CN118076776A - Silk-coated synthetic fabric - Google Patents

Silk-coated synthetic fabric Download PDF

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Publication number
CN118076776A
CN118076776A CN202280035273.2A CN202280035273A CN118076776A CN 118076776 A CN118076776 A CN 118076776A CN 202280035273 A CN202280035273 A CN 202280035273A CN 118076776 A CN118076776 A CN 118076776A
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China
Prior art keywords
silk
solution
spf
article
fibroin
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CN202280035273.2A
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Inventor
费秀竹
E·摩尔塔里诺
G·H·奥特曼
L·穆洛
M·汤加
J·戴维斯
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Natural Evolution Co
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Natural Evolution Co
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Priority claimed from PCT/US2022/020651 external-priority patent/WO2022197871A1/en
Publication of CN118076776A publication Critical patent/CN118076776A/en
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Abstract

The present disclosure provides novel fibroin coated articles and methods of making the same.

Description

Silk-coated synthetic fabric
Cross Reference to Related Applications
The present application claims the benefit of U.S. provisional patent application 63/161,929 filed on day 3, month 16 of 2021 and U.S. provisional patent application 63/319,765 filed on day 3, month 14 of 2022, each of which is incorporated herein by reference in its entirety.
Technical Field
The present disclosure is in the field of synthetic fabrics coated with fibroin and protein fragments.
Background
Silk is a natural polymer produced by a variety of insects and arachnids and comprises silk core proteins, silk fibroin and a gelatinous coating consisting of non-filiform proteins, sericin. The silk fiber has the characteristics of light weight, ventilation and low sensitization. The silk is comfortable when worn next to the skin and has good insulation property; the wearer is kept warm at cold temperatures and is cooler than many other fabrics at warm temperatures.
Disclosure of Invention
The present disclosure provides an article comprising a fabric and a coating, wherein the coating comprises a surfactant and/or emulsifier system, and a fibroin fragment having a molecular weight selected from the group consisting of about 1kDa to about 5kDa, about 5kDa to about 10kDa, about 6kDa 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, An average weight average molecular weight of about 39kDa to about 54kDa, about 39kDa to about 80kDa, about 40kDa to about 45kDa, about 45kDa to about 50kDa, about 50kDa to about 55kDa, about 55kDa to about 60kDa, about 60kDa to about 100kDa or about 80kDa to about 144kDa, and a polydispersity in the range of 1 to about 5. In some embodiments, the fibroin fragments have a polydispersity 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. In some embodiments, the fibroin fragments have a polydispersity of about 1.5 to about 3.0. In some embodiments, the fibroin fragments include one or more of low molecular weight fibroin fragments and medium molecular weight 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 fabric comprises one or more of the following: polyesters, polyamides, polyaramides, polytetrafluoroethylene, polyethylene, polypropylene, polyurethane, silicone, a mixture of polyurethane and polyethylene glycol, ultra high molecular weight polyethylene, high performance polyethylene, nylon, LYCRA (polyester-polyurethane copolymers, also known as span and elastomers), or mixtures thereof. In some embodiments, the coating further comprises 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 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, 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, 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 49:33, 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 52:48:48, 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 33:67, about 32:68, 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 fibroin fragments in the coating to the surfactant and/or emulsifier 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 fibroin fragments in the coating 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, 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 comprises one or more of the following: polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, polyoxyethylene castor oil, and any combination thereof. In some embodiments, the surfactant and/or emulsifier system comprises one or more of the following: polyoxyethylene (10-30) sorbitan monooleate, polyoxyethylene (10-30) sorbitan trioleate, polyoxyethylene (10-50) castor oil, and any combination thereof. In some embodiments, the surfactant and/or emulsifier system comprises one or more of the following: polyoxyethylene (20) sorbitan monooleate, polyoxyethylene (20) sorbitan trioleate, polyoxyethylene (29) castor oil, and any combination thereof. In some embodiments, the surfactant and/or emulsifier system comprises one or more of the following: 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 comprises one or more of the following: sorbitan mono fatty acid, sorbitan tri fatty acid, castor oil, and any combination thereof. In some embodiments, the surfactant and/or emulsifier system comprises one or more of the following: cocoyl glucoside, decyl glucoside, lauryl glucoside, sucrose cocoate, octyl/octanoyl glucoside, octanoyl/octyl glucoside, and any combination thereof. In some embodiments, the surfactant and/or emulsifier system has an HLB of from about 11 to about 13.50. In some embodiments, the surfactant and/or emulsifier system has an HLB of from about 11 to about 11.50, from about 11.50 to about 12, from about 12 to about 12.50, from about 12.50 to about 13, or from about 13 to about 13.50. In some embodiments, the article has improved moisture management compared to a similar article comprising a similar fabric but without the coating. In some embodiments, moisture management is assessed by a absorbency test, a vertical wicking test, or a drying rate test. In some embodiments, the article has improved drape as compared to a similar article comprising a similar fabric but without the coating. In some embodiments, the article has improved smoothness compared to a similar article comprising a similar fabric but without the coating. In some embodiments, the article has an improved hand as compared to a similar article comprising a similar fabric but without the coating. In some embodiments, the article has a lower charge density at a given pH value than a similar article comprising a similar fabric but without the coating.
The present disclosure provides a method of preparing a fibroin coated fabric, the method comprising: applying a solution comprising a surfactant and/or emulsifier system to the fabric; applying a fibroin fragment solution to the fabric; and drying the fabric. The present disclosure also provides a method of preparing a fibroin coated fabric, the method comprising: applying a solution comprising a surfactant and/or emulsifier system and a fibroin fragment to the fabric; and drying the fabric. In some embodiments, the concentration of the fibroin fragments in the solution ranges from 0.01g/L to about 100g/L. In some embodiments, the concentration of the surfactant and/or emulsifier system in the solution ranges from 0.01g/L to about 100g/L. In some embodiments, the fibroin fragment has a molecular weight selected from the group consisting of about 1kDa to about 5kDa, about 5kDa to about 10kDa, about 6kDa 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, about 39kDa to about 54kDa, about 39kDa to about 80kDa, about 40kDa to about 45kDa, An average weight average molecular weight of about 45kDa to about 50kDa, about 50kDa to about 55kDa, about 55kDa to about 60kDa, about 60kDa to about 100kDa or about 80kDa to about 144kDa, and a polydispersity in the range of 1 to about 5. In some embodiments, the fibroin fragments have a polydispersity 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. In some embodiments, the fibroin fragments have a polydispersity of about 1.5 to about 3.0. In some embodiments, the fibroin fragments include one or more of low molecular weight fibroin fragments and medium molecular weight fibroin fragments. In some embodiments, the solution further comprises about 0.01% (w/w) to about 10% (w/w) of sericin relative to the silk fibroin fragment. In some embodiments, the fabric comprises one or more of the following: polyesters, polyamides, polyaramides, polytetrafluoroethylene, polyethylene, polypropylene, polyurethane, silicone, a mixture of polyurethane and polyethylene glycol, ultra high molecular weight polyethylene, high performance polyethylene, nylon, LYCRA (polyester-polyurethane copolymers, also known as span and elastomers), or mixtures thereof. In some embodiments, the solution further comprises 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 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, 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, 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 49:33, 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 52:48:48, 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 33:67, about 32:68, 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 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. In some embodiments, the w/w ratio of 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, 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 comprises one or more of the following: polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, polyoxyethylene castor oil, and any combination thereof. In some embodiments, the surfactant and/or emulsifier system comprises one or more of the following: polyoxyethylene (10-30) sorbitan monooleate, polyoxyethylene (10-30) sorbitan trioleate, polyoxyethylene (10-50) castor oil, and any combination thereof. In some embodiments, the surfactant and/or emulsifier system comprises one or more of the following: polyoxyethylene (20) sorbitan monooleate, polyoxyethylene (20) sorbitan trioleate, polyoxyethylene (29) castor oil, and any combination thereof. In some embodiments, the surfactant and/or emulsifier system comprises one or more of the following: 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 comprises one or more of the following: sorbitan mono fatty acid, sorbitan tri fatty acid, castor oil, and any combination thereof. In some embodiments, the surfactant and/or emulsifier system comprises one or more of the following: cocoyl glucoside, decyl glucoside, lauryl glucoside, sucrose cocoate, octyl/octanoyl glucoside, octanoyl/octyl glucoside, and any combination thereof. In some embodiments, the surfactant and/or emulsifier system has an HLB of from about 11 to about 13.50. In some embodiments, the surfactant and/or emulsifier system has an HLB of from about 11 to about 11.50, from about 11.50 to about 12, from about 12 to about 12.50, from about 12.50 to about 13, or from about 13 to about 13.50. In some embodiments, the drying comprises heating. In some embodiments, the pH of the solution is acidic. In some embodiments, the pH of the solution is from about 3.5 to about 4, from about 4 to about 4.5, from about 4.5 to about 5, from about 5 to about 5.5, or from about 5.5 to about 6.
The present disclosure also provides an article of manufacture made by the methods described herein. Any one of claims 25 to 49. In some embodiments, the article has improved moisture management compared to a similar article comprising a similar fabric but without the coating. In some embodiments, moisture management is assessed by a absorbency test, a vertical wicking test, or a drying rate test. In some embodiments, the article has improved drape as compared to a similar article comprising a similar fabric but without the coating. In some embodiments, the article has improved smoothness compared to a similar article comprising a similar fabric but without the coating. In some embodiments, the article has an improved hand as compared to a similar article comprising a similar fabric but without the coating. In some embodiments, the article has a lower charge density at a given pH value than a similar article comprising a similar fabric but without the coating.
Drawings
FIG. 1 is a flow chart showing various embodiments for producing a fibroin fragment (SPF) of the present disclosure.
Fig. 2 is a flow chart showing various parameters that may be modified during the process of producing silk protein fragment solutions of the present disclosure during the extraction and solubilization steps.
FIG. 3 is a chart showing the absorbency of ACTIVATED SILK (active filaments) TM with an octyl/octanoyl glucoside coating on various interlocking nylon fabrics; the unfinished nylon interlocking fabric cannot absorb moisture due to poor absorbency; the absorbency of all nylon interlocking fabrics increases significantly after the reactive filaments TM are coated with an octyl/octanoyl glucoside coating.
FIG. 4 is a chart showing the absorbency of reactive filaments TM with octyl/octanoyl glucoside coating on various nylon fabrics in addition to interlocking structures; the unfinished nylon fabric cannot absorb moisture or is poor in absorbency; after coating the active filaments TM with an octyl/octanoyl glucoside coating, the absorbency of all nylon fabrics was significantly increased.
Fig. 5 is a graph showing unwashed water absorption profile produced by varying the concentration of polyoxyethylene (29) castor oil (and thus the HLB) in the emulsifier mixture prior to addition to the coating solution. The silk concentration in the coating solution was 1g/L in all samples.
Fig. 6 is a graph showing the unwashed hand feel rating curve produced by varying the concentration of polyoxyethylene (29) castor oil (and thus the HLB) in the emulsifier mixture prior to addition to the coating solution. The silk concentration in the coating solution was 1g/L in all samples.
Fig. 7A-7D are graphs showing the moisture management data of unwashed (fig. 7A), 5 washes (fig. 7B), 10 washes (fig. 7C), and 25 washes (fig. 7D) produced by varying the concentration of the emulsion mixture (polyoxyethylene (20) sorbitan monooleate, polyoxyethylene (20) sorbitan trioleate, polyoxyethylene (29) castor oil, and water in a ratio of 2:4:8:10) in the final coating solution; the silk concentration in the coating solution was 1g/L in all samples.
Fig. 8A-8D are graphs showing the hand feel grade results of unwashed (fig. 8A), 5 washes (fig. 8B), 10 washes (fig. 8C), and 25 washes (fig. 8D) produced by varying the concentration of the emulsion mixture (polyoxyethylene (20) sorbitan monooleate, polyoxyethylene (20) sorbitan trioleate, polyoxyethylene (29) castor oil, and water in a ratio of 2:4:8:10) in the final coating solution; 1 is the best hand feel grade fraction, 8 is the worst hand feel grade fraction; the silk concentration in the solution was 1g/L in all samples.
Fig. 9A-9D are graphs showing hand scale results for unwashed (fig. 9A), 5 washes (fig. 9B), 10 washes (fig. 9C), and 25 washes (fig. 9D) produced by varying the concentration of medium molecular weight filaments in the final coating solution; 1 is the best grade, 8 is the worst grade
Fig. 10A-10D are graphs showing the moisture management results of unwashed (fig. 10A), 5 washes (fig. 10B), 10 washes (fig. 10C), and 25 washes (fig. 10D) produced by varying the concentration of medium molecular weight filaments in the final coating solution.
Fig. 11A-11D are graphs showing UV/Vis quantification experiments of fabrics coated with low molecular weight reactive filaments and polyoxyethylene (20) monooleate solution. Fig. 11A: a plot of percent silk loss after five washes relative to fiber surface area is shown. Fig. 11B: a graph showing the quantitative quality of the filaments on the fabric after coating relative to the fiber surface area. Fig. 11C: a plot of percent silk loss after five washes relative to fabric type is shown. Fig. 11D: a graph showing the quantitative quality of the filaments on each fabric before and after five washes according to the fabric type.
Fig. 12 is a graph showing UV/Vis quantification experiments of fabrics coated with low molecular weight reactive filaments and polyoxyethylene (20) monooleate solution. The figure shows the quantitative mass of filaments on the fabric after coating relative to the fabric mass in grams per square meter (GSM). The quality depends on the type of weave, fiber content and filament denier.
Fig. 13A-13C include a series of graphs showing potentiometric titration curves for charge density measured at pH 5 for an unfinished heavy double knit nylon fabric (fig. 13A), a reactive filament finished heavy double knit nylon fabric (fig. 13B), and Archroma RPU wet finished heavy double knit nylon fabric (fig. 13C). Each fabric had titration curves obtained at unwashed (fig. 13A-13C, left panels) and five launderings (fig. 13A-13C, right panels). The change in charge density at pH 5 after washing is indicated as deltac.
Detailed Description
The present disclosure provides articles comprising coated fabrics, and methods of making such articles, wherein the coating comprises a surfactant and/or emulsifier system and a silk fibroin fragment.
Silk is a natural polymer produced by a variety of insects and arachnids. Silk produced by Bombyx mori (silkworm) comprises silk core protein, silk fibroin and a colloidal coating consisting of non-filamentous proteins and sericin. Fibroin is an FDA-approved, edible, nontoxic, and relatively inexpensive cocoon-derived protein. The structure and content of amino acids in fibroin is very similar to human tissue.
Methods of preparing fibroin fragments are known and are described, for example, in U.S. Pat. nos. 9,187,538, 9,511,012, 9,517,191, 9,522,107, 9,522,108, 9,545,369, and 10,166,177, all of which are incorporated herein by reference in their entirety.
Recent advances in silk material technology include the advent of top-down and bottom-up silk cocoon engineering, particularly the regeneration of cocoons into aqueous solutions of silk, and the use of genetic engineering to produce recombinant silk having a molecularly defined composition (Tran et al, a review of THE EMERGING roll of silk for THE TREATMENT of the eye, pharm.res.,2018, volume 35, pages 1-16). In recent years, fibroin has been reported to find application in ocular tissue reconstruction, corneal tissue engineering, and ocular surface repair due to its biocompatibility, adjustable properties, and transparency. It has been found that silk membranes support the growth of keratocytes and form layered epithelial cell sheets corresponding to amniotic membrane substrates (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 fibroin membranes as potential substrata for epithelial constructs used in the management of ocular surface disorders.Tissue Engineering Pan A,2008;14(7):1203-11.).) have demonstrated that fibroin and hydrolyzed peptide fragments inhibit the transcription and upstream activation of NF- κB protein subunits and pro-inflammatory molecules, which are normally 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. Biotech., 2012.22 (4): 494-500).
Definition of the definition
As used in the foregoing portion of the specification 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 pertains, unless defined otherwise. All patents and publications mentioned herein are incorporated by reference in their entirety.
All percentages, parts and ratios are based on the total weight of the eye care composition of the present disclosure, unless otherwise specified. All such weights as they pertain to listed ingredients are based on the active level and, therefore, do not include solvents or byproducts that may be included in commercially available materials, unless otherwise specified. The term "weight percent" may be expressed herein as "wt%" or% w/w.
As used herein, the terms "a" and "an" or "the" are generally construed to cover both the singular and the plural.
As used herein, the term "about" generally refers to a particular value that includes variations and acceptable error ranges as determined by one of ordinary skill in the art, which will depend in part on how the value is measured or determined, i.e., the limitations of the measurement system. For example, "about" may mean zero variation, as well as a range of + -20 percent, + -10 percent, or + -5 percent of a given numerical value.
For example, as used herein, the term "dermatologically acceptable carrier" means a carrier suitable for use in contact with mammalian keratinous tissue without causing any adverse effects (such as excessive toxicity, incompatibility, instability, allergic response). The dermatologically acceptable carrier may include, but is not limited to, water, liquid or solid emollients, moisturizers, 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, as determined by calculating the values of the different regions of the molecule, as described by Griffin method hlb=20×m h/M, where M h is the molecular mass of the hydrophilic portion of the surfactant and/or emulsifier, M is the molecular mass of the entire surfactant and/or emulsifier molecule, resulting in a result in the range of 0 to 20. An HLB value of 0 corresponds to a fully lipophilic molecule and an HLB value of 20 corresponds to a fully hydrophilic molecule. The HLB value can be used to predict the surfactant and/or emulsifier properties of a molecule: HLB <10: fat-soluble (water insoluble), HLB >10: water-soluble (lipid-insoluble), hlb=1-3: defoamer, 3-6: W/O (water-in-oil) emulsifier, 7-9: wetting spreading agent, 8-16: O/W (oil-in-water) emulsifier, 13-16: detergents, 16-18: solubilizing agents or hydrotropes.
As used herein, "average weight average molecular weight" refers to the average of two or more values of the weight average molecular weight of a fibroin or fragment thereof of the same composition, as determined by two or more separate experimental readings.
As used herein, the term "Polydispersity (PD)" of a polymer is generally used as a measure of the breadth of the molecular weight distribution of the polymer, and is defined by the formula polydispersityAnd (5) defining.
As used herein, the term "substantially uniform" may refer to fibroin-based protein fragments that are distributed in a normal distribution with respect to the identified molecular weight. As used herein, the term "substantially uniform" may refer to a uniform distribution of components or additives, such as fibroin fragments, dermatologically acceptable carriers, and the like, throughout the composition of the present disclosure.
As used herein, the terms "fibroin peptide", "fibroin fragment (silk fibroin protein fragment)" and "fibroin fragment (silk fibroin fragment)" are used interchangeably. When molecular size becomes an important parameter, the molecular weight or the number of amino acid units is defined.
As used herein, the term "fast-dissolving solid form" refers to fast-dissolving solid forms including freeze-dried forms (filter cakes, flakes, films) and compressed tablets.
As used herein, the term "peptide" or "protein" refers to chains of amino acids that are linked together by peptide bonds (also referred to as amide bonds). The basic distinguishing factors of 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, while proteins consist of 50 or more amino acids. Furthermore, the structure of peptides is often less well defined than proteins, which can take complex conformations called secondary, tertiary and quaternary structures.
As used herein, the term "silk fibroin" or "silk protein" is a definition provided in a class of structural proteins produced by certain silk-producing spider and insect species (see WIPO Pearl-WIPO's Multilingual Terminology Portal database https:// wipopearl. The silk fibroin can include fibroin, insect or spider silk proteins (e.g., spider silk proteins), recombinant spider proteins, silk proteins found in other spider silk types, such as tubular silk protein (TuSP), whip filaggrin, secondary ampullate silk protein, acinar silk protein, pear silk protein, polymeric silk gum), fibroin produced by genetically modified silkworms, or recombinant fibroin.
As used herein, the term "silk fibroin" refers to silk fibroin, silk fibroin produced by genetically modified silkworms, or recombinant silk fibroin (see (1) Narayan edit, encyclopedia of Biomedical Engineering, vol.2, elsevier,2019; 2) Kobayashi et al edit ,Encyclopedia of Polymeric Nanomaterials,Springer,2014,https://link.springer.com/referenceworkentry/10.1007%2F978-3-642-36199-9_323-1). in one embodiment, silk fibroin obtained from silkworms.
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), wherein the active agent is miscible with the polymer matrix excipient.
As used herein, the term "solid dispersion" refers to an active agent dispersed as crystalline or amorphous particles, wherein the active agent is dispersed in an amorphous polymer and randomly distributed among the polymer matrix excipients.
As used herein, the term "substantially uniform" may refer to fibroin-based protein fragments that are distributed in a normal distribution with respect to the identified molecular weight. As used herein, the term "substantially homogeneous" may also refer to a uniform distribution of components or additives (e.g., fibroin-based protein fragments, dermatologically acceptable carriers, etc.) throughout the silk eye care composition.
As used herein, the term "surface tension" refers to the tendency of a fluid surface to shrink to as small a surface area as possible. At the liquid-air interface, surface tension is created by the fact that the attractive forces of liquid molecules to each other (due to cohesive forces) are greater than the attractive forces of molecules in air to each other (due to adhesive forces). The net effect is an inward force on the surface of the liquid that causes the liquid to behave as if its surface were covered by a stretched elastic film. Since water molecules have a relatively high attraction to each other through a hydrogen bond network, water has a higher surface tension (72.8 mN/m at 20 ℃) than most other liquids.
SPF definition and Properties
As used herein, "silk protein fragments" (SPFs) include, but are not limited to, one or more of the following: "fibroin fragment" as defined herein; "recombinant silk fragments" as defined herein; "spider silk fragments" as defined herein; "fibroin-like protein fragments" as defined herein; "chemically modified silk fragments" as defined herein; and/or "sericin or sericin fragment" 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 a silk protein comprising or consisting of at least two identical repeating units, each independently selected from the amino acid sequence of a naturally occurring silk polypeptide or variant thereof, a naturally occurring silk polypeptide, or a combination of both.
SPF molecular weight and polydispersity
In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 1kDa to about 5 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 5kDa to about 10 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 10kDa to about 15 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 15kDa to about 20 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 14kDa to about 30 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 20kDa to about 25 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 25kDa to about 30 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 30kDa to about 35 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 35kDa to about 40 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 39kDa to about 54 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 40kDa to about 45 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 45kDa to about 50 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 50kDa to about 55 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 55kDa to about 60 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 60kDa to about 65 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 65kDa to about 70 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 70kDa to about 75 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 75kDa to about 80 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 80kDa to about 85 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 85kDa to about 90 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 90kDa to about 95 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 95kDa to about 100 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 100kDa to about 105 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 105kDa to about 110 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 110kDa to about 115 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 115kDa to about 120 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 120kDa to about 125 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 125kDa to about 130 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 130kDa to about 135 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 135kDa to about 140 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 140kDa to about 145 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 145kDa to about 150 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 150kDa to about 155 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 155kDa to about 160 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 160kDa to about 165 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 165kDa to about 170 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 170kDa to about 175 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 175kDa to about 180 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 180kDa to about 185 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 185kDa to about 190 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 190kDa to about 195 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 195kDa to about 200 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 200kDa to about 205 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 205kDa to about 210 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 210kDa to about 215 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 215kDa to about 220 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 220kDa to about 225 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 225kDa to about 230 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 230kDa to about 235 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 235kDa to about 240 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 240kDa to about 245 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 245kDa to about 250 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 250kDa to about 255 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 255kDa to about 260 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 260kDa to about 265 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 265kDa to about 270 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 270kDa to about 275 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 275kDa to about 280 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 280kDa to about 285 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 285kDa to about 290 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 290kDa to about 295 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 295kDa to about 300 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 300kDa to about 305 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 305kDa to about 310 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 310kDa to about 315 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 315kDa to about 320 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 320kDa to about 325 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 325kDa to about 330 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 330kDa to about 335 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 335kDa to about 340 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 340kDa to about 345 kDa. In one embodiment, the composition of the present disclosure comprises an SPF having an average weight average molecular weight selected from about 345kDa to about 350 kDa.
In some embodiments, the compositions of the present disclosure include SPF compositions selected from compositions #1001 to #2450 having a weight average molecular weight selected from about 1kDa to about 145kDa, and 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:
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As used herein, "low molecular weight", "low MW" or "low-MW" SPF may include SPFs having a weight average molecular weight or average weight average molecular weight selected from about 5kDa to about 38kDa, about 14kDa to about 30kDa, or about 6kDa to about 17 kDa. In some embodiments, the target low molecular weight of certain SPFs may be a weight average molecular weight of about 5kDa, about 6kDa, about 7kDa, about 8kDa, about 9kDa, about 10kDa, about 11kDa, about 12kDa, about 13kDa, about 14kDa, about 15kDa, 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, about 33kDa, about 34kDa, about 35kDa, about 36kDa, about 37kDa, or about 38 kDa.
As used herein, "medium molecular weight", "medium MW" or "medium-MW" SPF may include SPFs having a weight average molecular weight or average weight average molecular weight selected from about 31kDa to about 55kDa or about 39kDa to about 54 kDa. In some embodiments, the target medium molecular weight of certain SPFs may be a weight average molecular weight of about 31kDa, about 32kDa, about 33kDa, about 34kDa, about 35kDa, about 36kDa, about 37kDa, about 38kDa, about 39kDa, about 40kDa, about 41kDa, about 42kDa, about 43kDa, about 44kDa, about 45kDa, about 46kDa, about 47kDa, about 48kDa, about 49kDa, about 50kDa, about 51kDa, about 52kDa, about 53kDa, about 54kDa, or about 55 kDa.
As used herein, "high molecular weight", "high MW" or "high-MW" SPF may include SPFs having a weight average molecular weight or average weight average molecular weight selected from about 55kDa to about 150 kDa. In some embodiments, the high molecular weight of interest of certain SPFs may be about 55kDa, about 56kDa, about 57kDa, about 58kDa, about 59kDa, about 60kDa, about 61kDa, about 62kDa, about 63kDa, about 64kDa, about 65kDa, about 66kDa, about 67kDa, about 68kDa, about 69kDa, about 70kDa, about 71kDa, about 72kDa, about 73kDa, about 74kDa, about 75kDa, about 76kDa, about 77kDa, about 78kDa, about 79kDa, or about 80kDa.
In some embodiments, the molecular weights described herein (e.g., low molecular weight filaments, medium molecular weight filaments, high molecular weight filaments) can be converted to an approximate number of amino acids contained within the corresponding SPF, as will be appreciated by one of ordinary skill in the art. For example, the amino acids may have an average weight of about 110 daltons (i.e., 110 g/mol). Thus, in some embodiments, the molecular weight of a linear protein divided by 110 daltons may 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 the compositions described herein having a combination of low, medium, and/or high molecular weight SPFs, such low, medium, and/or high molecular weight SPFs may have the same or different polydispersity.
Fibroin fragments
Methods for preparing fibroin or fragments of fibroin and their use in various fields are known and described, for example, in U.S. Pat. nos. 9,187,538, 9,511,012, 9,517,191, 9,522,107, 9,522,108, 9,545,369 and 10,166,177, 10,287,728 and 10,301,768, all of which are incorporated herein by reference in their entirety. Raw silk from Bombyx mori (Bombyx mori) consists of two major proteins: fibroin (about 75%) and sericin (about 25%). Fibroin is a fibrous protein having a semi-crystalline structure that provides rigidity and strength. The term "fibroin" as used herein refers to the fiber of cocoons of silkworms having a weight average molecular weight of about 370,000 da. The crude silk fiber consists of double strands of fibroin. The adhesive substance that holds these double fibers together is sericin. Fibroin consists of a heavy chain (H chain) having a weight average molecular weight of about 350,000da and a light chain (L chain) having a weight average molecular weight of about 25,000 da. Fibroin is an amphiphilic polymer with large hydrophobic domains (which have a high molecular weight) that occupy the major components of the polymer. The hydrophobic region is interrupted by a small hydrophilic spacer, and the N-and C-termini of the chain are also highly hydrophilic. The hydrophobic domain of the H chain contains a repeating hexapeptide sequence of Gly-Ala-Gly-Ala-Gly-Ser and a repetition of Gly-Ala/Ser/Tyr dipeptide, which can form stable antiparallel fold (anti-parallel-sheet) crystallites. The amino acid sequence of the L chain is not repeated, so the L chain is more hydrophilic and relatively elastic. Hydrophilic (Tyr, ser) and hydrophobic (Gly, ala) segments in the fibroin molecule are alternately arranged to realize self-assembly of the fibroin molecule.
Provided herein are methods of producing pure and highly scalable silk fibroin fragment mixture solutions that can be used across a variety of industries for a variety of applications. Without wishing to be bound by any particular theory, it is believed that these methods are equally applicable to the fragmentation of any of the SPFs described herein, including, but not limited to, recombinant silk proteins, and the fragmentation of silk-like proteins or fibroin-like proteins.
The term "fibroin" as used herein includes silk fibroin and insect or spider silk proteins. In one embodiment, the fibroin is obtained from silkworm. Raw silk from silkworms consists of two main proteins: fibroin (about 75%) and sericin (about 25%). Fibroin is a fibrous protein having a semi-crystalline structure that provides rigidity and strength. The term "fibroin" as used herein refers to the fiber of cocoons of silkworms having a weight average molecular weight of about 370,000 da. Conversion of these insoluble fibroin fibrils to water-soluble fibroin fragments requires the addition of concentrated neutral salts (e.g., 8-10M lithium bromide) that interfere with intermolecular and intramolecular ionic bonding and hydrogen bonding that would otherwise render the fibroin insoluble in water. Methods of preparing fibroin fragments and/or compositions thereof are known and described, for example, in U.S. Pat. nos. 9,187,538, 9,511,012, 9,517,191, 9,522,107, 9,522,108, 9,545,369, and 10,166,177.
Raw silk cocoons from silkworms are cut into pieces. Silk cocoon fragments were treated in an aqueous solution of Na 2CO3 at about 100 ℃ for about 60 minutes to remove sericin (degumming). The volume of water used was equal to about 0.4x weight of raw silk and the amount of Na 2CO3 was about 0.848x weight of raw silk cocoon fragments. The resulting degummed silk cocoon fragments were rinsed three times with deionized water at about 60 c (20 minutes each rinse). The volume of rinse water per cycle was 0.2L x weight of raw silk cocoon fragments. Excess water is removed from the degummed silk cocoon fragments. After the deionized water washing step, the wet degummed silk cocoon fragments were dried at room temperature. The degummed silk cocoon fragments were mixed with the LiBr solution and the mixture was heated to about 100 ℃. The warmed mixture is placed in a drying oven and heated at about 100 ℃ for about 60 minutes to achieve complete solubilization of the native silk proteins. The resulting fibroin solution was filtered and dialyzed against deionized water using Tangential Flow Filtration (TFF) and a10 kDa membrane for 72 hours. The resulting aqueous fibroin solution had a concentration of about 8.5 wt.%. The 8.5% silk solution was then diluted with water to produce 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/water.
Silk dialysis by a series of water exchanges is a manual and time intensive process that can be accelerated by changing certain parameters, such as diluting the silk solution prior to dialysis. The dialysis process can be manufactured on a large scale by using semi-automatic equipment, such as tangential flow filtration systems.
In some embodiments, the silk solution is prepared under various preparation condition parameters, such as: 90℃for 30 minutes, 90℃for 60 minutes, 100℃for 30 minutes and 100℃for 60 minutes. Briefly, 9.3M LiBr was prepared and allowed to stand at room temperature for at least 30 minutes. 5mL of LiBr solution was added to 1.25g of silk and placed in a 60℃oven. Samples were taken from each group 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℃for 30 minutes, 90℃for 60 minutes, 100℃for 30 minutes and 100℃for 60 minutes. Briefly, a 9.3M LiBr solution was heated to one of four temperatures: 60 ℃, 80 ℃, 100 ℃ or boiling. 5mL of the hot LiBr solution was added to 1.25g of silk and placed in a 60℃oven. Samples were taken from each group at 1,4 and 6 hours.
In some embodiments, the silk solution is prepared under various preparation condition parameters, such as: four different silk extraction combinations were used: 90℃for 30 minutes, 90℃for 60 minutes, 100℃for 30 minutes and 100℃for 60 minutes. Briefly, a 9.3M LiBr solution was heated to one of four temperatures: 60 ℃, 80 ℃, 100 ℃ or boiling. 5mL of the hot LiBr solution was added to 1.25g of wire and placed in an oven at the same temperature as LiBr. Samples were taken from each group at 1, 4 and 6 hours. 1mL of each sample was added to 7.5mL of 9.3M LiBr and refrigerated for viscosity testing.
In some embodiments, the SPF is obtained by dissolving raw, un-degummed, partially degummed, or degummed silk fibers with a neutral lithium bromide salt. The raw silk is processed at a temperature and other conditions selected to remove any sericin and achieve the desired weight average molecular weight (M W) and Polydispersity (PD) of the fragment mixture. 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 is fibroin fragments and water with process contaminants at parts per million (ppm) to undetectable levels, acceptable levels in the pharmaceutical, medical, and consumer eye care markets. The concentration, size, and polydispersity of the SPF can be further varied depending on the desired application and performance requirements.
FIG. 1 is a flow chart showing various embodiments for producing pure silk fibroin fragments (SPFs) of the present disclosure. It should be understood that not all of the illustrated steps are necessary to prepare all of the silk solutions of the present disclosure. As shown in fig. 2, step a, cocoons (heat treated or not), silk fibers, silk powder, spider silk, or recombinant spider silk may be used as a silk source. If starting with raw silk cocoons from silkworms, the cocoons can be cut into small pieces, e.g., pieces of approximately equal size, step B1. Then in step C1a, the raw silk is extracted and rinsed to remove any sericin. This results in a raw silk that is substantially free of sericin. In one embodiment, the water is heated to a temperature of 84 ℃ to 100 ℃ (desirably boiling), and then Na 2CO3 (sodium carbonate) is added to the boiling water until Na 2CO3 is completely dissolved. Raw silk is added to boiling water/Na 2CO3 (100 ℃) and immersed for about 15-90 minutes where it is boiled for a longer period of time to produce smaller silk protein fragments. In one embodiment, the water volume is equal to about 0.4x raw silk weight and the Na 2CO3 volume is equal to about 0.848x raw silk weight. In one embodiment, the water volume is equal to 0.1x the weight of the raw silk, and the Na 2CO3 volume is kept at 2.12g/L.
Subsequently, the water-dissolved Na 2CO3 solution is drained and excess water/Na 2CO3 is removed from the fibroin fibers (e.g., by hand looping the fibroin extract, using a spin cycle of the machine, etc.). The resulting fibroin extract is rinsed with warm to hot water, typically in the temperature range of about 40 ℃ to about 80 ℃, to remove any residual adsorbed sericin or contaminants, and the volume of water is replaced at least once (repeated as many times as necessary). The obtained fibroin extract is substantially sericin-free fibroin. In one embodiment, the resulting fibroin extract is rinsed with water at a temperature of about 60 ℃. In one embodiment, the volume of rinse water per cycle is equal to 0.1L to 0.2L by weight of raw silk. It may be advantageous to agitate, invert or circulate the rinse water to maximize the rinse effect. After rinsing, excess water is removed from the extracted fibroin fibers (e.g., manually or by machine extrusion of the fibroin extract). Alternatively, methods known to those skilled in the art, such as pressure, temperature, or other agents or combinations thereof, may be used for sericin extraction. Alternatively, the silk gland (100% sericin-free silk protein) can be removed directly from the insect. This will result in a sericin-free liquid silk protein without any change in protein structure.
The extracted fibroin fibers were then completely dried. Once dried, the extracted fibroin is dissolved using a solvent added to the fibroin at a temperature from ambient temperature to boiling point, step C1b. In one embodiment, the solvent is a lithium bromide (LiBr) solution (LiBr having a boiling point of 140 ℃). Or the extracted silk fibroin fibers are not dried, but rather are wet and placed in a solvent; the solvent concentration can then be varied to achieve a similar concentration as when dry filaments are added to the solvent. The final concentration of LiBr solvent may be in the range of 0.1M to 9.3M. Complete dissolution of the extracted fibroin fibers can be achieved by varying the treatment time and temperature and the concentration of the dissolution solvent. Other solvents may be used including, but not limited to, phosphate phosphoric acid, calcium nitrate, calcium chloride solution, or other concentrated inorganic salt aqueous solutions. To ensure complete dissolution, the silk fibers should be completely immersed in the heated solvent solution and then maintained at a temperature of about 60 ℃ to about 140 ℃ for 1-168 hours. In one embodiment, the silk fibers should be completely immersed in the solvent solution and then placed in a drying oven at a temperature of about 100 ℃ for about 1 hour.
