovens such as models WTM V11, V21, and V41.

In some embodiments, SFS may be applied to the fabric during exhaust dyeing. In some embodiments, the process may involve loading the fibers into a bath originally known as a batch and allowing it to equilibrate with the solution. Exhaust dyeing may be the ability of silk fibroin molecules to migrate from solution onto the fibers or textile threads (persistent). The persistence of silk fibroin can be influenced by temperature or additives such as salt.

In some embodiments, the exhaust dyeing process can take from several minutes to several hours. When the fibers have absorbed or fixed as much silk fibroin as possible, the bath can be emptied and the fibers can be rinsed to remove any excess solution.

In some embodiments, an important parameter for exhaust dyeing may be what is known as the specific bath ratio. This accounts for the ratio of fiber mass to SFS bath volume and determines the amount of silk fibroin deposited on the fabric.

In some embodiments, SFS may be applied to the fabric during the jet dyeing process. A jet dyeing machine can be formed by a closed tubular system in which the fibers are placed. A jet of dye fluid is fed through a venturi to transport the fibers through the tube. Jets can create turbulence. This may prevent the fibers from contacting the tube wall and aid in SFS penetration. For example, a small SFS bath at the bottom of the container is required because the fibers are often exposed to relatively high concentrations of liquid in the transport tube. This arrangement may be sufficient for smooth movement of the container from the rear to the front.

In some embodiments, SFS may be applied during paddle staining. Although paddle dyeing machines can be commonly used for many forms of textiles, the method is most suitable for garments. Heat can be generated through direct steam injection into the coating bath. In one embodiment, the paddle dyeing machine operates through paddles that circulate both bath and garment in a perforated central island. Here, SFS, water, and steam for heat are added. An overhead paddle machine can be described as a bat that includes a paddle with a full width blade. The blade may generally be immersed several centimeters into the batt. This action can agitate the bath and hold down the garments being dyed, thus keeping them immersed in the dye liquor.

In some embodiments, the processing methods described herein include, but are not limited to, fiber speed, solution viscosity, solution added to the fibers, fiber coverage width, drying temperature, drying time, curing, One or more of the following parameters may be used to apply SFS to a fabric, including time, fiber tension, padder pressure, padder roller shore hardness, stenter temperature, and general drying and curing temperatures. In one embodiment, processing method parameters may also include condensation temperature, which may vary depending on the chemical recipe used to apply the SFS to the fabric.

In one embodiment, the fiber speed for the process of the present disclosure is less than about 0.1 m/min, or less than about 0.2 m/min, or less than about 0.3 m/min, or less than about 0.4 m/min. or less than about 0.5 m/min, or less than about 0.6 m/min, or less than about 0.7 m/min, or less than about 0.8 m/min, or less than about 0.9 m/min, or about 1 m/min. or less than about 2 m/min, or less than about 3 m/min, or less than about 4 m/min, or less than about 5 m/min, or less than about 6 m/min, or less than about 7 m/min, or about 8 m/min. or less than about 9 m/min, or less than about 10 m/min, or less than about 20 m/min, or less than about 30 m/min, or less than about 40 m/min, or less than about 50 m/min, or less than about 60 m/min It can be.

In one embodiment, the fiber speed for the process of the present disclosure is greater than about 0.1 m/min, or greater than about 0.2 m/min, or greater than about 0.3 m/min, or greater than about 0.4 m/min. , or more than about 0.5 m/min, or more than about 0.6 m/min, or more than about 0.7 m/min, or more than about 0.8 m/min, or more than about 0.9 m/min, or about 1 m/min or more than about 2 m/min, or more than about 3 m/min, or more than about 4 m/min, or more than about 5 m/min, or more than about 6 m/min, or more than about 7 m/min, or about 8 m/min. or more than about 9 m/min, or more than about 10 m/min, or more than about 20 m/min, or more than about 30 m/min, or more than about 40 m/min, or more than about 50 m/min, or more than about 60 m/min It can be.

In one embodiment, the solution viscosity of the process of the present disclosure is less than about 1000 mPas, or less than about 1500 mPas, or less than about 2000 mPas, or less than about 2500, or less than about 3000 mPas, or less than about 4000 mPas, or less than about 4500 mPas, or about less than 5000 mPas, or less than about 5500 mPas, or less than about 6000 mPas, or less than about 6500 mPas, or less than about 7000 mPas, or less than about 7500 mPas, or less than about 8000 mPas, or less than about 8500 mPas, or less than about 9000 mPas, or less than about 9500 mPas, or about It can be less than 10,000 mPas, or less than about 10,500 mPas, or less than about 11,000 mPas, or less than about 11,500 mPas, or less than about 12,000 mPas.

In one embodiment, the solution viscosity of the process of the present disclosure is greater than about 1000 mPas, or greater than about 1500 mPas, or greater than about 2000 mPas, or greater than about 2500, or greater than about 3000 mPas, or greater than about 4000 mPas, or greater than about 4500 mPas, or about More than 5000 mPas, or more than about 5500 mPas, or more than about 6000 mPas, or more than about 6500 mPas, or more than about 7000 mPas, or more than about 7500 mPas, or more than about 8000 mPas, or more than about 8500 mPas, or more than about 9000 mPas, or more than about 9500 mPas, or about It may be greater than 10,000 mPas, or greater than about 10,500 mPas, or greater than about 11,000 mPas, or greater than about 11,500 mPas, or greater than about 12,000 mPas.

In one embodiment, the solution is less than about 0.01 g/m ² , or less than about 0.02 g/m ² , or less than about 0.03 g/m ² , or less than about 0.04 g/m ² , or about 0 less than .05 g/ ^m2 , or less than about 0.06 g/ ^m2 , or less than about 0.07 g/ ^m2 , or less than about 0.08 g/ ^m2 , or less than about 0.09 g/ ^m2 , or about 0 less than .10 g/ ^m2 , or less than about 0.2 g/ ^m2 , or less than about 0.3 g/ ^m2 , or less than about 0.4 g/ ^m2 , or less than about 0.5 g/ ^m2 , or about 0 less than .6 g/ ^m2 , or less than about 0.7 g/ ^m2 , or less than about 0.8 g/ ^m2 , or less than about 0.9 g/ ^m2 , or less than about 1 g/ ^m2 , or about 2 g/m2 less than ² , or less than about 3 g/ ^m2 , or less than about 4 g/ ^m2 , or less than about 5 g/ ^m2 , or less than about 6 g/ ^m2 , or less than about 7 g/ ^m2 , or less than about 8 g/ ^m2 or less than about 9 g/m ² , or less than about 10 g/m ² , or less than about 20 g/m ² , or less than about 30 g/m ² , or less than about 40 g/m ² , or less than about 50 g/m ² , or ^{The fabrics} for the process of ^{the present} disclosure (e.g. ^, fibers).

In one embodiment, the solution is greater than about 0.01 g/m ² , or greater than about 0.02 g/m ² , or greater than about 0.03 g/m ² , or greater than about 0.04 g/m ² , or about 0 greater than .05 g/m ² , or greater than about 0.06 g/m ² , or greater than about 0.07 g/m ² , or greater than about 0.08 g/m ² , or greater than about 0.09 g/m ² , or about 0 greater than .10 g/m ² , or greater than about 0.2 g/m ² , or greater than about 0.3 g/m ² , or greater than about 0.4 g/m ² , or greater than about 0.5 g/m ² , or about 0 greater than .6 g/m ² , or greater than about 0.7 g/m ² , or greater than about 0.8 g/m ² , or greater than about 0.9 g/m ² , or greater than about 1 g/m ² , or about 2 g/m 2 greater than ² , or greater than about 3 g/m ² , or greater than about 4 g/m ² , or greater than about 5 g/m ² , or greater than about 6 g/m ² , or greater than about 7 g/m ² , or greater than about 8 g/m ² or greater than about 9 g/m ² , or greater than about 10 g/m ² , or greater than about 20 g/m ² , or greater than about 30 g/m ² , or greater than about 40 g/m ² , or greater than about 50 g/m ² , or Fabrics ^for the ^processes of ^{the present} disclosure ⁽ e.g., fibers).

In one embodiment, the fiber coverage width for the process of the present disclosure is less than about 1 mm, or less than about 2 mm, or less than about 3 mm, or less than about 4 mm, or less than about 5 mm, or less than about 6 mm, or less than about 7 mm. or less than about 8 mm, or less than about 9, or less than about 10 mm, or less than about 20 mm, or less than about 30 mm, or less than about 40 mm, or less than about 50 mm, or less than about 60 mm, or less than about 70 mm, or less than about 80 mm. or less than about 90 mm, or less than about 100 mm, or less than about 200, or less than about 300 mm, or less than about 400 mm, or less than about 500 mm, or less than about 600 mm, or less than about 700 mm, or less than about 800 mm, or less than about 900 mm. , or less than about 1000 mm, or less than about 2000 mm, or less than about 2000 mm, or less than about 3000 mm, or less than about 4000 mm, or less than about 5000 mm.

In one embodiment, the fiber coverage width for the process of the present disclosure is greater than about 1 mm, or greater than about 2 mm, or greater than about 3 mm, or greater than about 4 mm, or greater than about 5 mm, or greater than about 6 mm, or greater than about 7 mm. or more than about 8 mm, or more than about 9, or more than about 10 mm, or more than about 20 mm, or more than about 30 mm, or more than about 40 mm, or more than about 50 mm, or more than about 60 mm, or more than about 70 mm, or more than about 80 mm. , or more than about 90 mm, or more than about 100 mm, or more than about 200, or more than about 300 mm, or more than about 400 mm, or more than about 500 mm, or more than about 600 mm, or more than about 700 mm, or more than about 800 mm, or more than about 900 mm. , or greater than about 1000 mm, or greater than about 2000 mm, or greater than about 2000 mm, or greater than about 3000 mm, or greater than about 4000 mm, or greater than about 5000 mm.

In one embodiment, the drying and/or curing temperature for the process of the present disclosure is less than about 70°C, or less than about 75°C, or less than about 80°C, or less than about 85°C, or less than about 90°C, or less than about 95°C, or less than about 100°C, or less than about 110°C, or less than about 120°C, or less than about 130°C, or less than about 140°C, or less than about 150°C, or less than about 160°C, or about 170°C. or less than about 180°C, or less than about 190°C, or less than about 200°C, or less than about 210°C, or less than about 220°C, or less than about 230°C.

In one embodiment, the drying and/or curing temperature for the process of the present disclosure is greater than about 70°C, or greater than about 75°C, or greater than about 80°C, or greater than about 85°C, or greater than about 90°C, or greater than about 95°C, or greater than about 100°C, or greater than about 110°C, or greater than about 120°C, or greater than about 130°C, or greater than about 140°C, or greater than about 150°C, or greater than about 160°C, or about 170°C or greater than about 180°C, or greater than about 190°C, or greater than about 200°C, or greater than about 210°C, or greater than about 220°C, or greater than about 230°C.

In one embodiment, the drying time for the process of the present disclosure is less than about 10 seconds, or less than about 20 seconds, or less than about 30 seconds, or less than about 40 seconds, or less than about 50 seconds, or less than about 60 seconds. or less than about 2 minutes, or less than about 3 minutes, or less than about 4 minutes, or less than about 5 minutes, or less than about 6 minutes, or less than about 7 minutes, or less than about 8 minutes, or less than about 9 minutes, or It can be less than about 10 minutes, or less than about 20 minutes, or less than about 30 minutes, or less than about 40 minutes, or less than about 50 minutes, or less than about 60 minutes.

In one embodiment, the drying time for the process of the present disclosure is greater than about 10 seconds, or greater than about 20 seconds, or greater than about 30 seconds, or greater than about 40 seconds, or greater than about 50 seconds, or greater than about 60 seconds. , or more than about 2 minutes, or more than about 3 minutes, or more than about 4 minutes, or more than about 5 minutes, or more than about 6 minutes, or more than about 7 minutes, or more than about 8 minutes, or more than about 9 minutes, or It can be more than about 10 minutes, or more than about 20 minutes, or more than about 30 minutes, or more than about 40 minutes, or more than about 50 minutes, or more than about 60 minutes.

In one embodiment, the curing time for the process of the present disclosure is less than about 1 second, or less than about 2 seconds, or less than about 3 seconds, or less than about 4 seconds, or less than about 5 seconds, or less than about 6 seconds. or less than about 7 seconds, or less than about 8 seconds, or less than about 9 seconds, or less than about 10 seconds, or less than about 20 seconds, or less than about 30 seconds, or less than about 40 seconds, or less than about 50 seconds, or less than about 60 seconds, or less than about 2 minutes, or less than about 3 minutes, or less than about 4 minutes, or less than about 5 minutes, or less than about 6 minutes, or less than about 7 minutes, or less than about 8 minutes, or about 9 or less than about 10 minutes, or less than about 20 minutes, or less than about 30 minutes, or less than about 40 minutes, or less than about 50 minutes, or less than about 60 minutes.