The temperature at which the fibroin extract is added to the LiBr solution (and vice versa) has an effect on the time required to completely dissolve the fibroin and the resulting molecular weight and polydispersity of the final SPF mixture solution. In one embodiment, the silk solvent solution concentration is less than or equal to 20% w/v, and further, agitation during introduction or dissolution may be used to facilitate dissolution at different temperatures and concentrations. The temperature of the LiBr solution provides control over the molecular weight and polydispersity of the resulting mixture of silk protein fragments. In one embodiment, the higher temperature dissolves the filaments faster to provide enhanced process scalability and mass production of the filament solution. In one embodiment, the use of LiBr solution heated to a temperature of 80 ℃ to 140 ℃ reduces the time required to achieve complete dissolution in the oven. Varying the time and temperature of the dissolution solvent at 60 ℃ or above will vary and control the MW and polydispersity of the SPF mixture solution formed from the native fibroin of the original molecular weight.
Alternatively, step B2 may be performed by placing the whole cocoon directly in a solvent, such as LiBr, bypassing the extraction. This requires the subsequent filtration of the silkworm particles from the silk and solvent solution and removal of sericin using methods known in the art for separation of hydrophobic and hydrophilic proteins (such as column separation and/or chromatography, ion exchange, chemical precipitation with salts and/or pH, and/or enzymatic digestion and filtration or extraction), all of which are common examples of standard protein separation methods and not limitation, step C2. Alternatively, the extraction may be bypassed by placing the removed silkworm cocoon without heat treatment in a solvent such as LiBr. The above method can be used for sericin separation, and has the advantage that cocoons which are not subjected to heat treatment contain significantly less insect scraps.
Step E1 may be performed using dialysis to remove the dissolution solvent from the resulting solution of dissolved silk fibroin fragments by dialyzing the solution against a volume of water. Pre-filtration prior to dialysis aids in removing any debris (i.e., silkworm residue) from the silk and LiBr solution, step D. In one example, a 0.1% to 1.0% silk-LiBr solution is filtered using a 3 μm or 5 μm filter at a flow rate of 200-300mL/min prior to dialysis and possibly concentration as desired. The methods disclosed herein as described above utilize time and/or temperature to reduce the concentration from 9.3M LiBr to a range of 0.1M to 9.3M to facilitate filtration and downstream dialysis, particularly when considering the establishment of a scalable process. Alternatively, without additional time or temperature, the 9.3M LiBr-silk fibroin fragment solution can be diluted with water to facilitate debris filtration and dialysis. The result of the solubilization under the desired time and temperature filtration is a semitransparent particle-free, room temperature storage stable solution of silk fibroin fragments-LiBr of known MW and polydispersity. It is advantageous to replace the dialysis water periodically until the solvent is removed (e.g. after 1 hour, 4 hours, then every 12 hours for a total of 6 water changes). The total number of water volume changes may be varied based on the resulting concentration of solvent used for silk fibroin solubilization and fragmentation. After dialysis, the final silk solution may be further filtered to remove any remaining debris (i.e., silkworm residue).
Or Tangential Flow Filtration (TFF), which is a fast and efficient method for separating and purifying biomolecules, may be used to remove solvent from the resulting solubilized fibroin solution, step E2.TFF provides high purity aqueous solutions of silk protein fragments and ensures that the process can be scaled up to produce large quantities of solution in a controlled and reproducible manner. The silk-LiBr solution (from 20% down to 0.1% silk in water or LiBr) can be diluted prior to TFF. Prefiltering as described above prior to TFF treatment can maintain filtration efficiency and potentially avoid the creation of a silk gel boundary layer on the filter surface due to the presence of debris particles. Prefiltering prior to TFF also aids in removing any residual debris (i.e., silkworm residue) from the silk and LiBr solution that may result in spontaneous or long-term gelation of the resulting aqueous-only solution, step D. Recycled or single pass TFF can be used to produce a water-silk protein fragment solution of 0.1% silk to 30.0% silk (more preferably, 0.1% -6.0% silk). TFF films of different cut-off sizes may be required based on the desired concentration, molecular weight, and polydispersity of the silk fibroin fragment mixture in solution. For silk solutions of different molecular weights, made for example by varying the length of the extraction boiling time or the time and temperature in the dissolution solvent (e.g. LiBr), a membrane of 1-100kDa may be required. In one embodiment, a TFF 5 or 10kDa membrane is used to purify the silk protein fragment mixture solution and produce the final desired silk water ratio. Single pass TFF, and other methods known in the art, such as falling film evaporator, may also be used to concentrate the solution after removal of the dissolution solvent (e.g., liBr) (resulting in the desired concentration of 0.1% to 30% silk). This can be used as an alternative to standard HFIP concentration methods known in the art for preparing aqueous based solutions. Larger pore membranes can also be used to filter out small silk protein fragments and produce solutions of higher molecular weight silk with and/or without narrower polydispersity values.
The assay for detecting LiBr and Na 2CO3 can be performed using an HPLC system equipped with an Evaporative Light Scattering Detector (ELSD). Calculation was performed by linear regression of the resulting peak areas of the analytes plotted against concentration. More than one sample of many formulations of the present disclosure is used for sample preparation and analysis. Typically, four samples of different formulations are weighed directly into 10mL volumetric flasks. The sample was suspended in 5mL of 20mM ammonium formate (pH 3.0) and held at 2 to 8 ℃ for 2 hours with occasional shaking to extract the analyte from the membrane. After 2 hours, the solution was diluted with 20mM ammonium formate (pH 3.0). Sample solutions from the volumetric flask were transferred to HPLC vials and injected into the HPLC-ELSD system to evaluate sodium carbonate and lithium bromide.
Analytical methods developed for quantification of Na 2CO3 and LiBr in silk protein formulations were found to be linear in the range of 10-165 μg/mL, RSD 2% for injection accuracy, 1% for area, and 0.38% and 0.19% for retention time of sodium carbonate and lithium bromide, respectively. The assay can be used for quantitative determination of sodium carbonate and lithium bromide in silk protein preparations.
Fig. 2 is a flow chart showing various parameters that may be modified during the process of producing silk protein fragment solutions of the present disclosure during the extraction and solubilization steps. The selected process parameters can be varied to achieve different final solution characteristics, such as molecular weight and polydispersity, depending on the intended use. It should be understood that not all of the illustrated steps are necessary to prepare all of the silk solutions of the present disclosure.
In one embodiment, a silk protein fragment solution useful for a variety of applications is prepared according to the following steps: forming silk cocoon fragments from silkworms; extracting the fragments in an aqueous Na 2CO3 solution at about 100 ℃ for about 60 minutes, wherein the water volume is equal to about 0.4 x the weight of raw silk and the amount of Na 2CO3 is about 0.848 x the weight of fragments to form a silk fibroin extract; rinsing the fibroin extract three times in a volume of rinse water at about 60 ℃ for about 20 minutes each, wherein the rinse water for each cycle is equal to about 0.2L x the weight of the fragments; removing excess water from the fibroin extract; drying the fibroin extract; dissolving the dried silk fibroin extract in a LiBr solution, wherein the LiBr solution is first heated to about 100 ℃ to produce a silk-LiBr solution and maintained; placing the silk-LiBr solution in a drying oven at about 100 ℃ for about 60 minutes to achieve complete dissolution and further fragmentation of the native silk protein structure into a mixture having the desired molecular weight and polydispersity; filtering the solution to remove any residual debris from the silkworms; diluting the solution with water to obtain a 1.0 wt% silk solution; and removing the solvent from the solution using Tangential Flow Filtration (TFF). In one embodiment, a 10kDa membrane is used to purify the silk solution and produce the final desired silk water ratio. TFF can then be used to further concentrate the silk solution to a concentration of 2.0 wt% silk in water.
Without wishing to be bound by any particular theory, the extraction (i.e., time and temperature), liBr (i.e., temperature of the LiBr solution when added to the fibroin extract (or vice versa), and dissolution (i.e., time and temperature) parameters are varied to yield solvent-silk solutions of different viscosity, uniformity, and color. Nor is it intended to be bound by any particular theory, but increasing the extraction temperature, extending the extraction time, initially and over time using a higher temperature LiBr solution when dissolving the filaments, and increasing the time at temperature (e.g., in an oven or alternative heat source as shown herein) all result in a lower viscosity and more uniform solvent-filament solution.
The extraction step may be accomplished in a larger vessel, such as an industrial washer that may be maintained at a temperature of 60 ℃ to 100 ℃ or between. The rinsing step may also be accomplished in an industrial washing machine to eliminate the manual rinse cycle. Dissolution of the filaments in the LiBr solution may be carried out in a vessel other than a convection oven, such as a stirred tank reactor. Silk dialysis by a series of water exchanges is a manual and time intensive process that can be accelerated by changing certain parameters, such as diluting the silk solution prior to dialysis. The dialysis process can be manufactured on a large scale by using semi-automatic equipment, such as tangential flow filtration systems.
The extraction (i.e., time and temperature), liBr (i.e., temperature of the LiBr solution when added to the fibroin extract (or vice versa), and dissolution (i.e., time and temperature) parameters were varied to give solvent-silk solutions of different viscosity, uniformity, and color. Increasing the extraction temperature, extending the extraction time, using a higher temperature LiBr solution initially and over time when dissolving the filaments, and increasing the time at temperature (e.g., in an oven or alternative heat source as shown herein) all result in a lower viscosity and more uniform solvent-filament solution. Although almost all parameters result in a viable silk solution, a process that achieves complete dissolution in less than 4 to 6 hours is preferred for process scale-up.
In one embodiment, a solution of a fibroin fragment having a weight average value selected from about 6kDa to about 17kDa is prepared according to the following steps: degumming a silk source by adding the silk source to a boiling (100 ℃) aqueous sodium carbonate solution for a treatment time of about 30 minutes to about 60 minutes; removing sericin from the solution to produce a fibroin extract comprising undetectable sericin content; draining the solution from the fibroin extract; dissolving a fibroin extract in a lithium bromide solution having an onset temperature of about 60 ℃ to about 140 ℃ upon placing the fibroin extract in the lithium bromide solution; maintaining the fibroin-lithium bromide solution in an oven at a temperature of about 140 ℃ for a period of up to 1 hour; removing lithium bromide from the fibroin extract; and preparing an aqueous solution of silk protein fragments, the aqueous solution comprising: a fragment having a weight average molecular weight selected from about 6kDa to about 17kDa and a polydispersity of 1 to about 5 or about 1.5 to about 3.0. The method may further comprise drying the silk fibroin extract prior to the dissolving step. The aqueous solution of the fibroin fragments can contain less than 300ppm lithium bromide residues as measured using a high performance liquid chromatography lithium bromide assay. The aqueous solution of the fibroin fragments can comprise less than 100ppm sodium carbonate residues as measured using a high performance liquid chromatography sodium carbonate assay. The aqueous solution of the fibroin fragments can be lyophilized. In some embodiments, the fibroin fragment solution can be further processed into various forms, including gels, powders, and nanofibers.
In one embodiment, a solution of a fibroin fragment having a weight average molecular weight selected from about 17kDa to about 39kDa is prepared according to the following steps: adding a silk source to a boiling (100 ℃) aqueous sodium carbonate solution for a treatment time of about 30 minutes to about 60 minutes to result in degumming; removing sericin from the solution to produce a fibroin extract comprising undetectable levels of sericin content; draining the solution from the fibroin extract; dissolving a fibroin extract in a lithium bromide solution having an onset temperature of about 80 ℃ to about 140 ℃ upon placing the fibroin extract in the lithium bromide solution; maintaining the fibroin-lithium bromide solution in a drying oven at a temperature of about 60 ℃ to about 100 ℃ for a period of up to 1 hour; removing lithium bromide from the fibroin extract; and preparing an aqueous solution of the silk fibroin fragments, wherein the aqueous solution of the silk fibroin fragments comprises about 10ppm to about 300ppm lithium bromide residues, wherein the aqueous solution of the silk fibroin fragments comprises about 10ppm to about 100ppm sodium carbonate residues, wherein the aqueous solution of the silk fibroin fragments comprises fragments having a weight average molecular weight selected from about 17kDa to about 39kDa and a polydispersity of 1 to about 5 or about 1.5 to about 3.0. The method may further comprise drying the silk fibroin extract prior to the dissolving step. The aqueous solution of the fibroin fragments can contain less than 300ppm lithium bromide residues as measured using a high performance liquid chromatography lithium bromide assay. The aqueous solution of the fibroin fragments can comprise less than 100ppm sodium carbonate residues as measured using a high performance liquid chromatography sodium carbonate assay.
In some embodiments, a method of preparing an aqueous solution of a fibroin fragment having an average weight average molecular weight selected from about 6kDa to about 17kDa comprises the steps of: degumming a silk source by adding the silk source to a boiling (100 ℃) aqueous sodium carbonate solution for a treatment time of about 30 minutes to about 60 minutes; removing sericin from the solution to produce a fibroin extract comprising undetectable levels of sericin content; draining the solution from the fibroin extract; dissolving a fibroin extract in a lithium bromide solution having an onset temperature of about 60 ℃ to about 140 ℃ upon placing the fibroin extract in the lithium bromide solution; maintaining the fibroin-lithium bromide solution in an oven at a temperature of about 140 ℃ for at least 1 hour; removing lithium bromide from the fibroin extract; and preparing an aqueous solution of silk protein fragments, the aqueous solution comprising: a fragment having an average weight average molecular weight selected from about 6kDa to about 17kDa and a polydispersity of 1 to about 5 or about 1.5 to about 3.0. The method may further comprise drying the silk fibroin extract prior to the dissolving step. The aqueous solution of pure silk fibroin fragments can contain less than 300ppm lithium bromide residues as measured using a high performance liquid chromatography lithium bromide assay. The aqueous solution of pure silk fibroin fragments can contain less than 100ppm sodium carbonate residues as measured using a high performance liquid chromatography sodium carbonate assay. The method may further comprise adding a therapeutic agent to the aqueous solution of pure silk fibroin fragments. The method may further comprise adding a molecule selected from one of an antioxidant or an enzyme to the aqueous solution of pure silk fibroin fragments. The method may further comprise adding a vitamin to the aqueous solution of pure silk fibroin fragments. The vitamin may be vitamin C or a derivative thereof. The aqueous solution of pure silk fibroin fragments can be lyophilized. The method may further comprise adding an alpha hydroxy acid to the aqueous solution of pure silk fibroin fragments. The alpha hydroxy acid may be selected from glycolic acid, lactic acid, tartaric acid and citric acid. The method may further comprise adding hyaluronic acid or a salt form thereof to an aqueous solution of pure silk fibroin fragments at a concentration of about 0.5% to about 10.0%. The method may further comprise adding at least one of zinc oxide or titanium dioxide. Membranes can be prepared from aqueous solutions of pure silk fibroin fragments made by this method. The film may comprise from about 1.0% to about 50.0% by weight of vitamin C or a derivative thereof. The film may have a water content of about 2.0 wt% to about 20.0 wt%. The membrane may comprise about 30.0 wt.% to about 99.5 wt.% pure silk fibroin fragments. The gel may be prepared from an aqueous solution of pure silk fibroin fragments made by this method. The gel may comprise from about 0.5% to about 20.0% by weight of 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 of preparing an aqueous solution of a fibroin fragment having an average weight average molecular weight selected from about 17kDa to about 39kDa comprises the steps of: adding a silk source to a boiling (100 ℃) aqueous sodium carbonate solution for a treatment time of about 30 minutes to about 60 minutes to result in degumming; removing sericin from the solution to produce a fibroin extract comprising undetectable levels of sericin content; draining the solution from the fibroin extract; dissolving a fibroin extract in a lithium bromide solution having an onset temperature of about 80 ℃ to about 140 ℃ upon placing the fibroin extract in the lithium bromide solution; maintaining the fibroin-lithium bromide solution in a drying oven at a temperature of about 60 ℃ to about 100 ℃ for at least 1 hour; removing lithium bromide from the fibroin extract; and preparing an aqueous solution of pure silk fibroin fragments, wherein the aqueous solution of pure silk fibroin fragments comprises about 10ppm to about 300ppm lithium bromide residues, wherein the aqueous solution of silk fibroin fragments comprises about 10ppm to about 100ppm sodium carbonate residues, wherein the aqueous solution of pure silk fibroin fragments comprises fragments having an average weight average molecular weight selected from about 17kDa to about 39kDa and a polydispersity of 1 to about 5 or about 1.5 to about 3.0. The method may further comprise drying the silk fibroin extract prior to the dissolving step. The aqueous solution of pure silk fibroin fragments can contain less than 300ppm lithium bromide residues as measured using a high performance liquid chromatography lithium bromide assay. The aqueous solution of pure silk fibroin fragments can contain less than 100ppm sodium carbonate residues as measured using a high performance liquid chromatography sodium carbonate assay. The method may further comprise adding a therapeutic agent to the aqueous solution of pure silk fibroin fragments. The method may further comprise adding a molecule selected from one of an antioxidant or an enzyme to the aqueous solution of pure silk fibroin fragments. The method may further comprise adding a vitamin to the aqueous solution of pure silk fibroin fragments. The vitamin may be vitamin C or a derivative thereof. The aqueous solution of pure silk fibroin fragments can be lyophilized. The method may further comprise adding an alpha hydroxy acid to the aqueous solution of pure silk fibroin fragments. The alpha hydroxy acid may be selected from glycolic acid, lactic acid, tartaric acid and citric acid. The method may further comprise adding hyaluronic acid or a salt form thereof to an aqueous solution of pure silk fibroin fragments at a concentration of about 0.5% to about 10.0%. The method may further comprise adding at least one of zinc oxide or titanium dioxide. Membranes can be prepared from aqueous solutions of pure silk fibroin fragments made by this method. The film may comprise from about 1, 0% to about 50.0% by weight vitamin C or a derivative thereof. The film may have a water content of about 2.0 wt% to about 20.0 wt%. The membrane may comprise about 30.0 wt.% to about 99.5 wt.% pure silk fibroin fragments. The gel may be prepared from an aqueous solution of pure silk fibroin fragments made by this method. The gel may comprise from about 0.5% to about 20.0% by weight of 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 a fibroin fragment having a weight average molecular weight selected from about 39kDa to about 80kDa is prepared according to the following steps: adding the silk source to a boiling (100 ℃) aqueous sodium carbonate solution for a treatment time of about 30 minutes to result in degumming; removing sericin from the solution to produce a fibroin extract comprising undetectable levels of sericin content; draining the solution from the fibroin extract; dissolving a fibroin extract in a lithium bromide solution having an onset temperature of about 80 ℃ to about 140 ℃ upon placing the fibroin extract in the lithium bromide solution; maintaining the fibroin-lithium bromide solution in a drying oven at a temperature of about 60 ℃ to about 100 ℃ for a period of up to 1 hour; removing lithium bromide from the fibroin extract; and preparing an aqueous solution of the fibroin fragments, wherein the aqueous solution of the fibroin fragments comprises about 10ppm to about 300ppm of lithium bromide residues, about 10ppm to about 100ppm of sodium carbonate residues, fragments having a weight average molecular weight selected from about 39kDa to about 80kDa and a polydispersity of 1 to about 5 or about 1.5 to about 3.0. The method may further comprise drying the silk fibroin extract prior to the dissolving step. The aqueous solution of the fibroin fragments can contain less than 300ppm lithium bromide residues as measured using a high performance liquid chromatography lithium bromide assay. The aqueous solution of the fibroin fragments can comprise less than 100ppm sodium carbonate residues as measured using a high performance liquid chromatography sodium carbonate assay. In some embodiments, the method may further comprise adding an active agent (e.g., a therapeutic agent) to the aqueous solution of pure silk fibroin fragments. The method may further comprise adding an active agent selected from one of an antioxidant or an enzyme to the aqueous solution of pure silk fibroin fragments. The method may further comprise adding a vitamin to the aqueous solution of pure silk fibroin fragments. The vitamin may be vitamin C or a derivative thereof. The aqueous solution of pure silk fibroin fragments can be lyophilized. The method may further comprise adding an alpha hydroxy acid to the aqueous solution of pure silk fibroin fragments. The alpha hydroxy acid may be selected from glycolic acid, lactic acid, tartaric acid and citric acid. The method may further comprise adding hyaluronic acid or a salt form thereof to an aqueous solution of pure silk fibroin fragments at a concentration of about 0.5% to about 10.0%. Membranes can be prepared from aqueous solutions of pure silk fibroin fragments made by this method. The film may comprise from about 1.0% to about 50.0% by weight of vitamin C or a derivative thereof. The film may have a water content of about 2.0 wt% to about 20.0 wt%. The membrane may comprise about 30.0 wt.% to about 99.5 wt.% pure silk fibroin fragments. The gel may be prepared from an aqueous solution of pure silk fibroin fragments made by this method. The gel may comprise from about 0.5% to about 20.0% by weight of vitamin C or a derivative thereof. The gel may have a silk content of at least 2 wt% and a vitamin content of at least 20 wt%.
The molecular weight of the silk protein fragments can be based on specific parameters used during the extraction step, including extraction time and temperature; specific parameters used during the dissolution step include the LiBr temperature at which the wire is immersed in lithium bromide and the time the solution is maintained at a specific temperature; and specific parameters used during the filtering step. By controlling the process parameters using the disclosed methods, solutions of fibroin fragments having a polydispersity equal to or lower than 2.5 at various molecular weights selected from 5kDa to 200kDa, or 10kDa to 80kDa can be made. By varying the process parameters to obtain silk solutions with different molecular weights, a range of fragment mixture end products with a desired polydispersity equal to or less than 2.5 can be obtained targeted based on the desired performance requirements. For example, higher molecular weight silk films containing ophthalmic drugs can have a controlled slow release rate compared to lower molecular weight films, making them ideal for use as presentation carriers in eye care products. In addition, solutions of fibroin fragments having a polydispersity of greater than 2.5 can be obtained. Furthermore, two solutions having different average molecular weights and polydispersities may be mixed to produce a combined solution. Or liquid silk glands (100% sericin-free silk proteins) directly removed from insects can be used in combination with any silk fibroin fragment solution of the present disclosure. The molecular weight of the pure fibroin fragment composition was determined using High Pressure Liquid Chromatography (HPLC) with a 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 fibroin having different molecular weights and peptide chain size distributions (polydispersity, PD). This in turn affects the properties of regenerated silk fibroin, including mechanical strength, water solubility, and the like.
Parameters are changed during the process of processing raw silk cocoons into silk solution. Varying these parameters affects the MW of the resulting silk solution. Parameters of manipulation include (i) extraction time and temperature, (ii) temperature of LiBr, (iii) temperature of dissolution oven, and (iv) dissolution time. Experiments were performed to determine the effect of varying extraction time. Tables A-G summarize the results. The following are summaries:
the sericin extraction time of 30 minutes brings about a molecular weight greater than that of 60 minutes
Molecular weight decreases with the passage of time in the oven
LiBr and oven at 140℃below-9500 Da
-30 Min extraction with undigested silk at the time points of 1 hour and 4 hours
The 30-minute extraction results in a significantly higher molecular weight at the 1 hour time point, with a lower limit of confidence interval of 35,000Da
The molecular weight reached at the upper limit of the confidence interval ranges from 18000 to 216000Da (important for providing solutions with the specified upper limit).
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Experiments were performed to determine the effect of varying the extraction temperature. Table G summarizes the results. The following are summaries:
Sericin extraction at 90 ℃ results in a higher MW than sericin extraction at 100 °c extraction
Both-90 ℃ and 100 ℃ showed a decrease in MW with time in the oven.
Experiments were performed to determine the effect of changing the lithium bromide (LiBr) temperature when added to the filaments. Tables H-I summarize the results. The following are summaries:
has no influence on the molecular weight or confidence interval (all CI-10500-6500 Da)
Studies have shown that, since most substances are silk at room temperature, when LiBr is added and dissolution begins, the temperature at which the LiBr-silk dissolves rapidly drops below the original LiBr temperature
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Experiments were performed to determine the effect of v oven/dissolution temperature. Tables J-N summarize the results. The following are summaries:
The oven temperature has less effect on 60 minutes of extracted silk than on 30 minutes of extracted silk. Without wishing to be bound by theory, it is believed that the 30 minutes of silk is less degraded during extraction and thus the oven temperature has a greater effect on the larger MW, less degraded portions of the silk.
For 60 ℃ versus 140 ℃ oven, 30 minutes of extracted filaments show a very significant lower MW effect at higher oven temperatures, whereas 60 minutes of extracted filaments have a much smaller effect
An oven at-140℃results in a confidence interval with a lower limit of-6000 Da.
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Raw silk cocoons from silkworms are cut into pieces. Raw silk cocoon fragments are boiled in an aqueous solution of Na 2CO3 (about 100 ℃) for a period of about 30 minutes to about 60 minutes to remove sericin (degumming). The volume of water used was equal to about 0.4x weight of raw silk and the amount of Na 2CO3 was about 0.848x weight of raw silk cocoon fragments. The resulting degummed silk cocoon fragments were rinsed three times with deionized water at about 60 c (20 minutes each rinse). The volume of rinse water per cycle was 0.2L x weight of raw silk cocoon fragments. Excess water is removed from the degummed silk cocoon fragments. After the deionized water washing step, the wet degummed silk cocoon fragments were dried at room temperature. The degummed silk cocoon fragments were mixed with the LiBr solution and the mixture was heated to about 100 ℃. The warmed mixture is placed in a drying oven and heated at a temperature of about 60 ℃ to about 140 ℃ for about 60 minutes to achieve complete solubilization of the native silk proteins. The resulting solution was cooled to room temperature and then dialyzed using a3,500 da MWCO membrane to remove LiBr salts. Multiple exchanges were performed in deionized water until less than 1ppm of Br - ions were measured in hydrolyzed fibroin solution as read on Oakton Bromide (Br -) double-junction ion selective electrode.
The resulting aqueous fibroin solution has a concentration of about 8.0% w/v and contains pure fibroin fragments having an average weight average molecular weight selected from the group consisting of about 6kDa to about 16kDa, about 17kDa to about 39kDa and about 39kDa to about 80kDa, and a polydispersity of about 1.5 to about 3.0. 8.0% w/v was diluted with deionized water to provide 1.0% w/v, 2.0% w/v, 3.0% w/v, 4.0% w/v, 5.0% w/v based on the coating solution.
Various wire concentration percentages (%) were prepared by using Tangential Flow Filtration (TFF). In all cases, a 1% silk solution was used as input feed. As starting volume, a 1% silk solution in the range of 750-18,000mL was used. The solution was diafiltered in TFF to remove lithium bromide. Once below the specified residual LiBr level, the solution is subjected to ultrafiltration to increase the concentration by removal of water. See the examples below.
Six (6) silk solutions were used in a standard silk structure, with the following results:
solution #1 had a silk concentration of 5.9 wt.%, an average molecular weight of 19.8kDa and a PDI of 2.2 (prepared by 60 min boiling extraction, liBr dissolution for 1 hour at 100 ℃).
The silk concentration of solution #2 was 6.4 wt% (prepared by 30min boiling extraction, 60 ℃ LiBr dissolution for 4 hours).
The silk concentration of solution #3 was 6.17 wt% (prepared by 30 min boiling extraction, 100 ℃ LiBr dissolution for 1 hour).
The silk concentration of solution #4 was 7.30 wt%: a 7.30% silk solution was produced starting from a 30 minute extraction batch of 100g silk cocoons per batch. The extracted silk fibers were then dissolved in an oven at 100 ℃ for 1 hour using 100 ℃ 9.3 MLiBr. 100g of silk fibers were dissolved per batch to make 20% silk in LiBr. The filaments dissolved in LiBr were then diluted to 1% filaments and filtered through a5 μm filter to remove large debris. 15,500mL of 1% filter wire solution was used as the starting volume/diafiltration volume for TFF. Once LiBr was removed, the solution was ultrafiltered to a volume of about 1300 mL. 1262mL of 7.30% silk was then collected. Water was added to the feed to help remove the remaining solution, and 547ml of 3.91% silk was then collected.
The silk concentration of solution #5 was 6.44 wt%: a 6.44 wt% silk solution was produced starting from a 60 minute extraction batch of a mixture of 25, 33, 50, 75 and 100g cocoons per batch. The extracted silk fibers were then dissolved in an oven at 100 ℃ using 9.3M LiBr at 100 ℃ for 1 hour. Each batch dissolved 35, 42, 50 and 71g silk fibers to make 20% silk in LiBr and combined. The filaments dissolved in LiBr were then diluted to 1% filaments and filtered through a 5 μm filter to remove large debris. 17,000mL of 1% filter wire solution was used as the starting volume/diafiltration volume for TFF. Once LiBr was removed, the solution was ultrafiltered to a volume of about 3000 mL. 1490ml of 6.44% silk was then collected. Water was added to the feed to help remove the remaining solution, and then 1454mL of 4.88% silk was collected.
The silk concentration of solution #6 was 2.70 wt%: a 2.70% silk solution was produced starting from a 60 minute extraction batch of 25g silk cocoons per batch. The extracted silk fibers were then dissolved in an oven at 100 ℃ for 1 hour using 100 ℃ 9.3 MLiBr. 35.48g of silk fibers were dissolved per batch to make 20% silk in LiBr. The filaments dissolved in LiBr were then diluted to 1% filaments and filtered through a 5 μm filter to remove large debris. 1000mL of 1% filter wire solution was used as the starting volume/diafiltration volume for TFF. Once LiBr was removed, the solution was ultrafiltered to a volume of about 300 mL. 312mL of 2.7% silk was then collected.
The preparation of fibroin solutions with higher molecular weights is given in table O.
Preparation and Properties of fibroin solutions.
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The silk aqueous coating compositions for application to fabrics are given in table P and table Q below.
Three (3) silk solutions were used in the film preparation, with the following results:
Solution #1 was 5.9% silk concentration, average MW of 19.8kDa and 2.2PD (prepared by 60 min boiling extraction, liBr dissolution at 100℃for 1 hour). Degree (C)
Solution #2 was 6.4% silk concentration (prepared by 30 min boiling extraction, 60 ℃ LiBr dissolution for 4 hours).
Solution #3 was 6.17% silk concentration (prepared by 30min boiling extraction, 100 ℃ LiBr dissolution for 1 hour).
Films were prepared according to Rockwood et al (Nature Protocols; volume 6; phase 10; release on line at month 9, 2011; doi: 10.1038/nprot.2011.379). 4mL of 1% or 2% (wt/vol) silk in water was added to a 100mm Petri dish (which can change the silk volume for thicker or thinner films and is not important) and left to open dry overnight. The bottom of the vacuum dryer was filled with water. The dry film was placed in a desiccator and vacuum was applied to allow the film to water anneal (WATER ANNEAL) for 4 hours before being removed from the dish. The film cast from solution #1 did not give a structurally continuous film; the film was split into several pieces. These film fragments are dissolved in water despite the water annealing treatment.
Silk solutions of various molecular weights and/or molecular weight combinations may be optimized for gel applications. An example of such a method is provided below, but is not intended to be limiting in application or formulation. Three (3) silk solutions were used in the gel preparation, with the following results:
Solution #1 was 5.9% silk concentration, average MW of 19.8kDa and 2.2PD (prepared by 60 min boiling extraction, liBr dissolution at 100℃for 1 hour). Degree (C)
Solution #2 was 6.4% silk concentration (prepared by 30 min boiling extraction, 60 ℃ LiBr dissolution for 4 hours).
Solution #3 was 6.17% silk concentration (prepared by 30min boiling extraction, 100 ℃ LiBr dissolution for 1 hour).
"Egel" is an electro-gel (electrogelation) method as described by Rockwood et al. Briefly, 10ml of an aqueous wire solution was added to a 50ml conical tube and a pair of platinum wire electrodes were immersed in the wire solution. A 20 volt potential 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 during the 5 minute period of applied current.
Solutions #2 and #3 gel according to the published horseradish peroxidase (HRP) procedure. The properties appear to be typical of the disclosed solutions.
Materials and methods the following equipment and materials were used in the determination of the silk molecular weight: with chemstation software; agilent 1100 version 10.01; refractive Index Detector (RID); an analytical balance; volumetric flasks (1000 mL, 10mL, and 5 mL); HPLC grade water; ACS grade sodium chloride; ACS grade disodium hydrogen phosphate heptahydrate; phosphoric acid; dextran MW standard-nominal molecular weights 5kDa, 11.6kDa, 23.8kDa, 48.6kDa and 148kDa;50mL PET or polypropylene disposable centrifuge tube; straw with graduation; amber glass HPLC vial with Teflon cap; phenomenex PolySep GFC P-4000 columns (size: 7.8 mm. Times.300 mm).
The procedure steps are:
A) Preparation of 1L Mobile phase (0.1M sodium chloride solution in 0.0125M sodium phosphate buffer)
A 250mL clean dry beaker was taken, placed on a balance and peeled heavy. About 3.3509g of disodium phosphate heptahydrate was added to the beaker. The exact weight of the weighed disodium hydrogen phosphate was recorded. The weighed-in sodium phosphate was dissolved by adding 100mL of HPLC water to the beaker. Care was taken not to spill any contents of the beaker. The solution was carefully transferred to a clean dry 1000mL volumetric flask. The beaker was rinsed and the rinse was transferred to a volumetric flask. Rinsing was repeated 4-5 times. In a separate clean dry 250mL beaker, approximately 5.8440g of sodium chloride was weighed accurately. The weighed sodium chloride was dissolved in 50mL of water and the solution was transferred to a sodium phosphate solution in a volumetric flask. The beaker was rinsed and the rinse was transferred to a volumetric flask. The pH of the solution was adjusted to 7.0.+ -. 0.2 with phosphoric acid. The volume in the volumetric flask was made up to 1000mL with HPLC water and vigorously shaken to mix the solution uniformly. The solution was filtered through a 0.45 μm polyamide membrane filter. The solution was transferred to clean dry solvent bottles and the bottles were labeled. The volume of the solution can be varied as desired by varying the amounts of disodium phosphate heptahydrate and sodium chloride accordingly.
B) Preparation of dextran molecular weight Standard solution
At least five different molecular weight standards are used for each batch of samples run so that the expected value of the sample under test is encompassed by the value of the standard used. Six 20mL scintillation glass vials were individually labeled as molecular weight standards. About 5 mg of each dextran molecular weight standard was accurately weighed and the weight was recorded. Dextran molecular weight standards were dissolved in 5mL mobile phase to prepare 1mg/mL standard solutions.
C) Preparation of sample solutions
When preparing a sample solution, if there is a limit on how many samples can be provided, the preparation can be scaled up as long as the ratio is maintained. Depending on the type of sample and the silk protein content in the sample, enough sample is weighed into a 50mL disposable centrifuge tube on an analytical balance to prepare a 1mg/mL sample solution for analysis. The sample was dissolved in an equal volume of mobile phase to prepare a 1mg/mL solution. The tubes were covered tightly and the samples (in solution) were mixed. The sample solution was allowed to stand at room temperature for 30 minutes. The sample solution was gently mixed for an additional 1 minute and centrifuged at 4000RPM for 10 minutes.
D) HPLC analysis of samples
Transfer 1.0mL of all standard and sample solutions into a separate HPLC vial. Molecular weight standards (one sample per sample) and samples were injected in duplicate. All standards and sample solutions were analyzed using the following HPLC conditions:
Column PolySep GFC P-4000(7.8×300mm)
Column temperature 25℃
Detector for detecting a target object Refractive index detector (temperature 35 ℃ C.)
Injection quantity 25.0μL
Mobile phase Solution of 0.1M sodium chloride in 0.0125M sodium phosphate buffer
Flow rate 1.0mL/min
Run time 20.0min
Data analysis and calculation-calculation of average molecular weight using Cirrus software
Chromatographic data files of standard and analytical samples were uploaded into Cirrus SEC data collection and molecular weight analysis software. The weight average molecular weight (M w), number average molecular weight (M n), peak average molecular weight (M p) and polydispersity of the samples per sample introduction were calculated.
Spider silk segment
Spider silk is a natural polymer consisting of three domains: a repeating intermediate core domain and non-repeating N-and C-terminal domains that predominate in the protein chain. The large core domains are organized in a block copolymer-like arrangement in which two basic sequences-the crystalline polypeptide [ poly (A) or poly (GA) ] and the lower crystalline polypeptide (GGX or GPGXX (SEQ ID NO: 6)) -alternate in the core domains. Dragline (DRAGLINE SILK) is a protein complex consisting of large ampullate dragline 1 (MaSp 1) and large ampullate dragline 2 (MaSp 2). Both filaments were about 3500 amino acids long. MaSp1 can be found in the fiber core and periphery, while MaSp2 forms clusters in certain core regions. The large central domains of MaSp1 and MaSp2 are organized in a block copolymer-like arrangement, wherein the two basic sequences-the crystalline polypeptide [ poly (A) or poly (GA) ] and the lower crystalline polypeptide (GGX or GPGXX (SEQ ID NO: 6)) -alternate in the core domain. Specific secondary structures have been assigned to poly (A)/(GA), GGX and GPGXX (SEQ ID NO: 6) motifs, including beta-sheet, alpha-helix and beta-helix, respectively. The primary sequence, composition and secondary structural elements of the repetitive core domain determine the mechanical properties of the spider silk; rather than repeating the N-and C-terminal domains, it is critical to store liquid silk dope in the lumen and to form fibers in the spinning conduits.
The main difference between MaSp1 and MaSp2 is the presence of 15% proline (P) residues in the MaSp2, relative to the total amino acid content, whereas MaSp1 does not contain proline. By calculating the number of proline residues in the luffa spider (n.clavipes) dragline silk, the presence of these two proteins in the fiber can be estimated; 81% MaSp1 and 19% MaSp2. Different spiders have different MaSp1 and MaSp2 ratios. For example, dragline fibers from macula Jin Zhu (Argiope aurantia) of the family Araliaceae (orb weaver) contain 41% MaSp1 and 59% MaSp2. This change in the ratio of large pot gland filaments can determine the properties of the filaments.
For spiders of one Araneaceae species, at least seven different types of silk proteins are known. Filaments differ in primary sequence, physical properties, and function. For example, draglines used to construct frames, radiation (radii) and skeleton lines (lifelines) are known for their excellent mechanical properties, including strength, toughness and elasticity. The toughness of spider silk is higher than steel and Kevlar on an equal weight basis. The whip wire (flageliform silk) present in the catch helix (capture spirals) has a ductility of up to 500%. The small pot gland filaments present in the auxiliary spiral (auxiliary spirals) of the cylinder mould (orb-web) and the game package (PREY WRAPPING) have a high tenacity and strength almost similar to the large pot gland filaments, but do not shrink too much in water.
Spider filaments are known for their high tensile strength and toughness. Recombinant silk proteins also impart advantageous properties to cosmetic or dermatological compositions, in particular being able to improve hydration or softening, good film-forming properties and low surface density. The diverse and unique biomechanical properties, together with biocompatibility and slow degradation rates, make spider silk an excellent candidate as a biomaterial for tissue engineering, guided tissue repair and drug delivery, for cosmetic products (e.g. nail and hair enhancers, skin care products) and industrial materials (e.g. nanowires, nanofibers, surface coatings).
In one embodiment, the silk protein may comprise a polypeptide derived from a natural spider silk protein. The polypeptide is not particularly limited as long as it is derived from a natural spider silk protein, and examples of the polypeptide include natural spider silk proteins and recombinant spider silk proteins, such as variants, analogs, derivatives, and the like of natural spider silk proteins. In terms of excellent toughness, the polypeptides may be derived from the major dragline silk proteins produced in the major ampullate glands of spiders. Examples of major dragline silk proteins include major ampullate spidroin MaSp1 and MaSp2 from Nelumbo spiders (NEPHILA CLAVIPES), ADF3 and ADF4 from Aralia sericata (Araneus diadematus), and the like. Examples of polypeptides derived from major dragline silk proteins include variants, analogs, derivatives, and the like of major dragline silk proteins. In addition, the polypeptide may be derived from a flagellin produced in the flagellin of a spider. Examples of the flagellin include flagellin derived from a spider belonging to the genus Nelumbo, and the like.
Examples of the polypeptide derived from the main dragline silk protein include polypeptides comprising two or more units of the amino acid sequence represented by formula 1:rep1-REP2 (1), preferably polypeptides comprising five or more units thereof, more preferably polypeptides comprising ten or more units thereof. Or the polypeptide derived from the major dragline silk protein may be a polypeptide comprising a unit of the amino acid sequence represented by formula 1:rep1-REP2 (1) and having at the C-terminus the amino acid sequence represented by any one of SEQ ID NOs 52 to 54 (also described in U.S. patent 9,051,453, incorporated herein by reference in its entirety) or an amino acid sequence having 90% or more homology to the amino acid sequence represented by any one of SEQ ID NOs 52 to 54 (also described in U.S. patent 9,051,453, incorporated herein by reference in its entirety). In polypeptides derived from major dragline silk proteins, the units of the amino acid sequences represented by formulas 1:REP1-REP2 (1) may be identical to or may be different from each other. In the case of producing a recombinant protein using a microorganism such as E.coli (ESCHERICHIA COLI) as a host, the molecular weight of the polypeptide derived from the main dragline silk protein is 500kDa or less, or 300kDa or less, or 200kDa or less in view of productivity.
In formula (1), REP1 refers to polyalanine. In REP1, the number of alanine residues arranged in succession is preferably 2 or more, more preferably 3 or more, further preferably 4 or more, particularly preferably 5 or more. Furthermore, in REP1, the number of alanine residues in the continuous arrangement is preferably 20 or less, more preferably 16 or less, further preferably 12 or less, particularly preferably 10 or less. In formula (1), REP2 is an amino acid sequence consisting 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, more preferably 70% or more relative to the total number of amino acid residues contained therein.
In a primary tow, REP1 corresponds to a crystalline region in the fiber in which crystalline beta sheets are formed, and REP2 corresponds to an amorphous region in the fiber in which most of the portions lack a regular configuration and have greater flexibility. In addition, [ REP1-REP2] corresponds to a repeating region (repeating sequence) composed of a crystalline region and an amorphous region, which is a characteristic sequence of dragline 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 scallop silk polypeptide. In some embodiments, the recombinant silk protein fragments disclosed herein include recombinant spider silk polypeptides of the family Araneidae (Araneidae) or Araneids, or recombinant insect silk polypeptides of Bombyx mori (Bombyxmori). In some embodiments, the recombinant silk protein fragments disclosed herein comprise recombinant spider silk polypeptides of the family Araneidae (Araneidae) or Araneoids. In some embodiments, the recombinant silk protein fragments disclosed herein include block copolymers having repeat units derived from natural spider silk polypeptides of the family Araneidae (Araneidae) or Araneids. In some embodiments, the recombinant silk protein fragments disclosed herein include block copolymers having synthetic repeat units derived from a spider silk polypeptide of the family Araneidae (Araneidae) or Araneids and non-repeat units derived from natural repeat units of a spider silk polypeptide of the family Araneidae (Araneidae) or Araneids.
Recent advances in genetic engineering have provided routes to the production of various types of recombinant silk proteins. Recombinant DNA technology has been used to provide a more practical source of silk proteins. 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 have been described by Ausubel et al Current Protocols in Molecular Biology ≡8 (John Wiley & Sons 1987, (1990)), which is incorporated herein by reference. Gram-negative E.coli (E.coli) is an approved host for the production of proteins on an industrial scale. Thus, most recombinant filaments have been produced in E.coli. Coli is easy to handle, has a short generation time, is relatively low cost and can be scaled up for larger amounts of protein production.
Recombinant silk proteins can be produced by a transformed eukaryotic or prokaryotic system containing a cDNA encoding a silk protein, a fragment of such a protein, or an analog of such a protein. The recombinant DNA pathway is capable of producing recombinant filaments having a programmed sequence, secondary structure, architecture, and precise molecular weight. There are four main steps in the method: (i) designing and assembling synthetic silk-like genes into a gene "cassette" (ii) inserting such fragments into a DNA recombinant vector, (iii) transforming such recombinant DNA molecules into host cells and (iv) expression and purification of selected clones.
The term "recombinant vector" as used herein includes any vector known to the skilled person, 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 Chromosome (BAC), yeast Artificial Chromosome (YAC) or P1 Artificial Chromosome (PAC). The vector comprises an expression vector and a cloning vector. Expression vectors include plasmids as well as viral vectors and typically contain the desired coding sequence and appropriate DNA sequences necessary for expression of the operably linked coding sequence (operably linked coding sequence) in a particular host organism (e.g., bacteria, yeast or plant) or in an in vitro expression system. Cloning vectors are commonly used for engineering (engineering) and amplification of specific desired DNA fragments and may lack the functional sequences required for expression of the desired DNA fragments.
Prokaryotic systems include gram-negative bacteria or gram-positive bacteria. Prokaryotic expression vectors may include an origin of replication recognizable by the host organism, a homologous or heterologous promoter functional in the host, a DNA sequence encoding a spider silk protein, a fragment of such a protein, or a similar protein. Non-limiting examples of prokaryotic expression organisms are E.coli, bacillus subtilis, bacillus megaterium, corynebacterium glutamicum, anabaena, stemona, gluconobacter, rhodobacter, pseudomonas, paracoccus, bacillus (e.g., bacillus subtilis), brevibacterium, corynebacterium, rhizobium (Sinorhizobium), flavobacterium, klebsiella, enterobacter, lactobacillus, lactococcus, methylobacillus, propionibacterium, staphylococcus or Streptomyces cells.
Eukaryotic systems include yeast and insect, mammalian or plant cells. In this case, the expression vector may include a yeast plasmid replication origin or autonomous replication sequence, a promoter, a DNA sequence encoding a spider silk protein, a fragment or the like, 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, basidiomycetes (basidiosporogenous), ascomycetes (ascosporogenous), filamentous fungi such as Aspergillus niger, aspergillus oryzae, aspergillus nidulans, trichoderma reesei, cephalosporium acremonium (Acremoniumchrysogenum), candida, hansenula, kluyveromyces, saccharomyces (Saccharomyces) (e.g., saccharomyces cerevisiae), schizosaccharomyces, pichia (e.g., pichia) or yarrowia cells, etc., mammalian cells such as HeLa cells, COS cells, CHO cells, etc., insect cells such as Sf9 cells, MEL cells, etc., an "insect host cell" such as Spodoptera frugiperda or Spodoptera frugiperda cells, SF9 cells, SF-21 cells or High-Five cells, where SF-9 and SF-21 are ovarian cells from Spodoptera frugiperda and High-Five cells are egg cells from Spodoptera frugiperda, "plant host cells", such as tobacco, potato or pea cells.
Various heterologous host systems have been developed for the production of different types of recombinant silk. Recombinant portions of spider silk proteins and engineered filaments have been cloned and expressed in bacteria (e.coli), yeast (pichia), insects (silkworm larvae), plants (tobacco, soybean, potato, arabidopsis), mammalian cell lines (BHT/hamster) and transgenic animals (mice, goats). Most silk proteins made have an N-or C-terminal His-tag to make purification simple and produce sufficient protein.
In some embodiments, hosts suitable for expressing recombinant spider silk proteins using heterologous systems may include transgenic animals and plants. In some embodiments, hosts suitable for expressing recombinant spider silk proteins using heterologous systems comprise bacterial, yeast, mammalian cell lines. In some embodiments, a host suitable for expressing a recombinant spider silk protein using a heterologous system comprises E.coli. In some embodiments, a host suitable for expressing recombinant spider silk proteins using a heterologous system comprises a transgenic silkworm (b.mori) produced using genome editing techniques (e.g., CRISPR).
Recombinant silk proteins in the present disclosure comprise synthetic proteins based on repeat units of natural silk proteins. These may additionally comprise one or more natural non-repetitive silk protein sequences in addition to the synthetic repetitive silk protein sequences.
In some embodiments, "recombinant silk protein" refers to recombinant silk protein or fragments thereof. Recombinant production of fibroin and sericin has been reported. Various hosts are used for this production, including E.coli, saccharomyces cerevisiae, pseudomonas, rhodopseudomonas, bacillus and Streptomyces. See EP 0230702, incorporated herein by reference in its entirety.
Also provided herein are the design and biosynthesis of fibroin-like multi-block polymers comprising GAGAGX (SEQ ID NO: 1) hexapeptide (X is A, Y, V or S) derived from the repeat domain of the silk heavy chain (H chain) of a silk family.
In some embodiments, the present disclosure provides silk-like multi-block polymers derived from a repeat domain of a silk heavy chain (H chain) of a silkworm comprising GAGAGS (SEQ ID NO: 2) hexapeptide repeat units. GAGAGS (SEQ ID NO: 2) hexapeptide is the core unit of the H chain and plays an important role in the formation of the crystalline domain. The silk-like multiblock polymer containing GAGAGS (SEQ ID NO: 2) hexapeptide repeat units spontaneously aggregates into a beta-sheet structure similar to native silk fibroin, with any of the weight average molecular weights described herein in the silk-like multiblock polymer.
In some embodiments, the present disclosure provides silk peptide-like multiblock copolymers consisting of GAGAGS (SEQ ID NO: 2) hexapeptide repeat derived from the H chain of the silk heavy chain of a family and the E.coli produced mammalian elastin VPGVG (SEQ ID NO: 3) motif. In some embodiments, the present disclosure provides a fusion fibroin consisting of GAGAGS (SEQ ID NO: 2) hexapeptide repeat fragment derived from the H chain of silk heavy chain of a family and E.coli produced GVGVP (SEQ ID NO: 4), wherein there is any weight average molecular weight described herein in the fibroin-like multi-block polymer.
In some embodiments, the present disclosure provides a recombinant protein of Bombyx mori consisting of a repeat of (GAGAGS) 16 (SEQ ID NO: 55). In some embodiments, the present disclosure provides a recombinant protein consisting of (GAGAGS) 16 (SEQ ID NO: 55) repeat fragment and E.coli produced non-repeat (GAGAGS)16–F-COOH(SEQ ID NO:56)、(GAGAGS)16–F-F-COOH(SEQ ID NO:57)、(GAGAGS)16–F-F-F-COOH(SEQ ID NO:58)、(GAGAGS)16–F-F-F-F-COOH(SEQ ID NO:59)、(GAGAGS)16–F-F-F-F-F-F-F-F-COOH(SEQ ID NO:60)、(GAGAGS)16–F-F-F-F–F-F-F-F-F-F-F-F-COOH(SEQ ID NO:61), wherein F has the following amino acid sequence SGFGPVANGGSGEASSESDFGSSGFGPVANASSGEASSESDFAG (SEQ ID NO: 5), and wherein there is any weight average molecular weight as described herein in the silk-like multiblock polymer.
In some embodiments, "recombinant silk protein" refers to a recombinant spider silk protein or fragment thereof. Recombinant spider silk proteins have been reported to be produced based on partial cDNA clones. The recombinant spider silk protein thus produced comprises a portion of a repeat sequence derived from spider stick thread spider silk protein Spidroin from a spider of the genus spider web neo. See Xu et al (proc. Natl. Acad. Sci. U.S. A.; 87:7120-7124 (1990); cDNA clones encoding a portion of the repeat sequence of the second filaggrin Spidroin 2 from Nelumbo spiders and recombinant synthesis thereof are described in J. Biol. Chem.,1992,volume 267,pp.19320-19324. Spider silk proteins comprising protein fragments and variants by recombinant synthesis of transformed E.coli are described in U.S. Pat. No. 5,728,810 and 5,989,894. CDNA clones encoding small pot gland spider silk proteins and expression thereof are described in U.S. Pat. No. 5,733,771 and 5,756,677. CDNA clones encoding flagelliform gland silk proteins from orb-web spiking spiders are described in U.S. Pat. No. 5,994,099. U.S. Pat. No. 6,268,169 describes recombinant synthesis of spider silk-like proteins derived from the repeat peptide sequences present in the natural spider dragline of Nelumbo spiders by E.coli, bacillus subtilis and yeast recombinant expression systems WO 03/020916 describes golden spheres Nephila madagascariensis、Nephila senegalensis、Tetragnatha kauaiensis、Tetragnatha versicolor、Argiope aurantia、Argiope trifasciata、Gasteracantha mammosa and cDNA clones encoding small pot gland spider silk proteins and cDNA clones derived from the whole set of spider spidroin U.S. Pat. No. 35,585, and cDNA clones derived from the whole spider spidroin U.S. Pat. No. 5, mygalomorph Euagrus chisoseus.
In some embodiments, the recombinant spidroin is a hybrid of spidroin and insect silk, spidroin and collagen, spidroin and leg elastin, or spidroin and keratin. The spider silk repeat unit comprises or consists of the amino acid sequence of: the region comprises or consists of at least one peptide motif that is repeated within a naturally occurring major ampullate polypeptide, such as a dragline, minor ampullate, whip, polyglandular (aggregate), grape or pear-shaped (pyriform) spider silk polypeptide.
In some embodiments, the recombinant spidroin proteins in the present disclosure comprise synthetic spidroin proteins derived from the repeat units, the consensus sequence, and optionally one or more natural non-repeat spidroin sequences of the natural spidroin proteins. The repeat units of the natural spider silk polypeptide may include a dragline silk polypeptide or a whip gland spider silk polypeptide of the Araneidae (Araneidae) or Araneids.
As used herein, a spider silk "repeat unit" comprises or consists of at least one peptide motif that repeats within a naturally occurring major ampullate polypeptide, such as a dragline silk polypeptide, a minor ampullate polypeptide, a whip gland polypeptide, a polyvidone silk polypeptide, a viniform gland spider silk polypeptide, or a piriform gland spider silk polypeptide. "repeat unit" refers to a region (i.e., the same amino acid sequence) that corresponds in amino acid sequence to a region comprising or consisting of at least one peptide motif (e.g., AAAAAA (SEQ ID NO: 20) or GPGQQ (SEQ ID NO: 15)) that is repeated within a naturally occurring silk polypeptide (e.g., maSpI, ADF-3, ADF-4, or Flag) or to an amino acid sequence that is substantially similar thereto (i.e., a variant amino acid sequence). "repeat units" having an amino acid sequence that is "substantially similar" to the corresponding amino acid sequence (i.e., wild-type repeat units) within a naturally occurring silk polypeptide are also similar in their properties, e.g., silk proteins comprising "substantially similar repeat units" are insoluble and remain insoluble. "repeat units" having an amino acid sequence "identical" to the amino acid sequence of a naturally occurring silk polypeptide can be, for example, portions of the silk polypeptide corresponding to one or more peptide motifs of MaSpI (SEQ ID NO: 48), maSpII (SEQ ID NO: 49), ADF-3 (SEQ ID NO: 50), and/or ADF-4 (SEQ ID NO: 51). A "repeat unit" having an amino acid sequence "substantially similar" to the amino acid sequence of a naturally occurring silk polypeptide may be, for example, a portion of the silk polypeptide that corresponds to one or more peptide motifs of 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 has one or more amino acid substitutions at a particular amino acid position.
As used herein, the term "consensus peptide sequence" refers to an amino acid sequence that contains amino acids that frequently occur at a position (e.g., "G") and in which other amino acids not further defined are replaced by placeholders "X". In some embodiments, the consensus sequence is at least one of: (i) GPGXX (SEQ ID NO: 6), wherein X is an amino acid selected from A, S, G, Y, P and Q; (ii) GGX, wherein X is an amino acid selected from Y, P, R, S, A, T, N and Q, preferably Y, P and Q; (iii) A x, wherein x is an integer from 5 to 10.
The consensus peptide sequence of GPGXX (SEQ ID NO: 6) and GGX, i.e.the glycine-rich motif, provides flexibility to the silk polypeptide and thus to the line formed by the silk protein containing said motif. In detail, the iterative GPGXX (SEQ ID NO: 6) motif forms a rotary helix structure that confers elasticity to the silk polypeptide. Both the large pot gland and the flagelliforme silk have the GPGXX (SEQ ID NO: 6) motif. The iterative GGX motif is associated with a helical structure with three amino acids per turn and is present in most spidroin. GGX motifs can provide additional elasticity to the filament. The iterative polyalanine Ax (peptide) motif forms a crystalline β -sheet structure to provide strength to the silk polypeptide as described, for example, in WO 03/057727.
In some embodiments, the recombinant spider silk proteins in the present disclosure comprise two identical repeat units, each comprising at least one, preferably one, selected from the group consisting of: amino acid sequences derived from the human integrins GGRPSDTYG (SEQ ID NO: 7) and GGRPSSSYG (SEQ ID NO: 8). The arthropod elastin is an elastomeric protein found in most arthropods that provides low stiffness and high strength.
As used herein, "non-repeating unit" refers to an amino acid sequence that is "substantially similar" to the amino acid sequence described above within the corresponding non-repeating (carboxy-terminal) amino acid sequence (i.e., wild-type non-repeating (carboxy-terminal) unit) within a naturally occurring dragline silk polypeptide, preferably the 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's spider (also described in U.S. patent 9,217,017, which is incorporated herein by reference in its entirety), the 16 repeated C16 peptide (spider silk protein eADF, molecular weight 47.7kDa, AMSilk) comprising sequence GSSAAAAAAAASGPGGYGPENQGPSGPGGYGPGGP (SEQ ID NO: 9) from the ADF's natural sequence of 4. Non-repeating ADF-4 and variants thereof exhibit efficient assembly characteristics.
In synthesizing spider silk proteins, the recombinant silk proteins in the present disclosure in some embodiments comprise a C16 protein having the polypeptide sequence SEQ ID NO. 64 (also described in U.S. Pat. No. 8288512, incorporated herein by reference in its entirety). In addition to the polypeptide sequence shown in SEQ ID NO. 64, functional equivalents, functional derivatives and salts of such sequences are also specifically included.
"Functional equivalent" as used herein refers to a mutant having an amino acid different from the specifically mentioned amino acid at least one sequence position of the above-mentioned amino acid sequences.
In some embodiments, the recombinant spidroin proteins in the present disclosure comprise an effective amount of at least one natural or recombinant spidroin protein, including spidroin proteins, corresponding to Xu et al, PNAS, USA,87,7120, (1990) Spidroin major, hinman and Lewis, j.biol.chem.,267,19320, (1922) Spidroin major 2, recombinant spidroin proteins as described in U.S. patent application 2016/0222174 and U.S. patent 9,051,453、9,617,315、9,689,089、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 small spidroin proteins (minor Spidroins) as described in patent application WO 95/25165. The references cited above are each incorporated herein by reference in their entirety. Additional recombinant spidroin proteins suitable for use in the recombinant RSPF of the present disclosure include ADF3 and ADF4 from the "major ampullate gland" of the spider.
Recombinant filaments are also described in other patents and patent applications :US 2004590196、US 7,754,851、US2007654470、US 7,951,908、US2010785960、US 8,034,897、US20090263430、US2008226854、US20090123967、US 2005712095、US2007991037、US20090162896、US200885266、US 8,372,436、US2007989907、US2009267596、US2010319542、US 2009265344、US2012684607、US2004583227、US 8,030,024、US 2006643569、US 7,868,146、US2007991916、US 8,097,583、US2006643200、US 8,729,238、US 8,877,903、US20190062557、US20160280960、US 20110201783、US2008991916、US2011986662、US2012697729、US 20150328363、US 9,034,816、US20130172478、US 9,217,017、US 20170202995、US 8,721,991、US2008227498、US 9,233,067、US 8,288,512、US2008161364、US 7,148,039、US1999247806、US2001861597、US 2004887100、US 9,481,719、US 8,765,688、US200880705、US2010809102、US 8,367,803、US2010664902、US 7,569,660、US1999138833、US 2000591632、US20120065126、US20100278882、US2008161352、US20100015070、US2009513709、US20090194317、US2004559286、US 200589551、US2008187824、US20050266242、US20050227322 and US 20044418, which are incorporated herein by reference.
Recombinant filaments are also described in other patents and patent applications :US 20190062557、US20150284565、US20130225476、US20130172478、US 20130136779、US20130109762、US20120252294、US20110230911、US 20110201783、US20100298877、US10,478,520、US10,253,213、US 10,072,152、US 9,233,067、US 9,217,017、US 9,034,816、US 8,877,903、US 8,729,238、US 8,721,991、US 8,097,583、US 8,034,897、US 8,030,024、US 7,951,908、US 7,868,146 and US 7,754,851, which are incorporated herein by reference.
In some embodiments, the recombinant spider silk proteins in the present disclosure comprise or consist of 2 to 80 repeat units, each independently selected from GPGXX (SEQ ID NO: 6), GGX and A x as defined herein.
In some embodiments, the recombinant spider silk proteins in the present disclosure comprise or consist of repeat units each selected from the group :GPGAS(SEQ ID NO:10)、GPGSG(SEQ ID NO:11)、GPGGY(SEQ ID 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、AAAAA(SEQ ID NO:19)、AAAAAA(SEQ ID NO:20)、AAAAAAA(SEQ ID NO:21)、AAAAAAAA(SEQ ID NO:22)、AAAAAAAAA(SEQ ID NO:23)、AAAAAAAAAA(SEQ ID NO:24)、GGRPSDTYG(SEQ ID NO:7) and GGRPSSSYG(SEQ ID NO:8)、(i)GPYGPGASAAAAAAGGYGPGSGQQ(SEQ ID NO:25)、(ii)GSSAAAAAAAASGPGGYGPENQGPSGPGGYGPGGP(SEQ ID NO:9)、(iii)GPGQQGPGQQGPGQQGPGQQ(SEQ ID NO:26)、(iv)GPGGAGGPYGPGGAGGPYGPGGAGGPY(SEQ ID NO:27)、(v)GGTTIIEDLDITIDGADGPITISEELTI(SEQ ID NO:28)、(vi)PGSSAAAAAAAASGPGQGQGQGQGQGGRPSDTYG(SEQ ID NO:29)、(vii)SAAAAAAAAGPGGGNGGRPSDTYGAPGGGNGGRPSSSYG(SEQ ID NO:30)、(viii)GGAGGAGGAGGSGGAGGS(SEQ ID NO:31)、(ix)GPGGAGPGGYGPGGSGPGGYGPGGSGPGGY(SEQ ID NO:32)、(x)GPYGPGASAAAAAAGGYGPGCGQQ(SEQ ID NO:33)、(xi)GPYGPGASAAAAAAGGYGPGKGQQ(SEQ ID NO:34)、(xii)GSSAAAAAAAASGPGGYGPENQGPCGPGGYGPGGP(SEQ ID NO:35)、(xiii)GSSAAAAAAAASGPGGYGPKNQGPSGPGGYGPGGP(SEQ ID NO:36)、(xiv)GSSAAAAAAAASGPGGYGPKNQGPCGPGGYGPGGP(SEQ ID NO:37), consisting of or variants thereof as described in U.S. patent 8,877,903, e.g., synthetic spider peptides having a sequence order of GPGAS (SEQ ID NO: 10), GGY, GPGSG (SEQ ID NO: 11) in the peptide chain or AAAAAAAA (SEQ ID NO: 22), GPGGY (SEQ ID NO: 12), GPGGP (SEQ ID NO: 13) in the peptide chain, AAAAAAAA (SEQ ID NO: 22), GPGQG (SEQ ID NO: 17), GGR in the peptide chain.
In some embodiments, the present disclosure provides silk-like multiblock peptides that mimic repeat units derived from amino acids of a natural spider silk protein, such as Spidroin major domain, spidroin major domain, or Spidroin minor domain, and the pattern of variation between the repeat units (profile of variation) without altering their three-dimensional conformation, wherein the silk-like multiblock peptides comprise amino acid repeat units corresponding to one of the following sequences (I), (II), (III), and/or (IV).
[ (XGG) w(XGA)(GXG)x(AGA)y(G)zAG]p (SEQ ID NO: 38) formula (I), wherein: x corresponds to tyrosine or to glutamine, w is an integer equal to 2 or 3, X is an integer from 1 to 3, y is an integer from 5 to 7, z is an integer equal to 1 or2, and p is an integer and has any weight average molecular weight described herein, and/or
[ (GPG 2YGPGQ2)a(X')2S(A)b]p (SEQ ID NO: 39) formula (II) wherein 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, p is an integer, and has any weight average molecular weight described herein, and/or
[ (GR) (GA) l(A)m(GGX)n(GA)l(A)m]p (SEQ ID NO: 40) formula (III) and/or [ (GGX ") n(GA)m(A)l]p (SEQ ID NO: 41) formula (IV), wherein: x "corresponds to tyrosine, glutamine or alanine, L is an integer from 1 to 6, m is an integer from 0 to 4, n is an integer from 1 to 4, and p is an integer.
In some embodiments, the recombinant spidroin protein or spidroin protein analogue comprises the amino acid repeat unit of sequence (V):
[(Xaa Gly Gly)w(Xaa Gly Ala)(Gly Xaa Gly)x(Ala Gly Ala)y(Gly)zAla Gly]p Formula (V), wherein Xaa is tyrosine or glutamine, w is an integer equal to 2 or 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 protein in the present disclosure is selected from ADF-3 or variants thereof, ADF-4 or variants thereof, maSpI or variants thereof, maSpII or variants thereof, as described in U.S. patent 9,217,017.
In some embodiments, the present disclosure provides water-soluble recombinant spider silk proteins made in mammalian cells. The solubility of spider silk proteins made in mammalian cells can be attributed to the presence of COOH termini in these proteins to render them more hydrophilic. These COOH-terminated amino acids are absent from the spider silk proteins expressed in the microbial host.
In some embodiments, the recombinant spidroin proteins in the disclosure include water-soluble recombinant spidroin protein C16 modified with amino or carboxyl end groups selected from the group consisting of amino acid sequences :GCGGGGGG(SEQ ID NO:42)、GKGGGGGG(SEQ ID NO:43)、GCGGSGGGGSGGGG(SEQ ID NO:44)、GKGGGGGGSGGGG(SEQ ID NO:45) and GCGGGGGGSGGGG (SEQ ID NO: 46). In some embodiments, the recombinant spider silk proteins in the present disclosure comprise C 16NR4、C32NR4、C16、C32、NR4C16NR4、NR4C32NR4、NR3C16 NR3 or NR3C 32 NR3 such that the molecular weight of the proteins is within the ranges described herein.
In some embodiments, the recombinant spider silk proteins in the present disclosure comprise recombinant spider silk proteins having synthetic repeat peptide segments and amino acid sequences engineered from the natural sequence of ADF4 from spider silk, as described in U.S. patent 8,877,903. In some embodiments RSPF in the present disclosure includes the recombinant spidroin proteins described as having a repeating peptide unit derived from a natural spidroin protein, such as Spidroin major domain, spidroin major domain, or Spidroin minor domain, wherein the repeating peptide sequence is GSSAAAAAAAASGPGQGQGQGQGQGGRPSDTYG (SEQ ID NO: 47) or SAAAAAAAAGPGGGNGGRPSDTYGAPGGGNGGRPSSSYG (SEQ ID NO: 30), as described in U.S. patent 8,367,803, which is incorporated herein by reference in its entirety.
In some embodiments, the present disclosure provides recombinant spidroin proteins consisting of GPGGAGPGGYGPGGSGPGGYGPGGSGPGGY (SEQ ID NO: 32) repeats and having a molecular weight as described herein.
As used herein, the term "recombinant silk" refers to recombinant spider silk and/or silk proteins or fragments thereof. In one embodiment, the spider silk protein is selected from the group consisting of wrap silk (SWATHING SILK) (grape (Achniform) gland silk), egg bag silk (EGG SACSILK) (cylindrical (Cylindriform) gland silk), egg bag silk (EGG CASE SILK) (tubular (Tubuliform) gland silk), non-adhesive dragline silk (pot (Ampullate) gland silk), accessory wire (ATTACHING THREAD SILK) (pear gland silk), adhesive silk core fiber (whip (Flagelliform) gland silk), and adhesive silk outer fiber (poly gland silk). For example, recombinant spider silk proteins as described herein include proteins described in U.S. patent application 2016/0222174 and U.S. patent 9,051,453, 9,617,315, 9,689,089, 8,173,772, and 8,642,734.
Some organisms produce a variety of silk fibers with unique sequences, structural elements, and mechanical properties. For example, a circular mesh (orb weaving) spider has six unique types of glands to produce different silk polypeptide sequences that are polymerized into fibers that are compatible with the environment or life cycle niche (LIFECYCLE NICHE). These fibers are named after the glands from which they are derived, and the polypeptides are labeled with glandular abbreviations (e.g., "Ma") and "Sp", i.e., spider silk proteins (shorthand for spider silk fibroin). In the circular spider, these types include the large ampullate gland (MaSp, also known as dragline), the small ampullate gland (MiSp), the whip gland (Flag), the grape gland (AcSp), the tubular gland (TuSp), and the pear gland (PySp). This combination of polypeptide sequences that span fiber types, domains, and varies between organisms of different genus and species brings a large array of potential properties that can be controlled by commercial production of recombinant fibers. To date, most of the work on recombinant silk has focused on major ampullate spidroin protein (MaSp).
The parathyroid gland (AcSp) filaments tend to have high tenacity as a result of the combination of medium to high strength and medium to high ductility. AcSp filaments are characterized by a large block ("global repeat") size, which generally contains motifs of polyserine and GPX. Tubular gland (TuSp or CYLINDRICAL) filaments tend to have large diameters, as well as moderate strength and high ductility. TuSp filaments are characterized by their polyserine and polythreonine content, and short stretches of polyalanine. Large ampullate gland (MaSp) filaments tend to have high strength and moderate ductility. MaSp filaments may be one of two subtypes: maSp1 and MaSp2.MaSp1 filaments are generally less ductile than MaSp2 filaments and are characterized by polyalanine, GX and GGX motifs. MaSp2 filaments are characterized by polyalanine, GGX and GPX motifs. Small ampullate gland (mirp) filaments tend to have moderate strength and moderate ductility. MiSp filaments are characterized by GGX, GA and poly A motifs and typically contain spacer units of about 100 amino acids. Whip wires tend to have extremely high ductility and moderate strength. Flag filaments are generally characterized by GPG, GGX and short spacer motifs.
Silk polypeptides are characteristically composed of a repeat domain (REP) and non-repeat regions (e.g., C-terminal and N-terminal domains) flanking it. In one embodiment, both the C-terminal and N-terminal domains are 75-350 amino acids in length. The repeat domain exhibits a hierarchical structure. The repeat domain comprises a series of blocks (also referred to as repeat units). These blocks repeat in the silk repeat domain, sometimes perfect, and sometimes imperfect (constituting quasi-repeat domains). The length and composition of the blocks varies between different filament types and between different species. Table 1 of U.S. published application 2016/0222174, which is incorporated herein in its entirety, lists examples of block sequences from selected species and filament types, further examples being given in ringing, A.et al ,Spider silk proteins:recent advances in recombinant production,structure-function relationships and biomedical applications,Cell Mol.Life Sci.,68:2,pg 169-184(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 may be arranged in a regular pattern to form larger repeats (macro-repeats) that occur multiple times (typically 2-8 times) in the repeat domain of the silk sequence. The repeat blocks within the repeat domain or large repeat and the repeat large repeat within the repeat domain may be separated by a spacer unit.
Construction of certain spider block copolymer polypeptides from these blocks and/or large repeat domains according to certain embodiments of the present disclosure is described in U.S. published patent application 2016/0222174.
Recombinant block copolymer polypeptides based on spider silk sequences made by gene expression in recombinant prokaryotic or eukaryotic systems can be purified according to methods known in the art. In a preferred embodiment, commercially available expression/secretion systems can be used whereby the recombinant polypeptide is expressed and thereafter secreted from the host cell for easy purification from the surrounding medium. An alternative method involves purifying the recombinant block copolymer polypeptide from a cell lysate (cell residue after disruption of cell integrity) derived from prokaryotic or eukaryotic cells expressing the polypeptide, if an expression/secretion vector is not used. Methods of producing such cell lysates are known to those skilled in the art. In some embodiments, the recombinant block copolymer polypeptide is isolated from a cell culture supernatant.
The recombinant block copolymer polypeptide may be purified by affinity isolation, for example by immunological interaction with an antibody that specifically binds the recombinant polypeptide, or by a nickel column for isolating the recombinant polypeptide labeled with 6-8 histidine residues at its N-or C-terminus, an alternative tag may comprise a FLAG epitope or a hemagglutinin epitope. Alternative tags may comprise FLAG epitopes or hemagglutinin epitopes. Such methods are commonly used by skilled practitioners.
Solutions of such polypeptides (i.e., recombinant silk proteins) can then be prepared and used as described herein.
In another embodiment, the recombinant silk proteins can be prepared according to the methods described in U.S. patent 8,642,734 (which is incorporated herein by reference in its entirety) and used as described herein.