In one embodiment, the curing time for the process of the present disclosure is greater than about 1 second, or greater than about 2 seconds, or greater than about 3 seconds, or greater than about 4 seconds, or greater than about 5 seconds, or greater than about 6 seconds. or more than about 7 seconds, or more than about 8 seconds, or more than about 10 seconds, or more than about 20 seconds, or more than about 30 seconds, or more than about 40 seconds, or more than about 50 seconds, or More than about 60 seconds, or more than about 2 minutes, or more than about 3 minutes, or more than about 4 minutes, or more than about 5 minutes, or more than about 6 minutes, or more than about 7 minutes, or more than about 8 minutes, or about 9 or more than about 10 minutes, or more than about 20 minutes, or more than about 30 minutes, or more than about 40 minutes, or more than about 50 minutes, or more than about 60 minutes.

In one embodiment, the fiber tension for the process of the present disclosure is less than about 1N, or less than about 2N, or less than about 3N, or less than about 4N, or less than about 5N, or less than about 6N, or less than about 7N, or less than about 8N, or less than about 9N, or less than about 10N, or less than about 20N, or less than about 30N, or less than about 40N, or less than about 50N, or less than about 60N, or less than about 70N, or less than about 80N, or less than about 90N, or less than about 100N, or less than about 150N, or less than about 200N, or less than about 250N, or less than about 300N.

In one embodiment, the fiber tension for the process of the present disclosure is greater than about 1N, or greater than about 2N, or greater than about 3N, or greater than about 4N, or greater than about 5N, or greater than about 6N, or greater than about 7N, or more than about 8N, or more than about 9N, or more than about 10N, or more than about 20N, or more than about 30N, or more than about 40N, or more than about 50N, or more than about 60N, or more than about 70N, or more than about 80N, or more than about 90N, or more than about 100N, or more than about 150N, or more than about 200N, or more than about 250N, or more than about 300N.

In one embodiment, the padder pressure for the process of the present disclosure is less than about 1 N/mm, or less than about 2 N/mm, or less than about 3 N/mm, or less than about 4 N/mm, or less than about 4 N/mm, or less than about 5 N/mm, or less than about 6 N/mm, or less than about 7 N/mm, or less than about 8 N/mm, or less than about 9 N/mm, or less than about 10 N/mm, or less than about 20 N/mm, or It can be less than about 30 N/mm, or less than about 40 N/mm, or less than about 50 N/mm, or less than about 60 N/mm, or less than about 70 N/mm, or less than about 80 N/mm, or less than about 90 N/mm. .

In one embodiment, the padder pressure for the process of the present disclosure is greater than about 1 N/mm, or greater than about 2 N/mm, or greater than about 3 N/mm, or greater than about 4 N/mm, or greater than about 4 N/mm, or more than about 5 N/mm, or more than about 6 N/mm, or more than about 7 N/mm, or more than about 8 N/mm, or more than about 9 N/mm, or more than about 10 N/mm, or more than about 20 N/mm, or Can be greater than about 30 N/mm, or greater than about 40 N/mm, or greater than about 50 N/mm, or greater than about 60 N/mm, or greater than about 70 N/mm, or greater than about 80 N/mm, or greater than about 90 N/mm. .

In one embodiment, the padder roller shore hardness for the process of the present disclosure is less than about 70 Shore A, or less than about 75 Shore A, or less than about 80 Shore A, or less than about 85 Shore A, or about 90 It can be less than about 95 Shore A, or less than about 100 Shore A.

In one embodiment, the padder roller shore hardness for the process of the present disclosure is greater than about 70 Shore A, or greater than about 75 Shore A, or greater than about 80 Shore A, or greater than about 85 Shore A, or about 90 Shore A. It can be greater than about 95 Shore A, or greater than about 100 Shore A.

In one embodiment, the stenter temperature for the process of the present disclosure is less than about 70°C, or less than about 75°C, or less than about 80°C, or less than about 85°C, or less than about 90°C, or less than about 95°C. or less than about 100°C, or less than about 110°C, or less than about 120°C, or less than about 130°C, or less than about 140°C, or less than about 150°C, or less than about 160°C, or less than about 170°C, or It can be less than about 180°C, or less than about 190°C, or less than about 200°C, or less than about 210°C, or less than about 220°C, or less than about 230°C.

In one embodiment, the stenter temperature for the process of the present disclosure is greater than about 70°C, or greater than about 75°C, or greater than about 80°C, or greater than about 85°C, or greater than about 90°C, or greater than about 95°C. or greater than about 100°C, or greater than about 110°C, or greater than about 120°C, or greater than about 130°C, or greater than about 140°C, or greater than about 150°C, or greater than about 160°C, or greater than about 170°C, or It can be greater than about 180°C, or greater than about 190°C, or greater than about 200°C, or greater than about 210°C, or greater than about 220°C, or greater than about 230°C.

In one embodiment, typical drying temperatures for the processes of the present disclosure are less than about 110°C, or less than about 115°C, or less than about 120°C, or less than about 125°C, or less than about 130°C, or about It can be less than 135°C, or less than about 140°C, or less than about 145°C, or less than about 150°C.

In one embodiment, typical drying temperatures for the processes of the present disclosure are greater than about 110°C, or greater than about 115°C, or greater than about 120°C, or greater than about 125°C, or greater than about 130°C, or about It can be greater than 135°C, or greater than about 140°C, or greater than about 145°C, or greater than about 150°C.

In some embodiments, the material (e.g., fiber) coated with silk fibroin can be heat resistant to a selected temperature, and the selected temperature can be applied to the material (e.g., LYCRA). Selected to dry, cure, and/or heat set the dye. As used herein, "heat resistant" may refer to the properties of a silk fibroin coating deposited on a material, such that the silk fibroin coating and/or silk fibroin proteins are susceptible to drying, curing, washing cycles, and/or exhibits no substantial alteration in silk fibroin coating performance (i.e., "substantially (Do not modify). In some embodiments, the temperature selected is the glass transition temperature ( _Tg ) of the material to which the silk fibroin coating is applied. In some embodiments, the selected temperature is greater than about 65°C, or greater than about 70°C, or greater than about 80°C, or greater than about 90°C, or greater than about 100°C, or greater than about 110°C, or about greater than 120°C, or greater than about 130°C, or greater than about 140°C, or greater than about 150°C, or greater than about 160°C, or greater than about 170°C, or greater than about 180°C, or greater than about 190°C, or about 200°C or above about 210°C, or above about 220°C. In some embodiments, the selected temperature is less than about 65°C, or less than about 70°C, or less than about 80°C, or less than about 90°C, or less than about 100°C, or less than about 110°C, or about less than 120°C, or less than about 130°C, or less than about 140°C, or less than about 150°C, or less than about 160°C, or less than about 170°C, or less than about 180°C, or less than about 190°C, or about 200°C or less than about 210°C, or less than about 220°C.

In one embodiment, "substantially altering" silk fibroin coating performance refers to a control silk fibroin coating that has not been subjected to selected temperatures for drying, curing, washing cycles, and/or heat setting purposes. may be a reduction in selected properties of the silk fibroin coating, such as wetting time, absorption rate, diffusion rate, unidirectional moisture transport index, or overall moisture management capacity, as compared to the compared to control silk fibroin coatings that were not subjected to drying, curing, washing cycles, and/or selected temperatures for heat-setting purposes. less than about 1% decrease, or less than about 2% decrease, or less than about 3% decrease, or less than about 4% decrease, or less than about 5% decrease in moisture transport index, or overall moisture management capacity. or a decrease of less than about 6%, or a decrease of less than about 7%, or a decrease of less than about 8%, or a decrease of less than about 9%, or a decrease of less than about 10%, or a decrease of less than about 15%, or a decrease of less than about 20%, or a decrease of less than about 25%, or a decrease of less than about 30%, or a decrease of less than about 35%, or a decrease of less than about 40%, or a decrease of less than about 45%, or a decrease of less than about 50%. % reduction, or less than about 60% reduction, or less than about 70% reduction, or less than about 80% reduction, or less than about 90% reduction, or less than about 100% reduction. In some embodiments, a "wash cycle" includes at least one wash cycle, or at least two wash cycles, or at least three wash cycles, or at least four wash cycles, or at least five wash cycles. It can refer to a cycle.

In one embodiment, "substantially altering" silk fibroin coating performance refers to a control silk fibroin coating that has not been subjected to selected temperatures for drying, curing, washing cycles, and/or heat setting purposes. may be an increase in selected properties of the silk fibroin coating, such as wetting time, absorption rate, diffusion rate, unidirectional moisture transport index, or overall moisture management capacity, as compared to the compared to control silk fibroin coatings that were not subjected to drying, curing, washing cycles, and/or selected temperatures for heat-setting purposes. an increase of less than about 1%, or an increase of less than about 2%, or an increase of less than about 3%, or an increase of less than about 4%, or an increase of less than about 5% in the moisture transport index, or overall moisture management capacity. , or an increase of less than about 6%, or an increase of less than about 7%, or an increase of less than about 8%, or an increase of less than about 9%, or an increase of less than about 10%, or an increase of less than about 15%, or an increase of less than about 20%, or an increase of less than about 25%, or an increase of less than about 30%, or an increase of less than about 35%, or an increase of less than about 40%, or an increase of less than about 45%, or an increase of less than about 50 %, or less than about 60%, or less than about 70%, or less than about 80%, or less than about 90%, or less than about 100%. In some embodiments, a "wash cycle" includes at least one wash cycle, or at least two wash cycles, or at least three wash cycles, or at least four wash cycles, or at least five wash cycles. It can refer to a cycle.

In some embodiments, the SFS-coated article has one or more dyes that can be applied to the SFS-coated article to permanently fix the one or more dyes on the SFS-coated article. The dye may be heat set to fix the dye. In some embodiments, the SFS coated article can be heat set resistant, such that the SFS coating on the SFS coated article is greater than about 100°C, or greater than about 110°C, or greater than about 120°C. or greater than about 130°C, or greater than about 140°C, or greater than about 150°C, or greater than about 160°C, or greater than about 170°C, or greater than about 180°C, or greater than about 190°C, or greater than about 200°C, or It can withstand heat set temperatures of greater than about 210°C, or greater than about 220°C. In some embodiments, the selected temperature is less than about 100°C, or less than about 110°C, or less than about 120°C, or less than about 130°C, or less than about 140°C, or less than about 150°C, or about less than 160°C, or less than about 170°C, or less than about 180°C, or less than about 190°C, or less than about 200°C, or less than about 210°C, or less than about 220°C.

In one embodiment, a material coated with a silk fibroin coating described herein is coated with a silk fibroin coating after the silk fibroin coated material is subjected to heating and/or curing as described herein. It may be partially dissolved or otherwise partially incorporated within the portion. Without being limited to any one theory of this disclosure, the silk fibroin coated material is heated above about the glass transition temperature (Tg) of the material being coated. may be partially dissolved or otherwise partially incorporated within a portion of the .

In some embodiments, a material coated with a silk fibroin coating described herein may be sterile or may be sterilized to provide a sterile silk fibroin coated material. Alternatively, or in addition, the methods described herein can include sterile SFS prepared from sterile silk fibroin.

In some embodiments, fibrous structures compatible with the processes of the present disclosure include wovens, knits, and nonwovens.

In some embodiments, the coating patterns provided by the processes of the present disclosure include single-sided coatings, double-sided coatings, and/or full coatings.

In some embodiments, equipment manufacturers that can produce equipment configured to continuously coat SFS on textiles include, but are not limited to, Aigle, Amba Projex, Bombi; Bruckner, Cavitec, Crosta, Dienes Apparatebau, Eastsign, Europlasma, Fermor, Fontanet, Gaston Systems, Hansa Mixer, Harish, Has Group, Icomatex, Idealtech, Interspare, Isotex, Klieverik, KTP, M P, Mageba, Mahr Feinpruef, Matex, Mathis, Menzel LP, Meyer, Montforts, Morrison Textile, Mtex, Muller Frick, Muratex Textile, Reliant Machinery, Rollmac, Salvade, Sand vik Tps, Santex, Chmitt-Machinen, Schott & Meissner, Sellers, Sicam, Siltex, Starlinger, Swatik Group India, Techfull, TMT Manenti, Unitech Textile Machinery, Weko, Willy, Wumag Texroll, Yamuna, Zappa, and Zimmer Austria.

In some embodiments, equipment manufacturers capable of producing equipment configured to dry SFS coated on a textile fabric include, but are not limited to, Alea, Alkan Makina, Anglada, Atac Makina, Bianco, Bruckner, Campen, CHTC, CTMTC, Dilmenler, Elteksmak, Erbatech, Fontanet, Harish, Icomatex, Ilsung, Inspiron, Interspare, Master, Mathis, Monfongs, Monforts, Salvade, Schmitt-Maschinen, Sellers, Sicam, Siltex, Swastik Group, and others. India, Tacome, Tubetex, Turbang, Unitech Textile Machinery, and Yamuna.