In one embodiment, a recombinant spider silk protein is provided. The spider silk protein generally consists of 170 to 760 amino acid residues, such as 170 to 600 amino acid residues, preferably 280 to 600 amino acid residues, such as 300 to 400 amino acid residues, more preferably 340 to 380 amino acid residues. The small size is advantageous because longer spider silk proteins tend to form amorphous aggregates, which require the use of harsh solvents for dissolution and polymerization. The recombinant spidroin protein may comprise more than 760 residues, in particular in case the spidroin protein comprises more than two fragments derived from the N-terminal part of the spidroin protein, the spidroin protein comprises an N-terminal fragment consisting of at least one fragment (NT) derived from the corresponding part of the spidroin protein, and a repetitive fragment (REP) derived from the corresponding internal fragment of the spidroin protein. Optionally, the spider silk protein comprises a C-terminal fragment (CT) derived from a corresponding fragment of the spider silk protein. The spider silk protein generally comprises a single fragment (NT) derived from the N-terminal portion of the spider silk protein, but in preferred embodiments the N-terminal fragment comprises at least two, such as two, fragments (NTs) derived from the N-terminal portion of the spider silk protein. Thus, the spider silk proteins may be represented schematically by the formula NT m -REP or NT m -REP-CT, where m is 1 or higher, such as 2 or higher, preferably an integer in the range of 1-2, 1-4, 1-6, 2-4 or 2-6. Preferred spider silk proteins may be represented schematically by the formula NT 2 -REP or NT-REP, or NT 2 -REP-CT or NT-REP-CT. The protein fragments are typically covalently coupled via peptide bonds. In one embodiment, the spider silk protein consists of one or more NT fragments coupled to a REP fragment, optionally coupled to a CT fragment.
In one embodiment, the first step of the method of producing an isolated polymer of spider silk proteins involves expressing the polynucleic acid molecules encoding the spider silk proteins in a suitable host, such as E.coli. The protein thus obtained was isolated using standard procedures. Optionally, lipopolysaccharide and other pyrogens are actively removed at this stage.
In a second step of the method of producing an isolated polymer of 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 significantly aggregate at 60,000Xg and does not precipitate from the solvent. The liquid medium may be any suitable medium, such as an aqueous medium, preferably a physiological medium, typically a buffered aqueous medium, such as 10-50mM Tris-HCl buffer or phosphate buffer. The liquid medium has a pH of 6.4 or higher and/or an ionic composition that prevents polymerization of the spider silk proteins. That is, the liquid medium has a pH of 6.4 or higher or an ionic composition that prevents polymerization of the spidroin protein or both.
The skilled artisan can readily utilize the methods disclosed herein to prepare ionic compositions that prevent spider silk protein polymerization. Preferred ionic compositions that prevent spider silk proteins from polymerizing have an ionic strength greater than 300 mM. Specific examples of ionic compositions for preventing spider silk protein polymerization include combinations of more than 300mM NaCl, 100mM phosphate and these ions having the desired preventive effect on spider silk protein polymerization, for example, combinations of 10mM phosphate and 300mM NaCl.
The presence of the NT fragments improves the stability of the solution and prevents the formation of polymers under these conditions. This is advantageous when immediate polymerization may not be desirable, for example during protein purification, in high volume preparations or when other conditions need to be optimized. Preferably, the pH of the liquid medium is 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 the spider silk proteins. It is also advantageous to adjust the pH of the liquid medium to a range of 6.4-6.8, which provides sufficient solubility of the spider silk proteins, but facilitates subsequent adjustment of the pH to 6.3 or less.
In the third step, the properties of the liquid medium are adjusted to a pH of 6.3 or less and an ionic composition allowing polymerization. That is, if the liquid medium in which the spider silk proteins are dissolved has a pH of 6.4 or higher, the pH is lowered to 6.3 or lower. The skilled person is familiar with various ways of achieving this, generally involving the addition of strong or weak acids. If the liquid medium in which the spider silk proteins are dissolved has an ionic composition that prevents polymerization, the ionic composition is altered to allow polymerization. The skilled person is familiar with various ways of achieving this, such as dilution, dialysis or gel filtration. This step involves lowering the pH of the liquid medium to 6.3 or less and altering the ionic composition to allow polymerization, if desired. Preferably, the pH of the liquid medium is adjusted to 6.2 or less, such as 6.0 or less. In particular, it may be advantageous from a practical point of view to limit the pH decrease 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. In a preferred embodiment, the liquid medium of this step has a pH of 3 or higher, such as 4.2 or higher. The resulting pH range, e.g., 4.2-6.3, promotes rapid polymerization.
In a fourth step, the spider silk proteins are polymerized in a liquid medium having a pH of 6.3 or less and an ionic composition that allows for the polymerization of the spider silk proteins. Although the presence of the NT fragment improves the solubility of the spidroin at a pH of 6.4 or higher and/or an ionic composition that prevents spidroin from polymerizing, it accelerates polymer formation at a pH of 6.3 or lower when the ionic composition allows spidroin to polymerize. The resulting polymers are preferably solid and macroscopic (macroscopic), and they are formed in a liquid medium having a pH of 6.3 or less and an ionic composition that allows polymerization of the spider silk proteins. In a preferred embodiment, the liquid medium of this step has a pH of 3 or higher, such as 4.2 or higher. The resulting pH range, e.g., 4.2-6.3, promotes rapid polymerization, and the resulting polymers can be provided with the molecular weights described herein and prepared in solution form that can be used for article coating as necessary.
The skilled artisan can readily utilize the methods disclosed herein to prepare ionic compositions that allow polymerization of spider silk proteins. 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 allow spider silk protein polymerization include 150mM NaCl, 10mM phosphate, 20mM phosphate, and combinations of these ions that lack a prophylactic effect on spider silk protein polymerization, such as 10mM phosphate or a combination of 20mM phosphate and 150mM NaCl. The ionic strength of this liquid medium is preferably adjusted to the range of 1-250 mM.
Without wishing to be bound by any particular theory, it is believed that the NT fragment has two poles of opposite charge (oppositelycharged poles) and that environmental pH changes affect the charge balance on the protein surface, followed by polymerization, while the salt inhibits the same event.
At neutral pH, the energy expenditure (ENERGETIC COST) to bury the excess negative charge of the acid pole is expected to prevent polymerization. However, as dimers approach their isoelectric point at lower pH, attractive electrostatic forces eventually dominate, which accounts for the observed salt and pH-dependent polymerization properties of NT and NT-containing small spider silk proteins (minispidroin). It is proposed that in some embodiments, pH-induced NT polymerization and increased fiber assembly efficiency of NT-spidroin proteins are due to surface electrostatic potential changes and that acidic residue clusters at one pole of NT change their charge balance such that polymerization transitions occur at pH values of 6.3 or less.
In a fifth step, the resulting preferably solid spider silk protein polymer is isolated from the liquid medium. Optionally, this step involves active removal of lipopolysaccharide and other pyrogens from the spidroin polymer.
Without wishing to be bound by any particular theory, it has been observed that the formation of the spidroin polymer proceeds via the formation of water-soluble spidroin dimers. The present disclosure thus also provides a method of producing an isolated dimer of a spider silk protein, wherein the first two method steps are as described above. The spidroin is present as a dimer in a liquid medium having a pH of 6.4 or higher and/or an ionic composition that prevents polymerization of the spidroin. The third step involves isolation of the dimer obtained in the second step, and optionally removal of lipopolysaccharide and other pyrogens. In a preferred embodiment, the spidroin polymer of the disclosure consists of polymerized protein dimers. The present disclosure thus provides novel uses of spidroin proteins, preferably those disclosed herein, for producing dimers of spidroin proteins.
According to another aspect, the present disclosure provides a polymer of a spider silk protein as disclosed herein. In one embodiment, the polymer of such proteins may be obtained by any of the methods for the same according to the present disclosure. Accordingly, the present disclosure provides recombinant spidroin proteins, preferably those disclosed herein, for various uses in the production of spidroin polymers as recombinant silk-based coatings. According to one embodiment, the present disclosure provides a novel use of dimers of spidroin, preferably those disclosed herein, for producing isolated spidroin polymers as recombinant silk-based coatings. In these applications, it is preferred that the polymer is made in a liquid medium having a pH of 6.3 or less and an ionic composition that allows polymerization of the spidroin protein. In one embodiment, the pH of the liquid medium is 3 or higher, such as 4.2 or higher. The resulting pH range, e.g., 4.2-6.3, promotes rapid polymerization.
Using one or more methods of the present disclosure, the polymerization process can be controlled, and this enables optimization of parameters to obtain a silk polymer with desirable properties and shape.
In one embodiment, the recombinant silk proteins described herein include those described in U.S. patent 8,642,734, which is incorporated herein by reference in its entirety.
In another embodiment, the recombinant silk proteins described herein can be prepared according to the methods described in U.S. patent 9,051,453, which is incorporated herein by reference in its entirety.
The amino acid sequence represented by SEQ ID NO:52, also described in U.S. Pat. No. 9,051,453, is identical to the amino acid sequence consisting of 50 amino acid residues at the C-terminus of the amino acid sequence of ADF3 (NCBI 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 identical to the amino acid sequence represented by SEQ ID NO:52, also described in U.S. Pat. No. 9,051,453, from which 20 residues have been removed from the C-terminus. The amino acid sequence represented by SEQ ID NO:54, also described in U.S. Pat. No. 9,051,453, is identical to the amino acid sequence represented by SEQ ID NO:52, from which 29 residues have been removed from the C-terminus.
An example of a polypeptide comprising a unit of the amino acid sequence represented by formula 1 REP1-REP2 (1) and having at the C-terminus the amino acid sequence represented by any one of SEQ ID NOS: 52 to 54 or an amino acid sequence having 90% or more homology with the amino acid sequence represented by any one of SEQ ID NOS: 52 to 54 (also described in U.S. Pat. No. 9,051,453) is a polypeptide having the amino acid sequence represented by SEQ ID NO:65 (also described in U.S. Pat. No. 9,051,453, incorporated herein by reference in its entirety). A polypeptide having the amino acid sequence represented by SEQ ID NO. 65, also described in U.S. Pat. No. 9,051,453, is obtained by the following mutations: in the amino acid sequence of ADF3 (NCBI accession number: AAC47010, GI: 1263287) -an amino acid sequence consisting of a start codon, his 10 tag and the HRV3C protease (human rhinovirus 3C protease) recognition site (SEQ ID NO:66 also described in U.S. Pat. No. 9,051,453) has been added to its N-terminus, the 1 st to 13 th repeats were approximately doubled and translation ended at 1154 th amino acid residues. In a polypeptide having the amino acid sequence represented by SEQ ID NO. 65 as also described in U.S. Pat. No. 9,051,453, the C-terminal sequence is identical to the amino acid sequence represented by SEQ ID NO. 54.
In addition, a polypeptide containing a unit of an amino acid sequence represented by the formula 1 REP1-REP2 (1) and having at the C-terminus an amino acid sequence represented by any one of SEQ ID NOS: 52 to 54, which is also described in U.S. Pat. No. 9,051,453, or an amino acid sequence having 90% or more homology with an amino acid sequence represented by any one of SEQ ID NOS: 52 to 54, which is also described in U.S. Pat. No. 9,051,453, may be a protein having an amino acid sequence represented by SEQ ID NO:65, which is also described in U.S. Pat. No. 9,051,453, in which one or more amino acids have been substituted, deleted, inserted and/or added and having a repeat region composed of a crystalline region and an amorphous region.
Furthermore, an example of a polypeptide containing two or more units of the amino acid sequence represented by formula 1:REP1-REP2 (1) is an ADF 4-derived recombinant protein having the amino acid sequence represented by SEQ ID NO. 67 (also described in U.S. Pat. No. 9,051,453, incorporated herein by reference in its entirety). The amino acid sequence represented by SEQ ID NO:67, also described in U.S. patent 9,051,453, is an amino acid sequence obtained by adding an amino acid sequence consisting of a start codon, a His 10 tag and a HRV3C protease (human rhinovirus 3C protease) recognition site (SEQ ID NO:66, also described in U.S. patent 9,051,453) to the N-terminus of a partial amino acid sequence of ADF4 (NCBI accession number AAC47011, GI: 1263289) obtained from the NCBI database. Furthermore, the polypeptide comprising two or more units of the amino acid sequence represented by formula 1:REP1-REP2 (1) may be a polypeptide having the amino acid sequence represented by SEQ ID NO:67, which is also described in U.S. Pat. No. 9,051,453, wherein one or more amino acids have been substituted, deleted, inserted and/or added and has a repeat region consisting of a crystalline region and an amorphous region. Furthermore, examples of polypeptides comprising two or more units of the amino acid sequence represented by formula 1:REP1-REP2 (1) are MaSp 2-derived recombinant proteins having the amino acid sequence represented by SEQ ID NO. 68 (also described in U.S. Pat. No. 9,051,453, which is incorporated herein by reference in its entirety). The amino acid sequence represented by SEQ ID NO:68, also described in U.S. patent 9,051,453, is an amino acid sequence obtained by adding an amino acid sequence consisting of a start codon, a His 10 tag and a HRV3C protease (human rhinovirus 3C protease) recognition site (SEQ ID NO:66, also described in U.S. patent 9,051,453) to the N-terminus of a partial sequence of MaSp2 (NCBI accession number: AAT75313, GI: 50363147) obtained from the NCBI network database. In addition, the polypeptide comprising two or more units of the amino acid sequence represented by formula 1:REP1-REP2 (1) may be a polypeptide having the amino acid sequence represented by SEQ ID NO. 68, also described in U.S. Pat. No. 9,051,453, in which one or more amino acids have been substituted, deleted, inserted and/or added and which has a repeat region consisting of a crystalline region and an amorphous region.
Examples of the polypeptide derived from the flagelliform adenosin include a polypeptide comprising 10 or more units of the amino acid sequence represented by formula 2:REP3 (2), preferably a polypeptide comprising 20 or more units thereof, more preferably a polypeptide comprising 30 or more units thereof. In the case of producing a recombinant protein using a microorganism such as E.coli as a host, the molecular weight of the polypeptide derived from the flagelliforme is preferably 500kDa or less, more preferably 300kDa or less, further preferably 200kDa or less, in view of productivity.
In formula (2), REP 3 means an amino acid sequence consisting of Gly-Pro-Gly-Gly-X (SEQ ID NO: 69), wherein X means an amino acid selected from Ala, ser, tyr and Val.
Spider silk is primarily characterized by whip gland silk having no crystalline regions, but having repeat regions composed of amorphous regions. Since the main drawn filaments and the like have a repeating region composed of a crystalline region and an amorphous region, they are expected to have high stress and stretchability. Meanwhile, regarding the whip gland silk, although the stress is not as great as that of the main pulling silk, the stretchability is high. The reason for this is believed that most of the whip filaments consist of amorphous regions.
An example of a polypeptide containing 10 or more units of the amino acid sequence represented by formula 2:REP3 (2) is a recombinant protein derived from a flagellin having the amino acid sequence represented by SEQ ID NO 70 (also described in U.S. Pat. No. 9,051,453, incorporated herein by reference in its entirety). The amino acid sequence represented by SEQ ID NO. 70, also described in U.S. Pat. No. 9,051,453, is an amino acid sequence obtained by combining a partial sequence of the whip filamin of the Neoformula spider obtained from the NCBI database (NCBI accession number: AAF36090, GI: 7106224), especially an amino acid sequence thereof from the 1220 th residue to 1659 th residue at the N-terminus (corresponding to the repeat region and motif) (referred to as PR1 sequence), with a partial sequence of the whip filamin of the Neoformula spider obtained from the NCBI database (NCBI accession number: AAC38847, GI: 2833649), especially a C-terminal amino acid sequence thereof from the 816 th residue to 907 residues at the C-terminus, after which an amino acid sequence consisting of a start codon, his 10 tag and HRV 3C-protease recognition site (SEQ ID NO:66, also described in U.S. Pat. No. 9,051,453) is added to the N-terminus of the combined sequence. In addition, a polypeptide comprising 10 or more units of the amino acid sequence represented by formula 2:REP3 (2) may be a polypeptide having the amino acid sequence represented by SEQ ID NO. 70, also described in U.S. Pat. No. 9,051,453, in which one or more amino acids have been substituted, deleted, inserted and/or added and which has a repeat region consisting of an amorphous region.
The polypeptides may be produced using a host that has been transformed with an expression vector containing a gene encoding the polypeptide. The method of producing the gene is not particularly limited, and it may be produced by amplifying a gene encoding a natural spider silk protein derived from a cell of a spider by Polymerase Chain Reaction (PCR) or the like and cloning it, or may be chemically synthesized. The method of chemically synthesizing the gene is also not particularly limited, and it may be synthesized as follows, for example: oligonucleotides which have been automatically synthesized with AKTA oligopilot plus 10/100 (GE HEALTHCARE Japanese company) and the like are ligated by PCR based on information on the amino acid sequence of natural spider silk proteins obtained from NCBI network database and the like. In this case, in order to facilitate purification and observation of the protein, a gene encoding a protein having the above amino acid sequence, to the N-terminus of which an amino acid sequence consisting of an initiation codon and a His 10 tag has been added, may be synthesized.
Examples of expression vectors include plasmids, phages, viruses, etc., which express proteins based on DNA sequences. The plasmid-type expression vector is not particularly limited as long as it allows expression of the target gene in the host cell and can amplify itself. For example, in the case of using E.coli Rosetta (DE 3) as a host, pET22b (+) plasmid vector, pCold plasmid vector or the like can be used. Among these, the pET22b (+) plasmid vector is preferably used in view of productivity of the protein. Examples of hosts include animal cells, plant cells, microorganisms, and the like.
The polypeptide used in the present disclosure is preferably a polypeptide derived from ADF3, ADF3 being one of the two major dragline silk proteins of spider. Such polypeptides have the advantage of being essentially high in strength-elongation and toughness and easy to synthesize.
Thus, recombinant silk proteins (e.g., recombinant spider silk-based proteins) used in accordance with embodiments, articles, and/or methods described herein can include one or more of the above-described or U.S. patent 8,173,772、8,278,416、8,618,255、8,642,734、8,691,581、8,729,235、9,115,204、9,157,070、9,309,299、9,644,012、9,708,376、9,051,453、9,617,315、9,968,682、9,689,089、9,732,125、9,856,308、9,926,348、10,065,997、10,316,069 and 10,329,332; and recombinant silk proteins listed in U.S. patent publications 2009/0226969、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、2016/0222174、2017/0283474、2017/0088675、2019/0135880、2015/0329587、2019/0040109、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、2019/0329526、2020/0031886、2018/0080147、2019/0352349、2020/0043085、2019/0144819、2019/0228449、2019/0340666、2020/0000091、2019/0194710、2019/0151505、2018/0265555、2019/0352330、2019/0248847 and 2019/037891 (which are incorporated herein by reference in their entirety).
Fibroin-like protein fragments
Recombinant silk proteins in the present disclosure comprise synthetic proteins based on repeat units of natural silk proteins. These may additionally comprise one or more natural non-repetitive silk protein sequences in addition to the synthetic repetitive silk protein sequences. As used herein, a "fibroin-like protein fragment" refers to a protein fragment having a molecular weight and polydispersity as defined herein and a degree of homology to a protein selected from the group consisting of a natural silk protein, a silk fibroin heavy chain, a silk fibroin light chain, or any protein comprising one or more GAGAGS (SEQ ID NO: 2) hexaamino acid repeat units. In some embodiments, the degree of homology is selected from 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 silk fibroin heavy chain, a silk fibroin light chain, or any protein comprising one or more GAGAGS (SEQ ID NO: 2) hexaamino acid repeat units comprises about 9% to about 45% glycine, or about 9% glycine, or about 10% glycine, about 43% glycine, about 44% glycine, about 45% glycine, or about 46% glycine. As described herein, a protein such as a natural silk protein, a silk fibroin heavy chain, a silk fibroin light chain, or any protein comprising one or more GAGAGS (SEQ ID NO: 2) hexaamino acid repeat units comprises about 13% to 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, a protein, such as a natural silk protein, a silk fibroin heavy chain, a silk fibroin light chain, or any protein comprising one or more GAGAGS (SEQ ID NO: 2) hexaamino acid repeat units, comprises 9% to about 12% serine, or about 9% serine, or about 10% serine, or about 11% serine, or about 12% serine.
In some embodiments, a fibroin-like protein described herein comprises 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%, about 50%, about 51%, about 52%, about 53%, about 54%, or about 55% glycine. In some embodiments, a fibroin-like protein described herein comprises 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%, or about 39% alanine. In some embodiments, a fibroin-like protein described herein comprises 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 fibroin-like proteins described herein can independently comprise any amino acid known to be comprised in natural fibroin. In some embodiments, the fibroin-like proteins described herein can independently exclude any amino acids known to be comprised in natural fibroin. In some embodiments, the average 2/6 amino acids, 3/6 amino acids, or 4/6 amino acids in the fibroin-like proteins described herein is glycine. In some embodiments, the average 1/6 amino acids, 2/6 amino acids, or 3/6 amino acids in the fibroin-like proteins described herein are alanine. In some embodiments, the average 0/6 amino acids, 1/6 amino acids, or 2/6 amino acids in the fibroin-like proteins described herein are serine.
Sericin or sericin fragment
The main body of the raw silk is fibroin fiber, and the fibroin fiber is coated with an adhesive substance sericin. Sericin is a colloidal silk protein covering the surface of a silk thread, consisting of highly sterically hindered amino acids rich in chemical reactivity (such as serine, threonine and aspartic acid, and glycine and alanine). Sericin is important in controlling the dissolution of silk and producing high quality silk in a number of processes for producing silk from raw silk. In addition, it plays an extremely important role as an adhesion functional protein. When silk fibers are used as garment material, most of the sericin covering the silk threads is removed and discarded, and therefore sericin is a valuable unused resource.
In some embodiments, the silk protein fragments described herein comprise sericin or a fragment of sericin. Methods of preparing sericin or fragments of sericin and their use in various fields are known and described herein and are also described, for example, in U.S. Pat. nos. 7,115,388, 7,157,273 and 9,187,538, all of which are incorporated herein by reference in their entirety.
In some embodiments, sericin removed from raw silk cocoons, such as in a degumming step, may be collected and used in the methods described herein. Sericin may also be reconstituted from a powder and used in the compositions and methods of the present disclosure.
Other Properties of SPF
The compositions of the present disclosure are "biocompatible" or exhibit "biocompatibility," meaning that the compositions are compatible with living tissue or living systems due to being non-toxic, harmless, or non-physiologically reactive and not causing an immune rejection or inflammatory response. Such biocompatibility may be demonstrated by the participants applying the compositions of the present disclosure topically to their skin for an extended period of time. In one embodiment, the extended period of time is about 3 days. In one embodiment, the extended period of time is about 7 days. In one embodiment, the extended period of time is about 14 days. In one embodiment, the extended period of time is about 21 days. In one embodiment, the extended period of time is about 30 days. In one embodiment, the extended period of time is selected from the group consisting of: 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 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 (which may be biocompatible compositions) (e.g., biocompatible coatings comprising filaments) may be evaluated and conform to international standard ISO 10993-1, titled "Biological evaluation of medical devices–Part 1:Evaluation and testing within a risk management process". In some embodiments, one or more of cytotoxicity, sensitization, blood compatibility, pyrogenicity, implantation, genotoxicity, carcinogenicity, reproductive and developmental toxicity, and degradation of a composition described herein (which may be a biocompatible composition) may be assessed according to ISO 106993-1.
The compositions of the present disclosure are "hypoallergenic", meaning that they are relatively unlikely to cause allergic reactions. Such hyposensitization may be demonstrated by participants topically applying the compositions of the present disclosure to their skin for an extended period of time. In one embodiment, the extended period of time is about 3 days. In one embodiment, the extended period of time is about 7 days. In one embodiment, the extended period of time is about 14 days. In one embodiment, the extended period of time is about 21 days. In one embodiment, the extended period of time is about 30 days. In one embodiment, the extended period of time is selected from the group consisting of: 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 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 from 10 days to 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 from 18 months to 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 from 30 months to 36 months. In one embodiment, the stability of the compositions of the present disclosure is from 36 months to 48 months. In one embodiment, the stability of the compositions of the present disclosure is from 48 months to 60 months.
In one embodiment, the SPF compositions of the present disclosure are insoluble in aqueous solutions due to the crystallinity of the protein. In one embodiment, the SPF compositions of the present disclosure are soluble in aqueous solutions. In one embodiment, the SPF of the compositions of the present disclosure comprises about 2/3 of the crystalline portion and about 1/3 of the amorphous region. In one embodiment, the SPF of the compositions of the present disclosure comprises about half of the crystalline portion and about half of the amorphous region. In one embodiment, the SPF of the compositions of the present disclosure comprises 99% crystalline portions and 1% amorphous regions. In one embodiment, the SPF of the compositions of the present disclosure comprises 95% crystalline portions and 5% amorphous regions. In one embodiment, the SPF of the compositions of the present disclosure comprises 90% crystalline portions and 10% amorphous regions. In one embodiment, the SPF of the compositions of the present disclosure comprises 85% crystalline portions and 15% amorphous regions. In one embodiment, the SPF of the compositions of the present disclosure comprises 80% crystalline portions and 20% amorphous regions. In one embodiment, the SPF of the compositions of the present disclosure comprises 75% crystalline portions and 25% amorphous regions. In one embodiment, the SPF of the compositions of the present disclosure comprises 70% crystalline portions and 30% amorphous regions. In one embodiment, the SPF of the compositions of the present disclosure comprises 65% crystalline portions and 35% amorphous regions. In one embodiment, the SPF of the compositions of the present disclosure comprises 60% crystalline portions and 40% amorphous regions. In one embodiment, the SPF of the compositions of the present disclosure comprises 50% crystalline portions and 50% amorphous regions. In one embodiment, the SPF of the compositions of the present disclosure comprises 40% crystalline portions and 60% amorphous regions. In one embodiment, the SPF of the compositions of the present disclosure comprises 35% crystalline portions and 65% amorphous regions. In one embodiment, the SPF of the compositions of the present disclosure comprises 30% crystalline portions and 70% amorphous regions. In one embodiment, the SPF of the compositions of the present disclosure comprises 25% crystalline portions and 75% amorphous regions. In one embodiment, the SPF of the compositions of the present disclosure comprises 20% crystalline portions and 80% amorphous regions. In one embodiment, the SPF of the compositions of the present disclosure comprises 15% crystalline portions and 85% amorphous regions. In one embodiment, the SPF of the compositions of the present disclosure comprises 10% crystalline portions and 90% amorphous regions. In one embodiment, the SPF of the compositions of the present disclosure comprises a 5% crystalline portion and 90% amorphous region. In one embodiment, the SPF of the compositions of the present disclosure comprises a 1% crystalline portion and 99% amorphous regions.
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 compositions that exhibit 0.05% (w/w) or less of residues. In one embodiment, substantially free of inorganic residues refers to compositions that exhibit 0.01% (w/w) or less of residues. In one embodiment, the amount of inorganic residue is from 0ppm ("undetectable" or "ND") to 1000ppm. In one embodiment, the amount of inorganic residue is from ND to about 500ppm. In one embodiment, the amount of inorganic residue is from ND to about 400ppm. In one embodiment, the amount of inorganic residue is from ND to about 300ppm. In one embodiment, the amount of inorganic residue is from ND to about 200ppm. In one embodiment, the amount of inorganic residue is from ND to about 100ppm. In one embodiment, the amount of inorganic residues is from 10ppm to 1000ppm.
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 means that the composition exhibits 0.05% (w/w) or less of residues. In one embodiment, substantially free of organic residues means that the composition exhibits 0.01% (w/w) or less of residues. In one embodiment, the amount of organic residue is from 0ppm ("undetectable" or "ND") to 1000ppm. In one embodiment, the amount of organic residue is from ND to about 500ppm. In one embodiment, the amount of organic residue is from ND to about 400ppm. In one embodiment, the amount of organic residue is from ND to about 300ppm. In one embodiment, the amount of organic residue is from ND to about 200ppm. In one embodiment, the amount of organic residue is ND to about 100ppm. In one embodiment, the amount of organic residue is from 10ppm to 1000ppm.
The compositions of the present disclosure exhibit "biocompatibility," meaning that the compositions are compatible with living tissue or living systems due to being non-toxic, harmless, or non-physiologically reactive and not causing immune rejection. Such biocompatibility may be demonstrated by the participants applying the compositions of the present disclosure topically to their skin for an extended period of time. In one embodiment, the extended period of time is about 3 days. In one embodiment, the extended period of time is about 7 days, in one embodiment about 14 days, and in one embodiment about 21 days. In one embodiment, the extended period of time is about 30 days. In one embodiment, the extended period of time is selected from the group consisting of: 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 9 months, about 10 months, about 11 months, about 12 months, and indefinitely.
The compositions of the present disclosure are "hypoallergenic", meaning that they are relatively unlikely to cause allergic reactions. Such hyposensitization may be demonstrated by participants topically applying the compositions of the present disclosure to their skin for an extended period of time. In one embodiment, the extended period of time is about 3 days. In one embodiment, the extended period of time is about 7 days. In one embodiment, the extended period of time is about 14 days. In one embodiment, the extended period of time is about 21 days. In one embodiment, the extended period of time is about 30 days. In one embodiment, the extended period of time is selected from the group consisting of: 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 9 months, about 10 months, about 11 months, about 12 months, and indefinitely.
The following are non-limiting examples of suitable ranges for the preparation of the silk solutions of the present disclosure and the various parameters used for the preparation. The silk solutions of the present disclosure can include one or more, but not necessarily all, of these parameters, and can be prepared using various combinations of ranges of such parameters.
In one embodiment, the percentage of SPF in the solution is less than 30.0 wt%. In one embodiment, the percentage of SPF in the solution is less than 25.0 wt%. In one embodiment, the percentage of SPF in the solution is less than 20.0 wt%. In one embodiment, the percentage of SPF in the solution is less than 19.0 wt%. In one embodiment, the percentage of SPF in the solution is less than 18.0 wt%. In one embodiment, the percentage of SPF in the solution is less than 17.0 wt%. In one embodiment, the percentage of SPF in the solution is less than 16.0 wt%. In one embodiment, the percentage of SPF in the solution is less than 15.0 wt%. In one embodiment, the percentage of SPF in the solution is less than 14.0 wt%. In one embodiment, the percentage of SPF in the solution is less than 13.0 wt%. In one embodiment, the percentage of SPF in the solution is less than 12.0 wt%. In one embodiment, the percentage of SPF in the solution is less than 11.0 wt%. In one embodiment, the percentage of SPF in the solution is less than 10.0 wt%. In one embodiment, the percentage of SPF in the solution is less than 9.0 wt%. In one embodiment, the percentage of SPF in the solution is less than 8.0 wt%. In one embodiment, the percentage of SPF in the solution is less than 7.0 wt%. In one embodiment, the percentage of SPF in the solution is less than 6.0 wt%. In one embodiment, the percentage of SPF in the solution is less than 5.0 wt%. In one embodiment, the percentage of SPF in the solution is less than 4.0 wt%. In one embodiment, the percentage of SPF in the solution is less than 3.0 wt%. In one embodiment, the percentage of SPF in the solution is less than 2.0 wt%. In one embodiment, the percentage of SPF in the solution is less than 1.0 wt%. In one embodiment, the percentage of SPF in the solution is less than 0.9 wt%. In one embodiment, the percentage of SPF in the solution is less than 0.8 wt%. In one embodiment, the percentage of SPF in the solution is less than 0.7 wt%. In one embodiment, the percentage of SPF in the solution is less than 0.6 wt%. In one embodiment, the percentage of SPF in the solution is less than 0.5 wt%. In one embodiment, the percentage of SPF in the solution is less than 0.4 wt%. In one embodiment, the percentage of SPF in the solution is less than 0.3 wt%. In one embodiment, the percentage of SPF in the solution is less than 0.2 wt%. In one embodiment, the percentage of SPF in the solution is less than 0.1 wt%.
In one embodiment, the percentage of SPF in the solution is greater than 0.1 wt%. In one embodiment, the percentage of SPF in the solution is greater than 0.2 wt%. In one embodiment, the percentage of SPF in the solution is greater than 0.3 wt%. In one embodiment, the percentage of SPF in the solution is greater than 0.4 wt%. In one embodiment, the percentage of SPF in the solution is greater than 0.5 wt%. In one embodiment, the percentage of SPF in the solution is greater than 0.6 wt%. In one embodiment, the percentage of SPF in the solution is greater than 0.7 wt%. In one embodiment, the percentage of SPF in the solution is greater than 0.8 wt%. In one embodiment, the percentage of SPF in the solution is greater than 0.9 wt%. In one embodiment, the percentage of SPF in the solution is greater than 1.0 wt%. In one embodiment, the percentage of SPF in the solution is greater than 2.0 wt%. In one embodiment, the percentage of SPF in the solution is greater than 3.0 wt%. In one embodiment, the percentage of SPF in the solution is greater than 4.0 wt%. In one embodiment, the percentage of SPF in the solution is greater than 5.0 wt%. In one embodiment, the percentage of SPF in the solution is greater than 6.0 wt%. In one embodiment, the percentage of SPF in the solution is greater than 7.0 wt%. In one embodiment, the percentage of SPF in the solution is greater than 8.0 wt%. In one embodiment, the percentage of SPF in the solution is greater than 9.0 wt%. In one embodiment, the percentage of SPF in the solution is greater than 10.0 wt%. In one embodiment, the percentage of SPF in the solution is greater than 11.0 wt%. In one embodiment, the percentage of SPF in the solution is greater than 12.0 wt%. In one embodiment, the percentage of SPF in the solution is greater than 13.0 wt%. In one embodiment, the percentage of SPF in the solution is greater than 14.0 wt%. In one embodiment, the percentage of SPF in the solution is greater than 15.0 wt%. In one embodiment, the percentage of SPF in the solution is greater than 16.0 wt%. In one embodiment, the percentage of SPF in the solution is greater than 17.0 wt%. In one embodiment, the percentage of SPF in the solution is greater than 18.0 wt%. In one embodiment, the percentage of SPF in the solution is greater than 19.0 wt%. In one embodiment, the percentage of SPF in the solution is greater than 20.0 wt%. In one embodiment, the percentage of SPF in the solution is greater than 25.0 wt%.
In one embodiment, the percentage of SPF in the solution ranges from about 0.1 wt% to about 30.0 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 0.1 wt% to about 25.0 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 0.1 wt% to about 20.0 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 0.1 wt% to about 15.0 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 0.1 wt% to about 10.0 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 0.1 wt% to about 9.0 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 0.1 wt% to about 8.0 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 0.1 wt% to about 7.0 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 0.1 wt% to about 6.5 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 0.1 wt% to about 6.0 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 0.1 wt% to about 5.5 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 0.1 wt% to about 5.0 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 0.1 wt% to about 4.5 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 0.1 wt% to about 4.0 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 0.1 wt% to about 3.5 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 0.1 wt% to about 3.0 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 0.1 wt% to about 2.5 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 0.1 wt% to about 2.0 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 0.1 wt% to about 2.4 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 0.5 wt% to about 5.0 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 0.5 wt% to about 4.5 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 0.5 wt% to about 4.0 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 0.5 wt% to about 3.5 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 0.5 wt% to about 3.0 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 0.5 wt% to about 2.5 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 1.0 wt% to about 4.0 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 1.0 wt% to about 3.5 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 1.0 wt% to about 3.0 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 1.0 wt% to about 2.5 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 1.0 wt% to about 2.4 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 1.0 wt% to about 2.0 wt%.
In one embodiment, the percentage of SPF in the solution ranges from about 20.0 wt% to about 30.0 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 0.1 wt% to about 10.0 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 1.0 wt% to about 10.0 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 2 wt% to about 10.0 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 0.1 wt% to about 6.0 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 6.0 wt% to about 10.0 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 6.0 wt% to about 8.0 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 6.0 wt% to about 9.0 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 10.0 wt% to about 20.0 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 11.0 wt% to about 19.0 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 12.0 wt% to about 18.0 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 13.0 wt% to about 17.0 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 14.0 wt% to about 16.0 wt%. In one embodiment, the percentage of SPF in the solution is about 1.0 wt%. In one embodiment, the percentage of SPF in the solution is about 0.5 wt%. In one embodiment, the percentage of SPF in the solution is about 1.5 wt%. In one embodiment, the percentage of SPF in the solution is about 2.0 wt%. In one embodiment, the percentage of SPF in the solution is about 2.4 wt%. In one embodiment, the percentage of SPF in the solution is 3.0 wt%. In one embodiment, the percentage of SPF in the solution is 3.5 wt%. In one embodiment, the percentage of SPF in the solution is about 4.0 wt%. In one embodiment, the percentage of SPF in the solution is about 4.5 wt%. In one embodiment, the percentage of SPF in the solution is about 5.0 wt%. In one embodiment, the percentage of SPF in the solution is about 5.5 wt%. In one embodiment, the percentage of SPF in the solution is about 6.0 wt%. In one embodiment, the percentage of SPF in the solution is about 6.5 wt%. In one embodiment, the percentage of SPF in the solution is about 7.0 wt%. In one embodiment, the percentage of SPF in the solution is about 7.5 wt%. In one embodiment, the percentage of SPF in the solution is about 8.0 wt%. In one embodiment, the percentage of SPF in the solution is about 8.5 wt%. In one embodiment, the percentage of SPF in the solution is about 9.0 wt%. In one embodiment, the percentage of SPF in the solution is about 9.5 wt%. In one embodiment, the percentage of SPF in the solution is about 10.0 wt%.
In one embodiment, the percentage of sericin in the solution is less than 25.0 wt.% detectable. In one embodiment, the percentage of sericin in the solution is less than 5.0 wt.% detectable. In one embodiment, the percentage of sericin in the solution is 1.0 wt%. In one embodiment, the percentage of sericin in the solution is 2.0 wt%. In one embodiment, the percentage of sericin in the solution is 3.0 wt%. In one embodiment, the percentage of sericin in the solution is 4.0 wt%. In one embodiment, the percentage of sericin in the solution is 5.0 wt%. In one embodiment, the percentage of sericin in the solution is 10.0 wt%. In one embodiment, the percentage of sericin in the solution is 25.0 wt%.
In some embodiments, the fibroin fragments of the present disclosure are shelf-stable (they do not gel slowly or spontaneously when stored in aqueous solution and do not aggregate with fragments over time, thus the molecular weight does not increase) for 10 days to 3 years, depending on storage conditions, percentage of SPF, and number of shipments and shipping conditions. In addition, the pH may be varied to extend shelf life and/or support shipping conditions by preventing premature folding and aggregation of the filaments. In one embodiment, the stability of the LiBr-silk fragment solution is from 0 to 1 year. In one embodiment, the stability of the LiBr-silk fragment solution is from 0 to 2 years. In one embodiment, the stability of the LiBr-silk fragment solution is from 0 to 3 years. In one embodiment, the stability of the LiBr-silk fragment solution is from 0 to 4 years. In one embodiment, the stability of the LiBr-silk fragment solution is from 0 to 5 years. In one embodiment, the stability of the LiBr-silk fragment solution is from 1 to 2 years. In one embodiment, the stability of the LiBr-silk fragment solution is from 1 to 3 years. In one embodiment, the stability of the LiBr-silk fragment solution is from 1 to 4 years. In one embodiment, the stability of the LiBr-silk fragment solution is from 1 to 5 years. In one embodiment, the stability of the LiBr-silk fragment solution is from 2 to 3 years. In one embodiment, the stability of the LiBr-silk fragment solution is from 2 to 4 years. In one embodiment, the stability of the LiBr-silk fragment solution is from 2 to 5 years. In one embodiment, the stability of the LiBr-silk fragment solution is 3 to 4 years. In one embodiment, the stability of the LiBr-silk fragment solution is from 3 to 5 years. In one embodiment, the stability of the LiBr-silk fragment solution is from 4 to 5 years.
In one embodiment, the stability of the compositions of the present disclosure is from 10 days to 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 from 18 months to 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 from 30 months to 36 months. In one embodiment, the stability of the compositions of the present disclosure is from 36 months to 48 months. In one embodiment, the stability of the compositions of the present disclosure is from 48 months to 60 months.
In one embodiment, the composition of the present disclosure having SPF has undetectable levels of LiBr residue. In one embodiment, the amount of LiBr residue in the compositions of the present disclosure is from 10ppm to 1000ppm. In one embodiment, the amount of LiBr residue in the compositions of the present disclosure is from 10ppm to 300ppm. In one embodiment, the amount of LiBr residue in the compositions of the present disclosure is less than 25ppm. In one embodiment, the amount of LiBr residue in the compositions of the present disclosure is less than 50ppm. In one embodiment, the amount of LiBr residue in the compositions of the present disclosure is less than 75ppm. In one embodiment, the amount of LiBr residue in the compositions of the present disclosure is less than 100ppm. In one embodiment, the amount of LiBr residue in the compositions of the present disclosure is less than 200ppm. In one embodiment, the amount of LiBr residue in the compositions of the present disclosure is less than 300ppm. In one embodiment, the amount of LiBr residue in the compositions of the present disclosure is less than 400ppm. In one embodiment, the amount of LiBr residue in the compositions of the present disclosure is less than 500ppm. In one embodiment, the amount of LiBr residue in the compositions of the present disclosure is less than 600ppm. In one embodiment, the amount of LiBr residue in the compositions of the present disclosure is less than 700ppm. In one embodiment, the amount of LiBr residue in the compositions of the present disclosure is less than 800ppm. In one embodiment, the amount of LiBr residue in the compositions of the present disclosure is less than 900ppm. In one embodiment, the amount of LiBr residue in the compositions of the present disclosure is less than 1000ppm. In one embodiment, the amount of LiBr residue in the compositions of the present disclosure is less than 500ppm. In one embodiment, the amount of LiBr residue in the compositions of the present disclosure is no detectable to 450ppm. In one embodiment, the amount of LiBr residue in the compositions of the present disclosure is no more than 400ppm detected. In one embodiment, the amount of LiBr residue in the compositions of the present disclosure is less than 350ppm detected. In one embodiment, the amount of LiBr residue in the compositions of the present disclosure is less than 300ppm. In one embodiment, the amount of LiBr residue in the compositions of the present disclosure is less than 250ppm. In one embodiment, the amount of LiBr residue in the compositions of the present disclosure is no more than 200ppm detected. In one embodiment, the amount of LiBr residue in the compositions of the present disclosure is less than 150ppm detected. In one embodiment, the amount of LiBr residue in the compositions of the present disclosure is no detectable to 100ppm. In one embodiment, the amount of LiBr residue in the compositions of the present disclosure is from 100ppm to 200ppm. In one embodiment, the amount of LiBr residue in the compositions of the present disclosure is from 200ppm to 300ppm. In one embodiment, the amount of LiBr residue in the compositions of the present disclosure is from 300ppm to 400ppm. In one embodiment, the amount of LiBr residue in the compositions of the present disclosure is from 400ppm to 500ppm.
In one embodiment, the composition of the present disclosure having SPF has undetectable levels of Na 2CO3 residues. In one embodiment, the amount of Na 2CO3 residue in the compositions of the present disclosure is less than 100ppm. In one embodiment, the amount of Na 2CO3 residue in the compositions of the present disclosure is less than 200ppm. In one embodiment, the amount of Na 2CO3 residue in the compositions of the present disclosure is less than 300ppm. In one embodiment, the amount of Na 2CO3 residue in the compositions of the present disclosure is less than 400ppm. In one embodiment, the amount of Na 2CO3 residue in the compositions of the present disclosure is less than 500ppm. In one embodiment, the amount of Na 2CO3 residue in the compositions of the present disclosure is less than 600ppm. In one embodiment, the amount of Na 2CO3 residue in the compositions of the present disclosure is less than 700ppm. In one embodiment, the amount of Na 2CO3 residue in the compositions of the present disclosure is less than 800ppm. In one embodiment, the amount of Na 2CO3 residue in the compositions of the present disclosure is less than 900ppm. In one embodiment, the amount of Na 2CO3 residue in the compositions of the present disclosure is less than 1000ppm. In one embodiment, the amount of Na 2CO3 residue in the compositions of the present disclosure is less than 500ppm. In one embodiment, the amount of Na 2CO3 residue in the compositions of the present disclosure is no more than 450ppm detected. In one embodiment, the amount of Na 2CO3 residue in the compositions of the present disclosure is no more than 400ppm detected. In one embodiment, the amount of Na 2CO3 residue in the compositions of the present disclosure is less than 350ppm detected. In one embodiment, the amount of Na 2CO3 residue in the compositions of the present disclosure is less than 300ppm. In one embodiment, the amount of Na 2CO3 residue in the compositions of the present disclosure is less than 250ppm. In one embodiment, the amount of Na 2CO3 residue in the compositions of the present disclosure is no more than 200ppm detected. In one embodiment, the amount of Na 2CO3 residue in the compositions of the present disclosure is less than 150ppm detected. In one embodiment, the amount of Na 2CO3 residue in the compositions of the present disclosure is no more than 100ppm detected. In one embodiment, the amount of Na 2CO3 residue in the compositions of the present disclosure is 100ppm to 200ppm. In one embodiment, the amount of Na 2CO3 residue in the compositions of the present disclosure is 200ppm to 300ppm. In one embodiment, the amount of Na 2CO3 residue in the compositions of the present disclosure is 300ppm to 400ppm. In one embodiment, the amount of Na 2CO3 residue in the compositions of the present disclosure is 400ppm to 500ppm.
One unique feature of the SPF compositions of the present disclosure is storage stability (they do not gel slowly or spontaneously when stored in aqueous solution and do not aggregate with time and thus do not increase in molecular weight) of 10 days to 3 years, depending on storage conditions, silk percentages and shipping times and shipping conditions. In addition, the pH may be varied to extend shelf life and/or support shipping conditions by preventing premature folding and aggregation of the filaments. In one embodiment, the SPF solution compositions of the present disclosure have storage stability at Room Temperature (RT) for up to 2 weeks. In one embodiment, the SPF solution compositions of the present disclosure have storage stability for up to 4 weeks at room temperature. In one embodiment, the SPF solution compositions of the present disclosure have storage stability at room temperature for up to 6 weeks. In one embodiment, the SPF solution compositions of the present disclosure have storage stability at room temperature for up to 8 weeks. In one embodiment, the SPF solution compositions of the present disclosure have storage stability for up to 10 weeks at room temperature. In one embodiment, the SPF solution compositions of the present disclosure have storage stability at room temperature for up to 12 weeks. In one embodiment, the SPF solution compositions of the present disclosure have a storage stability of from about 4 weeks to about 52 weeks at room temperature.
Table R below shows the storage stability test results of embodiments of the SPF compositions of the present disclosure.
In some embodiments, the water solubility of silk membranes derived from silk fibroin fragments as described herein can be altered by solvent annealing (water annealing or methanol annealing), chemical crosslinking, enzymatic crosslinking, and heat treatment.
In some embodiments, the annealing process may involve initiating β -sheet formation in a solution of fibroin fragments used as the coating material. Techniques have been described for annealing (e.g., increasing crystallinity) or otherwise promoting "molecular stacking" of fibroin-based fragments. In some embodiments, the amorphous silk film is annealed in the presence of a solvent selected from water or an organic solvent to introduce the β -sheet. In some embodiments, the amorphous wire film is annealed in the presence of water to introduce beta sheet (water annealing process). In some embodiments, the amorphous fibroin fragment film is annealed in the presence of methanol to introduce β -sheet. In some embodiments, annealing (e.g., β -sheet formation) is initiated by the 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 steam is used as an intermediate plasticizer or catalyst to promote the stacking of the beta sheet. In some embodiments, the water annealing process may be performed under vacuum. Suitable such methods have been described in 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):1686-1696.
An important feature of the water annealing process is to drive the formation of crystalline β -sheets in the peptide chains of the fibroin fragments to enable self-assembly of the fibroin into a continuous film. In some embodiments, the crystallinity of the fibroin fragment film is controlled by controlling the temperature of the water vapor and the duration of annealing. In some embodiments, annealing is performed at a temperature of about 65 ℃ to about 110 ℃. In some embodiments, the temperature of the water is maintained at about 80 ℃, and the annealing is performed at a temperature selected from the group consisting of about 65 ℃, about 70 ℃, about 75 ℃, about 80 ℃, about 85 ℃, about 90 ℃, about 95 ℃, about 100 ℃, about 105 ℃, and about 110 ℃.
In some embodiments, the annealing process is continued for a period of time selected from the group consisting of: 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 to about 110 minutes, about 5 minutes to about 120 minutes, about 5 minutes to about 130 minutes, about 10 minutes to about 40 minutes, about 10 minutes to about 50 minutes, about 10 minutes to about 60 minutes, about 10 minutes to about 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 to about 60 minutes, about 20 minutes to about 70 minutes, about 20 minutes to about 80 minutes, about 20 minutes to about 90 minutes, about 20 minutes to about 100 minutes, about 20 minutes to about 110 minutes, about 20 minutes to about 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 to about 110 minutes, about 30 minutes to about 120 minutes, about 30 minutes to about 130 minutes, about 35 minutes to about 40 minutes, about 35 minutes to about 50 minutes, about 35 minutes to about 60 minutes, about 35 minutes to about 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 to about 80 minutes, about 45 minutes to about 90 minutes, about 45 minutes to about 100 minutes, about 45 minutes to about 110 minutes, about 45 minutes to about 120 minutes, and about 45 minutes to about 130 minutes. In some embodiments, the annealing process lasts for a period of time from about 1 minute to about 60 minutes. In some embodiments, the annealing process lasts for a period of time from about 45 minutes to about 60 minutes. Longer water annealing post-treatments correspond to increased crystallinity of the fibroin fragments.
In some embodiments, the annealed silk fibroin fragment membranes are immersed in 100% methanol at room temperature for 60 minutes. Methanol annealing changes the composition of the fibroin fragment film from a predominantly amorphous random coil to a crystalline antiparallel beta sheet structure.
In some embodiments, SPF as described herein can be used to prepare SPF microparticles by precipitation with methanol. Alternative flash drying, fluidized bed drying, spray drying or vacuum drying may 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 fragments. In some embodiments, the SPF powder comprises medium molecular weight silk fibroin fragments. In some embodiments, the SPF powder comprises a mixture of low molecular weight silk fibroin fragments and medium molecular weight silk fibroin fragments.
As used herein, the term "substantially free of sericin" or "substantially free of sericin" refers to silk fibers in which a majority of sericin has been removed. In one embodiment, a silk fibroin substantially free of sericin refers to a silk fibroin having about 0.01 wt% to about 10.0 wt% sericin. In one embodiment, a silk fibroin substantially free of sericin refers to a silk fibroin having about 0.01 wt% to about 9.0 wt% sericin. In one embodiment, a silk fibroin substantially free of sericin refers to a silk fibroin having about 0.01 wt% to about 8.0 wt% sericin. In one embodiment, a silk fibroin substantially free of sericin refers to a silk fibroin having about 0.01 wt% to about 7.0 wt% sericin. In one embodiment, a silk fibroin substantially free of sericin refers to a silk fibroin having about 0.01 wt% to about 6.0 wt% sericin. In one embodiment, a silk fibroin substantially free of sericin refers to a silk fibroin having about 0.01 wt% to about 5.0 wt% sericin. In one embodiment, a silk fibroin substantially free of sericin refers to a silk fibroin having about 0 wt% to about 4.0 wt% sericin. In one embodiment, a silk fibroin substantially free of sericin refers to a silk fibroin having about 0.05 wt% to about 4.0 wt% sericin. In one embodiment, a silk fibroin substantially free of sericin refers to a silk fibroin having about 0.1 wt% to about 4.0 wt% sericin. In one embodiment, a silk fibroin substantially free of sericin refers to a silk fibroin having about 0.5 wt% to about 4.0 wt% sericin. In one embodiment, a silk fibroin substantially free of sericin refers to a silk fibroin having about 1.0 wt% to about 4.0 wt% sericin. In one embodiment, a silk fibroin substantially free of sericin refers to a silk fibroin having about 1.5 wt% to about 4.0 wt% sericin. In one embodiment, a silk fibroin substantially free of sericin refers to a silk fibroin having about 2.0 wt% to about 4.0 wt% sericin. In one embodiment, a silk fibroin substantially free of sericin refers to a silk fibroin having about 2.5 wt% to about 4.0 wt% sericin. In one embodiment, a silk fibroin substantially free of sericin refers to a silk fibroin having a sericin content of about 0.01 wt% to about 0.1 wt%. In one embodiment, a substantially sericin-free fibroin refers to a fibroin having a sericin content of less than about 0.1% by weight. In one embodiment, a substantially sericin-free fibroin refers to a fibroin having a sericin content of less than about 0.05% by weight. In one embodiment, a degumming loss of about 26.0 wt.% to about 31.0 wt.% is obtained when the silk source is added to a boiling (100 ℃) aqueous sodium carbonate solution for a treatment time of about 30 minutes to about 60 minutes.
The following are non-limiting examples of suitable ranges for the preparation of the silk solutions of the present disclosure and the various parameters used for the preparation. The silk solutions of the present disclosure can include one or more, but not necessarily all, of these parameters, and can be prepared using various combinations of ranges of such parameters.
In one embodiment, the percentage of SPF in the solution is less than 30.0 wt%. In one embodiment, the percentage of SPF in the solution is less than 25.0 wt%. In one embodiment, the percentage of SPF in the solution is less than 20.0 wt%. In one embodiment, the percentage of SPF in the solution is less than 19.0 wt%. In one embodiment, the percentage of SPF in the solution is less than 18.0 wt%. In one embodiment, the percentage of SPF in the solution is less than 17.0 wt%. In one embodiment, the percentage of SPF in the solution is less than 16.0 wt%. In one embodiment, the percentage of SPF in the solution is less than 15.0 wt%. In one embodiment, the percentage of SPF in the solution is less than 14.0 wt%. In one embodiment, the percentage of SPF in the solution is less than 13.0 wt%. In one embodiment, the percentage of SPF in the solution is less than 12.0 wt%. In one embodiment, the percentage of SPF in the solution is less than 11.0 wt%. In one embodiment, the percentage of SPF in the solution is less than 10.0 wt%. In one embodiment, the percentage of SPF in the solution is less than 9.0 wt%. In one embodiment, the percentage of SPF in the solution is less than 8.0 wt%. In one embodiment, the percentage of SPF in the solution is less than 7.0 wt%. In one embodiment, the percentage of SPF in the solution is less than 6.0 wt%. In one embodiment, the percentage of SPF in the solution is less than 5.0 wt%. In one embodiment, the percentage of SPF in the solution is less than 4.0 wt%. In one embodiment, the percentage of SPF in the solution is less than 3.0 wt%. In one embodiment, the percentage of SPF in the solution is less than 2.0 wt%. In one embodiment, the percentage of SPF in the solution is less than 1.0 wt%. In one embodiment, the percentage of SPF in the solution is less than 0.9 wt%. In one embodiment, the percentage of SPF in the solution is less than 0.8 wt%. In one embodiment, the percentage of SPF in the solution is less than 0.7 wt%. In one embodiment, the percentage of SPF in the solution is less than 0.6 wt%. In one embodiment, the percentage of SPF in the solution is less than 0.5 wt%. In one embodiment, the percentage of SPF in the solution is less than 0.4 wt%. In one embodiment, the percentage of SPF in the solution is less than 0.3 wt%. In one embodiment, the percentage of SPF in the solution is less than 0.2 wt%. In one embodiment, the percentage of SPF in the solution is less than 0.1 wt%.
In one embodiment, the percentage of SPF in the solution is greater than 0.1 wt%. In one embodiment, the percentage of SPF in the solution is greater than 0.2 wt%. In one embodiment, the percentage of SPF in the solution is greater than 0.3 wt%. In one embodiment, the percentage of SPF in the solution is greater than 0.4 wt%. In one embodiment, the percentage of SPF in the solution is greater than 0.5 wt%. In one embodiment, the percentage of SPF in the solution is greater than 0.6 wt%. In one embodiment, the percentage of SPF in the solution is greater than 0.7 wt%. In one embodiment, the percentage of SPF in the solution is greater than 0.8 wt%. In one embodiment, the percentage of SPF in the solution is greater than 0.9 wt%. In one embodiment, the percentage of SPF in the solution is greater than 1.0 wt%. In one embodiment, the percentage of SPF in the solution is greater than 2.0 wt%. In one embodiment, the percentage of SPF in the solution is greater than 3.0 wt%. In one embodiment, the percentage of SPF in the solution is greater than 4.0 wt%. In one embodiment, the percentage of SPF in the solution is greater than 5.0 wt%. In one embodiment, the percentage of SPF in the solution is greater than 6.0 wt%. In one embodiment, the percentage of SPF in the solution is greater than 7.0 wt%. In one embodiment, the percentage of SPF in the solution is greater than 8.0 wt%. In one embodiment, the percentage of SPF in the solution is greater than 9.0 wt%. In one embodiment, the percentage of SPF in the solution is greater than 10.0 wt%. In one embodiment, the percentage of SPF in the solution is greater than 11.0 wt%. In one embodiment, the percentage of SPF in the solution is greater than 12.0 wt%. In one embodiment, the percentage of SPF in the solution is greater than 13.0 wt%. In one embodiment, the percentage of SPF in the solution is greater than 14.0 wt%. In one embodiment, the percentage of SPF in the solution is greater than 15.0 wt%. In one embodiment, the percentage of SPF in the solution is greater than 16.0 wt%. In one embodiment, the percentage of SPF in the solution is greater than 17.0 wt%. In one embodiment, the percentage of SPF in the solution is greater than 18.0 wt%. In one embodiment, the percentage of SPF in the solution is greater than 19.0 wt%. In one embodiment, the percentage of SPF in the solution is greater than 20.0 wt%. In one embodiment, the percentage of SPF in the solution is greater than 25.0 wt%.
In one embodiment, the percentage of SPF in the solution ranges from about 0.1 wt% to about 30.0 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 0.1 wt% to about 25.0 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 0.1 wt% to about 20.0 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 0.1 wt% to about 15.0 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 0.1 wt% to about 10.0 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 0.1 wt% to about 9.0 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 0.1 wt% to about 8.0 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 0.1 wt% to about 7.0 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 0.1 wt% to about 6.5 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 0.1 wt% to about 6.0 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 0.1 wt% to about 5.5 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 0.1 wt% to about 5.0 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 0.1 wt% to about 4.5 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 0.1 wt% to about 4.0 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 0.1 wt% to about 3.5 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 0.1 wt% to about 3.0 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 0.1 wt% to about 2.5 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 0.1 wt% to about 2.0 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 0.1 wt% to about 2.4 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 0.5 wt% to about 5.0 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 0.5 wt% to about 4.5 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 0.5 wt% to about 4.0 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 0.5 wt% to about 3.5 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 0.5 wt% to about 3.0 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 0.5 wt% to about 2.5 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 1.0 wt% to about 4.0 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 1.0 wt% to about 3.5 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 1.0 wt% to about 3.0 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 1.0 wt% to about 2.5 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 1.0 wt% to about 2.4 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 1.0 wt% to about 2.0 wt%.
In one embodiment, the percentage of SPF in the solution ranges from about 20.0 wt% to about 30.0 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 0.1 wt% to about 10.0 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 1.0 wt% to about 10.0 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 2 wt% to about 10.0 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 0.1 wt% to about 6.0 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 6.0 wt% to about 10.0 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 6.0 wt% to about 8.0 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 6.0 wt% to about 9.0 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 10.0 wt% to about 20.0 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 11.0 wt% to about 19.0 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 12.0 wt% to about 18.0 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 13.0 wt% to about 17.0 wt%. In one embodiment, the percentage of SPF in the solution ranges from about 14.0 wt% to about 16.0 wt%. In one embodiment, the percentage of SPF in the solution is about 1.0 wt%. In one embodiment, the percentage of SPF in the solution is about 1.5 wt%. In one embodiment, the percentage of SPF in the solution is about 2.0 wt%. In one embodiment, the percentage of SPF in the solution is about 2.4 wt%. In one embodiment, the percentage of SPF in the solution is 3.0 wt%. In one embodiment, the percentage of SPF in the solution is 3.5 wt%. In one embodiment, the percentage of SPF in the solution is about 4.0 wt%. In one embodiment, the percentage of SPF in the solution is about 4.5 wt%. In one embodiment, the percentage of SPF in the solution is about 5.0 wt%. In one embodiment, the percentage of SPF in the solution is about 5.5 wt%. In one embodiment, the percentage of SPF in the solution is about 6.0 wt%. In one embodiment, the percentage of SPF in the solution is about 6.5 wt%. In one embodiment, the percentage of SPF in the solution is about 7.0 wt%. In one embodiment, the percentage of SPF in the solution is about 7.5 wt%. In one embodiment, the percentage of SPF in the solution is about 8.0 wt%. In one embodiment, the percentage of SPF in the solution is about 8.5 wt%. In one embodiment, the percentage of SPF in the solution is about 9.0 wt%. In one embodiment, the percentage of SPF in the solution is about 9.5 wt%. In one embodiment, the percentage of SPF in the solution is about 10.0 wt%.
In one embodiment, the percentage of sericin in the solution is less than 25.0 wt.% detectable. In one embodiment, the percentage of sericin in the solution is less than 5.0 wt.% detectable. In one embodiment, the percentage of sericin in the solution is 1.0 wt%. In one embodiment, the percentage of sericin in the solution is 2.0 wt%. In one embodiment, the percentage of sericin in the solution is 3.0 wt%. In one embodiment, the percentage of sericin in the solution is 4.0 wt%. In one embodiment, the percentage of sericin in the solution is 5.0 wt%. In one embodiment, the percentage of sericin in the solution is 10.0 wt%. In one embodiment, the percentage of sericin in the solution is 25.0 wt%.
In some embodiments, the fibroin-based protein fragments of the present disclosure are shelf stable (they do not gel slowly or spontaneously when stored in aqueous solution and do not aggregate with fragments over time, thus the molecular weight does not increase) for 10 days to 3 years, depending on storage conditions, percentage of SPF and number of shipments and shipping conditions. In addition, the pH may be varied to extend shelf life and/or support shipping conditions by preventing premature folding and aggregation of the filaments. In one embodiment, the stability of the LiBr-silk fragment solution is from 0 to 1 year. In one embodiment, the stability of the LiBr-silk fragment solution is from 0 to 2 years. In one embodiment, the stability of the LiBr-silk fragment solution is from 0 to 3 years. In one embodiment, the stability of the LiBr-silk fragment solution is from 0 to 4 years. In one embodiment, the stability of the LiBr-silk fragment solution is from 0 to 5 years. In one embodiment, the stability of the LiBr-silk fragment solution is from 1 to 2 years. In one embodiment, the stability of the LiBr-silk fragment solution is from 1 to 3 years. In one embodiment, the stability of the LiBr-silk fragment solution is from 1 to 4 years. In one embodiment, the stability of the LiBr-silk fragment solution is from 1 to 5 years. In one embodiment, the stability of the LiBr-silk fragment solution is from 2 to 3 years. In one embodiment, the stability of the LiBr-silk fragment solution is from 2 to 4 years. In one embodiment, the stability of the LiBr-silk fragment solution is from 2 to 5 years. In one embodiment, the stability of the LiBr-silk fragment solution is 3 to 4 years. In one embodiment, the stability of the LiBr-silk fragment solution is from 3 to 5 years. In one embodiment, the stability of the LiBr-silk fragment solution is from 4 to 5 years.
In one embodiment, the stability of the compositions of the present disclosure is from 10 days to 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 from 18 months to 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 from 30 months to 36 months. In one embodiment, the stability of the compositions of the present disclosure is from 36 months to 48 months. In one embodiment, the stability of the compositions of the present disclosure is from 48 months to 60 months.
In one embodiment, the selected properties of the SPF coated article, which may be enhanced as compared to the uncoated article, may include one or more of the following: wash dimensional stability, dry cleaning dimensional stability, post-wash appearance, post-dry cleaning appearance, wash color fastness, dry cleaning color fastness, non-chlorine bleach color fastness, seam torque/spin (for knits), bleed color fastness, rub color fastness, water color fastness, light color fastness, perspiration color fastness, chlorinated swimming pool water color fastness, seawater color fastness, tensile strength, seam slip, tear strength, seam break strength, abrasion resistance, pilling resistance, stretch recovery, burst strength, mold transfer color fastness (labels) upon storage, ozone color fastness, fuzz retention, flex and tilt, saliva color fastness, crocking resistance, wrinkle resistance (e.g., garment appearance, fabric crease retention, fabric appearance smoothness), water repellency, water resistance, stain resistance (e.g., water repellency, oil repellency, water/alcohol repellency), vertical wicking, water absorbency, drying rate, soil release, air permeability, wicking, antimicrobial properties, uv protection, torque resistance, odor resistance, biocompatibility, wet time, absorption rate, spreading speed, cumulative one-way transport, flame retardant properties, stain resistance, fabric softening properties, pH adjustment properties, anti-felting properties, and overall moisture management capability.
In any of the foregoing embodiments, at least one property of the article is improved, wherein the improved property is wash-resistant dimensional stability, and wherein the amount of property improvement relative to the uncoated article is selected from the group consisting of: 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 at least 500%.
In any of the foregoing embodiments, at least one property of the article is improved, wherein the improved property is wash-resistant dimensional retention, and wherein the amount of property improvement relative to the uncoated article is selected from the group consisting of: 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 at least 500%.
In any of the foregoing embodiments, at least one property of the article is improved, wherein the improved property is shrink resistance, and wherein the amount of property improvement relative to the uncoated article is selected from the group consisting of: 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 at least 500%.
Compositions and methods comprising silk protein fragment coatings
In one embodiment, the present disclosure may include textiles, such as fibers, yarns, fabrics, or other materials, and combinations thereof, which may be coated with the SPF mixture solutions (i.e., fibroin solutions (SFS)) as described herein to produce coated articles. In one embodiment, the coated article 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 chemical agents that may enhance the properties of the coated article.
In one embodiment, the textile may be a flexible material (woven or nonwoven) comprising a network of natural and/or synthetic fibers, threads, yarns, or combinations thereof. SFS can be applied at any stage of textile processing, from individual fibers to yarns, fabrics, threads, or combinations thereof.
In one embodiment, the fibers may be natural fibers, which may comprise a natural cellulosic matrix, wherein the natural cellulosic matrix may comprise one or more of the following: (1) A slurry, such as flax, hemp, kenaf, jute, hemp and/or ramie slurry; (2) Leaves, such as flax, hemp, sisal, abaca, banana, henna, ramie, indian hemp and/or coir; and (3) seed hairs, such as cotton seed hairs and/or kapok seed hairs. In one embodiment, the fibers may be natural fibers, which may comprise a natural fiber protein matrix, wherein the natural fiber protein matrix may include one or more of the following: (1) Hair, such as alpaca, camel, cashmere, american camel, mohair and/or alpaca; (2) wool, such as sheep wool; (3) filaments, such as silk. In one embodiment, the fibers may be natural fibers, which may comprise a natural fiber mineral matrix, including asbestos. In one embodiment, the fibers may be rayon, which may comprise a rayon organic natural polymer matrix, which may include one or more of the following: (1) Cellulosic substrates such as bamboo, rayon, lyocell, acetate, and/or triacetate; (2) a protein matrix, such as azuron (azlon); (3) alginate; and (4) rubber. In one embodiment, the fibers may be rayon, which may comprise a rayon organic synthetic matrix, which may include one or more of the following: acrylic, anidicks (anidex), aramid, fluorocarbon, modacrylic, novoloid, nylon, netrill (nytril), olefins, PBI, polycarbonate, polyester, rubber, saran, span, venter (vinal), veillon (vinvon). In one embodiment, the fibers may be rayon, which may comprise a rayon inorganic matrix, which may include one or more of the following: glass materials, metal materials, and carbon materials.
In one embodiment, the yarn may include natural fibers, which may comprise a natural cellulosic matrix, wherein the natural cellulosic matrix may be from: (1) A slurry, such as flax, hemp, kenaf, jute, hemp and/or ramie slurry; (2) Leaves, such as flax, hemp, sisal, abaca, banana, henna, ramie, indian hemp and/or coir; or (3) seed hairs, such as cotton seed hairs and/or kapok seed hairs. In one embodiment, the yarn may include natural fibers, which may comprise a natural fiber protein matrix, wherein the natural fiber protein matrix may be from: (1) Hair, such as alpaca, camel, cashmere, american camel, mohair and/or alpaca; (2) wool, such as sheep wool; or (3) filaments, such as silk. In one embodiment, the yarn may comprise natural fibers, which may comprise a natural fiber mineral matrix, including asbestos. In one embodiment, the yarn may include a rayon, which may comprise a rayon organic natural polymer matrix, which may include: (1) Cellulosic substrates such as bamboo, rayon, lyocell, acetate, and/or triacetate; (2) a protein matrix, such as azuron (azlon); (3) alginate; or (4) rubber. In one embodiment, the yarn may include a rayon, which may include a rayon organic synthetic matrix, which may include: acrylic, anidicks (anidex), aramid, fluorocarbon, modacrylic, novoloid, nylon, netrill (nytril), olefins, PBI, polycarbonate, polyester, rubber, saran, span, venter (vinal), veillon (vinvon). In one embodiment, the yarn may include rayon, which may include a rayon inorganic matrix, which may include glass materials, metallic materials, carbon materials, and/or specialty materials.
In one embodiment, the fabric may include natural fibers and/or yarns that may comprise a natural cellulosic matrix, wherein the natural cellulosic matrix may be from: (1) A slurry, such as flax, hemp, kenaf, jute, hemp and/or ramie slurry; (2) Leaves, such as flax, hemp, sisal, abaca, banana, henna, ramie, indian hemp and/or coir; or (3) seed hairs, such as cotton seed hairs and/or kapok seed hairs. In one embodiment, the fabric may include natural fibers and/or yarns that may comprise a natural fiber protein matrix, wherein the natural fiber protein matrix may be from: (1) Hair, such as alpaca, camel, cashmere, american camel, mohair and/or alpaca; (2) wool, such as sheep wool; or (3) filaments, such as silk. In one embodiment, the fabric may include natural fibers and/or yarns that may comprise a natural fiber mineral matrix including asbestos. In one embodiment, the fabric may include rayon and/or yarn, which may comprise a rayon organic natural polymer matrix, which may include: (1) Cellulosic substrates such as bamboo, rayon, lyocell, acetate, and/or triacetate; (2) a protein matrix, such as azuron (azlon); (3) alginate; or (4) rubber. In one embodiment, the fabric may include rayon and/or yarn, which may comprise a rayon organic synthetic matrix, which may include: acrylic, anidicks (anidex), aramid, fluorocarbon, modacrylic, novoloid, nylon, netrill (nytril), olefins, PBI, polycarbonate, polyester, rubber, saran, span, venter (vinal), veillon (vinvon). In one embodiment, the fabric may include rayon and/or yarn that may include a rayon inorganic matrix that may include glass materials, metallic materials, carbon materials, and/or specialty materials.
In some embodiments, the fabric may include alpaca fibers, alpaca wool, llama fibers, llama wool, cotton, sheep wool, podium, dog wool (chiengora), arctic musk (qiviut), yak wool, rabbit wool, lamb wool, moat wool, tibetan wool, rockin (lopi), camel wool, pash Mi Na cashmere, angora wool, silk, spider silk, manila hemp fibers, coconut fibers, flax fibers, jute fibers, kapok fibers, hemp fibers, raffia fibers, bamboo fibers, hemp, modal fibers, pineapple fibers, ramie, hemp, soy protein fibers, polyesters, polyamides, polyaramides, polytetrafluoroethylene, polyethylene, polypropylene, polyurethane, silicone, polyurethane and polyethylene glycol blends, 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 fabric comprises pile. In some embodiments, the fabric comprises an inert synthetic material such as 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 copolymers, also known as span and elastomers), rayon, or mixtures thereof.
In some embodiments, the fabric comprises one or more selected from the group consisting of: cotton, silk, alpaca wool, llama wool, cotton, cashmere, sheep wool, and combinations thereof. In some embodiments, the fabric comprises one or more of natural pile, synthetic pile, alpaca pile, llama pile, cashmere, sheep pile, moat pile, camel hair, or angora pile.
In some embodiments, the articles described herein may comprise a synthetic fiber component in an amount of 100% by weight (w/w) of the article. In some embodiments, the articles described herein may comprise a synthetic fiber component in an amount greater than 1%、2%、3%、4%、5%、6%、7%、8%、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% by weight (w/w) of the article, with the remainder of the article being a non-synthetic fiber component by weight (w/w), as described herein. In some embodiments, the articles described herein may comprise a synthetic fiber component in an amount of less than 1%、2%、3%、4%、5%、6%、7%、8%、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% by weight (w/w) of the article, with the remainder of the article being a non-synthetic fiber component by weight (w/w), as described herein. In some embodiments, the articles described herein may comprise a synthetic fiber component in an amount of about 1%、2%、3%、4%、5%、6%、7%、8%、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% by weight (w/w) of the article, with the remainder of the article being a non-synthetic fiber component by weight (w/w), as described herein.