The following sections describe specific embodiments.
Section 1. An article comprising a fiber and a coating, the coating comprising a surfactant and/or emulsifier system and silk fibroin fragments of about 1 kDa to about 5 kDa, about 5 kDa to about 10 kDa, about 6 kDa to about 17 kDa, about 10 kDa. ~about 15kDa, about 14kDa to about 30kDa, about 15kDa to about 20kDa, about 17kDa to about 39kDa, about 20kDa to about 25kDa, about 25kDa to about 30kDa, about 30kDa to about 35kDa, about 35kDa to about 40kDa, about 39kDa to about An average weight selected from 54 kDa, about 39 kDa to about 80 kDa, about 40 kDa to about 45 kDa, about 45 kDa to about 50 kDa, about 50 kDa to about 55 kDa, about 55 kDa to about 60 kDa, about 60 kDa to about 100 kDa, or about 80 kDa to about 144 kDa. Silk fibroin fragments having an average molecular weight and a polydispersity ranging from 1 to about 5.
Section 2. Silk fibroin fragments have a particle size of 1 to about 1.5, about 1.5 to about 2.0, about 2.0 to about 2.5, about 2.5 to about 3.0, about 3.0 to about 3. 5, about 3.5 to about 4.0, about 4.0 to about 4.5, or about 4.5 to about 5.0.
Section 3. The article of paragraph 1, wherein the silk fibroin fragments have a polydispersity of about 1.5 to about 3.0.
Section 4. 2. The article of paragraph 1, wherein the silk fibroin fragments include one or more of low molecular weight silk fibroin fragments and medium molecular weight silk fibroin fragments.
Section 5. 5. The article of any one of paragraphs 1-4, further comprising from about 0.01% (w/w) to about 10% (w/w) sericin based on the silk fibroin fragment.
Section 6. The fibers include polyester, polyamide, polyaramid, polytetrafluoroethylene, polyethylene, polypropylene, polyurethane, silicone, mixtures of polyurethane and polyethylene glycol, ultra-high molecular weight polyethylene, high performance polyethylene, nylon, LYCRA (polyester-polyurethane copolymer, SPANDEX and 6. Article according to any one of clauses 1 to 5, comprising one or more of the following: (also known as elastomers), or mixtures thereof.
Section 7. 7. The article of any one of paragraphs 1-6, wherein the coating further comprises one or more of a wetting agent, an antifoaming agent, a softening agent, a wicking agent, and an antimicrobial agent.
Section 8. The w/w ratio of silk fibroin fragments to surfactant and/or emulsifier system in the coating is about 99:1, about 98:2, about 97:3, about 96:4, about 95:5, about 94: 6, about 93:7, about 92:8, about 91:9, about 90:10, about 89:11, about 88:12, about 87:13, about 86:14, about 85:15, about 84: 16, about 83:17, about 82:18, about 81:19, about 80:20, about 79:21, about 78:22, about 77:23, about 76:24, about 75:25, about 74: 26, about 73:27, about 72:28, about 71:29, about 70:30, about 69:31, about 68:32, about 67:33, about 66:34, about 65:35, about 64: 36, about 63:37, about 62:38, about 61:39, about 60:40, about 59:41, about 58:42, about 57:43, about 56:44, about 55:45, about 54: 46, about 53:47, about 52:48, about 51:49, about 50:50, about 49:51, about 48:52, about 47:53, about 46:54, about 45:55, about 44: 56, about 43:57, about 42:58, about 41:59, about 40:60, about 39:61, about 38:62, about 37:63, about 36:64, about 35:65, about 34: 66, about 33:67, about 32:68, about 31:69, about 30:70, about 29:71, about 28:72, about 27:73, about 26:74, about 25:75, about 24: 76, about 23:77, about 22:78, about 21:79, about 20:80, about 19:81, about 18:82, about 17:83, about 16:84, about 15:85, about 14: 86, about 13:87, about 12:88, about 11:89, about 10:90, about 9:91, about 8:92, about 7:93, about 6:94, about 5:95, about 4: 96, about 3:97, about 2:98, or about 1:99.
Section 9. The w/w ratio of silk fibroin fragments to surfactant and/or emulsifier in the coating is about 1:1, about 1:2, about 1:4, about 1:8, about 1:16, or about 1: The article according to any one of paragraphs 1 to 7, which is 32.
Section 10. The w/w ratio of silk fibroin fragments to surfactant and/or emulsifier system in the coating is about 1:1, about 1:2, about 1:3, about 1:4, about 1:5, about 1: 6, about 1:7, about 1:8, about 1:9, about 1:10, about 1:11, about 1:12, about 1:13, about 1:14, about 1:15, about 1: 16, about 1:17, about 1:18, about 1:19, about 1:20, about 1:21, about 1:22, about 1:23, about 1:24, about 1:25, about 1: 26, about 1:27, about 1:28, about 1:29, about 1:30, about 1:31, or about 1:32.
Section 11. 1 to 10, wherein the surfactant and/or emulsifier system comprises one or more of polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, polyoxyethylene castor oil, and any combination thereof. Articles described in any one of paragraphs.
Section 12. The surfactant and/or emulsifier system may be polyoxyethylene (10-30) sorbitan monooleate, polyoxyethylene (10-30) sorbitan trioleate, polyoxyethylene (10-50) castor oil, and any of them. Article according to any one of paragraphs 1 to 10, comprising one or more of the combinations of.
Section 13. The surfactant and/or emulsifier system is one of polyoxyethylene (20) sorbitan monooleate, polyoxyethylene (20) sorbitan trioleate, polyoxyethylene (29) castor oil, and any combinations thereof. Article according to any one of paragraphs 1 to 10, comprising one or more.
Section 14. The surfactant and/or emulsifier system is polyoxyethylene (20) sorbitan monolaurate, polyoxyethylene (20) sorbitan monopalmitate, polyoxyethylene (20) sorbitan monostearate, polyoxyethylene (20) sorbitan. 11. An article according to any one of paragraphs 1 to 10, comprising one or more of tristearate, and any combination thereof.
Section 15. Article according to any one of paragraphs 1 to 10, wherein the surfactant and/or emulsifier system comprises one or more of sorbitan monofatty acids, sorbitan trifatty acids, castor oil, and any combinations thereof. .
Section 16. The surfactant and/or emulsifier system comprises one or more of coco glucoside, decyl glucoside, lauryl glucoside, coconut sucrose, caprylic/caprylyl glucoside, caprylyl/capryl glucoside, and any combination thereof. The article described in any one of items 1 to 15.
Section 17. 17. The article of any one of paragraphs 1-16, wherein the surfactant and/or emulsifier system has an HLB of about 11 to about 13.50.
Section 18. The surfactant and/or emulsifier system is about 11 to about 11.50, about 11.50 to about 12, about 12 to about 12.50, about 12.50 to about 13, or about 13 to about 13.50. The article according to any one of paragraphs 1 to 16, having an HLB of . In some embodiments, the surfactant and/or emulsifier system is about 11, about 11.1, about 11.2, about 11.3, about 11.4, about 11.5, about 11.6, about 11.7, about 11.8, about 11.9, about 12, about 12.1, about 12.2, about 12.3, about 12.4, about 12.5, about 12.6, about 12 .7, about 12.8, about 12.9, about 13, about 13.1, about 13.2, about 13.3, about 13.4, about 13.5, about 13.6, about 13.7 , about 13.8, about 13.9, or about 14.
Section 19. 19. An article according to any one of paragraphs 1 to 18, wherein the article has improved moisture management compared to a similar article comprising similar fibers but without a coating.
Section 20. Article according to paragraph 19, wherein the moisture management is evaluated by a water absorption test, a vertical wicking test, or a drying rate test.
Section 21. 21. An article according to any one of paragraphs 1 to 20, wherein the article has improved drapability compared to a similar article comprising similar fibers but without a coating.
Section 22. 22. An article according to any one of paragraphs 1 to 21, wherein the article has improved smoothness compared to a similar article comprising similar fibers but without a coating.
Section 23. 23. An article according to any one of paragraphs 1 to 22, wherein the article has an improved hand compared to a similar article comprising similar fibers but without a coating.
Section 24. 24. An article according to any one of paragraphs 1 to 23, wherein the article has a lower charge density at a given pH value compared to a similar article comprising similar fibers but without a coating.
Section 25. A method of making silk fibroin coated fibers, the method comprising applying to the fibers a solution containing a surfactant and/or emulsifier system, applying a silk fibroin fragment solution to the fibers, and drying the fibers. and methods including.
Section 26. A method of making fibers coated with silk fibroin, the method comprising applying to the fibers a solution comprising a surfactant and/or emulsifier system and silk fibroin fragments, and drying the fibers. .
Section 27. 27. The method of paragraph 25 or 26, wherein the concentration of silk fibroin fragments in the solution ranges from 0.01 g/L to about 100 g/L.
Section 28. 28. A method according to any one of paragraphs 25 to 27, wherein the concentration of the surfactant and/or emulsifier system in the solution ranges from 0.01 g/L to about 100 g/L.
Section 29. Silk fibroin fragments are about 1 kDa to about 5 kDa, about 5 kDa to about 10 kDa, about 6 kDa to about 17 kDa, about 10 kDa to about 15 kDa, about 14 kDa to about 30 kDa, about 15 kDa to about 20 kDa, about 17 kDa to about 39 kDa, about 20 kDa to about 25 kDa, about 25 kDa to about 30 kDa, about 30 kDa to about 35 kDa, about 35 kDa to about 40 kDa, about 39 kDa to about 54 kDa, about 39 kDa to about 80 kDa, about 40 kDa to about 45 kDa, about 45 kDa to about 50 kDa, about 50 kDa to about 55 kDa , about 55 kDa to about 60 kDa, about 60 kDa to about 100 kDa, or about 80 kDa to about 144 kDa, and a polydispersity in the range of 1 to about 5. The method described in paragraph 1.
Section 30. Silk fibroin fragments have a particle size of 1 to about 1.5, about 1.5 to about 2.0, about 2.0 to about 2.5, about 2.5 to about 3.0, about 3.0 to about 3. 5, having a polydispersity of about 3.5 to about 4.0, about 4.0 to about 4.5, or about 4.5 to about 5.0. Method described.
Section 31. 30. The method of any one of paragraphs 25-29, wherein the silk fibroin fragments have a polydispersity of about 1.5 to about 3.0.
Section 32. 30. The method of any one of paragraphs 25-29, wherein the silk fibroin fragments comprise one or more of low molecular weight silk fibroin fragments and medium molecular weight silk fibroin fragments.
Section 33. 33. The method of any one of paragraphs 25-32, wherein the solution further comprises from about 0.01% (w/w) to about 10% (w/w) sericin relative to the silk fibroin fragments.
Section 34. The fibers include polyester, polyamide, polyaramid, polytetrafluoroethylene, polyethylene, polypropylene, polyurethane, silicone, mixtures of polyurethane and polyethylene glycol, ultra-high molecular weight polyethylene, high performance polyethylene, nylon, LYCRA (polyester-polyurethane copolymer, SPANDEX and 34. The method according to any one of paragraphs 25 to 33, comprising one or more of the following: (also known as elastomers), or mixtures thereof.
Section 35. 35. The method of any one of paragraphs 25-34, wherein the solution further comprises one or more of a wetting agent, an antifoaming agent, a softening agent, a wicking agent, and an antimicrobial agent.
Section 36. The w/w ratio of silk fibroin fragments to surfactant and/or emulsifier system is about 99:1, about 98:2, about 97:3, about 96:4, about 95:5, about 94:6, about 93:7, about 92:8, about 91:9, about 90:10, about 89:11, about 88:12, about 87:13, about 86:14, about 85:15, about 84:16, about 83:17, about 82:18, about 81:19, about 80:20, about 79:21, about 78:22, about 77:23, about 76:24, about 75:25, about 74:26, about 73:27, about 72:28, about 71:29, about 70:30, about 69:31, about 68:32, about 67:33, about 66:34, about 65:35, about 64:36, about 63:37, about 62:38, about 61:39, about 60:40, about 59:41, about 58:42, about 57:43, about 56:44, about 55:45, about 54:46, about 53:47, about 52:48, about 51:49, about 50:50, about 49:51, about 48:52, about 47:53, about 46:54, about 45:55, about 44:56, about 43:57, about 42:58, about 41:59, about 40:60, about 39:61, about 38:62, about 37:63, about 36:64, about 35:65, about 34:66, about 33:67, approximately 32:68, approximately 31:69, approximately 30:70, approximately 29:71, approximately 28:72, approximately 27:73, approximately 26:74, approximately 25:75, approximately 24:76, approximately 23:77, approximately 22:78, approximately 21:79, approximately 20:80, approximately 19:81, approximately 18:82, approximately 17:83, approximately 16:84, approximately 15:85, approximately 14:86, approximately 13:87, about 12:88, about 11:89, about 10:90, about 9:91, about 8:92, about 7:93, about 6:94, about 5:95, about 4:96, about 3:3:97, about 2:98, or about 1:99.
Section 37. The w/w ratio of silk fibroin fragments to surfactant and/or emulsifier system is about 1:1, about 1:2, about 1:4, about 1:8, about 1:16, or about 1:32. The method according to any one of paragraphs 25 to 35.
Section 38. The w/w ratio of silk fibroin fragments to surfactant and/or emulsifier system is about 1:1, about 1:2, about 1:3, about 1:4, about 1:5, about 1:6, about 1:7, about 1:8, about 1:9, about 1:10, about 1:11, about 1:12, about 1:13, about 1:14, about 1:15, about 1:16, about 1:17, about 1:18, about 1:19, about 1:20, about 1:21, about 1:22, about 1:23, about 1:24, about 1:25, about 1:26, about 36. The method of any one of paragraphs 25-35, wherein the ratio is 1:27, about 1:28, about 1:29, about 1:30, about 1:31, or about 1:32.
Section 39. 25-38, wherein the surfactant and/or emulsifier system comprises one or more of polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, polyoxyethylene castor oil, and any combination thereof The method described in any one of paragraphs.
Section 40. The surfactant and/or emulsifier system may be polyoxyethylene (10-30) sorbitan monooleate, polyoxyethylene (10-30) sorbitan trioleate, polyoxyethylene (10-50) castor oil, and any of them. 39. The method of any one of paragraphs 25-38, comprising one or more of the combinations of.
Section 41. The surfactant and/or emulsifier system is one of polyoxyethylene (20) sorbitan monooleate, polyoxyethylene (20) sorbitan trioleate, polyoxyethylene (29) castor oil, and any combinations thereof. 39. The method of any one of paragraphs 25-38, comprising one or more.
Section 42. The surfactant and/or emulsifier system is polyoxyethylene (20) sorbitan monolaurate, polyoxyethylene (20) sorbitan monopalmitate, polyoxyethylene (20) sorbitan monostearate, polyoxyethylene (20) sorbitan. 39. The method of any one of paragraphs 25-38, comprising one or more of tristearate, and any combination thereof.