In some embodiments, the coating further comprises a cross-linking agent. In some embodiments, any of the SPFs described herein, including fibroin or fibroin-based protein fragments, are chemically modified with a precursor linker comprising a cross-linking agent to form a silk conjugate. In some embodiments, the fabric is covalently linked to a cross-linking agent. In some embodiments, the cross-linking agent is covalently linked to the surfactant and/or emulsifier. In some embodiments, the cross-linking agent is covalently attached to the fabric and the surfactant and/or emulsifier. In some embodiments, the cross-linking agent is covalently attached to the fabric and SPF.
The precursor linker may be selected from any of the following natural crosslinkers: caffeic acid, tannic acid, genipin (genipin), procyanidins, and the like. The precursor crosslinks may be selected from any of the following enzymatic crosslinks: glutamine transaminase cross-links, hydrolase cross-links, peptidase cross-links (e.g., sortase SrtA from staphylococcus aureus), oxidoreductase cross-links, tyrosinase cross-links, laccase cross-links, peroxidase cross-links (e.g., horseradish peroxidase), lysyl oxidase cross-links, peptide ligases (e.g., sphenopsis 1, peptide ligases, subtilisin, etc.), and the like.
In some embodiments, the fibroin or fibroin-based protein fragments are chemically modified by a precursor linker to form a silk conjugate with a crosslinker or activator independently selected from the group consisting of an N-hydroxysuccinimide ester crosslinker, an imido ester crosslinker, a aminobenzoate sulfosuccinimidyl ester, a methacrylate, a silane, a silicate, an alkyne compound, an azide, an aldehyde, a carbodiimide crosslinker, a dicyclohexylcarbodiimide activator, a dicyclohexylcarbodiimide crosslinker, a maleimide crosslinker, a haloacetyl crosslinker, a pyridyl disulfide crosslinker, a hydrazide crosslinker, an alkoxyamine crosslinker, a reductive amination crosslinker, an aryl azide crosslinker, a diazine crosslinker, an azide-phosphine crosslinker, a transferase crosslinker, a hydrolase crosslinker, a transglutaminase crosslinker, a peptidase crosslinker, an oxidoreductase crosslinker, a tyrosinase crosslinker, a laccase crosslinker, a peroxidase crosslinker, a lysyl oxidase crosslinker, and any combination thereof. Some chemically modified fibroin has been described in J Mater chem.2009, 6/23, 19 (36), 6443-6450, including cyanuric chloride activated coupling, carbodiimide coupling, arginine masking, chlorosulfonic acid reaction, diazo coupling, tyrosinase catalyzed grafting, and poly (methacrylate) grafting.
In some embodiments, the article further comprises a cross-linking agent. In some embodiments, the crosslinker is a polyphenol compound comprising 12 phenolic hydroxyl groups, having a molecular weight of about 500-4000Da, and having about 5-7 aromatic rings per 1000 Da. In some embodiments, the crosslinking agent is a polyphenol compound selected from the group consisting of: curcumin, demethoxycurcumin, bisdemethoxycurcumin, resveratrol, caffeic acid, tannins, gallotannins, procyanidins, hydrolyzable tannins, phlorizin, gallic acid, chlorogenic acid, carnosol, capsaicin, 6-shogaol, 6-gingerol, flavonoids, flavanols, neoflavonoids, arbutin, cynara, apigenin, isolongrass, luteolin, nobiletin, hesperetin, yangonin, galangin, kaempferol, myricetin, quercetin, rutin, limonin, curcurocitrin, eriodictyol, hesperidin, naringenin, naringin, pinocembrin, quercetin, chickpea A, chrysin, daidzein, equol, spinononetin, genistein, daidzein, lignin, and combinations thereof.
In one embodiment, the coating is applied at the yarn level to the article comprising the fabric. In one embodiment, the coating is applied at the fabric level. In one embodiment, the thickness of the coating is selected from the group consisting of about 5nm, about 10nm, about 15nm, about 20nm, about 25nm, about 50nm, about 100nm, about 200nm, about 500nm, about 1 μm, about 5 μm, about 10 μm, and about 20 μm. In one embodiment, the thickness of the coating is selected from the range of about 5nm to about 100nm, about 100nm to about 200nm, about 200nm to about 500nm, 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.
In one embodiment, the fabric is treated with a polymer, such as Polyglycolide (PGA), polyethylene glycol, copolymers of glycolide, glycolide/L-lactide copolymers (PGA/PLLA), glycolide/trimethylene carbonate copolymers (PGA/TMC), polylactides (PLA), stereo copolymers of PLA, poly-L-lactide (PLLA), poly-DL-lactide (PDLLA), L-lactide/DL-lactide copolymers, copolymers of PLA, lactide/tetramethylglycolide copolymers, lactide/trimethylene carbonate copolymers, lactide/delta-valerolactone copolymers, lactide/epsilon-caprolactone copolymers, polyglycolide peptides, and the like PLA/polyethylene oxide copolymers, asymmetric 3, 6-substituted poly-1, 4-dioxane-2, 5-diones, poly-beta-hydroxybutyrate (PHBA), PHBA/beta-hydroxyvalerate copolymers (PHBA/HVA), poly-beta-hydroxypropionate (PHPA), poly-p-dioxanone (PDS), poly-delta-valerolactone, poly-epsilon-caprolactone, methyl methacrylate-N-vinylpyrrolidine copolymers, polyesteramides, polyesters of oxalic acid, polydihydropyrans, poly-2-alkyl cyanoacrylates, polyurethanes (PU), polyvinyl alcohol (PVA), polypeptides, poly-beta-malic acid (PMLA), poly-beta-alkanoic acids, polyvinyl alcohols (PVA), polyethylene oxides (PEO), chitin polymers, polyethylene, polypropylene, polyacetal, polyamide, polyester, polysulfone, polyetheretherketone, polyethylene terephthalate, polycarbonate, polyaryletherketone, and polyetherketoneketone.
In one embodiment, the textile may be manufactured by one or more of the following processes: weaving, knitting and non-weaving processes. In one embodiment, the weaving process may include plain, twill, and/or satin weaving. In one embodiment, the knitting process may include weft knitting (e.g., circular knitting, flat bed knitting, and/or full-forming knitting) and/or warp knitting (e.g., teryle knitting, raschel knitting, and/or crochet knitting). In one embodiment, the nonwoven process may include stabilizing fibers (e.g., dry-laid and/or wet-laid) and/or continuous filaments (e.g., spin-laid and/or melt-blown).
In one embodiment, the present disclosure provides an article comprising a fabric coated with silk protein fragments. In one embodiment, the present disclosure provides an article comprising a fabric coated with silk protein fragments, wherein the fabric is a fabric for use in human garments (including functional and/or athletic garments). In one embodiment, the present disclosure provides an article comprising a fabric coated with silk protein fragments, and wherein the fabric exhibits improved moisture management properties and/or microbial growth tolerance. In one embodiment, the present disclosure provides an article comprising a fabric coated with silk protein fragments, wherein the fabric is a fabric for home furnishing. In one embodiment, the present disclosure provides an article comprising a fabric coated with silk protein fragments, wherein the fabric is for automotive interiors. In one embodiment, the present disclosure provides an article comprising a fabric coated with silk protein fragments, wherein the fabric is for use in aircraft interiors. In one embodiment, the present disclosure provides an article comprising a fabric coated with silk protein fragments, wherein the fabric is used for interior trim of transportation vehicles for public, commercial, military, or other uses (including buses and trains). In one embodiment, the present disclosure provides an article comprising a fabric coated with silk protein fragments, wherein the fabric is used for interior trim of products requiring high abrasion resistance compared to conventional interior trim.
In one embodiment, the present disclosure provides an article comprising a fabric coated with silk protein fragments, wherein the fabric is a fabric manufactured as an edging on an automotive interior trim. In one embodiment, the present disclosure provides an article comprising a fabric coated with silk protein fragments, wherein the article is a fabric product manufactured as a steering wheel. In one embodiment, the present disclosure provides an article comprising a fabric coated with silk protein fragments, wherein the fabric is a fabric product manufactured as a headrest. In one embodiment, the present disclosure provides an article comprising a fabric coated with silk protein fragments, wherein the fabric is a fabric product manufactured as an armrest. In one embodiment, the present disclosure provides an article comprising a fabric coated with silk protein fragments, wherein the fabric is a fabric product manufactured as an automotive floor mat. In one embodiment, the present disclosure provides an article comprising a fabric coated with silk protein fragments, wherein the fabric is a fabric product manufactured as an automobile or vehicle carpet. In one embodiment, the present disclosure provides an article comprising a fabric coated with silk protein fragments, wherein the fabric is a fabric product manufactured as an automotive edging. In one embodiment, the present disclosure provides an article comprising a fabric coated with silk protein fragments, wherein the fabric is a fabric product manufactured as a child car seat. In one embodiment, the present disclosure provides an article comprising a fabric coated with silk protein fragments, wherein the fabric is a fabric product manufactured as a seat belt or a safety belt. In one embodiment, the present disclosure provides an article comprising a fabric coated with silk protein fragments, wherein the fabric is a fabric product manufactured as an instrument panel. In one embodiment, the present disclosure provides an article comprising a fabric coated with silk protein fragments, wherein the fabric is a fabric product manufactured as a seat. In one embodiment, the present disclosure provides an article comprising a fabric coated with silk protein fragments, wherein the fabric is a fabric product manufactured as a seat panel. In one embodiment, the present disclosure provides an article comprising a fabric coated with silk protein fragments, wherein the fabric is a fabric product manufactured as an interior panel. In one embodiment, the present disclosure provides an article comprising a fabric coated with silk protein fragments, wherein the fabric is a fabric product manufactured as an airbag cover. In one embodiment, the present disclosure provides an article comprising a fabric coated with silk protein fragments, wherein the fabric is a fabric product manufactured as an airbag. In one embodiment, the present disclosure provides an article comprising a fabric coated with silk protein fragments, wherein the fabric is a fabric product manufactured as a sun visor. In one embodiment, the present disclosure provides an article comprising a fabric coated with silk protein fragments, wherein the fabric is a fabric product manufactured as a strand. In one embodiment, the present disclosure provides an article coated with silk protein fragments, wherein the article is a cushion. In one embodiment, the present disclosure provides an article coated with silk protein fragments, wherein the article is an automotive, aircraft or other vehicle insulation. In some embodiments, the coating comprises an article coated with a fibroin fragment having a weight average molecular weight ranging from about 1kDa to about 350kDa, wherein the fibroin fragment has an average weight average molecular weight ranging from about 5 to about 10kDa, about 6kDa to about 17kDa, about 17kDa to about 39kDa, about 39kDa to about 80kDa, about 60 to about 100kDa and about 80kDa to about 144kDa, wherein the fibroin fragment has a polydispersity of about 1.5 to about 3.0 or about 1.0 to about 5.0, and optionally, wherein the protein or protein fragment does not spontaneously or gradually gel and does not change significantly in color or turbidity when in solution for at least 10 days prior to coating the fabric. The coating comprises a fibroin fragment having a weight average molecular weight ranging from about 5kDa to about 144kDa, wherein the average weight average molecular weight of the fibroin fragment is selected from the group consisting of about 5 to about 10kDa, about 6kDa to about 17kDa, about 17kDa to about 39kDa, about 39kDa to about 80kDa, about 60 to about 100kDa and about 80kDa to about 144kDa, wherein the polydispersity of the fibroin fragment is about 1.5 to about 3.0, and optionally wherein the protein or protein fragment does not spontaneously or gradually gel and does not significantly change in color or turbidity when in solution for at least 10 days prior to coating the fabric.
In one embodiment, the present disclosure provides an article comprising a fabric coated with silk protein fragments. In one embodiment, the article is a fabric used in the manufacture of tents, sleeping bags, poncho and soft wall coolers. In one embodiment, the fabric is a fabric used in the manufacture of athletic equipment. In one embodiment, the fabric is a fabric for use in the manufacture of outdoor equipment. In one embodiment, the webbing is webbing used to make high-foot equipment such as harnesses and backpacks. In one embodiment, the fabric is a fabric used to make rock climbing equipment. In one embodiment, the fabric is canvas. In one embodiment, the fabric is a fabric used to make hats. In one embodiment, the fabric is a fabric for use in making umbrellas. In one embodiment, the fabric is a fabric used to make a tent. In one embodiment, the fabric is a fabric for use in making a baby basket, a baby blanket, or a baby garment. In one embodiment, the fabric is a fabric used to make gloves, such as steering gloves or athletic gloves. In one embodiment, the fabric is a fabric used to make athletic pants (such as loose pants, jogging pants, yoga pants, or athletic pants). In one embodiment, the fabric is a fabric used to make a jersey (such as a blouse, jogger, yoga, or athletic jersey). In one embodiment, the fabric is a fabric for use in manufacturing beach equipment such as beach umbrellas, beach chairs, beach carpets, and beach towels. In one embodiment, the fabric is a fabric used to make jackets or jackets. In one embodiment, the fabric is a fabric used in the manufacture of medical garments (such as surgical drapes, gowns, sleeves, laboratory coats, wound dressings, sterilization wraps, surgical masks, retention bandages, support devices, compression bandages, shoe covers, surgical carpets, and the like). The coating comprises silk-based proteins or fragments thereof having a weight average molecular weight in the range of about 5kDa to about 144 kDa.
In one embodiment, the present disclosure provides an article comprising a textile coated with a fibroin-based protein or fragment thereof. In one embodiment, the textile is a textile used in the manufacture of tents, sleeping bags, poncho and soft wall coolers. In one embodiment, the textile is a textile for use in manufacturing athletic equipment. In one embodiment, the textile is a textile for use in manufacturing outdoor equipment. In one embodiment, the textile is a textile used to make high foot equipment such as harnesses and backpacks. In one embodiment, the textile is a textile for use in manufacturing rock climbing equipment. In one embodiment, the textile is canvas. In one embodiment, the textile is a textile for manufacturing caps. In one embodiment, the textile is a textile for use in making an umbrella. In one embodiment, the textile is a textile used to make a tent. In one embodiment, the textile is a textile for manufacturing a baby basket, a baby blanket, or a baby garment. In one embodiment, the textile is a textile used to make a glove, such as a steering glove or athletic glove. In one embodiment, the textile is a textile used to make athletic pants (such as loose pants, jogging pants, yoga pants, or athletic pants). In one embodiment, the textile is a textile used to make a jersey (such as a blouse, jogger, yoga, or athletic jersey). In one embodiment, the textile is a textile for manufacturing beach equipment such as beach umbrellas, beach chairs, beach carpets, and beach towels. In one embodiment, the textile is a textile used to make a jacket or outer garment. In one embodiment, the textile is a textile for manufacturing medical garments (such as surgical drapes, gowns, sleeves, laboratory coats, wound dressings, sterilization wraps, surgical masks, retention bandages, support devices, compression bandages, shoe covers, surgical carpets, and the like). The coating comprises a silk-based protein or fragment thereof having a weight average molecular weight ranging from about 1kDa to about 350kDa, wherein the average weight average molecular weight of the silk-based protein or fragment thereof is selected from the group consisting of about 5 to about 10kDa, about 6kDa to about 17kDa, about 17kDa to about 39kDa, about 39kDa to about 80kDa, about 60 to about 100kDa and about 80kDa to about 144kDa, wherein the polydispersity of the silk-based protein or fragment thereof is about 1.0 to about 5.0, and optionally, wherein the protein or protein fragment does not spontaneously or gradually gel and does not significantly change in color or turbidity when in solution for at least 10 days prior to coating the fabric.
In one embodiment, the present disclosure provides a shoe coated with a fibroin-based protein or fragment thereof. In one embodiment, the present disclosure provides a shoe coated with a fibroin-based protein or fragment thereof, wherein the shoe exhibits improved properties relative to an uncoated shoe. In one embodiment, the present disclosure provides a shoe coated with a fibroin-based protein or fragment thereof, wherein the shoe exhibits improved properties relative to an uncoated shoe, and wherein the improved properties are stain resistance. In one embodiment, the present disclosure provides a shoe coated with a fibroin-based protein or fragment thereof, wherein the shoe exhibits improved properties relative to an uncoated shoe, and wherein the shoe is made of natural leather or synthetic leather. The coating comprises a silk-based protein or fragment thereof having a weight average molecular weight ranging from about 1kDa to about 350kDa or from about 5kDa to about 144kDa, wherein the average weight average molecular weight of the silk-based protein or fragment thereof is selected from the group consisting of about 5 to about 10kDa, about 6kDa to about 17kDa, about 17kDa to about 39kDa, about 39kDa to about 80kDa, about 60 to about 100kDa and about 80kDa to about 144kDa, wherein the polydispersity of the silk-based protein or fragment thereof is from about 1.0 to about 5.0 or from about 1.5 to about 3.0, and optionally wherein the protein or protein fragment does not spontaneously or gradually gel and does not significantly change in color or turbidity when in solution for at least 10 days prior to coating the fabric.
In one aspect, the present disclosure provides a method of making a silk-coated fabric and/or article using the silk protein fragments of the present disclosure. In some embodiments, the silk-coated fabric is a fibroin-coated fabric. In some embodiments, the silk-coated article is a silk fibroin-coated article. In some embodiments, the present disclosure further includes an article of manufacture made by the methods of the present disclosure. In some embodiments, the present disclosure also includes an article comprising a coated fabric prepared by the methods of the present disclosure. In some embodiments, the present disclosure also includes a coated fabric prepared by the method of the present invention.
In some embodiments, the present disclosure includes a method of making a fibroin coated fabric, the method comprising applying a solution comprising a reducing agent to the fabric, applying a fibroin solution to the fabric, and drying the fabric.
In some embodiments, the present disclosure includes a method of improving dimensional retention of a fabric when laundered, the method comprising applying a solution comprising a reducing agent to the fabric, applying a fibroin solution to the fabric, and drying the fabric.
In one aspect, the present disclosure includes a method of improving dimensional retention of a fabric when laundered, the method comprising coating a surface of the fabric with a solution comprising a reducing agent, preparing a fibroin solution comprising fibroin fragments, coating the surface of the fabric with the fibroin solution, and drying the surface of the fabric that has been coated with the fibroin solution, wherein after laundering, the coated fabric substantially retains its original dimensions prior to laundering.
The present disclosure contemplates any surfactant and/or emulsifier. In one non-limiting example, surfactants and/or emulsifiers are used in combination with the fibroin solution to treat the fabric. In one non-limiting example, surfactants and/or emulsifiers are used to pre-treat the surface of the fabric to improve the surface affinity between the silk protein fragments and the fabric. 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, sucrose cocoate, octyl/octanoyl glucoside, and octanoyl/octyl glucoside. In some embodiments, the surfactant and/or emulsifier is selected from the group consisting of polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, and polyoxyethylene castor oil. In some embodiments, the surfactant and/or emulsifier is selected from the group consisting of polyoxyethylene (10-30) sorbitan monooleate, polyoxyethylene (10-30) sorbitan trioleate, and polyoxyethylene (10-50) castor oil. In some embodiments, the surfactant and/or emulsifier is selected from the group consisting of 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 mono fatty acid. In some embodiments, the surfactant and/or emulsifier comprises sorbitan tri-fatty acid. In some embodiments, the surfactant and/or emulsifier comprises castor oil. In some embodiments, the surfactant and/or emulsifier has a given degree of ethoxylation, which can be adjusted to produce a particular HLB value.
In some embodiments, the concentration of the surfactant and/or emulsifier in the solution ranges from 0.01g/L to about 100g/L. In some embodiments, the concentration of the surfactant and/or emulsifier in the solution ranges from 0.1g/L to about 50g/L. In some embodiments, the concentration of the surfactant and/or emulsifier in the solution ranges from 0.5g/L to about 25g/L. In some embodiments, the concentration of the surfactant and/or emulsifier in the solution ranges from 1g/L to about 20g/L. In some embodiments, the concentration of the surfactant and/or emulsifier in the solution ranges from about 20g/L to about 50g/L. In some embodiments, the concentration of the surfactant and/or emulsifier is about 1g/L. In some embodiments, the concentration of the surfactant and/or emulsifier is about 2g/L. In some embodiments, the concentration of the surfactant and/or emulsifier is about 3g/L. In some embodiments, the concentration of the surfactant and/or emulsifier is about 4g/L. In some embodiments, the concentration of the surfactant and/or emulsifier is about 5g/L. In some embodiments, the concentration of the surfactant and/or emulsifier is about 6g/L. In some embodiments, the concentration of the surfactant and/or emulsifier is about 7g/L. In some embodiments, the concentration of the surfactant and/or emulsifier is about 8g/L. In some embodiments, the concentration of the surfactant and/or emulsifier is about 9g/L. In some embodiments, the concentration of the surfactant and/or emulsifier is about 10g/L. In some embodiments, the concentration of the surfactant and/or emulsifier is about 11g/L. In some embodiments, the concentration of the surfactant and/or emulsifier is about 12g/L. In some embodiments, the concentration of the surfactant and/or emulsifier is about 13g/L. In some embodiments, the concentration of the surfactant and/or emulsifier is about 14g/L. In some embodiments, the concentration of the surfactant and/or emulsifier is about 15g/L. In some embodiments, the concentration of the surfactant and/or emulsifier is about 16g/L. In some embodiments, the concentration of the surfactant and/or emulsifier is about 17g/L. In some embodiments, the concentration of the surfactant and/or emulsifier is about 18g/L. In some embodiments, the concentration of the surfactant and/or emulsifier is about 19g/L. In some embodiments, the concentration of the surfactant and/or emulsifier is about 20g/L. In some embodiments, the concentration of the surfactant and/or emulsifier is about 21g/L. In some embodiments, the concentration of the surfactant and/or emulsifier is about 22g/L. In some embodiments, the concentration of the surfactant and/or emulsifier is about 23g/L. In some embodiments, the concentration of the surfactant and/or emulsifier is about 24g/L. In some embodiments, the concentration of the surfactant and/or emulsifier is about 25g/L. In some embodiments, the concentration of the surfactant and/or emulsifier is about 26g/L. In some embodiments, the concentration of the surfactant and/or emulsifier is about 27g/L. In some embodiments, the concentration of the surfactant and/or emulsifier is about 28g/L. In some embodiments, the concentration of the surfactant and/or emulsifier is about 29g/L. In some embodiments, the concentration of the surfactant and/or emulsifier is about 30g/L. In some embodiments, the concentration of the surfactant and/or emulsifier is about 31g/L. In some embodiments, the concentration of the surfactant and/or emulsifier is about 32g/L. In some embodiments, the concentration of the surfactant and/or emulsifier is about 33g/L. In some embodiments, the concentration of the surfactant and/or emulsifier is about 34g/L. In some embodiments, the concentration of the surfactant and/or emulsifier is about 35g/L. In some embodiments, the concentration of the surfactant and/or emulsifier is about 36g/L. In some embodiments, the concentration of the surfactant and/or emulsifier is about 37g/L. In some embodiments, the concentration of the surfactant and/or emulsifier is about 38g/L. In some embodiments, the concentration of the surfactant and/or emulsifier is about 39g/L. In some embodiments, the concentration of the surfactant and/or emulsifier is about 40g/L. In some embodiments, the concentration of the surfactant and/or emulsifier is about 41g/L. In some embodiments, the concentration of the surfactant and/or emulsifier is about 42g/L. In some embodiments, the concentration of the surfactant and/or emulsifier is about 43g/L. In some embodiments, the concentration of the surfactant and/or emulsifier is about 44g/L. In some embodiments, the concentration of the surfactant and/or emulsifier is about 45g/L. In some embodiments, the concentration of the surfactant and/or emulsifier is about 46g/L. In some embodiments, the concentration of the surfactant and/or emulsifier is about 47g/L. In some embodiments, the concentration of the surfactant and/or emulsifier is about 48g/L. In some embodiments, the concentration of the surfactant and/or emulsifier is about 49g/L. In some embodiments, the concentration of the surfactant and/or emulsifier is about 50g/L.
In some embodiments, the concentration of the fibroin fragments in the solution ranges from 0.01g/L to about 100g/L. In some embodiments, the concentration of the fibroin fragments in the solution ranges from 0.1g/L to about 50g/L. In some embodiments, the concentration of the fibroin fragments in the solution ranges from 0.5g/L to about 25g/L. In some embodiments, the concentration of the fibroin fragments in the solution ranges from 1g/L to about 20g/L. In some embodiments, the concentration of the fibroin fragments in the solution ranges from about 20g/L to about 50g/L. In some embodiments, the concentration of the fibroin fragments is about 1g/L. In some embodiments, the concentration of the fibroin fragments is about 2g/L. In some embodiments, the concentration of the fibroin fragments is about 3g/L. In some embodiments, the concentration of the fibroin fragments is about 4g/L. In some embodiments, the concentration of the fibroin fragments is about 5g/L. In some embodiments, the concentration of the fibroin fragments is about 6g/L. In some embodiments, the concentration of the fibroin fragments is about 7g/L. In some embodiments, the concentration of the fibroin fragments is about 8g/L. In some embodiments, the concentration of the fibroin fragments is about 9g/L. In some embodiments, the concentration of the fibroin fragments is about 10g/L. In some embodiments, the concentration of the fibroin fragments is about 11g/L. In some embodiments, the concentration of the fibroin fragments is about 12g/L. In some embodiments, the concentration of the fibroin fragments is about 13g/L. In some embodiments, the concentration of the fibroin fragments is about 14g/L. In some embodiments, the concentration of the fibroin fragments is about 15g/L. In some embodiments, the concentration of the fibroin fragments is about 16g/L. In some embodiments, the concentration of the fibroin fragments is about 17g/L. In some embodiments, the concentration of the fibroin fragments is about 18g/L. In some embodiments, the concentration of the fibroin fragments is about 19g/L. In some embodiments, the concentration of the fibroin fragments is about 20g/L. In some embodiments, the concentration of the fibroin fragments is about 21g/L. In some embodiments, the concentration of the fibroin fragments is about 22g/L. In some embodiments, the concentration of the fibroin fragments is about 23g/L. In some embodiments, the concentration of the fibroin fragments is about 24g/L. In some embodiments, the concentration of the fibroin fragments is about 25g/L. In some embodiments, the concentration of the fibroin fragments is about 26g/L. In some embodiments, the concentration of the fibroin fragments is about 27g/L. In some embodiments, the concentration of the fibroin fragments is about 28g/L. In some embodiments, the concentration of the fibroin fragments is about 29g/L. In some embodiments, the concentration of the fibroin fragments is about 30g/L. In some embodiments, the concentration of the fibroin fragments is about 31g/L. In some embodiments, the concentration of the fibroin fragments is about 32g/L. In some embodiments, the concentration of the fibroin fragments is about 33g/L. In some embodiments, the concentration of the fibroin fragments is about 34g/L. In some embodiments, the concentration of the fibroin fragments is about 35g/L. In some embodiments, the concentration of the fibroin fragments is about 36g/L. In some embodiments, the concentration of the fibroin fragments is about 37g/L. In some embodiments, the concentration of the fibroin fragments is about 38g/L. In some embodiments, the concentration of the fibroin fragments is about 39g/L. In some embodiments, the concentration of the fibroin fragments is about 40g/L. In some embodiments, the concentration of the fibroin fragments is about 41g/L. In some embodiments, the concentration of the fibroin fragments is about 42g/L. In some embodiments, the concentration of the fibroin fragments is about 43g/L. In some embodiments, the concentration of the fibroin fragments is about 44g/L. In some embodiments, the concentration of the fibroin fragments is about 45g/L. In some embodiments, the concentration of the fibroin fragments is about 46g/L. In some embodiments, the concentration of the fibroin fragments is about 47g/L. In some embodiments, the concentration of the fibroin fragments is about 48g/L. In some embodiments, the concentration of the fibroin fragments is about 49g/L. In some embodiments, the concentration of the fibroin fragments is about 50g/L.
In some embodiments of the present invention, in some embodiments, the w/w ratio of fibroin fragments to surfactants and/or emulsifiers 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 59:57, about 43:45:45, about 46:45:45, about 55:45:42, about 56:45. 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 6:6, about 6:94, about 95:95, about 2:98, about 2:95. In some embodiments, the w/w ratio of fibroin fragments to surfactant and/or emulsifier in the solution is about 1:1.
In some embodiments of the present invention, in some embodiments, the w/w ratio of fibroin fragments to surfactants and/or emulsifiers in the preparation 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 59:57, about 43:45:45, about 46:45:45, about 55:45:42, about 56:45. 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 6:6, about 6:94, about 95:95, about 2:98, about 2:95. In some embodiments, the w/w ratio of fibroin fragments to surfactant and/or emulsifier in the preparation is about 1:1.
In some embodiments, the fibroin solution comprises low molecular weight fibroin-based protein fragments, medium molecular weight fibroin-based protein fragments, and/or high molecular weight fibroin-based protein fragments. In some embodiments, the fibroin solution comprises low molecular weight fibroin-based protein fragments. In some embodiments, the fibroin solution comprises medium molecular weight fibroin-based protein fragments.
In some embodiments, drying the surface of the fabric includes heating the surface of the fabric without substantially altering the fibroin coating properties.
In some embodiments, the method includes the additional step of drying the surface of the fabric. In some embodiments, the additional drying step is performed after coating the surface of the fabric with a solution comprising a reducing agent. In some embodiments, the additional drying step is performed prior to coating the surface with the fibroin solution.
In some embodiments, after washing, the fabric substantially retains its original dimensions prior to washing. In some embodiments, after washing, the fabric retains a substantial majority of its original dimensions prior to washing, as compared to a similar fabric that has not been similarly treated with surfactant and/or emulsifier and fibroin solution
In any of the foregoing embodiments, at least one property of the article is improved, wherein the improved property is wash-resistant dimensional stability, and wherein the amount of property improvement relative to the uncoated article is selected from the group consisting of: 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 at least 500%.
In any of the foregoing embodiments, at least one property of the article is improved, wherein the improved property is moisture management. In some embodiments, moisture management is improved as compared to a similar article comprising a similar fabric but without the coating. Moisture management may be assessed by any method known in the art, such as, but not limited to, by a absorbency test, a vertical wicking test, or a dry rate test. The moisture management may be improved by 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%, or at least 500%.
In any of the foregoing embodiments, at least one property of the article is improved, wherein the improved property is wash-resistant dimensional retention, and wherein the amount of property improvement relative to the uncoated article is selected from the group consisting of: 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 at least 500%.
In any of the foregoing embodiments, at least one property of the article is improved, wherein the improved property is shrink resistance, and wherein the amount of property improvement relative to the uncoated article is selected from the group consisting of: 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 at least 500%.
In one embodiment, the foregoing improved property, or any other improved property described herein, is measured after a certain machine wash (e.g., a wash by a home washing machine) cycle selected from the group consisting of: 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.
In one embodiment, the concentration of the fibroin solution is less than 30.0% w/v. In one embodiment, the concentration of the fibroin solution is less than 25.0% w/v. In one embodiment, the concentration of the fibroin solution is less than 20.0% w/v. In one embodiment, the concentration of the fibroin solution is less than 19.0% w/v. In one embodiment, the concentration of the fibroin solution is less than 18.0% w/v. In one embodiment, the concentration of the fibroin solution is less than 17.0% w/v. In one embodiment, the concentration of the fibroin solution is less than 16.0% w/v. In one embodiment, the concentration of the fibroin solution is less than 15.0% w/v. In one embodiment, the concentration of the fibroin solution is less than 14.0% w/v. In one embodiment, the concentration of the fibroin solution is less than 13.0% w/v. In one embodiment, the concentration of the fibroin solution is less than 12.0% w/v. In one embodiment, the concentration of the fibroin solution is less than 11.0% w/v. In one embodiment, the concentration of the fibroin solution is less than 10.0% w/v. In one embodiment, the concentration of the fibroin solution is less than 9.0% w/v. In one embodiment, the concentration of the fibroin solution is less than 8.0% w/v. In one embodiment, the concentration of the fibroin solution is less than 7.0% w/v. In one embodiment, the concentration of the fibroin solution is less than 6.0% w/v. In one embodiment, the concentration of the fibroin solution is less than 5.0% w/v. In one embodiment, the concentration of the fibroin solution is less than 4.0% w/v. In one embodiment, the concentration of the fibroin solution is less than 3.0% w/v. In one embodiment, the concentration of the fibroin solution is less than 2.0% w/v. In one embodiment, the concentration of the fibroin solution is less than 1.0% w/v. In one embodiment, the concentration of the fibroin solution is less than 0.9% w/v. In one embodiment, the concentration of the fibroin solution is less than 0.8% w/v. In one embodiment, the concentration of the fibroin solution is less than 0.7% w/v. In one embodiment, the concentration of the fibroin solution is less than 0.6% w/v. In one embodiment, the concentration of the fibroin solution is less than 0.5% w/v. In one embodiment, the concentration of the fibroin solution is less than 0.4% w/v. In one embodiment, the concentration of the fibroin solution is less than 0.3% w/v. In one embodiment, the concentration of the fibroin solution is less than 0.2% w/v. In one embodiment, the concentration of the fibroin solution is less than 0.1% w/v.
In one embodiment, the concentration of the fibroin solution is greater than 0.1% w/v. In one embodiment, the concentration of the fibroin solution is greater than 0.2% w/v. In one embodiment, the concentration of the fibroin solution is greater than 0.3% w/v. In one embodiment, the concentration of the fibroin solution is greater than 0.4% w/v. In one embodiment, the concentration of the fibroin solution is greater than 0.5% w/v. In one embodiment, the concentration of the fibroin solution is greater than 0.6% w/v. In one embodiment, the concentration of the fibroin solution is greater than 0.7% w/v. In one embodiment, the concentration of the fibroin solution is greater than 0.8% w/v. In one embodiment, the concentration of the fibroin solution is greater than 0.9% w/v. In one embodiment, the concentration of the fibroin solution is greater than 1.0% w/v. In one embodiment, the concentration of the fibroin solution is greater than 2.0% w/v. In one embodiment, the concentration of the fibroin solution is greater than 3.0% w/v. In one embodiment, the concentration of the fibroin solution is greater than 4.0% w/v. In one embodiment, the concentration of the fibroin solution is greater than 5.0% w/v. In one embodiment, the concentration of the fibroin solution is greater than 6.0% w/v. In one embodiment, the concentration of the fibroin solution is greater than 7.0% w/v. In one embodiment, the concentration of the fibroin solution is greater than 8.0% w/v. In one embodiment, the concentration of the fibroin solution is greater than 9.0% w/v. In one embodiment, the concentration of the fibroin solution is greater than 10.0% w/v. In one embodiment, the concentration of the fibroin solution is greater than 11.0% w/v. In one embodiment, the concentration of the fibroin solution is greater than 12.0% w/v. In one embodiment, the concentration of the fibroin solution is greater than 13.0% w/v. In one embodiment, the concentration of the fibroin solution is greater than 14.0% w/v. In one embodiment, the concentration of the fibroin solution is greater than 15.0% w/v. In one embodiment, the concentration of the fibroin solution is greater than 16.0% w/v. In one embodiment, the concentration of the fibroin solution is greater than 17.0% w/v. In one embodiment, the concentration of the fibroin solution is greater than 18.0% w/v. In one embodiment, the concentration of the fibroin solution is greater than 19.0% w/v. In one embodiment, the concentration of the fibroin solution is greater than 20.0% w/v. In one embodiment, the concentration of the fibroin solution is greater than 25.0% w/v.