Section 43. The method according to any one of paragraphs 25 to 38, wherein the surfactant and/or emulsifier system comprises one or more of sorbitan monofatty acids, sorbitan trifatty acids, castor oil, and any combinations thereof. .
Section 44. The surfactant and/or emulsifier system comprises one or more of coco glucoside, decyl glucoside, lauryl glucoside, coconut sucrose, caprylic/caprylyl glucoside, caprylyl/capryl glucoside, and any combination thereof. The method according to any one of paragraphs 25 to 43.
Section 45. 45. The method of any one of paragraphs 25-44, wherein the surfactant and/or emulsifier system has an HLB of about 11 to about 13.50.
Section 46. The surfactant and/or emulsifier system is about 11 to about 11.50, about 11.50 to about 12, about 12 to about 12.50, about 12.50 to about 13, or about 13 to about 13.50. 45. The method according to any one of paragraphs 25 to 44, having an HLB of . In some embodiments, the surfactant and/or emulsifier system is about 11, about 11.1, about 11.2, about 11.3, about 11.4, about 11.5, about 11.6, about 11.7, about 11.8, about 11.9, about 12, about 12.1, about 12.2, about 12.3, about 12.4, about 12.5, about 12.6, about 12 .7, about 12.8, about 12.9, about 13, about 13.1, about 13.2, about 13.3, about 13.4, about 13.5, about 13.6, about 13.7 , about 13.8, about 13.9, or about 14.
Section 47. 47. The method of any one of paragraphs 25-46, wherein drying comprises heating.
Section 48. 48. The method according to any one of paragraphs 25 to 47, wherein the pH of the solution is acidic.
Section 49. The pH of the solution is about 3.5 to about 4, about 4 to about 4.5, about 4.5 to about 5, about 5 to about 5.5, or about 5.5 to about 6. 47. The method according to any one of paragraphs 47 to 47. In some embodiments, the pH of the solution is about 3.5, about 3.6, about 3.7, about 3.8, about 3.9, about 4, about 4.1, about 4.2, about 4.3, about 4.4, about 4.5, about 4.6, about 4.7, about 4.8, about 4.9, about 5, about 5.1, about 5.2, about 5 .3, about 5.4, about 5.5, about 5.6, about 5.7, about 5.8, about 5.9, or about 6.
Section 50. An article prepared by the method according to any one of paragraphs 25 to 49.
Section 51. 51. The article of clause 50, wherein the article has improved moisture management compared to a similar article comprising similar fibers but without a coating.
Section 52. 52. The article of paragraph 51, wherein moisture management is evaluated by a water absorption test, a vertical wicking test, or a drying rate test.
Section 53. 53. An article according to any one of paragraphs 50 to 52, wherein the article has improved drapability compared to a similar article comprising similar fibers but without a coating.
Section 54. 54. An article according to any one of paragraphs 50 to 53, wherein the article has improved smoothness compared to a similar article comprising similar fibers but without a coating.
Section 55. 55. An article according to any one of paragraphs 50 to 54, wherein the article has an improved hand compared to a similar article comprising similar fibers but without a coating.
Section 56. 56. An article according to any one of paragraphs 50 to 55, wherein the article has a lower charge density at a given pH value compared to a similar article comprising similar fibers but without a coating.
Section 57. According to any one of paragraphs 1 to 24 or 50 to 56, wherein the amount of silk fibroin fragments in the article is about 0.01 g to 0.5 g per 1500 m ² (denier) to 4000 m ² (denier). goods.
Section 58. According to any one of paragraphs 1 to 24, or 50 to 56, wherein the amount of silk fibroin fragments in the article is about 0.03 g to 0.35 g per 1500 m ² (denier) to 4000 m ² (denier). goods.
Section 59. According to any one of paragraphs 1 to 24, or 50 to 56, wherein the amount of silk fibroin fragments in the article is about 0.05 g to 0.2 g per 3000 m ² (denier) to 4000 m ² (denier). goods.
Section 60. According to any one of paragraphs 1 to 24, or 50 to 56, wherein the amount of silk fibroin fragments in the article is about 0.2 g to 0.35 g per 1000 m ² (denier) to 2500 m ² (denier). goods.
Section 61. The amount of silk fibroin fragments in the article is about 0.01 g/1000-4500 m ² (denier), about 0.02 g/1000-4500 m ² (denier), about 0.03 g/1000-4500 m ² (denier), about 0.04g/1000-4500m ² (denier), approximately 0.05g/1000-4500m ² (denier), approximately 0.06g/1000-4500m ² (denier), approximately 0.07g/1000-4500m ² (denier) , about 0.08g/1000-4500m ² (denier), about 0.09g/1000-4500m ² (denier), about 0.10g/1000-4500m ² (denier), about 0.11g/1000-4500m ² ( 0.12g/1000~4500m ² (Denier), approx. 0.13g/1000~4500m ² (Denier), approx. 0.14g/1000~4500m ² (Denier), approx. 0.15g/1000~4500m ² (denier), approximately 0.16g/1000-4500m ² (denier), approximately 0.17g/1000-4500m ² (denier), approximately 0.18g/1000-4500m ² (denier), approximately 0.19g/1000 ～4500m ² (denier), about 0.2g/1000-4500m ² (denier), about 0.21g/1000-4500m ² (denier), about 0.22g/1000-4500m ² (denier), about 0.23g /1000-4500m ² (denier), approximately 0.24g/1000-4500m ² (denier), approximately 0.25g/1000-4500m ² (denier), approximately 0.26g/1000-4500m ² (denier), approximately 0 .27g/1000-4500m ² (denier), about 0.28g/1000-4500m ² (denier), about 0.29g/1000-4500m ² (denier), about 0.3g/1000-4500m ² (denier), Approx. 0.31g/1000-4500m ² (denier), Approx. 0.32g/1000-4500m ² (denier), Approx. 0.33g/1000-4500m ² (denier), Approx. 0.34g/1000-4500m ² (denier) ), approx. 0.35g/1000-4500m ² (denier), approx. 0.36g/1000-4500m ² (denier), approx. 0.37g/1000-4500m ² (denier), approx. 0.38g/1000-4500m ² (denier), approx. 0.39g/1000~4500m ² (denier), approx. 0.4g/1000~4500m ² (denier), approx. 0.41g/1000~4500m ² (denier), approx. 0.42g/1000~ 4500m ² (denier), approximately 0.43g/1000-4500m ² (denier), approximately 0.44g/1000-4500m ² (denier), approximately 0.45g/1000-4500m ² (denier), approximately 0.46g/ 1000-4500m ² (denier), about 0.47g/1000-4500m ² (denier), about 0.48g/1000-4500m ² (denier), about 0.49g/1000-4500m ² (denier), or about 0 .5 g/1000 to 4500 m ² (denier), the article according to any one of items 1 to 24 or 50 to 56.
Section 101. An article comprising a fiber and a coating, the coating comprising a surfactant and silk fibroin fragments having a weight of about 1 kDa to about 5 kDa, about 5 kDa to about 10 kDa, about 6 kDa to about 17 kDa, about 10 kDa to about 15 kDa, about 14kDa to about 30kDa, about 15kDa to about 20kDa, about 17kDa to about 39kDa, about 20kDa to about 25kDa, about 25kDa to about 30kDa, about 30kDa to about 35kDa, about 35kDa to about 40kDa, about 39kDa to about 54kDa, about 39kDa to about an average weight average molecular weight selected from about 80 kDa, about 40 kDa to about 45 kDa, about 45 kDa to about 50 kDa, about 50 kDa to about 55 kDa, about 55 kDa to about 60 kDa, about 60 kDa to about 100 kDa, or about 80 kDa to about 144 kDa, and 1 silk fibroin fragments having a polydispersity in the range of from about 5 to about 5.
Section 102. Silk fibroin fragments have a particle size of 1 to about 1.5, about 1.5 to about 2.0, about 2.0 to about 2.5, about 2.5 to about 3.0, about 3.0 to about 3. 102. The article of paragraph 101, having a polydispersity of 5, about 3.5 to about 4.0, about 4.0 to about 4.5, or about 4.5 to about 5.0.
Section 103. 102. The article of paragraph 101, wherein the silk fibroin fragments have a polydispersity of about 1.5 to about 3.0.
Section 104. 102. The article of paragraph 101, wherein the silk fibroin fragments include one or more of low molecular weight silk fibroin fragments and medium molecular weight silk fibroin fragments.
Section 105. 105. The article of any one of paragraphs 101-104, further comprising about 0.01% (w/w) to about 10% (w/w) sericin based on the silk fibroin fragment.
Section 66. The fibers include polyester, polyamide, polyaramid, polytetrafluoroethylene, polyethylene, polypropylene, polyurethane, silicone, mixtures of polyurethane and polyethylene glycol, ultra-high molecular weight polyethylene, high performance polyethylene, nylon, LYCRA (polyester-polyurethane copolymer, SPANDEX and 106. An article according to any one of paragraphs 101 to 105, comprising one or more of the following: (also known as elastomers), or mixtures thereof.
Section 107. 107. The article of any one of paragraphs 101-106, wherein the coating further comprises one or more of a wetting agent, an antifoaming agent, a softening agent, a wicking agent, and an antimicrobial agent.
Section 108. The w/w ratio of silk fibroin fragments to surfactant in the coating is about 99:1, about 98:2, about 97:3, about 96:4, about 95:5, about 94:6, about 93: 7, about 92:8, about 91:9, about 90:10, about 89:11, about 88:12, about 87:13, about 86:14, about 85:15, about 84:16, about 83: 17, about 82:18, about 81:19, about 80:20, about 79:21, about 78:22, about 77:23, about 76:24, about 75:25, about 74:26, about 73: 27, about 72:28, about 71:29, about 70:30, about 69:31, about 68:32, about 67:33, about 66:34, about 65:35, about 64:36, about 63: 37, about 62:38, about 61:39, about 60:40, about 59:41, about 58:42, about 57:43, about 56:44, about 55:45, about 54:46, about 53: 47, about 52:48, about 51:49, about 50:50, about 49:51, about 48:52, about 47:53, about 46:54, about 45:55, about 44:56, about 43: 57, about 42:58, about 41:59, about 40:60, about 39:61, about 38:62, about 37:63, about 36:64, about 35:65, about 34:66, about 33: 67, about 32:68, about 31:69, about 30:70, about 29:71, about 28:72, about 27:73, about 26:74, about 25:75, about 24:76, about 23: 77, about 22:78, about 21:79, about 20:80, about 19:81, about 18:82, about 17:83, about 16:84, about 15:85, about 14:86, about 13: 87, about 12:88, about 11:89, about 10:90, about 9:91, about 8:92, about 7:93, about 6:94, about 5:95, about 4:96, about 3: 97, about 2:98, or about 1:99.
Section 109. 108. The article of any one of paragraphs 101-107, wherein the w/w ratio of silk fibroin fragments to surfactant in the coating is about 1:1.
Section 110. Article according to any one of paragraphs 101 to 109, wherein the surfactant is selected from coco glucoside, decyl glucoside, lauryl glucoside, coconut sucrose, capryl/caprylyl glucoside, and caprylyl/capryl glucoside.
Section 111. Article according to any one of paragraphs 101 to 109, wherein the surfactant is selected from caprylyl/caprylyl glucoside and caprylyl/capryl glucoside.
Section 112. 112. An article according to any one of paragraphs 101-111, wherein the article has improved moisture management compared to a similar article comprising similar fibers but without a coating.
Section 113. 113. The article of paragraph 112, wherein moisture management is evaluated by a water absorption test, a vertical wicking test, or a drying rate test.
Section 114. A method of making silk fibroin coated fibers, the method comprising applying a solution containing a surfactant to the fibers, applying a silk fibroin fragment solution to the fibers, and drying the fibers. ,Method.
Section 115. A method of making silk fibroin coated fibers, the method comprising applying a solution comprising a surfactant and silk fibroin fragments to the fibers and drying the fibers.
Section 116. 116. The method of paragraph 114 or 115, wherein the concentration of silk fibroin fragments in the solution ranges from 0.01 g/L to about 100 g/L.
Section 117. 117. The method of any one of paragraphs 114-116, wherein the concentration of surfactant in the solution ranges from 0.01 g/L to about 100 g/L.
Section 118. The w/w ratio of silk fibroin fragments to surfactant is about 99:1, about 98:2, about 97:3, about 96:4, about 95:5, about 94:6, about 93:7, about 92:8, approximately 91:9, approximately 90:10, approximately 89:11, approximately 88:12, approximately 87:13, approximately 86:14, approximately 85:15, approximately 84:16, approximately 83:17, approximately 82:18, approximately 81:19, approximately 80:20, approximately 79:21, approximately 78:22, approximately 77:23, approximately 76:24, approximately 75:25, approximately 74:26, approximately 73:27, approximately 72:28, about 71:29, about 70:30, about 69:31, about 68:32, about 67:33, about 66:34, about 65:35, about 64:36, about 63:37, about 62:38, about 61:39, about 60:40, about 59:41, about 58:42, about 57:43, about 56:44, about 55:45, about 54:46, about 53:47, about 52:48, about 51:49, about 50:50, about 49:51, about 48:52, about 47:53, about 46:54, about 45:55, about 44:56, about 43:57, about 42:58, about 41:59, about 40:60, about 39:61, about 38:62, about 37:63, about 36:64, about 35:65, about 34:66, about 33:67, about 32:68, approximately 31:69, approximately 30:70, approximately 29:71, approximately 28:72, approximately 27:73, approximately 26:74, approximately 25:75, approximately 24:76, approximately 23:77, approximately 22:78, approximately 21:79, approximately 20:80, approximately 19:81, approximately 18:82, approximately 17:83, approximately 16:84, approximately 15:85, approximately 14:86, approximately 13:87, approximately 12:88, about 11:89, about 10:90, about 9:91, about 8:92, about 7:93, about 6:94, about 5:95, about 4:96, about 3:97, about 2:98, or about 1:99.
Section 119. 119. The method of any one of paragraphs 114-118, wherein the solution further comprises one or more of a wetting agent, an antifoaming agent, a softening agent, a wicking agent, and an antimicrobial agent.
Section 120. Silk fibroin fragments are about 1 kDa to about 5 kDa, about 5 kDa to about 10 kDa, about 6 kDa to about 17 kDa, about 10 kDa to about 15 kDa, about 14 kDa to about 30 kDa, about 15 kDa to about 20 kDa, about 17 kDa to about 39 kDa, about 20 kDa to about 25 kDa, about 25 kDa to about 30 kDa, about 30 kDa to about 35 kDa, about 35 kDa to about 40 kDa, about 39 kDa to about 54 kDa, about 39 kDa to about 80 kDa, about 40 kDa to about 45 kDa, about 45 kDa to about 50 kDa, about 50 kDa to about 55 kDa , about 55 kDa to about 60 kDa, about 60 kDa to about 100 kDa, or about 80 kDa to about 144 kDa, and a polydispersity in the range of 1 to about 5. The method described in paragraph 1.
Section 121. Silk fibroin fragments have a particle size of 1 to about 1.5, about 1.5 to about 2.0, about 2.0 to about 2.5, about 2.5 to about 3.0, about 3.0 to about 3. 5, having a polydispersity of about 3.5 to about 4.0, about 4.0 to about 4.5, or about 4.5 to about 5.0. Method described.
Section 122. 121. The method of any one of paragraphs 114-120, wherein the silk fibroin fragments have a polydispersity of about 1.5 to about 3.0.
Section 123. 121. The method of any one of paragraphs 114-120, wherein the silk fibroin fragments comprise one or more of low molecular weight silk fibroin fragments and medium molecular weight silk fibroin fragments.
Section 124. 124. The method of any one of paragraphs 114-123, wherein the solution further comprises about 0.01% (w/w) to about 10% (w/w) sericin relative to the silk fibroin fragments.
Section 125. The fibers include polyester, polyamide, polyaramid, polytetrafluoroethylene, polyethylene, polypropylene, polyurethane, silicone, mixtures of polyurethane and polyethylene glycol, ultra-high molecular weight polyethylene, high performance polyethylene, nylon, LYCRA (polyester-polyurethane copolymer, SPANDEX and 125. The method according to any one of paragraphs 114 to 124, comprising one or more of the following: (also known as elastomers), or mixtures thereof.
Section 126. 126. The method according to any one of paragraphs 114 to 125, wherein the surfactant is selected from coco glucoside, decyl glucoside, lauryl glucoside, coconut fatty acid sucrose, caprylic/caprylyl glucoside, and caprylyl/capryl glucoside.
Section 127. 126. A method according to any one of paragraphs 114 to 125, wherein the surfactant is selected from caprylyl/caprylyl glucoside and caprylyl/capryl glucoside.
Section 128. 128. The method of any one of paragraphs 114-127, wherein drying comprises heating.
Section 129. 129. The method of paragraph 128, wherein heating does not substantially alter coating performance.
Section 130. 129. The method according to any one of paragraphs 114 to 129, wherein the pH of the solution is acidic.
Section 131. 129. The method of any one of paragraphs 114-129, wherein the pH of the solution is from about 4 to about 4.5.
Section 132. An article prepared by the method according to any one of paragraphs 114 to 131.
Section 133. 133. The article of paragraph 132, wherein the article has improved moisture management compared to a similar article comprising similar fibers but no coating.
Section 134. 134. The article of paragraph 133, wherein moisture management is evaluated by a water absorption test, a vertical wicking test, or a drying rate test.
Section 201. An article comprising a fiber and a coating, the coating comprising a surfactant and/or an emulsifier, and silk fibroin fragments of about 1 kDa to about 5 kDa, about 5 kDa to about 10 kDa, about 6 kDa to about 17 kDa, about 10 kDa to about 15 kDa, about 14 kDa to about 30 kDa, about 15 kDa to about 20 kDa, about 17 kDa to about 39 kDa, about 20 kDa to about 25 kDa, about 25 kDa to about 30 kDa, about 30 kDa to about 35 kDa, about 35 kDa to about 40 kDa, about 39 kDa to about 54 kDa , about 39 kDa to about 80 kDa, about 40 kDa to about 45 kDa, about 45 kDa to about 50 kDa, about 50 kDa to about 55 kDa, about 55 kDa to about 60 kDa, about 60 kDa to about 100 kDa, or about 80 kDa to about 144 kDa. silk fibroin fragments having a molecular weight and a polydispersity ranging from 1 to about 5.
Section 202. Silk fibroin fragments have a particle size of 1 to about 1.5, about 1.5 to about 2.0, about 2.0 to about 2.5, about 2.5 to about 3.0, about 3.0 to about 3. 202. The article of paragraph 201, having a polydispersity of 5, about 3.5 to about 4.0, about 4.0 to about 4.5, or about 4.5 to about 5.0.
Section 203. 202. The article of paragraph 201, wherein the silk fibroin fragments have a polydispersity of about 1.5 to about 3.0.
Section 204. 202. The article of paragraph 201, wherein the silk fibroin fragments include one or more of low molecular weight silk fibroin fragments and medium molecular weight silk fibroin fragments.
Section 205. 205. The article of any one of paragraphs 201-204, further comprising about 0.01% (w/w) to about 10% (w/w) sericin based on the silk fibroin fragment.
Section 206. The fibers include polyester, polyamide, polyaramid, polytetrafluoroethylene, polyethylene, polypropylene, polyurethane, silicone, mixtures of polyurethane and polyethylene glycol, ultra-high molecular weight polyethylene, high performance polyethylene, nylon, LYCRA (polyester-polyurethane copolymer, SPANDEX and 206. An article according to any one of paragraphs 201 to 205, comprising one or more of the following: (also known as elastomers), or mixtures thereof.
Section 207. 207. The article of any one of paragraphs 201-206, wherein the coating further comprises one or more of a wetting agent, an antifoaming agent, a softening agent, a wicking agent, and an antimicrobial agent.
Section 208. The w/w ratio of silk fibroin fragments to surfactant and/or emulsifier in the coating is about 99:1, about 98:2, about 97:3, about 96:4, about 95:5, about 94:6 , about 93:7, about 92:8, about 91:9, about 90:10, about 89:11, about 88:12, about 87:13, about 86:14, about 85:15, about 84:16 , about 83:17, about 82:18, about 81:19, about 80:20, about 79:21, about 78:22, about 77:23, about 76:24, about 75:25, about 74:26 , about 73:27, about 72:28, about 71:29, about 70:30, about 69:31, about 68:32, about 67:33, about 66:34, about 65:35, about 64:36 , about 63:37, about 62:38, about 61:39, about 60:40, about 59:41, about 58:42, about 57:43, about 56:44, about 55:45, about 54:46 , about 53:47, about 52:48, about 51:49, about 50:50, about 49:51, about 48:52, about 47:53, about 46:54, about 45:55, about 44:56 , about 43:57, about 42:58, about 41:59, about 40:60, about 39:61, about 38:62, about 37:63, about 36:64, about 35:65, about 34:66 , about 33:67, about 32:68, about 31:69, about 30:70, about 29:71, about 28:72, about 27:73, about 26:74, about 25:75, about 24:76 , about 23:77, about 22:78, about 21:79, about 20:80, about 19:81, about 18:82, about 17:83, about 16:84, about 15:85, about 14:86 , about 13:87, about 12:88, about 11:89, about 10:90, about 9:91, about 8:92, about 7:93, about 6:94, about 5:95, about 4:96 , about 3:97, about 2:98, or about 1:99.
Section 209. The w/w ratio of silk fibroin fragments to surfactant and/or emulsifier in the coating is about 1:1, about 1:2, about 1:4, about 1:8, about 1:16, or about 1: 32. The article according to any one of paragraphs 201-207, wherein the article is:
Section 210. Any one of paragraphs 201 to 209, wherein the emulsifier and/or surfactant is selected from polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, polyoxyethylene castor oil, and any combination thereof. Articles listed in section.
Section 211. The emulsifier and/or surfactant may be polyoxyethylene (10-30) sorbitan monooleate, polyoxyethylene (10-30) sorbitan trioleate, polyoxyethylene (10-50) castor oil, and any of them. An article according to any one of paragraphs 201 to 209, selected from a combination.
Section 212. The emulsifier and/or surfactant is selected from polyoxyethylene (20) sorbitan monooleate, polyoxyethylene (20) sorbitan trioleate, polyoxyethylene (29) castor oil, and any combinations thereof. Article according to any one of paragraphs 201 to 209.
Section 213. Article according to any one of paragraphs 201 to 212, wherein the emulsifier and/or surfactant has an HLB of 11 to 13.50.
Section 214. 214. The article of any one of paragraphs 201-213, wherein the article has improved moisture management compared to a similar article comprising similar fibers but without a coating.
Section 215. 215. The article of paragraph 214, wherein moisture management is evaluated by a water absorption test, a vertical wicking test, or a drying rate test.
Section 216. 214. The article of any one of paragraphs 201-213, wherein the article has improved drapability compared to a similar article comprising similar fibers but without a coating.
Section 217. 214. The article of any one of paragraphs 201-213, wherein the article has improved smoothness compared to a similar article comprising similar fibers but without a coating.
Section 218. 214. An article according to any one of paragraphs 201-213, wherein the article has an improved hand compared to a similar article comprising similar fibers but no coating.
Section 219. A method of making silk fibroin coated fibers, the method comprising applying to the fibers a solution containing a surfactant and/or emulsifier system, applying a silk fibroin fragment solution to the fibers, and drying the fibers. and methods including.
Section 220. A method of making fibers coated with silk fibroin, the method comprising applying to the fibers a solution comprising a surfactant and/or emulsifier system and silk fibroin fragments, and drying the fibers. .
Section 221. 221. The method of paragraph 219 or 220, wherein the concentration of silk fibroin fragments in the solution ranges from 0.01 g/L to about 100 g/L.
Section 222. 222. A method according to any one of paragraphs 219-221, wherein the concentration of the surfactant and/or emulsifier system in the solution ranges from 0.01 g/L to about 100 g/L.
Section 223. The w/w ratio of silk fibroin fragments to surfactant and/or emulsifier system is about 99:1, about 98:2, about 97:3, about 96:4, about 95:5, about 94:6, about 93:7, about 92:8, about 91:9, about 90:10, about 89:11, about 88:12, about 87:13, about 86:14, about 85:15, about 84:16, about 83:17, about 82:18, about 81:19, about 80:20, about 79:21, about 78:22, about 77:23, about 76:24, about 75:25, about 74:26, about 73:27, about 72:28, about 71:29, about 70:30, about 69:31, about 68:32, about 67:33, about 66:34, about 65:35, about 64:36, about 63:37, about 62:38, about 61:39, about 60:40, about 59:41, about 58:42, about 57:43, about 56:44, about 55:45, about 54:46, about 53:47, about 52:48, about 51:49, about 50:50, about 49:51, about 48:52, about 47:53, about 46:54, about 45:55, about 44:56, about 43:57, about 42:58, about 41:59, about 40:60, about 39:61, about 38:62, about 37:63, about 36:64, about 35:65, about 34:66, about 33:67, about 32:68, about 31:69, about 30:70, about 29:71, about 28:72, about 27:73, about 26:74, about 25:75, about 24:76, about 23:77, approximately 22:78, approximately 21:79, approximately 20:80, approximately 19:81, approximately 18:82, approximately 17:83, approximately 16:84, approximately 15:85, approximately 14:86, approximately 13:87, about 12:88, about 11:89, about 10:90, about 9:91, about 8:92, about 7:93, about 6:94, about 5:95, about 4:96, about 3:97, about 2:98, or about 1:99.
Section 224. The w/w ratio of silk fibroin fragments to surfactant and/or emulsifier system is about 1:1, about 1:2, about 1:4, about 1:8, about 1:16, or about 1:32. The method of any one of paragraphs 219-222, wherein:
Section 225. 219-224, wherein the emulsifier and/or surfactant system comprises one or more of polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, polyoxyethylene castor oil, and any combination thereof The method described in any one of paragraphs.
Section 226. The emulsifier and/or surfactant system may be polyoxyethylene (10-30) sorbitan monooleate, polyoxyethylene (10-30) sorbitan trioleate, polyoxyethylene (10-50) castor oil, and any of them. The method of any one of paragraphs 219-224, comprising one or more of the combinations of.
Section 227. The emulsifier and/or surfactant system is one of polyoxyethylene (20) sorbitan monooleate, polyoxyethylene (20) sorbitan trioleate, polyoxyethylene (29) castor oil, and any combination thereof. 225. The method of any one of paragraphs 219-224, comprising one or more.
Section 228. A method according to any one of paragraphs 219 to 224, wherein the emulsifier and/or surfactant system has an HLB of 11 to 13.50.
Section 229. 229. The method of any one of paragraphs 219-228, wherein the solution further comprises one or more of a wetting agent, an antifoaming agent, a softening agent, a wicking agent, and an antimicrobial agent.
Section 230. Silk fibroin fragments are about 1 kDa to about 5 kDa, about 5 kDa to about 10 kDa, about 6 kDa to about 17 kDa, about 10 kDa to about 15 kDa, about 14 kDa to about 30 kDa, about 15 kDa to about 20 kDa, about 17 kDa to about 39 kDa, about 20 kDa to about 25 kDa, about 25 kDa to about 30 kDa, about 30 kDa to about 35 kDa, about 35 kDa to about 40 kDa, about 39 kDa to about 54 kDa, about 39 kDa to about 80 kDa, about 40 kDa to about 45 kDa, about 45 kDa to about 50 kDa, about 50 kDa to about 55 kDa , about 55 kDa to about 60 kDa, about 60 kDa to about 100 kDa, or about 80 kDa to about 144 kDa, and a polydispersity in the range of 1 to about 5. The method described in paragraph 1.
Section 231. Silk fibroin fragments have a particle size of 1 to about 1.5, about 1.5 to about 2.0, about 2.0 to about 2.5, about 2.5 to about 3.0, about 3.0 to about 3. 5, having a polydispersity of about 3.5 to about 4.0, about 4.0 to about 4.5, or about 4.5 to about 5.0. Method described.
Section 232. 231. The method of any one of paragraphs 219-230, wherein the silk fibroin fragments have a polydispersity of about 1.5 to about 3.0.
Section 233. 233. The method of any one of paragraphs 219-232, wherein the silk fibroin fragments comprise one or more of a low molecular weight silk fibroin fragment and a medium molecular weight silk fibroin fragment.
Section 234. 234. The method of any one of paragraphs 219-233, wherein the solution further comprises from about 0.01% (w/w) to about 10% (w/w) sericin relative to the silk fibroin fragments.
Section 235. The fibers include polyester, polyamide, polyaramid, polytetrafluoroethylene, polyethylene, polypropylene, polyurethane, silicone, mixtures of polyurethane and polyethylene glycol, ultra-high molecular weight polyethylene, high performance polyethylene, nylon, LYCRA (polyester-polyurethane copolymer, SPANDEX and 235. The method of any one of paragraphs 219-234, comprising one or more of the following: (also known as elastomers), or mixtures thereof.
Section 236. 236. The method of any one of paragraphs 219-235, wherein drying comprises heating.
Section 237. 237. The method according to any one of paragraphs 219-236, wherein the pH of the solution is acidic.
Section 238. 237. The method of any one of paragraphs 219-236, wherein the pH of the solution is from about 4 to about 4.5.
Section 239. An article prepared by the method of any one of paragraphs 219-238.
Section 240. 240. The article of paragraph 239, wherein the article has improved moisture management compared to a similar article comprising similar fibers but no coating.
Section 241. 241. The article of paragraph 240, wherein moisture management is evaluated by a water absorption test, a vertical wicking test, or a drying rate test.
Section 242. 240. The article of paragraph 239, wherein the article has improved drape properties as compared to similar articles comprising similar fibers but without a coating.
Section 243. 240. The article of clause 239, wherein the article has improved smoothness compared to a similar article comprising similar fibers but no coating.
Section 244. 240. The article of paragraph 239, wherein the article has an improved hand as compared to a similar article comprising similar fibers but no coating.