In one embodiment, the concentration of the fibroin solution ranges from about 0.1% w/v to about 30.0% w/v. In one embodiment, the concentration of the fibroin solution ranges from about 0.1% w/v to about 25.0% w/v. In one embodiment, the concentration of the fibroin solution ranges from about 0.1% w/v to about 20.0% w/v. In one embodiment, the concentration of the fibroin solution ranges from about 0.1% w/v to about 15.0% w/v. In one embodiment, the concentration of the fibroin solution ranges from about 0.1% w/v to about 10.0% w/v. In one embodiment, the concentration of the fibroin solution ranges from about 0.1% w/v to about 9.0% w/v. In one embodiment, the concentration of the fibroin solution ranges from about 0.1% w/v to about 8.0% w/v. In one embodiment, the concentration of the fibroin solution ranges from about 0.1% w/v to about 7.0% w/v. In one embodiment, the concentration of the fibroin solution ranges from about 0.1% w/v to about 6.5% w/v. In one embodiment, the concentration of the fibroin solution ranges from about 0.1% w/v to about 6.0% w/v. In one embodiment, the concentration of the fibroin solution ranges from about 0.1% w/v to about 5.5% w/v. In one embodiment, the concentration of the fibroin solution ranges from about 0.1% w/v to about 5.0% w/v. In one embodiment, the concentration of the fibroin solution ranges from about 0.1% w/v to about 4.5% w/v. In one embodiment, the concentration of the fibroin solution ranges from about 0.1% w/v to about 4.0% w/v. In one embodiment, the concentration of the fibroin solution ranges from about 0.1% w/v to about 3.5% w/v. In one embodiment, the concentration of the fibroin solution ranges from about 0.1% w/v to about 3.0% w/v. In one embodiment, the concentration of the fibroin solution ranges from about 0.1% w/v to about 2.5% w/v. In one embodiment, the concentration of the fibroin solution ranges from about 0.1% w/v to about 2.0% w/v. In one embodiment, the concentration of the fibroin solution ranges from about 0.1% w/v to about 2.4% w/v. In one embodiment, the concentration of the fibroin solution ranges from about 0.5% w/v to about 5.0% w/v. In one embodiment, the concentration of the fibroin solution ranges from about 0.5% w/v to about 4.5% w/v. In one embodiment, the concentration of the fibroin solution ranges from about 0.5% w/v to about 4.0% w/v. In one embodiment, the concentration of the fibroin solution ranges from about 0.5% w/v to about 3.5% w/v. In one embodiment, the concentration of the fibroin solution ranges from about 0.5% w/v to about 3.0% w/v. In one embodiment, the concentration of the fibroin solution ranges from about 0.5% w/v to about 2.5% w/v. In one embodiment, the concentration of the fibroin solution ranges from about 1.0% w/v to about 4.0% w/v. In one embodiment, the concentration of the fibroin solution ranges from about 1.0% w/v to about 3.5% w/v. In one embodiment, the concentration of the fibroin solution ranges from about 1.0% w/v to about 3.0% w/v. In one embodiment, the concentration of the fibroin solution ranges from about 1.0% w/v to about 2.5% w/v. In one embodiment, the concentration of the fibroin solution ranges from about 1.0% w/v to about 2.4% w/v. In one embodiment, the concentration of the fibroin solution ranges from about 1.0% w/v to about 2.0% w/v.
In one embodiment, the concentration of the fibroin solution ranges from about 20.0% w/v to about 30.0% w/v. In one embodiment, the concentration of the fibroin solution ranges from about 0.1% w/v to about 10.0% w/v. In one embodiment, the concentration of the fibroin solution ranges from about 1.0% w/v to about 10.0% w/v. In one embodiment, the concentration of the fibroin solution ranges from about 2% w/v to about 10.0% w/v. In one embodiment, the concentration of the fibroin solution ranges from about 0.1% w/v to about 6.0% w/v. In one embodiment, the concentration of the fibroin solution ranges from about 6.0% w/v to about 10.0% w/v. In one embodiment, the concentration of the fibroin solution ranges from about 6.0% w/v to about 8.0% w/v. In one embodiment, the concentration of the fibroin solution ranges from about 6.0% w/v to about 9.0% w/v. In one embodiment, the concentration of the fibroin solution ranges from about 10.0% w/v to about 20.0% w/v. In one embodiment, the concentration of the fibroin solution ranges from about 11.0% w/v to about 19.0% w/v. In one embodiment, the concentration of the fibroin solution ranges from about 12.0% w/v to about 18.0% w/v. In one embodiment, the concentration of the fibroin solution ranges from about 13.0% w/v to about 17.0% w/v. In one embodiment, the concentration of the fibroin solution ranges from about 14.0% w/v to about 16.0% w/v. In one embodiment, the concentration of the fibroin solution is about 1.0% w/v. In one embodiment, the concentration of the fibroin solution is about 0.5% w/v. In one embodiment, the concentration of the fibroin solution is about 1.5% w/v. In one embodiment, the concentration of the fibroin solution is about 2.0 wt%. In one embodiment, the concentration of the fibroin solution is about 2.4% w/v. In one embodiment, the concentration of the fibroin solution is 3.0% w/v. In one embodiment, the concentration of the fibroin solution is 3.5% w/v. In one embodiment, the concentration of the fibroin solution is about 4.0% w/v. In one embodiment, the concentration of the fibroin solution is about 4.5% w/v. In one embodiment, the concentration of the fibroin solution is about 5.0% w/v. In one embodiment, the concentration of the fibroin solution is about 5.5% w/v. In one embodiment, the concentration of the fibroin solution is about 6.0% w/v. In one embodiment, the concentration of the fibroin solution is about 6.5% w/v. In one embodiment, the concentration of the fibroin solution is about 7.0% w/v. In one embodiment, the concentration of the fibroin solution is about 7.5% w/v. In one embodiment, the concentration of the fibroin solution is about 8.0% w/v. In one embodiment, the concentration of the fibroin solution is about 8.5% w/v. In one embodiment, the concentration of the fibroin solution is about 9.0% w/v. In one embodiment, the concentration of the fibroin solution is about 9.5% w/v. In one embodiment, the concentration of the fibroin solution is about 10.0% w/v.
In some embodiments, the SFS comprises an acidic agent. In some embodiments, the acidic agent is a Bronsted (Bronsted) acid. In one embodiment, the acidic agent comprises one or more of citric acid and acetic acid. In one embodiment, the acidic agent facilitates the deposition and coating of the SPF mixture (i.e., SFS coating) on the textile to be coated, as compared to the absence of the acidic agent. In one embodiment, the acidic agent improves crystallization of the SPF mixture at the textile to be coated.
In one embodiment, the acidic agent is added at a concentration (% w/w or% w/v) or by volume (v/v) of 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 greater than about 0.006%, or greater than about 0.007%, or greater than about 0.008%, or greater than about 0.009%, or greater than about 0.01%, or greater than about 0.02%, or greater than about 0.03%, or 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 0.1%, or greater than about 0.2%, or greater than about 0.3%, or greater than about 0.4%, or greater than about 0.5%, or greater than about 0.6%, or greater than about 0.7%, or greater than about 8%, or greater than about 0.3%, or greater than about 0.0.3%, or greater than about 0.0.0% by volume.
In one embodiment, the acidic agent is added at a concentration (% w/w or% w/v) or by volume (v/v) of 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 less than about 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 less than about 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 less than 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 0.3%, or less than about 0.0.3%, or less than about 0.3%, or less than about 0.0.0% by weight.
In some embodiments, the SFS can 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 greater 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 can include an acidic agent and can 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 greater 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 with or without surfactants and/or emulsifiers has a pH ranging from about 3 to 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, SFS can be applied to fibers and/or yarns having a diameter of less than about 100nm, or less than about 200nm, or less than about 300nm, or less than about 400nm, or less than about 500nm, or less than about 600nm, or less than about 700nm, or less than about 800nm, or less than about 900nm, or less than about 1000nm, 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 2 μm, or less than about 5mm, or less than about 10mm, or less than about 20mm, or less than about 70mm, or less than about 40mm, or less than about 80mm, or about 50mm, or less than about 80mm, or about 500mm, or about 0mm, or about 40mm, or less than about 0mm, or about 500mm, or about 0mm, or about 3mm or about 5 mm.
In some embodiments, SFS can be applied to fibers and/or yarns having a diameter greater than about 100nm, or greater than about 200nm, or greater than about 300nm, or greater than about 400nm, or greater than about 500nm, or greater than about 600nm, or greater than about 700nm, or greater than about 800nm, or greater than about 900nm, or greater than about 1000nm, 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 greater than about 70 μm, or greater than about 80 μm, or greater than about 90 μm, or greater than about 100 μm, or greater than about 200 μm, or greater than about 300 μm, or greater than about 400 μm, or greater than about 500 μm, or greater than about 600 μm, or greater than about 2 μm, or greater than about 5 μm, or greater than about 10mm, or greater than about 20mm, or greater than about 40mm, or greater than about 70mm, or greater than about 40mm, or greater than about 50mm, or greater than about 60mm, or greater than about 70mm, or greater than about 80mm, or greater than about 50mm, or greater than about 500mm, or greater than about 5mm, or greater than about 500mm, or greater than about 0mm, or greater than about 500mm, or greater than about 5mm, or greater than about 10mm, or greater than about 5 mm.
In some embodiments, SFS can be applied to fibers and/or yarns having a length of less than about 100nm, or less than about 200nm, or less than about 300nm, or less than about 400nm, or less than about 500nm, or less than about 600nm, or less than about 700nm, or less than about 800nm, or less than about 900nm, or less than about 1000nm, 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 2 μm, or less than about 5mm, or less than about 10mm, or less than about 20mm, or less than about 70mm, or less than about 40mm, or less than about 80mm, or about 50mm, or less than about 80mm, or about 500mm, or about 0mm, or about 40mm, or less than about 0mm, or about 500mm, or about 0mm, or about 3mm or about 5 mm.
In some embodiments, SFS can be applied to fibers and/or yarns having a length greater than about 100nm, or greater than about 200nm, or greater than about 300nm, or greater than about 400nm, or greater than about 500nm, or greater than about 600nm, or greater than about 700nm, or greater than about 800nm, or greater than about 900nm, or greater than about 1000nm, 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 greater than about 70 μm, or greater than about 80 μm, or greater than about 90 μm, or greater than about 100 μm, or greater than about 200 μm, or greater than about 300 μm, or greater than about 400 μm, or greater than about 500 μm, or greater than about 600 μm, or greater than about 2 μm, or greater than about 5 μm, or greater than about 10mm, or greater than about 20mm, or greater than about 40mm, or greater than about 70mm, or greater than about 40mm, or greater than about 50mm, or greater than about 60mm, or greater than about 70mm, or greater than about 80mm, or greater than about 50mm, or greater than about 500mm, or greater than about 5mm, or greater than about 500mm, or greater than about 0mm, or greater than about 500mm, or greater than about 5mm, or greater than about 10mm, or greater than about 5 mm.
In some embodiments, the SFS may be applied to fibers and/or yarns having a weight (g/m 2) of less than about 1g/m 2, or less than about 2g/m 2, or less than about 3g/m 2, or less than about 4g/m 2, or less than about 5g/m 2, or less than about 6g/m 2, or less than about 7g/m 2, or less than about 8g/m 2, or less than about 9g/m 2, a, Or less than about 10g/m 2, or less than about 20g/m 2, or less than about 30g/m 2, or less than about 40g/m 2, or less than about 50g/m 2, or less than about 60g/m 2, or less than about 70g/m 2, or less than about 80g/m 2, or less than about 90g/m 2, or less than about 100g/m 2, or less than about 200g/m 2, Or less than about 300g/m 2, or less than about 400g/m 2, or less than about 500g/m 2.
In some embodiments, the SFS may be applied to fibers and/or yarns having a weight (g/m 2) of greater than about 1g/m 2, or greater than about 2g/m 2, or greater than about 3g/m 2, or greater than about 4g/m 2, or greater than about 5g/m 2, or greater than about 6g/m 2, or greater than about 7g/m 2, or greater than about 8g/m 2, or greater than about 9g/m 2, Or greater than about 10g/m 2, or greater than about 20g/m 2, or greater than about 30g/m 2, or greater than about 40g/m 2, or greater than about 50g/m 2, or greater than about 60g/m 2, or greater than about 70g/m 2, or greater than about 80g/m 2, or greater than about 90g/m 2, or greater than about 100g/m 2, or greater than about 200g/m 2, Or greater than about 300g/m 2, or greater than about 400g/m 2, or greater than about 500g/m 2.
In some embodiments, the SFS can be applied to a fabric having a thickness of less than about 100nm, or less than about 200nm, or less than about 300nm, or less than about 400nm, or less than about 500nm, or less than about 600nm, or less than about 700nm, or less than about 800nm, or less than about 900nm, or less than about 1000nm, 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 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 about 3mm, or less than about 3mm, or about 4mm, or less than about 10mm, or about 8mm, or less than about 3 mm.
In some embodiments, SFS can be applied to a fabric having a thickness greater than about 100nm, or greater than about 200nm, or greater than about 300nm, or greater than about 400nm, or greater than about 500nm, or greater than about 600nm, or greater than about 700nm, or greater than about 800nm, or greater than about 900nm, or greater than about 1000nm, 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 greater than about 70 μm, or greater than about 80 μm, or greater than about 90 μm, or greater than about 100 μm, or greater than about 200 μm, or greater than about 300 μm, or greater than about 400 μm, or greater than about 500 μm, or greater than about 600 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 greater than about 70 μm, or greater than about 80 μm, or greater than about 90 μm, or greater than about 100 μm, or greater than about 500 mm, or greater than about 3mm, or greater than about 7mm, or greater than about 10mm, or about 4 mm.
In some embodiments, the SFS may be applied to the fabric, the fabric has a width of less than about 100nm, or less than about 200nm, or less than about 300nm, or less than about 400nm, or less than about 500nm, or less than about 600nm, or less than about 700nm, or less than about 800nm, or less than about 900nm, or less than about 1000nm, 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 900 μm, or less than about 800 μm, or less than about 60 μm. Or less than about 1000 μm, or less than about 2mm, or less than about 3mm, or less than about 4mm, or less than about 5mm, or less than about 6mm, or less than about 7mm, or less than about 8mm, or less than about 9mm, or less than about 10mm, or less than about 20mm, or less than about 30mm, or less than about 40mm, or less than about 50mm, or less than about 60mm, or less than about 70mm, or less than about 80mm, or less than about 90mm, or less than about 100mm, or less than about 200mm, or less than about 300mm, or less than about 400mm, or less than about 500mm, or less than about 600mm, or less than about 700mm, or less than about 800mm, or less than about 900mm, or less than about 1000mm, or less than about 2m, or less than about 3m, or less than about 4m, or less than about 5m.
In some embodiments, SFS can be applied to a fabric having a width greater than about 100nm, or greater than about 200nm, or greater than about 300nm, or greater than about 400nm, or greater than about 500nm, or greater than about 600nm, or greater than about 700nm, or greater than about 800nm, or greater than about 900nm, or greater than about 1000nm, 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 greater than about 70 μm, or greater than about 80 μm, or greater than about 90 μm, or greater than about 100 μm, or greater than about 200 μm, or greater than about 300 μm, or greater than about 400 μm, or greater than about 500 μm, or greater than about 600 μm, or greater than about 2 μm, or greater than about 5 μm, or greater than about 40mm, or greater than about 50mm, or greater than about 60mm, or greater than about 70mm, or greater than about 80mm, or greater than about 40mm, or greater than about 50mm, or greater than about 5mm, or greater than about 500mm, or greater than about 5mm, or greater than about 40mm, or about 50mm, or greater than about 5mm, or about 500mm, or greater than about 5mm, or about 0mm, or greater than about 5mm, or greater than about 10mm, or greater than about 5mm, or about 5 mm.
In some embodiments, the SFS can be applied to a fabric having a length of less than about 100nm, or less than about 200nm, or less than about 300nm, or less than about 400nm, or less than about 500nm, or less than about 600nm, or less than about 700nm, or less than about 800nm, or less than about 900nm, or less than about 1000nm, 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 2 μm, or less than about 5 μm, or less than about 10mm, or less than about 20mm, or less than about 30mm, or less than about 40mm, or less than about 70mm, or less than about 80mm, or less than about 50mm, or about 80mm, or less than about 0mm, or about 80mm, or about 0, or about 500mm, or about 0, or about 10mm or about 0.
In some embodiments, the SFS may be applied to the fabric, the fabric has a length greater than about 100nm, or greater than about 200nm, or greater than about 300nm, or greater than about 400nm, or greater than about 500nm, or greater than about 600nm, or greater than about 700nm, or greater than about 800nm, or greater than about 900nm, or greater than about 1000nm, 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 greater than about 70 μm, or greater than about 80 μm, or greater than about 90 μm, or greater than about 100 μm, or greater than about 200 μm, or greater than about 300 μm, or greater than about 400 μm, or greater than about 500 μm, or greater than about 600 μm, or greater than about 700 μm, or greater than about 300 μm or greater than about 800 μm, or greater than about 900 μm, or greater than about 1000 μm, or greater than about 2mm, or greater than about 3mm, or greater than about 4mm, or greater than about 5mm, or greater than about 6mm, or greater than about 7mm, or greater than about 8mm, or greater than about 9mm, or greater than about 10mm, or greater than about 20mm, or greater than about 30mm, or greater than about 40mm, or greater than about 50mm, or greater than about 60mm, or greater than about 70mm, or greater than about 80mm, or greater than about 90mm, or greater than about 100mm, or greater than about 200mm, or greater than about 300mm, or greater than about 400mm, or greater than about 500mm, or greater than about 600mm, or greater than about 700mm, or greater than about 800mm, or greater than about 900mm, or greater than about 1000mm.
In some embodiments, the SFS can be applied to a fabric having a stretch percentage of 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 less than 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 percentage of a fabric having an unstretched width can be determined and the fabric stretched to the stretched width, then the unstretched width is subtracted from the stretched width to give a net stretched width, which is then divided and multiplied by 100 to give the stretch percentage (%)
In some embodiments, the SFS can be applied to a fabric having a stretch percentage of 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 greater than about 8%, or greater than about 9%, or greater than about 10%, or greater than about 20%, or greater than about 30%, or greater than about 40%, or greater than about 50%, or greater than about 60%, or greater than about 70%, or greater than about 80%, or greater than about 90%, or greater than about 100%, or greater than about 110%, or greater than about 120%, or greater than about 130%, or greater than about 140%, or greater than 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 may be applied to a fabric having a tensile energy (N/cm 2) of less than about 1cN/cm 2, or less than about 2cN/cm 2, or less than about 3cN/cm 2, or less than about 4cN/cm 2, or less than about 5cN/cm 2, or less than about 5cN/cm 2, or less than about 6cN/cm 2, or less than about 7cN/cm 2, Or less than about 8cN/cm 2, or less than about 9cN/cm 2, or less than about 10cN/cm 2, or less than about 20cN/cm 2, or less than about 30cN/cm 2, or less than about 40cN/cm 2, or less than about 50cN/cm 2, or less than about 60cN/cm 2, or less than about 70cN/cm 2, or less than about 80cN/cm 2, Or less than about 90cN/cm 2, or less than about 100cN/cm 2, or less than about 2N/cm 2, or less than about 3N/cm 2, or less than about 4N/cm 2, or less than about 5N/cm 2, or less than about 6N/cm 2, or less than about 7N/cm 2, or less than about 8N/cm 2, or less than about 9N/cm 2, or less than about 10N/cm 2, a method of making a semiconductor device, and a semiconductor device, Or less than about 20N/cm 2, or less than about 30N/cm 2, or less than about 40N/cm 2, or less than about 50N/cm 2, or less than about 60N/cm 2, or less than about 70N/cm 2, or less than about 80N/cm 2, or less than about 90N/cm 2, or less than about 100N/cm 2, or less than about 150N/cm 2, Or less than about 200N/cm 2.
In some embodiments, the SFS may be applied to a fabric having a tensile energy (N/cm 2) of greater than about 1cN/cm 2, or greater than about 2cN/cm 2, or greater than about 3cN/cm 2, or greater than about 4cN/cm 2, or greater than about 5cN/cm 2, or greater than about 5cN/cm 2, or greater than about 6cN/cm 2, or greater than about 7cN/cm 2, Or greater than about 8cN/cm 2, or greater than about 9cN/cm 2, or greater than about 10cN/cm 2, or greater than about 20cN/cm 2, or greater than about 30cN/cm 2, or greater than about 40cN/cm 2, or greater than about 50cN/cm 2, or greater than about 60cN/cm 2, or greater than about 70cN/cm 2, or greater than about 80cN/cm 2, Or greater than about 90cN/cm 2, or greater than about 100cN/cm 2, or greater than about 2N/cm 2, or greater than about 3N/cm 2, or greater than about 4N/cm 2, or greater than about 5N/cm 2, or greater than about 6N/cm 2, or greater than about 7N/cm 2, or greater than about 8N/cm 2, or greater than about 9N/cm 2, or greater than about 10N/cm 2, Or greater than about 20N/cm 2, or greater than about 30N/cm 2, or greater than about 40N/cm 2, or greater than about 50N/cm 2, or greater than about 60N/cm 2, or greater than about 70N/cm 2, or greater than about 80N/cm 2, or greater than about 90N/cm 2, or greater than about 100N/cm 2, or greater than about 150N/cm 2, Or greater than about 200N/cm 2.
In some embodiments, the SFS may be applied to a fabric having a shear stiffness (N/cm-degree) of less than about 1 cN/cm-degree, or less than about 2 cN/cm-degree, or less than about 3 cN/cm-degree, or less than about 4 cN/cm-degree, or less than about 5 cN/cm-degree, or less than about 6 cN/cm-degree, or less than about 7 cN/cm-degree, or less than about 8 cN/cm-degree, or less than about 9 cN/cm-degree, or less than about 10 cN/cm-degree, or less than about 20 cN/cm-degree, or less than about 30 cN/cm-degree, or less than about 40 cN/cm-degree, or less than about 50 cN/cm-degree, or less than about 60 cN/cm-degree, or less than about 70 cN/cm-degree, or less than about 80 cN/cm-degree, or less than about 9 cN/cm-degree, or less than about 10 cN/cm-degree, or less than about 30 cN/cm-degree, or less than about 40 cN/cm-degree, or less than about 20 cN/cm-degree, or less than about 50 cN/cm-degree, or less than about 70N/cm-degree, or less than about 80N/cm-degree, or less than about 90N/cm-degree, or less than about 100N/cm-degree, or less than about 150N/cm-degree, or less than about 200N/cm-degree.
In some embodiments, the SFS may be applied to a fabric having a shear stiffness (N/cm-degree) of greater than about 1 cN/cm-degree, or greater than about 2 cN/cm-degree, or greater than about 3 cN/cm-degree, or greater than about 4 cN/cm-degree, or greater than about 5 cN/cm-degree, or greater than about 6 cN/cm-degree, or greater than about 7 cN/cm-degree, or greater than about 8 cN/cm-degree, or greater than about 9 cN/cm-degree, or greater than about 10 cN/cm-degree, or greater than about 20 cN/cm-degree, or greater than about 30 cN/cm-degree, or greater than about 40 cN/cm-degree, or greater than about 50 cN/cm-degree, or greater than about 60 cN/cm-degree, or greater than about 70 cN/cm-degree, or greater than about 80 cN/cm-degree, or greater than about 7 cN/cm-degree, or greater than about 9 cN/cm-degree, or greater than about 10 cN/cm-degree, or greater than about 20 cN/cm-degree, or greater than about 30 cN/cm-degree, or greater than about 40 cN/cm-degree, or greater than about 50 cN/cm-degree, or greater than about 70N/cm-degree, or greater than about 80N/cm-degree, or greater than about 90N/cm-degree, or greater than about 100N/cm-degree, or greater than about 150N/cm-degree, or greater than about 200N/cm-degree.
In some embodiments, the SFS may be applied to a fabric having a flexural rigidity (N.cm 2/cm) of 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 7cN cm 2/cm, or less than about 8cN cm 2/cm, or less than about 9cN cm 2/cm, or less than about 10cN cm 2/cm, or less than about 20cN cm 2/cm, or less than about 30cN cm 2/cm, or less than about 40cN cm 2/cm, or less than about 50cN cm 2/cm, or less than about 60cN cm 2/cm, Or less than about 70cN cm 2/cm, or less than about 80cN cm 2/cm, or less than about 90cN cm 2/cm, or less than about 100cN cm 2/cm, or less than about 2N cm 2/cm, or less than about 3N cm 2/cm, or less than about 4N cm 2/cm, or less than about 5N cm 2/cm, or less than about 6N cm 2/cm, Or less than about 7N.cm 2/cm, or less than about 8N.cm 2/cm, or less than about 9N.cm 2/cm, or less than about 10N.cm 2/cm, or less than about 20N.cm 2/cm, or less than about 30N.cm 2/cm, or less than about 40N.cm 2/cm, or less than about 50N.cm 2/cm, or less than about 60deg.N.cm 2/cm, Or less than about 70N cm 2/cm, or less than about 80N cm 2/cm, or less than about 90N cm 2/cm, or less than about 100N cm 2/cm, or less than about 150N cm 2/cm, or less than about 200N cm 2/cm.
In some embodiments, the SFS may be applied to a fabric having a flexural rigidity (N.cm 2/cm) of 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 7cN cm 2/cm, or greater than about 8cN cm 2/cm, or greater than about 9cN cm 2/cm, or greater than about 10cN cm 2/cm, or greater than about 20cN cm 2/cm, or greater than about 30cN cm 2/cm, or greater than about 40cN cm 2/cm, or greater than about 50cN cm 2/cm, or greater than about 60cN cm 2/cm, Or greater than about 70cN cm 2/cm, or greater than about 80cN cm 2/cm, or greater than about 90cN cm 2/cm, or greater than about 100cN cm 2/cm, or greater than about 2N cm 2/cm, or greater than about 3N cm 2/cm, or greater than about 4N cm 2/cm, or greater than about 5N cm 2/cm, or greater than about 6N cm 2/cm, Or greater than about 7N.cm 2/cm, or greater than about 8N.cm 2/cm, or greater than about 9N.cm 2/cm, or greater than about 10N.cm 2/cm, or greater than about 20N.cm 2/cm, or greater than about 30N.cm 2/cm, or greater than about 40N.cm 2/cm, or greater than about 50N.cm 2/cm, or greater than about 60deg.N.cm 2/cm, Or greater than about 70N cm 2/cm, or greater than about 80N cm 2/cm, or greater than about 90N cm 2/cm, or greater than about 100N cm 2/cm, or greater than about 150N cm 2/cm, or greater than about 200N cm 2/cm.
In some embodiments, the SFS may be applied to a fabric having a compressive energy (N.cm/cm 2) of less than about 1 cN.cm/cm 2, or less than about 2 cN.cm/cm 2, or less than about 3 cN.cm/cm 2, or less than about 4 cN.cm/cm 2, or less than about 5c N.cm 2, or less than about 5 cN.cm/cm 2, or less than about 6 cN.cm/cm 2, Or less than about 7 cN.cm/cm 2, or less than about 8 cN.cm/cm 2, or less than about 9 cN.cm/cm 2, or less than about 10 cN.cm/cm 2, or less than about 20 cN.cm/cm 2, or less than about 30 cN.cm/cm 2, or less than about 40 cN.cm/cm 2, or less than about 50 cN.cm/cm 2, or less than about 60 cN.cm/cm 2, Or less than about 70 cN.cm/cm 2, or less than about 80 cN.cm/cm 2, or less than about 90 cN.cm/cm 2, or less than about 100 cN.cm/cm 2, or less than about 2 N.cm/cm 2, or less than about 3 N.cm/cm 2, or less than about 4 N.cm/cm 2, or less than about 5 N.cm/cm 2, or less than about 6 N.cm/cm 2, Or less than about 7N.cm/cm 2, or less than about 8N.cm/cm 2, or less than about 9N.cm/cm 2, or less than about 10N.cm/cm 2, or less than about 20N.cm/cm 2, or less than about 30N.cm/cm 2, or less than about 40N.cm/cm 2, or less than about 50N.cm/cm 2, or less than about 60deg.N.cm/cm 2, Or less than about 70 N.cm/cm 2, or less than about 80 N.cm/cm 2, or less than about 90 N.cm/cm 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 may be applied to a fabric having a compressive energy (N.cm/cm 2) of 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 greater than about 5 cN.cm/cm 2, or greater than about 5 cN.cm/cm 2, or greater than about 6 cN.cm/cm 2, Or greater than about 7 cN.cm/cm 2, or greater than about 8 cN.cm/cm 2, or greater than about 9 cN.cm/cm 2, or greater than about 10 cN.cm/cm 2, or greater than about 20 cN.cm/cm 2, or greater than about 30 cN.cm/cm 2, or greater than about 40 cN.cm/cm 2, or greater than about 50 cN.cm/cm 2, or greater than about 60 cN.cm/cm 2, Or greater than about 70 cN.cm/cm 2, or greater than about 80 cN.cm/cm 2, or greater than about 90 cN.cm/cm 2, or greater than about 100 cN.cm/cm 2, or greater than about 2 N.cm/cm 2, or greater than about 3 N.cm/cm 2, or greater than about 4 N.cm/cm 2, or greater than about 5 N.cm/cm 2, or greater than about 6 N.cm/cm 2, Or greater than about 7N.cm/cm 2, or greater than about 8N.cm/cm 2, or greater than about 9N.cm/cm 2, or greater than about 10N.cm/cm 2, or greater than about 20N.cm/cm 2, or greater than about 30N.cm/cm 2, or greater than about 40N.cm/cm 2, or greater than about 50N.cm/cm 2, or greater than about 60deg.N.cm/cm 2, Or greater than about 70 N.cm/cm 2, or greater than about 80 N.cm/cm 2, or greater than about 90 N.cm/cm 2, or greater than about 100 N.cm/cm 2, or greater than about 150 N.cm/cm 2, or greater than about 200 N.cm/cm 2.
In some embodiments, the SFS can be applied to a fabric having a coefficient of friction of 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 0.15, 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 less than about 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 less than about 0.75, 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.
In some embodiments, the SFS can be applied to a fabric having a coefficient of friction 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 0.15, 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 greater than about 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 greater than about 0.75, 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.
In some embodiments, the chemical finish may be applied to the textile before or after coating the textile with the SFS. In one embodiment, the chemical finish may be intended to apply a chemical agent and/or SFS to a textile, including fibers, yarns and fabrics, or to garments made from such fibers, yarns and fabrics, to alter the properties of the original textile or garment and to achieve properties that are not otherwise present in the textile or garment. For chemical finishes, textiles treated with such chemical finishes may act as surface treatments and/or the treatments may alter elemental analysis of the treated textile matrix polymer.
In one embodiment, one type of chemical finish may include the application of certain fibroin-based solutions to textiles. For example, SFS may be applied to the fabric after dyeing, but there may be instances where it may be desirable to apply SFS during processing, during dyeing, or after assembling the garment from the selected textile or fabric, thread, or yarn. In some embodiments, after application, the SFS may be dried with heat. The SFS can then be secured to the surface of the textile in a process step known as curing.
In some embodiments, the SFS may be provided in concentrated form suspended in water. In some embodiments, the SFS can have a concentration (% w/w or% w/v) or by volume (v/v) of less than about 50%, or less than about 45%, or less than about 40%, or less than about 35%, 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 less than about 0.00001%. In some embodiments, the SFS can have a concentration by weight (% w/w or% w/v) or by volume (v/v) of greater than about 50%, or greater than about 45% or greater than about 40% or greater than about 35% or greater than about 30% or greater than about 25% or greater than about 20% or greater than about 15% or greater than about 10% or greater than about 5% or greater than about 4% or greater than about 3% or greater than about 2% or greater than about 1% or greater than about 0.1% or greater than about 0.01% or greater than about 0.001% or greater than about 0.0001% or greater than about 0.00001%.
In some embodiments, the concentration of the solution and the moisture absorption rate of the material determine the amount of a fibroin solution (SFS), which can comprise silk-based proteins or fragments thereof, which can be immobilized or adhered to the coated textile. The moisture absorption rate can be expressed as follows:
The total amount of SFS added to the textile material can be expressed by the following formula:
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With respect to methods of applying SFS to textiles more broadly, SFS may be applied to textiles through pad or roller application processes, saturation and removal processes, and/or topical application processes. Further, the method of wire application (i.e., SFS application or coating) may include bath coating, kiss roll coating, spray coating, and/or double-sided roll coating. In some embodiments, the coating process (e.g., bath coating, kiss roll coating, spray coating, double sided roll coating, saturation and removal application and/or topical application), drying process, and curing process may be varied as described herein to alter one or more selected textile (e.g., fabric) properties of the resulting coated textile, wherein such properties include, but are not limited to, wetting time, absorption rate, spreading speed, cumulative unidirectional transport, and/or overall moisture management capability. In some embodiments, the aforementioned selected properties may be enhanced by altering one or more of the coating process, drying process, and curing process as described herein.
In one embodiment, padding application may be used for dry or wet textiles. For example, it may be applied to the fabric after the dyeing process. The fabric may be fed into a water bath solution and saturation may be achieved. The fabric to be coated can then be passed over a set of rollers to extract excess bath solution to the desired% moisture absorption based on a number of variables. Variables that affect% moisture absorption include roll and material, fabric composition and structure, and SFS viscosity.
In one embodiment, padding is applied to the wet textile may be used to reduce the cost of drying the textile after dyeing. The fabric exiting the backing roll may remain at a higher weight percent than the fabric entering the backing roll to maintain SFS deposition on the fabric; the SFS solution may need to take into account any dilution that occurs due to the presence of water on the incoming fabric.
In one embodiment, saturation and removal application is a low moisture absorption process that may, for example, address some of the problems associated with removing large amounts of water during drying. Since the fabric can be dried inwardly in the oven from the outer surface, the water can move from inside to outside, resulting in a higher coating concentration on the outer surface. At lower water content, migration may be reduced due to higher solution viscosity. However, reduced moisture absorption may lead to uneven solution deposition.
In one embodiment, vacuum suction may be used as a low moisture absorption method. The saturated fabric may be subjected to a vacuum that pulls the solution from the fabric and returns the solution to the applicator ring. Air sparging can be a method of providing low moisture absorption. The saturated fabric may be subjected to high pressure steam which removes the solution from the fabric and returns the solution to the application ring.
In one embodiment, a porous bowl process may be used for low moisture absorption. The solid backing roll may be replaced with a rubber coated fiber roll. The saturated fabric may be subjected to the pressure of the roller because the porosity of the roller may allow more solution to be extruded from the fabric.
In one embodiment, a transfer pad process may be used for low moisture absorption. The saturated fabric may pass through two continuous dry nonwoven fabrics and may be compressed at low pressure. The nonwoven fabric may extract excess solution from the treated fabric.
In one embodiment, topical application may be used as a low moisture absorption application method that deposits the desired amount of SFS onto the fabric without removing any excess material. The method described above can be used for single sided coating applications, but there are variations that can allow for double sided coating.
In one embodiment, kiss roll coating may be used as a localized application method to transfer SFS from a roll (i.e., kiss roll) to one side of the fabric. The solution viscosity, the roller surface finish, the speed of the roller, the speed of the fabric, the contact angle of the fabric on the roller, and the nature of the fabric are parameters that control the amount of solution deposited on the fabric.
In one embodiment, the variation of kiss roll technology may be a Triatex MA system that uses two moisture content sensors to determine the solution absorbed at the kiss rolls and adjusts the kiss roll controllable variables to maintain consistency of the solution deposition onto the fabric.
In one embodiment, loop transfer application may be used as a topical application method that transfers SFS from a saturated loop fabric to the fabric to be coated between low pressure backup rolls. Two roll forms may allow minimal contact with the fabric, while three roll forms may allow greater contact with the fabric.
In one embodiment, engraved roll application may be used as a topical application method that can transfer metered SFS onto a fabric. This can be achieved by engraving a pattern containing a controlled amount of SFS with a precise depth and design on the surface of the roll. A blade may be used to remove any solution deposited on the surface of the roll to maintain consistent transfer of the solution to the fabric to be coated.
In one embodiment, cylinder printing may be used as a topical application method that can deposit SFS onto a fabric by allowing a solution to permeate through a roller screen. The solution may be contained in the screen printing roll core at a set level while any excess solution may be removed from the inner roll wall using a blade to provide a clean surface for the next rotation of the screen printing roll.
In one embodiment, magnetic roll coating may be used as a topical application method that may deposit SFS from kiss rolls onto the fabric to be coated. The kiss roll is semi-immersed in the bath solution and the magnetic field generated in the fabric drive roll determines the amount of pressure applied by the kiss roll, thereby controlling the solution absorption rate.
In one embodiment, spraying may be used as a topical application method that can transfer SFS to a fabric by atomizing a solution. The spray pattern may be controlled by the nozzle pattern, size, and air flow. Spray application may be used for single sided application as well as for double sided application.
In one embodiment, foam application may use a topical application method that can transfer SFS to the fabric. The foam may be created by replacing a portion of the water in the solution with air, thereby reducing the amount of water applied to the fabric. Foam application may be used for single sided application or double sided application, where the same foam may be deposited by squeeze rolls, or different foam solutions may be provided by transfer rolls or by slit applicators.
In one embodiment, the application of the SFS may be performed after the garment is assembled. In one embodiment, the process may be performed in a washing and dyeing machine or spray booth. For example, the washing and dyeing machine may be shaped like a household front-end washing machine, which allows the process to be performed when exhausted after dyeing or with a separate treatment cycle. In one embodiment, the spray booth machine may include a manual or fully automated process. For example, the garment may be worn by a mannequin and an operator or anthropomorphic robot may spray the solution onto the fabric.