The embodiments encompassed herein will now be described with reference to the following examples. These examples are provided for illustrative purposes only, and the disclosure encompassed herein should not be construed as being limited in any way to these examples, but rather as encompassing any variations that become evident as a result of the teachings provided herein.

Compositions of the present disclosure can be made by various methods known in the art. Such methods include those in the Examples below and methods specifically exemplified below. Modifications of such methods, including techniques commonly practiced in the textile art, may also be used.

Example 1: Silk Fibroin and Surfactants Used on Synthetic Fibers As illustrated in this example, silk fibroin can be used with surfactants on synthetic fibers.

Activated Silk™ molecules containing sugar-derived caprylic/caprylyl glucosides provide enhanced moisture management properties for various types of nylon fibers.

The comfort properties of clothing, especially those leisure and sportswear, are primarily determined by their moisture management properties. Moisture management is the ability of textile fibers to absorb moisture (sweat) from the skin, transport it to the outer surface, and release it to the environment. With the continued demand for comfortable clothing, there is great potential for growth in this area.

Moisture management performance can be enhanced by employing microfiber technology, which increases the specific surface area of the fibers and thus allows for higher rates of liquid transport, and by the application of various chemical finishes. The former option is very cost intensive, making chemical finishing options more convenient for most manufacturers.

Despite the variety of moisture management treatments available for nylon, sustainable chemicals from natural derivatives without waste management concerns have not been widely reported. Therefore, it is very important to identify green chemicals for moisture management treatments that are easy to handle for end users, water supplies, the environment, and those doing the manufacturing.

Coating of Nylon Fibers The coating solution was prepared by adjusting the pH of the water to 4-4.5 by using acetic acid and then adding caprylic/caprylyl glucoside to the desired concentration (0.1%). Activated Silk™ is then added, the amount being controlled at a 1:1 (v/v) ratio for capryl/caprylyl glucoside. The pH of the final solution is checked and adjusted if it is outside the range of 4-4.5.

The coating solution is applied to the nylon fibers using a pad roller at a speed of 3 meters/min through a pad and curing method. Wet pickup is controlled to 60%±3% by adjusting roller pressure.

The fibers are dried and cured in an oven at 160°C for 1.5 minutes and then allowed to rest overnight before performance testing.

Performance Testing Moisture management can be evaluated by various test standards such as water absorption test, vertical wicking test, drying rate test. Although the results are expressed in different ways through different test methods, the characterization of moisture management performance is correlated.

In this development, a modified AATCC79-Test Method for Absorbency of Textiles is implemented to determine moisture management performance.

Test Results Figures 3 and 4 are test results for Activated Silk with caprylic/caprylyl glucoside coatings on various nylon fibers, including interlock, jersey, warp knit, and spacer structures. The results show that this new solution has a universal improvement in absorbency over various nylon fibers and exhibits its universal improvement in moisture management performance.

Figure 3. Absorbency of Activated Silk™ with caprylic/caprylyl glucoside coating on extensive interlocking nylon fibers. Raw nylon interlock fibers do not absorb water and have poor absorbency. After Activated Silk™ with caprylic/caprylyl glucoside coating, the absorbency of all nylon interlock fibers increases significantly.

Figure 4. Absorbency of Activated Silk™ with caprylic/caprylyl glucoside coatings on various nylon fibers other than interlock structures. Raw nylon fibers do not absorb water or have poor absorbency, and after Activated Silk™ with a caprylic/caprylyl glucoside coating, the absorbency of all nylon fibers is significantly lower. To increase.

Example 2: Silk fibroin and emulsifiers and/or surfactants used on synthetic fibers As illustrated in this example, silk fibroin can be used with surfactants and/or emulsifiers on synthetic fibers. . In a non-limiting example, silk fibroin fragments were used with an emulsion of three ethoxylated fatty acids to provide smooth and drapeable properties to nylon and polyester fibers without interfering with the moisture management properties imparted by the wicking agent. gave the feel of Wicking agents in textiles are commonly used to improve the comfort properties of leisure and sportswear by improving the moisture management properties of nylon and polyester fibers. However, a common problem with many wicking agents is that they are composed of hydrophilic surfactants or polymers that draw water between the fibers of the fabric, making the fibers feel heavier and coarser than without them. That's true. The common use of these surfactants as moisture management agents provides the potential for new developments in the field of softeners that do not inhibit moisture management properties, while also imparting a smooth and drapey hand feel. There is sex. Currently, most softeners have two problems: (i) many of them are oil-based, so their hydrophobic character inhibits water absorption; and (ii) many softeners are Derived from petrochemical sources, raising waste concerns and sustainability issues. Despite the relatively large number of polymeric and oil-based products available that enhance both the hand and moisture management capabilities of fibers, the selection of softeners with 100% bio-based origin is limited. Therefore, there is a need to develop a 100% bio-based natural softener that does not interfere with the moisture management properties of the fiber and imparts good hand when combined with a wicking agent.

While not wishing to be bound by any particular theory, the system described herein is based on a combination of activated silk acting as an emulsifier and softening agent, with activated silk acting as a moisture wicking agent. Contains a mixture of ethoxylated monooleate and trioleate fatty acids and hydroxy fatty acids with an average HLB value of 12.1 (calculated using Equation 1). In this system, variations in the ratio of fatty acids to hydroxy fatty acids give varying HLB values (as seen in Table 2). This, in turn, changes the wash fastness and softening ability of the coating.

Coating of Nylon Fibers The emulsified mixture of surfactants was 2:4: polyoxyethylene (20) sorbitan monooleate, polyoxyethylene (20) sorbitan trioleate, polyoxyethylene (29) castor oil, and water. It is prepared by combining in a ratio (mass ratio) of 8:10. The mixture is then sonicated for 3 hours.

A solution of wicking agent is then prepared by adding Activated Silk™ moisture management agent at a concentration of 1 g/L to the water. The solution pH is then adjusted to 4.5-5 using acetic acid.

After the wicking agent solution is made, the surfactant emulsion mixture is then added to the solution in the mass ratio defined in Table 1.

The solution is applied to the fibers through a padding and curing method with a padding speed of 3 meters/min and a wet pick-up of 50% controlled by roller pressure.

The fibers are then cured in a drying oven at 160° C. for 1.5 to 3 minutes depending on the fiber and allowed to equilibrate overnight.

Coating of Polyester Fibers The emulsified mixture of surfactants was 2:4: polyoxyethylene (20) sorbitan monooleate, polyoxyethylene (20) sorbitan trioleate, polyoxyethylene (29) castor oil, and water. It is prepared by combining in a ratio (mass ratio) of 8:10. The mixture is then sonicated for 3 hours.

A solution of wicking agent is then prepared by adding Activated Silk™ moisture management agent at a concentration of 1 g/L to the water. The solution pH is then adjusted to 4.5-5 using acetic acid.

After the wicking agent solution is made, the surfactant emulsion mixture is then added to the solution in the mass ratio defined in Table 1.

The solution is applied to the fibers through a padding and curing method with a padding speed of 3 meters/min and a wet pick-up of 50% controlled by roller pressure.

The fibers are then cured in a 135° C. drying oven for 1-2 minutes depending on the fiber and allowed to equilibrate overnight.

Test Methods Fiber Performance All samples were tested for hand feel using a panel of N=3 judges and compared based on the factors of drapeability (ease of deformation of the fiber when acted upon by the user) and smoothness (apparent roughness of the fiber when rubbed by the user's hand). This test follows a method defined by the in-house method. Moisture management inhibition was also tested using a water absorption test defined by the in-house method.

Silk wash fastness Quantification of silk deposited on surfaces was measured using UV/vis absorbance. A standard curve was constructed using various concentrations of silk in water. The absorbance at the 276 nm wavelength (tyrosine absorption peak) was then measured and a linear curve was generated correlating absorbance to solution concentration.

Testing the mass of silk remaining on the fiber. The fiber was soaked overnight in 7.6 M LiBr solution under sonication. The fiber was then removed from the solution and the UV/Vis absorbance of the solution was measured to obtain a measure of the silk concentration in the solution. Using the volume of the solution, the concentration of silk in the solution, and the mass of the fiber, it is possible to calculate the mass of silk remaining on the fiber.

Test Results Surfactant System HLB Adjustment Concentration with Low Weight Silk From the moisture management data, the optimum concentration for minimum absorption time is 2 g/L polyoxyethylene (29) castor oil (mixture HLB: 12.39). However, as the concentration increases up to 16 g/L (mixture HLB: 11.94), there is only an average increase of 17% in absorption time, and no fibers fail to meet the maximum criterion of 2 seconds absorption time (Fig. 5). . From a hand feel perspective, the hand feeling generally improves as the concentration of polyoxyethylene (29) castor oil increases (Figure 6).

Figure 5. No-wash hygroscopicity curves generated by varying the concentration of polyoxyethylene (29) castor oil in the emulsifier mixture (thereby varying the HLB) before addition to the coating solution. Note that in all samples, the silk concentration in the coating solution was 1 g/L.

Figure 6. No-wash hand-feel ranking curves generated by varying the concentration of polyoxyethylene (29) castor oil in the emulsifier mixture (thereby varying the HLB) before adding it to the coating solution. Note that the silk concentration in the coating solution is 1 g/L for all samples.

Surfactant System Concentration Test As seen in Figure 5, moisture management data from 0 to 25 washes for all tested polyester and nylon fibers coated with wicking agents and natural softeners. Shows negligible degradation in performance. The data show that all fibers except Jintex Green had absorption times of less than 3 seconds from 0 to 25 washes (Figures 7A-7D).

As seen in Figure 6, in terms of hand performance improvement, at 0 washes, there is a clear improvement in the hand of the fiber as the concentration of natural softener increases. There is a slight degradation in performance after washing, but there is also an improvement after 5, 10, and 25 washes (Figure 8).

Figures 7A-7D illustrate the emulsion mixture (2:4:8:10 ratio of polyoxyethylene (20) sorbitan monooleate, polyoxyethylene (20) sorbitan trioleate, polyoxyethylene (20) sorbitan trioleate, polyoxyethylene (20) in the final coating solution. 29) No wash (Fig. 7A), 5 washes (Fig. 7B), 10 washes (Fig. 7C), and 25 washes (Fig. 7C) produced by varying the concentrations of castor oil, and water). Figure 7D is a chart showing the moisture management data of Figure 7D), where the silk concentration in the coating solution was 1 g/L for all samples.

Figures 8A-8D illustrate the emulsion mixture (2:4:8:10 ratio of polyoxyethylene (20) sorbitan monooleate, polyoxyethylene (20) sorbitan trioleate, polyoxyethylene (20) sorbitan trioleate, polyoxyethylene (20) in the final coating solution. 29) No wash (Fig. 8A), 5 washes (Fig. 8B), 10 washes (Fig. 8C), and 25 washes (Fig. 8C) produced by varying the concentrations of castor oil, and water). Figure 8D) is a chart showing the feel ranking results of Figure 8D), where 1 is the highest score and 8 is the lowest feel ranking score, and the silk concentration in the solution is 1 g/L for all samples.

Polyoxyethylene (20) Sorbitan Monooleate with Medium Weight Silk From the moisture management data, there is little variation in absorption time with increasing medium weight silk. Without wishing to be bound by any particular theory, the absorption time of medium weight silk is generally higher than its lighter weight counterpart. With 20 g/L low molecular weight silk, there is only one fiber that exceeds the 2 second cutoff criterion. However, even with 0 washes, there is still one fiber passing through this point. This behavior only worsens as the number of washes increases when comparing the same fibers between low and medium weight silks (FIGS. 10A-10D).

Similar to the moisture management data, from a feel perspective there appears to be no discernible trend due to increased medium weight silk in the coating solution (Figures 9A-9D).

Figures 9A-9D show no wash (Figure 9A), 5 washes (Figure 9B), and 10 washes (Figure 9C) produced by varying the concentration of medium molecular weight silk in the final coating solution. and 25 washes (FIG. 9D), where 1 is the highest rank and 8 is the lowest rank.

Figures 10A-10D show no wash (Figure 10A), 5 washes (Figure 10B), and 10 washes (Figure 10C) produced by varying the concentration of medium molecular weight silk in the final coating solution. , and moisture management results from 25 washes (FIG. 10D).

Quantification of silk on nylon fibers Using UV/Vis absorbance, the concentration of silk in solution can be measured by measuring the absorbance of the 276 nm peak of the silk spectrum. A standard curve was made through serial dilutions of the stock solution to quantify the amount of silk remaining on the fiber. After measuring the absorbance of each solution, a linear curve was fitted, allowing for conversion of solution absorbance to solution concentration. Silk can be removed from silk-coated fibers by sonicating the samples in 9M LiBr solution for 3 hours. The remaining silk solution can then be measured to quantify the amount of silk removed from the fiber. To determine fiber surface area, microscopy was performed on the filament cross-section of each fiber to obtain the fiber denier, after which the surface area was calculated.

As can be seen in Figure 1 ID, silk is still present on the fibers after washing, but the amount is reduced. When comparing the percent silk mass per sample, increasing fiber surface area appears to increase silk mass loss from the fibers (FIG. 11A). However, the opposite can be said for silk incorporation on fibers. The increase in fiber surface area appears to correlate with less incorporation of silk on the fibers (FIG. 11B). Without wishing to be bound by any particular theory, it is believed that there is a correlation between the adhesion of silk to the fiber and the surface of the fiber.

FIGS. 11A-11D are graphs showing UV/Vis quantification experiments of low molecular weight activated silk and fibers coated with polyoxyethylene (20) monooleate solution. FIG. 11A: Graph showing the percentage of silk lost after 5 washes in terms of fiber surface area. FIG. 11B: Graph showing quantified mass of silk on fibers after coating in terms of fiber surface area. FIG. 11C: Graph showing the percentage of silk lost after 5 washes with respect to fiber type. FIG. 11D: Graph showing the silk mass quantified in each fiber before and after 5 washes, depending on fiber type.

FIG. 12 is a chart showing UV/Vis quantification experiments of low molecular weight activated silk and fibers coated with polyoxyethylene (20) monooleate solution. The graph shows the quantified mass of silk on the fiber after coating in terms of fiber mass in grams per cubic meter (GSM). This mass depends on the knit type, fiber content, and filament denier.

Silk Surface Charge Test Potentiometric titrations were performed on silk coated nylon fibers, Archroma RPU coated fibers, and nylon fiber controls. Different nylon fibers were coated in a solution of Activated Silk (20 g/L) and polyoxyethylene (20) sorbitan monooleate (2 g/L) or in a solution containing 2% Archroma RPU fluid. Each fiber sample was washed in a front loading washing machine using AATCC non-softening non-bleach detergent for 5 washes. In the titration process, 0.1 M sodium chloride was used as the counterion and hydrochloric acid or sodium hydroxide was used as the titrant.

The resulting titration curves are shown in Figures 13A-13C for the silk-coated fibers (ΔC = -0.00316Cg ^-1 ) and for the untreated fibers (ΔC = 0.00008Cg ^-1 ). ) or Archroma RPU liquid (ΔC=0.00055Cg ⁻¹ ) at pH 5. While not wishing to be bound by any particular theory, this suggests that after washing, the silk-coated surface had a higher concentration than the untreated control or the positively charged Archroma RPU-coated fibers. Indicates that it is negatively charged.

Figures 13A-13C show unprocessed weight double knit nylon fibers (Figure 13A), weight double knit nylon fibers with an activated silk finish (Figure 13B), and weight double knit nylon fibers with an Archroma RPU humectant finish (Figure 13B). For Figure 13C), we include a series of charts showing potentiometric titration curves where charge density was measured at pH 5. Each fiber has a titration curve obtained without washing (FIGS. 13A-13C, left panel) and with five washes (FIGS. 13A-13C, right panel). The change in charge density at pH 5 after washing is shown as ΔC.

Claims (56)

An article comprising a fiber and a coating, the coating comprising a surfactant and/or emulsifier system and silk fibroin fragments of about 1 kDa to about 5 kDa, about 5 kDa to about 10 kDa, about 6 kDa to about 17 kDa, about 10kDa to about 15kDa, about 14kDa to about 30kDa, about 15kDa to about 20kDa, about 17kDa to about 39kDa, about 20kDa to about 25kDa, about 25kDa to about 30kDa, about 30kDa to about 35kDa, about 35kDa to about 40kDa, about 39kDa to about An average selected from about 54 kDa, about 39 kDa to about 80 kDa, about 40 kDa to about 45 kDa, about 45 kDa to about 50 kDa, about 50 kDa to about 55 kDa, about 55 kDa to about 60 kDa, about 60 kDa to about 100 kDa, or about 80 kDa to about 144 kDa. Silk fibroin fragments having a weight average molecular weight and a polydispersity ranging from 1 to about 5. The silk fibroin fragment has a particle size of 1 to about 1.5, about 1.5 to about 2.0, about 2.0 to about 2.5, about 2.5 to about 3.0, about 3.0 to about 3 5. The article of claim 1, having a polydispersity of .5, about 3.5 to about 4.0, about 4.0 to about 4.5, or about 4.5 to about 5.0. The article of claim 1, wherein the silk fibroin fragments have a polydispersity of about 1.5 to about 3.0. 2. The article of claim 1, wherein the silk fibroin fragments include one or more of low molecular weight silk fibroin fragments and medium molecular weight silk fibroin fragments. 5. The article of any one of claims 1-4, further comprising from about 0.01% (w/w) to about 10% (w/w) sericin relative to the silk fibroin fragment. The fibers may be polyester, polyamide, polyaramid, polytetrafluoroethylene, polyethylene, polypropylene, polyurethane, silicone, a mixture of polyurethane and polyethylene glycol, ultra-high molecular weight polyethylene, high performance polyethylene, nylon, LYCRA (polyester-polyurethane copolymer, SPANDEX). An article according to any one of claims 1 to 5, comprising one or more of the following: (also known as elastomers and elastomers), or mixtures thereof. An article according to any preceding claim, wherein the coating further comprises one or more of a wetting agent, an antifoaming agent, a softening agent, a wicking agent, and an antimicrobial agent. The w/w ratio of silk fibroin fragments to the surfactant and/or emulsifier system in the coating is about 99:1, about 98:2, about 97:3, about 96:4, about 95:5, about 94:6, approximately 93:7, approximately 92:8, approximately 91:9, approximately 90:10, approximately 89:11, approximately 88:12, approximately 87:13, approximately 86:14, approximately 85:15, approximately 84:16, approximately 83:17, approximately 82:18, approximately 81:19, approximately 80:20, approximately 79:21, approximately 78:22, approximately 77:23, approximately 76:24, approximately 75:25, approximately 74:26, about 73:27, about 72:28, about 71:29, about 70:30, about 69:31, about 68:32, about 67:33, about 66:34, about 65:35, about 64:36, about 63:37, about 62:38, about 61:39, about 60:40, about 59:41, about 58:42, about 57:43, about 56:44, about 55:45, about 54:46, about 53:47, about 52:48, about 51:49, about 50:50, about 49:51, about 48:52, about 47:53, about 46:54, about 45:55, about 44:56, about 43:57, about 42:58, about 41:59, about 40:60, about 39:61, about 38:62, about 37:63, about 36:64, about 35:65, about 34:66, about 33:67, about 32:68, about 31:69, about 30:70, about 29:71, about 28:72, about 27:73, about 26:74, about 25:75, about 24:76, approximately 23:77, approximately 22:78, approximately 21:79, approximately 20:80, approximately 19:81, approximately 18:82, approximately 17:83, approximately 16:84, approximately 15:85, approximately 14:86, about 13:87, about 12:88, about 11:89, about 10:90, about 9:91, about 8:92, about 7:93, about 6:94, about 5:95, about 8. An article according to any one of claims 1 to 7, which is 4:96, about 3:97, about 2:98, or about 1:99. The w/w ratio of silk fibroin fragments to the surfactant and/or emulsifier in the coating is about 1:1, about 1:2, about 1:4, about 1:8, about 1:16, or about 1:32. Article according to any one of claims 1 to 7. The w/w ratio of silk fibroin fragments to the surfactant and/or emulsifier system in the coating is about 1:1, about 1:2, about 1:3, about 1:4, about 1:5, about 1:6, about 1:7, about 1:8, about 1:9, about 1:10, about 1:11, about 1:12, about 1:13, about 1:14, about 1:15, about 1:16, about 1:17, about 1:18, about 1:19, about 1:20, about 1:21, about 1:22, about 1:23, about 1:24, about 1:25, about 1:26, about 1:27, about 1:28, about 1:29, about 1:30, about 1:31, or about 1:32. Goods. The article of any one of claims 1 to 10, wherein the surfactant and/or emulsifier system comprises one or more of polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, polyoxyethylene castor oil, and any combination thereof. The surfactant and/or emulsifier system may include polyoxyethylene (10-30) sorbitan monooleate, polyoxyethylene (10-30) sorbitan trioleate, polyoxyethylene (10-50) castor oil, and the like. Article according to any one of claims 1 to 10, comprising one or more of any combination. The surfactant and/or emulsifier system may include polyoxyethylene (20) sorbitan monooleate, polyoxyethylene (20) sorbitan trioleate, polyoxyethylene (29) castor oil, and any combination thereof. An article according to any one of claims 1 to 10, comprising one or more. The surfactant and/or emulsifier system is polyoxyethylene (20) sorbitan monolaurate, polyoxyethylene (20) sorbitan monopalmitate, polyoxyethylene (20) sorbitan monostearate, polyoxyethylene (20) An article according to any one of claims 1 to 10, comprising one or more of sorbitan tristearate, and any combination thereof. 11. The surfactant and/or emulsifier system comprises one or more of sorbitan mono-fatty acids, sorbitan tri-fatty acids, castor oil, and any combination thereof. Goods. the surfactant and/or emulsifier system comprises one or more of coco glucoside, decyl glucoside, lauryl glucoside, coconut sucrose, caprylic/caprylyl glucoside, caprylyl/capryl glucoside, and any combination thereof; Article according to any one of claims 1 to 15. 17. An article according to any preceding claim, wherein the surfactant and/or emulsifier system has an HLB of about 11 to about 13.50. The surfactant and/or emulsifier system has a molecular weight of about 11 to about 11.50, about 11.50 to about 12, about 12 to about 12.50, about 12.50 to about 13, or about 13 to about 13. 17. Article according to any one of claims 1 to 16, having an HLB of 50. An article according to any preceding claim, wherein the article has improved moisture management compared to a similar article comprising similar fibers but without a coating. The article of claim 19, wherein moisture management is evaluated by a water absorption test, a vertical wicking test, or a drying rate test. 21. An article according to any preceding claim, wherein the article has improved drapability compared to a similar article comprising similar fibers but without a coating. An article according to any preceding claim, wherein the article has improved smoothness compared to a similar article comprising similar fibers but without a coating. The article of any one of claims 1 to 22, wherein the article has improved hand feel compared to a similar article containing similar fibers but without a coating. The article of any one of claims 1 to 23, wherein the article has a lower charge density at a given pH value compared to a similar article comprising similar fibers but not comprising a coating. 1. A method of making a silk fibroin coated fiber, comprising:
applying a solution comprising a surfactant and/or emulsifier system to the fibers;
applying a silk fibroin fragment solution to the fibers;
and drying the fibers. 1. A method of making a silk fibroin coated fiber, comprising:
applying a solution comprising a surfactant and/or emulsifier system and silk fibroin fragments to the fibers;
and drying the fibers. 27. The method of claim 25 or 26, wherein the concentration of the silk fibroin fragments in solution ranges from 0.01 g/L to about 100 g/L. 28. A method according to any one of claims 25 to 27, wherein the concentration of the surfactant and/or emulsifier system in solution ranges from 0.01 g/L to about 100 g/L. The silk fibroin fragment is about 1 kDa to about 5 kDa, about 5 kDa to about 10 kDa, about 6 kDa to about 17 kDa, about 10 kDa to about 15 kDa, about 14 kDa to about 30 kDa, about 15 kDa to about 20 kDa, about 17 kDa to about 39 kDa, about 20 kDa ~about 25kDa, about 25kDa to about 30kDa, about 30kDa to about 35kDa, about 35kDa to about 40kDa, about 39kDa to about 54kDa, about 39kDa to about 80kDa, about 40kDa to about 45kDa, about 45kDa to about 50kDa, about 50kDa to about 29. Any of claims 25-28 having an average weight average molecular weight selected from 55 kDa, about 55 kDa to about 60 kDa, about 60 kDa to about 100 kDa, or about 80 kDa to about 144 kDa, and a polydispersity ranging from 1 to about 5. The method described in paragraph (1). The silk fibroin fragment has a particle size of 1 to about 1.5, about 1.5 to about 2.0, about 2.0 to about 2.5, about 2.5 to about 3.0, about 3.0 to about 3 .5, about 3.5 to about 4.0, about 4.0 to about 4.5, or about 4.5 to about 5.0. The method described in. 30. The method of any one of claims 25-29, wherein the silk fibroin fragments have a polydispersity of about 1.5 to about 3.0. 30. The method of any one of claims 25-29, wherein the silk fibroin fragments comprise one or more of low molecular weight silk fibroin fragments and medium molecular weight silk fibroin fragments. 33. The method of any one of claims 25-32, wherein the solution further comprises about 0.01% (w/w) to about 10% (w/w) sericin relative to the silk fibroin fragments. The fibers may be polyester, polyamide, polyaramid, polytetrafluoroethylene, polyethylene, polypropylene, polyurethane, silicone, a mixture of polyurethane and polyethylene glycol, ultra-high molecular weight polyethylene, high performance polyethylene, nylon, LYCRA (polyester-polyurethane copolymer, SPANDEX). and elastomers), or mixtures thereof. 35. A method according to any one of claims 25 to 34, wherein the solution further comprises one or more of a wetting agent, an antifoaming agent, a softening agent, a wicking agent, and an antimicrobial agent. the w/w ratio of silk fibroin fragments to the surfactant and/or emulsifier system is about 99:1, about 98:2, about 97:3, about 96:4, about 95:5, about 94:6, Approximately 93:7, approximately 92:8, approximately 91:9, approximately 90:10, approximately 89:11, approximately 88:12, approximately 87:13, approximately 86:14, approximately 85:15, approximately 84:16, Approximately 83:17, approximately 82:18, approximately 81:19, approximately 80:20, approximately 79:21, approximately 78:22, approximately 77:23, approximately 76:24, approximately 75:25, approximately 74:26, Approximately 73:27, approximately 72:28, approximately 71:29, approximately 70:30, approximately 69:31, approximately 68:32, approximately 67:33, approximately 66:34, approximately 65:35, approximately 64:36, approximately 63:37, approximately 62:38, approximately 61:39, approximately 60:40, approximately 59:41, approximately 58:42, approximately 57:43, approximately 56:44, approximately 55:45, approximately 54:46, Approximately 53:47, approximately 52:48, approximately 51:49, approximately 50:50, approximately 49:51, approximately 48:52, approximately 47:53, approximately 46:54, approximately 45:55, approximately 44:56, Approximately 43:57, approximately 42:58, approximately 41:59, approximately 40:60, approximately 39:61, approximately 38:62, approximately 37:63, approximately 36:64, approximately 35:65, approximately 34:66, Approximately 33:67, approximately 32:68, approximately 31:69, approximately 30:70, approximately 29:71, approximately 28:72, approximately 27:73, approximately 26:74, approximately 25:75, approximately 24:76, Approximately 23:77, approximately 22:78, approximately 21:79, approximately 20:80, approximately 19:81, approximately 18:82, approximately 17:83, approximately 16:84, approximately 15:85, approximately 14:86, Approximately 13:87, approximately 12:88, approximately 11:89, approximately 10:90, approximately 9:91, approximately 8:92, approximately 7:93, approximately 6:94, approximately 5:95, approximately 4:96, 36. The method of any one of claims 25-35, wherein the ratio is about 3:97, about 2:98, or about 1:99. The w/w ratio of silk fibroin fragments to the surfactant and/or emulsifier system is about 1:1, about 1:2, about 1:4, about 1:8, about 1:16, or about 1:32. The method according to any one of claims 25 to 35. the w/w ratio of silk fibroin fragments to the surfactant and/or emulsifier system is about 1:1, about 1:2, about 1:3, about 1:4, about 1:5, about 1:6, about 1:7, about 1:8, about 1:9, about 1:10, about 1:11, about 1:12, about 1:13, about 1:14, about 1:15, about 1:16, Approximately 1:17, approximately 1:18, approximately 1:19, approximately 1:20, approximately 1:21, approximately 1:22, approximately 1:23, approximately 1:24, approximately 1:25, approximately 1:26, 36. The method of any one of claims 25-35, wherein the ratio is about 1:27, about 1:28, about 1:29, about 1:30, about 1:31, or about 1:32. 25. The surfactant and/or emulsifier system comprises one or more of polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, polyoxyethylene castor oil, and any combinations thereof. 39. The method according to any one of items 38 to 38. The surfactant and/or emulsifier system may include polyoxyethylene (10-30) sorbitan monooleate, polyoxyethylene (10-30) sorbitan trioleate, polyoxyethylene (10-50) castor oil, and the like. 39. A method according to any one of claims 25 to 38, comprising one or more of any combination. The surfactant and/or emulsifier system may include polyoxyethylene (20) sorbitan monooleate, polyoxyethylene (20) sorbitan trioleate, polyoxyethylene (29) castor oil, and any combination thereof. 39. A method according to any one of claims 25 to 38, comprising one or more. The method of any one of claims 25 to 38, wherein the surfactant and/or emulsifier system comprises one or more of polyoxyethylene (20) sorbitan monolaurate, polyoxyethylene (20) sorbitan monopalmitate, polyoxyethylene (20) sorbitan monostearate, polyoxyethylene (20) sorbitan tristearate, and any combination thereof. 39. According to any one of claims 25 to 38, the surfactant and/or emulsifier system comprises one or more of sorbitan monofatty acids, sorbitan trifatty acids, castor oil, and any combinations thereof. Method. the surfactant and/or emulsifier system comprises one or more of coco glucoside, decyl glucoside, lauryl glucoside, coconut sucrose, caprylic/caprylyl glucoside, caprylyl/capryl glucoside, and any combination thereof; A method according to any one of claims 25 to 43. 45. The method of any one of claims 25-44, wherein the surfactant and/or emulsifier system has an HLB of about 11 to about 13.50. The surfactant and/or emulsifier system has a molecular weight of about 11 to about 11.50, about 11.50 to about 12, about 12 to about 12.50, about 12.50 to about 13, or about 13 to about 13. 45. A method according to any one of claims 25 to 44, having an HLB of 50. 47. A method according to any one of claims 25 to 46, wherein said drying comprises heating. 48. A method according to any one of claims 25 to 47, wherein the pH of the solution is acidic. 5. The solution has a pH of about 3.5 to about 4, about 4 to about 4.5, about 4.5 to about 5, about 5 to about 5.5, or about 5.5 to about 6. 48. The method according to any one of 25 to 47. An article prepared by a method according to any one of claims 25-49. 51. The article of claim 50, wherein the article has improved moisture management compared to a similar article comprising similar fibers but no coating. 52. The article of claim 51, wherein moisture management is assessed by a water absorption test, a vertical wicking test, or a drying rate test. 53. An article according to any one of claims 50 to 52, wherein the article has improved drapability compared to a similar article comprising similar fibers but without a coating. 54. An article according to any one of claims 50 to 53, wherein the article has improved smoothness compared to a similar article comprising similar fibers but without a coating. The article of any one of claims 50 to 54, wherein the article has improved hand feel compared to a similar article containing similar fibers but not containing a coating. 56. An article according to any one of claims 50 to 55, wherein the article has a lower charge density at a given pH value compared to a similar article comprising similar fibers but without a coating.