In one embodiment, the SFS may be a water-based solution that, after application to the textile, may require thermal gasification to inject the SFS onto the textile. Thermal gasification can be applied by heat transfer through radiation using equipment such as infrared or radio frequency dryers.
In one embodiment, the thermal gasification may be applied by convection of hot air circulating in an oven to a desired temperature while the fabric is clamped and conveyed by a conveyor belt. This allows complete control of the fabric width dimension.
In one embodiment, the thermal gasification may be applied by conduction by contacting the textile with a heated drum or calender drum. Since the fabric is not clamped, control over the width of the fabric is minimal.
In one embodiment, the curing of the SFS on the textile may be accomplished in successive cycles or in separate cycles using the same equipment used for thermal gasification.
In one embodiment, the cure time temperature may depend on the textile polymer content and the preferred method of bonding the SFS to the particular polymer. The curing process may not begin until the thermal gasification is completed.
In some embodiments, the sensor may be used to monitor SFS deposition on textiles and drying and curing steps.
In some embodiments, to monitor the deposition of SFS, a non-contact sensor may be used, such as the sensor provided by model Pleva AF of water-based microwave absorption. The measurement of the material humidity may be based on microwave absorption of water. The semiconductor oscillator transmits microwave energy through a network. The unabsorbed portion of the energy may be received by the microwave receiver at an opposite side. The absorption is a measure of absolute moisture content. The microwave sensor is capable of detecting and measuring moisture levels of a minimum of 0 to 2000gH 2O/m2.
In some embodiments, for wide web treatment, multiple sensors may be paired side-by-side, transmitting data analysis to a centralized control system loop that is able to add more solution in the lower region of the web.
In some embodiments, another sensor based on microwave technology, such as Aqualot of Mahlo, may be used. Instead of measuring the attenuation of microwaves by the number of water molecules in the gap, the sensor can evaluate the shift of the resonance frequencies of the two standing waves relative to each other.
In some embodiments, another non-contact sensor for SFS may be IR-3000 based on near infrared sensing technology of MoistTech. The sensor measures the near infrared energy reflected at a given wavelength, which is inversely proportional to the number of absorbing molecules in the fabric.
In some embodiments, the residual moisture at the end of the curing process may be measured to further confirm the drying and curing process. In addition to the sensors described above, mahlo's contact sensor (such as Textometer RMS) may also be used to measure humidity by conductivity.
In some embodiments, monitoring the end of the drying process stage may be accomplished by measuring the fabric temperature with a non-contact temperature sensor. When the wet product enters the dryer, the wet product is first heated to a cool-limit temperature. In some embodiments, when the water content drops to the residual moisture level, the product temperature may begin to rise again. The closer the product temperature is to the circulating air temperature in the dryer, the slower the temperature continues to rise. In some embodiments, at a certain temperature threshold (referred to as a fixed temperature), the temperature required for processing, fixing, or condensing is reached.
In some embodiments, to determine the residence time of the desired product temperature, a high temperature resistant infrared pyrometer may be used to contactlessly measure the surface temperature of the product at multiple locations in the dryer. Mahlo PERMASET VMT are infrared pyrometers that can be assembled into multiple units to monitor the temperature of the entire dryer. Setex is another manufacturer, such as model WTM V11, V21 and V41, who provides fabric temperature sensors for dryers and ovens.
In some embodiments, the SFS may be applied to the textile during dip dyeing. In some embodiments, the process may involve adding the fabric to a bath initially referred to as a batch, and allowing the fabric to equilibrate with the solution. Dip dyeing may be the ability of molecules of fibroin to migrate from solution onto the fibers or threads of a textile (substantivity). The substantivity of fibroin can be affected by temperature or additives such as salts.
In some embodiments, the dip dyeing process may take from minutes to hours. When the fabric has absorbed or immobilized as much of the fibroin as possible, the bath can be emptied and the fabric can be rinsed to remove any excess solution.
In some embodiments, an important parameter in dip dyeing may be the so-called specific bath ratio. It describes the ratio of the mass of fabric to the volume of the SFS bath and determines the amount of fibroin deposited on the fabric.
In some embodiments, SFS may be applied to the textile during jet dyeing. The jet dyeing machine may be formed by a closed tubular system in which the fabric is placed. In order to transport the fabric through the tube, a jet of dye liquor is provided through a venturi tube. The jet may create turbulence. This can assist SFS penetration and prevent the fabric from contacting the tube wall. For example, because fabrics are typically exposed to relatively high concentrations of liquid in the transfer tube, a small SFS bath is required at the bottom of the container. 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. Paddle dyeing machines are commonly used for many forms of textiles, but the method is most suitable for clothing. Heat can be generated by spraying steam directly into the coating bath. In one embodiment, the paddle dyeing machine is operated by paddles that circulate the bath and the laundry in a porous center island (perforated CENTRAL ISLAND). Where SFS, water and heated steam are added. An overhead paddle machine may be described as a bucket with paddles that have full width blades. The blade may be immersed in the bucket, typically a few centimeters. This action can agitate the bath and push down the garments to be dyed, thereby immersing them in the dye liquor.
In some embodiments, the treatment methods set forth herein may be used to apply SFS to textiles with one or more of the following parameters including, but not limited to, fabric speed, solution viscosity, solution added to the fabric, fabric range width, drying temperature, drying time, curing time, fabric tension, padding pressure, padding roller shore hardness, stenter temperature, and common drying and curing temperatures. In one embodiment, the treatment process parameters may also include a condensing temperature, which may vary depending on the chemical protocol used to apply the SFS to the textile.
In one embodiment, the fabric speed for the methods of the present disclosure may be less than about 0.1m/min, or less than about 0.2m/min, or less than about 0.3m/min, or less than about 0.4m/min, or less than about 0.5m/min, or less than about 0.6m/min, or less than about 0.7m/min, or less than about 0.8m/min, or less than about 0.9m/min, or less than about 1m/min, or less than about 2m/min, or less than about 3m/min, or less than about 4m/min, or less than about 5m/min, or less than about 6m/min, or less than about 7m/min, or less than about 8m/min, or less than about 9m/min, or less than about 10m/min, or less than about 20m/min, or less than about 30m/min, or less than about 40m/min, or less than about 50m/min, or less than about 60m/min.
In one embodiment, the fabric speed for the methods of the present disclosure may be greater than about 0.1m/min, or greater than about 0.2m/min, or greater than about 0.3m/min, or greater than about 0.4m/min, or greater than about 0.5m/min, or greater than about 0.6m/min, or greater than about 0.7m/min, or greater than about 0.8m/min, or greater than about 0.9m/min, or greater than about 1m/min, or greater than about 2m/min, or greater than about 3m/min, or greater than about 4m/min, or greater than about 5m/min, or greater than about 6m/min, or greater than about 7m/min, or greater than about 8m/min, or greater than about 9m/min, or greater than about 10m/min, or greater than about 20m/min, or greater than about 30m/min, or greater than about 40m/min, or greater than about 50m/min, or greater than about 60m/min.
In one embodiment, the solution viscosity for the methods of the present disclosure may be less than about 1000mPas, or less than about 1500mPas, or less than about 2000mPas, or less than about 2500, or less than about 3000mPas, or less than about 4000mPas, or less than about 4500mPas, or less than about 5000mPas, or less than about 5500mPas, or less than about 6000mPas, or less than about 6500mPas, or less than about 7000mPas, or less than about 7500mPas, or less than about 8000mPas, or less than about 8500mPas, or less than about 9000mPas, or less than about 9500mPas, or less than about 10000mPas, or less than about 10500mPas, or less than about 11000mPas, or less than about 11500mPas, or less than about 12000mPas.
In one embodiment, the solution viscosity for the methods of the present disclosure may be greater than about 1000mPas, or greater than about 1500mPas, or greater than about 2000mPas, or greater than about 2500, or greater than about 3000mPas, or greater than about 4000mPas, or greater than about 4500mPas, or greater than about 5000mPas, or greater than about 5500mPas, or greater than about 6000mPas, or greater than about 6500mPas, or greater than about 7000mPas, or greater than about 7500mPas, or greater than about 8000mPas, or greater than about 8500mPas, or greater than about 9000mPas, or greater than about 9500mPas, or greater than about 10000mPas, or greater than about 10500mPas, or greater than about 11000mPas, or greater than about 11500mPas, or greater than about 12000mPas.
In one embodiment, for the methods of the present disclosure, the solution can be added to a textile (e.g., fabric) in an amount of less than about 0.01g/m 2, or less than about 0.02g/m 2, or less than about 0.03g/m 2, or less than about 0.04g/m 2, or less than about 0.05g/m 2, or less than about 0.06g/m 2, or less than about 0.07g/m 2, or less than about 0.08g/m 2, Or less than about 0.09g/m 2, or less than about 0.10g/m 2, or less than about 0.2g/m 2, or less than about 0.3g/m 2, or less than about 0.4g/m 2, or less than about 0.5g/m 2, or less than about 0.6g/m 2, or less than about 0.7g/m 2, or less than about 0.8g/m 2, or less than about 0.9g/m 2, Or less than about 1g/m 2, or less than about 2g/m 2, or less than about 3g/m 2, or less than about 4g/m 2, or less than about 5g/m 2, or less than about 6g/m 2, or less than about 7g/m 2, or less than about 8g/m 2, or less than about 9g/m 2, or less than about 10g/m 2, or less than about 20g/m 2, or less than about 30g/m 2, a composition of matter of about, Or less than about 40g/m 2, or less than about 50g/m 2, or less than about 60g/m 2, or less than about 70g/m 2, or less than about 80g/m 2, or less than about 90g/m 2, or less than about 100g/m 2.
In one embodiment, for the methods of the present disclosure, the solution can be added to a textile (e.g., fabric) in an amount greater than about 0.01g/m 2, or greater than about 0.02g/m 2, or greater than about 0.03g/m 2, or greater than about 0.04g/m 2, or greater than about 0.05g/m 2, or greater than about 0.06g/m 2, or greater than about 0.07g/m 2, or greater than about 0.08g/m 2, Or greater than about 0.09g/m 2, or greater than about 0.10g/m 2, or greater than about 0.2g/m 2, or greater than about 0.3g/m 2, or greater than about 0.4g/m 2, or greater than about 0.5g/m 2, or greater than about 0.6g/m 2, or greater than about 0.7g/m 2, or greater than about 0.8g/m 2, or greater than about 0.9g/m 2, Or greater than about 1g/m 2, or greater than about 2g/m 2, or greater than about 3g/m 2, or greater than about 4g/m 2, or greater than about 5g/m 2, or greater than about 6g/m 2, or greater than about 7g/m 2, or greater than about 8g/m 2, or greater than about 9g/m 2, or greater than about 10g/m 2, or greater than about 20g/m 2, or greater than about 30g/m 2, a, Or greater than about 40g/m 2, or greater than about 50g/m 2, or greater than about 60g/m 2, or greater than about 70g/m 2, or greater than about 80g/m 2, or greater than about 90g/m 2, or greater than about 100g/m 2.
In one embodiment, the fabric width ranges for the methods of the present disclosure may be less than about 1mm, or less than about 2mm, or less than about 3mm, or less than about 4mm, or less than about 5mm, or less than about 6mm, or less than about 7mm, or less than about 8mm, or less than about 9mm, or less than about 10mm, or less than about 20mm, or less than about 30mm, or less than about 40mm, or less than about 50mm, or less than about 60mm, or less than about 70mm, or less than about 80mm, or less than about 90mm, or less than about 100mm, or less than about 200, or less than about 300mm, or less than about 400mm, or less than about 500mm, or less than about 600mm, or less than about 700mm, or less than about 800mm, or less than about 900mm, or less than about 1000mm, or less than about 2000mm, or less than about 3000mm, or less than about 4000mm, or less than about 5000mm.
In one embodiment, the fabric width ranges for the methods of the present disclosure may be greater than about 1mm, or greater than about 2mm, or greater than about 3mm, or greater than about 4mm, or greater than about 5mm, or greater than about 6mm, or greater than about 7mm, or greater than about 8mm, or greater than about 9mm, or greater than about 10mm, or greater than about 20mm, or greater than about 30mm, or greater than about 40mm, or greater than about 50mm, or greater than about 60mm, or greater than about 70mm, or greater than about 80mm, or greater than about 90mm, or greater than about 100mm, or greater than about 200 mm, or greater than about 300mm, or greater than about 400mm, or greater than about 500mm, or greater than about 600mm, or greater than about 700mm, or greater than about 800mm, or greater than about 900mm, or greater than about 1000mm, or greater than about 2000mm, or greater than about 3000mm, or greater than about 4000mm, or greater than about 5000mm.
In one embodiment, the drying and/or curing temperature for the methods of the present disclosure may be less than about 70 ℃, or less than about 75 ℃, or less than about 80 ℃, or less than about 85 ℃, or less than about 90 ℃, or less than about 95 ℃, 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 less than 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 ℃, or less than about 210 ℃, or less than about 220 ℃, or less than about 230 ℃.
In one embodiment, the drying and/or curing temperature for the methods of the present disclosure may be greater than about 70 ℃, or greater than about 75 ℃, or greater than about 80 ℃, or greater than about 85 ℃, or greater than about 90 ℃, or greater than about 95 ℃, or greater than about 100 ℃, or greater than about 110 ℃, or greater than about 120 ℃, or greater than about 130 ℃, or greater than about 140 ℃, or greater than 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 ℃, or greater than about 210 ℃, or greater than about 220 ℃, or greater than about 230 ℃.
In one embodiment, the drying time for the methods of the present disclosure may be 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 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 methods of the present disclosure may be 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 greater than about 2 minutes, or greater than about 3 minutes, or greater than about 4 minutes, or greater than about 5 minutes, or greater than about 6 minutes, or greater than about 7 minutes, or greater than about 8 minutes, or greater than about 9 minutes, or greater than about 10 minutes, or greater than about 20 minutes, or greater than about 30 minutes, or greater than about 40 minutes, or greater than about 50 minutes, or greater than about 60 minutes.
In one embodiment, the cure time for the methods of the present disclosure may be 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 less than about 9 minutes, 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 cure time for the methods of the present disclosure may be 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 greater than about 7 seconds, or greater than about 8 seconds, or greater than about 9 seconds, or 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 greater than about 2 minutes, or greater than about 3 minutes, or greater than about 4 minutes, or greater than about 5 minutes, or greater than about 6 minutes, or greater than about 7 minutes, or greater than about 8 minutes, or greater than about 9 minutes, or greater than about 10 minutes, or greater than about 20 minutes, or greater than about 30 minutes, or greater than about 40 minutes, or greater than about 50 minutes, or greater than about 60 minutes.
In one embodiment, the fabric tension for the methods of the present disclosure may be 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 fabric tension for the methods of the present disclosure may be 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 greater than about 8N, or greater than about 9N, or greater than about 10N, or greater than about 20N, or greater than about 30N, or greater than about 40N, or greater than about 50N, or greater than about 60N, or greater than about 70N, or greater than about 80N, or greater than about 90N, or greater than about 100N, or greater than about 150N, or greater than about 200N, or greater than about 250N, or greater than about 300N.
In one embodiment, the padding machine pressure used in the methods of the present disclosure may be less than about 1N/mm, or less than about 2N/mm, or less than about 3N/mm, or less than about 4N/mm, or less than about 5N/mm, or less than about 6N/mm, or less than about 7N/mm, or less than about 8N/mm, or less than about 9N/mm, or less than about 10N/mm, or less than about 20N/mm, or less than about 30N/mm, or less than about 40N/mm, or less than about 50N/mm, or less than about 60N/mm, or less than about 70N/mm, or less than about 80N/mm, or less than about 90N/mm.
In one embodiment, the padding machine pressure used in the methods of the present disclosure may be greater than about 1N/mm, or greater than about 2N/mm, or greater than about 3N/mm, or greater than about 4N/mm, or greater than about 5N/mm, or greater than about 6N/mm, or greater than about 7N/mm, or greater than about 8N/mm, or greater than about 9N/mm, or greater than about 10N/mm, or greater than about 20N/mm, or greater than about 30N/mm, or greater than about 40N/mm, or greater than about 50N/mm, or greater than about 60N/mm, or greater than about 70N/mm, or greater than about 80N/mm, or greater than about 90N/mm.
In one embodiment, the pad mill roll shore hardness used in the methods of the present disclosure may be 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 less than about 90 shore a, or less than about 95 shore a, or less than about 100 shore a.
In one embodiment, the pad mill roll shore hardness used in the methods of the present disclosure may be 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 greater than about 90 shore a, or greater than about 95 shore a, or greater than about 100 shore a.
In one embodiment, the stenter temperature for the methods of the present disclosure may be less than about 70 ℃, or less than about 75 ℃, or less than about 80 ℃, or less than about 85 ℃, or less than about 90 ℃, or less than about 95 ℃, 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 less than 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 ℃, or less than about 210 ℃, or less than about 220 ℃, or less than about 230 ℃.
In one embodiment, the stenter temperature for the methods of the present disclosure may be greater than about 70 ℃, or greater than about 75 ℃, or greater than about 80 ℃, or greater than about 85 ℃, or greater than about 90 ℃, or greater than about 95 ℃, or greater than about 100 ℃, or greater than about 110 ℃, or greater than about 120 ℃, or greater than about 130 ℃, or greater than about 140 ℃, or greater than 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 ℃, or greater than about 210 ℃, or greater than about 220 ℃, or greater than about 230 ℃.
In one embodiment, the collective drying temperature for the methods of the present disclosure may be less than about 110 ℃, or less than about 115 ℃, or less than about 120 ℃, or less than about 125 ℃, or less than about 130 ℃, or less than about 135 ℃, or less than about 140 ℃, or less than about 145 ℃, or less than about 150 ℃.
In one embodiment, the common drying temperature for the methods of the present disclosure may be greater than about 110 ℃, or greater than about 115 ℃, or greater than about 120 ℃, or greater than about 125 ℃, or greater than about 130 ℃, or greater than about 135 ℃, or greater than about 140 ℃, or greater than about 145 ℃, or greater than about 150 ℃.
In some embodiments, the fibroin coated material (e.g., fabric) can withstand a selected temperature, wherein the selected temperature is selected for drying, curing, and/or heat setting a dye that can be applied to the material (e.g., LYCRA). As used herein, "heat resistant" may refer to the properties of a fibroin coating deposited on a material, wherein the fibroin coating and/or fibroin does not exhibit a significant improvement in the performance of the fibroin coating (i.e., the "significant improvement" in the fibroin coating performance) as compared to a control material having a comparable fibroin coating that is not subjected to a selected temperature for drying, curing, washing cycle, and/or heat setting purposes. In some embodiments, the selected temperature is the glass transition temperature (T g) of the material after the fibroin coating is applied. In some embodiments, the selected temperature is greater than about 65 ℃, or greater than about 70 ℃, or greater than about 80 ℃, or greater than about 90 ℃, or greater than about 100 ℃, or greater than about 110 ℃, or greater than about 120 ℃, or greater than about 130 ℃, or greater than about 140 ℃, or greater than 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 ℃, or greater than about 210 ℃, or greater than about 220 ℃. In some embodiments, the selected temperature is less than about 65 ℃, 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 less than 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 ℃, or less than about 210 ℃, or less than about 220 ℃.
In one embodiment, a "significant improvement" in the performance of a fibroin coating can be a reduction in a selected property of the fibroin coating, such as a wet time, an absorptivity, a spread speed, a cumulative one-way transport, or a total moisture management capacity, as compared to a control fibroin coating that has not been subjected to a selected temperature for drying, curing, washing cycle, and/or heat setting purposes, wherein such a reduction is less than about 1% reduction, or less than about 2% reduction, or less than about 3% reduction, or less than about 4% reduction, or less than about 5% reduction, or less than about 6% reduction, or less than about 7% reduction, or less than about 8% reduction, or less than about 9% reduction, or less than about 10% reduction, or less than about 15% reduction, or less than about 20% reduction, or less than about 25% reduction, or less than about 40% reduction, less than about 60% reduction, less than about 40% reduction, less than about 80% reduction, less than about 40% reduction, less than about 60% reduction, or less than about 80% reduction, or less than about 40% reduction, or less than about 60% reduction of the total moisture management capacity, as compared to a control fibroin coating that has not been subjected to the selected temperature for drying, curing, washing cycle, and/heat setting. In some embodiments, a "wash cycle" may refer to 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.
In one embodiment, a "significant improvement" in the performance of a fibroin coating can be an increase in a selected property of the fibroin coating, such as wetting time, absorptivity, spreading rate, cumulative unidirectional transport, or overall moisture management capacity, as compared to a control fibroin coating that has not been subjected to a selected temperature for drying, curing, washing cycle, and/or heat setting purposes, wherein such increase is less than about 1% increase in wetting time, absorptivity, spreading rate, cumulative unidirectional transport, or overall moisture management capacity, or less than about 2% increase, or less than about 3% increase, or less than about 4% increase, or less than about 5% increase, or less than about 6% increase, or less than about 7% increase, or less than about 8% increase, or less than about 9% increase, or less than about 10% increase, or less than about 15% increase, or less than about 20% increase, or less than about 25% increase, or less than about 40% increase, less than about 80% increase, less than about 40% or less than about 40% increase, less than about 60% increase, less than about 40% or less than about 80% increase, less than about 60% or less than about 50% increase, or less than about 40% increase of about 30% or less than about 40% increase of total moisture management capacity. In some embodiments, a "wash cycle" may refer to 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.
In some embodiments, the SFS coated article may be subjected to heat setting to solidify the one or more dyes that may be applied to the SFS coated article, thereby permanently solidifying the one or more dyes on the SFS coated article. In some embodiments, the SFS coated article may be heat-set, wherein the SFS coating on the SFS coated article is resistant to heat-set temperatures greater than about 100 ℃, or greater than about 110 ℃, or greater than about 120 ℃, or greater than about 130 ℃, or greater than about 140 ℃, or greater than 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 ℃, or greater than about 210 ℃, or greater than about 220 ℃. In some embodiments, the selected temperature is 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 less than 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 ℃, or less than about 210 ℃, or less than about 220 ℃.
In one embodiment, a fibroin coated material as described herein can be partially dissolved or partially incorporated into a portion of the material after the fibroin coated material is subjected to heating and/or curing as described herein. Without being limited by any one theory of the present disclosure, when the fibroin-coated material is heated to greater than about the glass transition temperature (Tg) of the coated material, the fibroin coating can be partially dissolved or partially incorporated into a portion of the material.
In some embodiments, the fibroin coated material as described herein can be sterile or can be sterilized to provide a sterilized fibroin coated material. Alternatively or in addition, the methods described herein may include sterile SFS prepared from sterile fibroin.
In some embodiments, fabric constructions compatible with the methods of the present disclosure include woven, knitted, and nonwoven fabrics.
In some embodiments, the coating pattern provided by the methods of the present disclosure includes single sided coating, double sided coating, and/or bulk coating.
In some embodiments, device manufacturers capable of producing devices 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、Monforts、Morrison Textile、Mtex、Muller Frick、Muratex Textile、Reliant Machinery、Rollmac、Salvade、Sandvik 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, device manufacturers capable of producing devices configured to dry SFS coated on textiles 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 India、Tacome、Tubetex、Turbang、Unitech Textile Machinery and yamula.
The following clauses describe certain embodiments.
Clause 1 an article comprising a fabric and a coating, wherein the coating comprises a surfactant and/or emulsifier system, and a fibroin fragment having an average weight average molecular weight selected from the group consisting of about 1kDa to about 5kDa, about 5kDa to about 10kDa, about 6kDa 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, about 39kDa to about 54kDa, about 39kDa to about 80kDa, about 40kDa to about 45kDa, about 45kDa to about 50kDa, about 50kDa to about 55kDa, about 55kDa to about 60kDa, about 60kDa to about 100kDa, or about 80kDa to about 144kDa, and a polydispersity ranging from 1 to about 5.
Clause 2 the article of clause 1, wherein the fibroin fragments have a polydispersity 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.
Clause 3 the article of clause 1, wherein the fibroin fragments have a polydispersity of about 1.5 to about 3.0.
Clause 4 the article of manufacture of clause 1, wherein the silk fibroin fragments comprise one or more of low molecular weight silk fibroin fragments and medium molecular weight silk fibroin fragments.
Clause 5 the article of any of clauses 1-4, further comprising about 0.01% (w/w) to about 10% (w/w) of a sericin relative to the silk fibroin fragment.
The article of any one of clauses 1 to 5, wherein the fabric comprises one or more of the following: polyesters, polyamides, polyaramides, polytetrafluoroethylene, polyethylene, polypropylene, polyurethane, silicone, a mixture of polyurethane and polyethylene glycol, ultra high molecular weight polyethylene, high performance polyethylene, nylon, LYCRA (polyester-polyurethane copolymers, also known as span and elastomers), or mixtures thereof.
The article of any one of clauses 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.
Clause 8 the article of any of clauses 1 to 7, wherein the w/w ratio of fibroin fragments in the coating 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, 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 58:58, about 55:42:45, about 44:45:45, about 45:43:44. 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 92, about 7:94, about 6:94, about 1:98, about 2:95, about 2:96, about 1:98, about 2:96.
The article of any one of clauses 1-7, wherein the w/w ratio of the 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.
The article of any one of clauses 1-7, wherein the w/w ratio of 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.
The article of any one of clauses 1 to 10, wherein the surfactant and/or emulsifier system comprises one or more of the following: polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, polyoxyethylene castor oil, and any combination thereof.
The article of any one of clauses 1 to 10, wherein the surfactant and/or emulsifier system comprises one or more of the following: polyoxyethylene (10-30) sorbitan monooleate, polyoxyethylene (10-30) sorbitan trioleate, polyoxyethylene (10-50) castor oil, and any combination thereof.
The article of any one of clauses 1 to 10, wherein the surfactant and/or emulsifier system comprises one or more of the following: polyoxyethylene (20) sorbitan monooleate, polyoxyethylene (20) sorbitan trioleate, polyoxyethylene (29) castor oil, and any combination thereof.
The article of any one of clauses 1 to 10, wherein the surfactant and/or emulsifier system comprises one or more of the following: polyoxyethylene (20) sorbitan monolaurate, polyoxyethylene (20) sorbitan monopalmitate, polyoxyethylene (20) sorbitan monostearate, polyoxyethylene (20) sorbitan tristearate, and any combination thereof.
The article of any one of clauses 1 to 10, wherein the surfactant and/or emulsifier system comprises one or more of the following: sorbitan mono fatty acid, sorbitan tri fatty acid, castor oil, and any combination thereof.
The article of any one of clauses 1 to 15, wherein the surfactant and/or emulsifier system comprises one or more of the following: cocoyl glucoside, decyl glucoside, lauryl glucoside, sucrose cocoate, octyl/octanoyl glucoside, octanoyl/octyl glucoside, and any combination thereof.
The article of any one of clauses 1 to 16, wherein the surfactant and/or emulsifier system has an HLB of from about 11 to about 13.50.
The article of any one of clauses 1 to 16, wherein the surfactant and/or emulsifier system has an HLB 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 13.50. In some embodiments, the surfactant and/or emulsifier system has an HLB of 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.
Clause 19 the article of any of clauses 1 to 18, wherein the article has improved moisture management as compared to a similar article comprising a similar fabric but no coating.
Clause 20 the article of clause 19, wherein the moisture management is assessed by a absorbency test, a vertical wicking test, or a drying rate test.
Clause 21 the article of any of clauses 1 to 20, wherein the article has improved drape as compared to a similar article comprising a similar fabric but without the coating.
The article of any one of clauses 1 to 21, wherein the article has improved smoothness as compared to a similar article comprising a similar fabric but no coating.
Clause 23 the article of any of clauses 1 to 22, wherein the article has an improved hand as compared to a similar article comprising a similar fabric but without the coating.
Clause 24 the article of any of clauses 1 to 23, wherein the article has a lower charge density at a given pH value than a similar article comprising a similar fabric but without the coating.
Clause 25. A method of making a fibroin coated fabric, the method comprising: applying a solution comprising a surfactant and/or emulsifier system to the fabric; applying a fibroin fragment solution to the fabric; and drying the fabric.
Clause 26. A method of making a fibroin coated fabric, the method comprising: applying a solution comprising a surfactant and/or emulsifier system and a fibroin fragment to the fabric; and drying the fabric.
Clause 27. The method of clause 25 or 26, wherein the concentration of the silk fibroin fragments in the solution ranges from 0.01g/L to about 100g/L.
The method of any one of clauses 25 to 27, wherein the concentration of the surfactant and/or emulsifier system in solution ranges from 0.01g/L to about 100g/L.
The method of any one of clauses 25 to 28, wherein the silk fibroin fragment has an average weight average molecular weight selected from the group consisting of about 1kDa to about 5kDa, about 5kDa to about 10kDa, about 6kDa 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, about 39kDa to about 54kDa, about 39kDa to about 80kDa, about 40kDa to about 45kDa, about 45kDa to about 50kDa, about 50kDa to about 55kDa, about 55kDa to about 60kDa, about 60kDa to about 100kDa, or about 80kDa to about 144kDa, and a polydispersity ranging from 1 to about 5.
The method of any one of clauses 25 to 29, wherein the fibroin fragments have a polydispersity 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 of any one of clauses 25 to 29, wherein the polydispersity of the fibroin fragments is about 1.5 to about 3.0.
The method of any one of clauses 25-29, 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.
The method of any one of clauses 25-32, wherein the solution further comprises about 0.01% (w/w) to about 10% (w/w) of sericin relative to the silk fibroin fragment.
The method of any one of clauses 25 to 33, wherein the fabric comprises one or more of the following: polyesters, polyamides, polyaramides, polytetrafluoroethylene, polyethylene, polypropylene, polyurethane, silicone, a mixture of polyurethane and polyethylene glycol, ultra high molecular weight polyethylene, high performance polyethylene, nylon, LYCRA (polyester-polyurethane copolymers, also known as span and elastomers), or mixtures thereof.
The method of any one of clauses 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.
Clause 36 the method of any of clauses 25 to 35, wherein the w/w ratio of 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, 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, about 58:57, about 43:42, about 45:44, about 45:42, about 46:44. 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 6:6, about 6:94, about 95:95, about 2:98, about 2:95.
The method of any one of clauses 25 to 35, wherein 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 of any one of clauses 25 to 35, wherein 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, 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.
The method of any one of clauses 25 to 38, wherein the surfactant and/or emulsifier system comprises one or more of the following: polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, polyoxyethylene castor oil, and any combination thereof.
The method of any one of clauses 25 to 38, wherein the surfactant and/or emulsifier system comprises one or more of the following: polyoxyethylene (10-30) sorbitan monooleate, polyoxyethylene (10-30) sorbitan trioleate, polyoxyethylene (10-50) castor oil, and any combination thereof.
The method of any one of clauses 25 to 38, wherein the surfactant and/or emulsifier system comprises one or more of the following: polyoxyethylene (20) sorbitan monooleate, polyoxyethylene (20) sorbitan trioleate, polyoxyethylene (29) castor oil, and any combination thereof.
The method of any one of clauses 25 to 38, wherein the surfactant and/or emulsifier system comprises one or more of the following: polyoxyethylene (20) sorbitan monolaurate, polyoxyethylene (20) sorbitan monopalmitate, polyoxyethylene (20) sorbitan monostearate, polyoxyethylene (20) sorbitan tristearate, and any combination thereof.
The method of any one of clauses 25 to 38, wherein the surfactant and/or emulsifier system comprises one or more of the following: sorbitan mono fatty acid, sorbitan tri fatty acid, castor oil, and any combination thereof.
The method of any one of clauses 25 to 43, wherein the surfactant and/or emulsifier system comprises one or more of the following: cocoyl glucoside, decyl glucoside, lauryl glucoside, sucrose cocoate, octyl/octanoyl glucoside, octanoyl/octyl glucoside, and any combination thereof.
Clause 45 the method of any of clauses 25 to 44, wherein the surfactant and/or emulsifier system has an HLB of about 11 to about 13.50.
The method of any of clauses 25 to 44, wherein the surfactant and/or emulsifier system has an HLB 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 13.50. In some embodiments, the surfactant and/or emulsifier system has an HLB of 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.
The method of any one of clauses 25 to 46, wherein the drying comprises heating.
The method of any one of clauses 25 to 47, wherein the pH of the solution is acidic.
The method of any one of clauses 25 to 47, wherein 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. 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.
Clause 50 an article of manufacture made by the method of any of clauses 25 to 49.
Clause 51 the article of clause 50, wherein the article has improved moisture management as compared to a similar article comprising a similar fabric but without the coating.
Clause 52 the article of clause 51, wherein the moisture management is assessed by a absorbency test, a vertical wicking test, or a drying rate test.
Clause 53 the article of any of clauses 50 to 52, wherein the article has improved drape as compared to a similar article comprising a similar fabric but without the coating.
Clause 54 the article of any of clauses 50 to 53, wherein the article has improved smoothness as compared to a similar article comprising a similar fabric but no coating.
Clause 55 the article of any of clauses 50 to 54, wherein the article has an improved hand as compared to a similar article comprising a similar fabric but no coating.
Clause 56 the article of any of clauses 50 to 55, wherein the article has a lower charge density at a given pH value than a similar article comprising a similar fabric but without the coating.
Clause 57 the article of any of clauses 1 to 24, or 50 to 56, wherein the amount of fibroin fragments in the article is about 0.01g to 0.5g/1500m 2 (denier) to 4000m 2 (denier).
The article of any one of clauses 1 to 24, or 50 to 56, wherein the amount of fibroin fragments in the article is about 0.03g to 0.35g/1500m 2 (denier) to 4000m 2 (denier).
Clause 59 the article of any of clauses 1 to 24, or 50 to 56, wherein the amount of fibroin fragments in the article is about 0.05g to 0.2g/3000m 2 (denier) to 4000m 2 (denier).
Clause 60 the article of any of clauses 1 to 24, or 50 to 56, wherein the amount of fibroin fragments in the article is about 0.2g to 0.35g/1000m 2 (denier) to 2500m 2 (denier).
Clause 61 the article of any of clauses 1 to 24, or 50 to 56, wherein the amount of fibroin fragments in the article is about 0.01g/1000 to 4500m 2 (denier), about 0.02g/1000 to 4500m 2 (denier), about 0.03g/1000 to 4500m 2 (denier), about 0.04g/1000 to 4500m 2 (denier), about 0.05g/1000 to 4500m 2 (denier), About 0.06g/1000-4500m 2 (denier), about 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 (denier), about 0.12g/1000-4500m 2 (denier), About 0.13g/1000-4500m 2 (denier), about 0.14g/1000-4500m 2 (denier), about 0.15g/1000-4500m 2 (denier), about 0.16g/1000-4500m 2 (denier), about 0.17g/1000-4500m 2 (denier), about 0.18g/1000-4500m 2 (denier), about 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), about 0.24g/1000-4500m 2 (denier), about 0.25g/1000-4500m 2 (denier), about 0.26g/1000-4500m 2 (denier), About 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), about 0.31g/1000-4500m 2 (denier), about 0.32g/1000-4500m 2 (denier), about 0.33g/1000-4500m 2 (denier), About 0.34g/1000-4500m 2 (denier), about 0.35g/1000-4500m 2 (denier), about 0.36g/1000-4500m 2 (denier), about 0.37g/1000-4500m 2 (denier), about 0.38g/1000-4500m 2 (denier), about 0.39g/1000-4500m 2 (denier), about 0.4g/1000-4500m 2 (denier), About 0.41g/1000-4500m 2 (denier), about 0.42g/1000-4500m 2 (denier), about 0.43g/1000-4500m 2 (denier), about 0.44g/1000-4500m 2 (denier), about 0.45g/1000-4500m 2 (denier), about 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 0.5g/1000-4500m 2 (denier).
Clause 101 an article comprising a fabric and a coating, wherein the coating comprises a surfactant and a fibroin fragment having an average weight average molecular weight selected from the group consisting of about 1kDa to about 5kDa, about 5kDa to about 10kDa, about 6kDa 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, about 39kDa to about 54kDa, about 39kDa to about 80kDa, about 40kDa to about 45kDa, about 45kDa to about 50kDa, about 50kDa to about 55kDa, about 55kDa to about 60kDa, about 60kDa to about 100kDa or about 80kDa to about 144kDa, and a polydispersity ranging from 1 to about 5.
Clause 102 the article of clause 101, wherein the fibroin fragments have a polydispersity 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.
Clause 103 the article of clause 101, wherein the fibroin fragments have a polydispersity of about 1.5 to about 3.0.
Clause 104 the article of manufacture of clause 101, wherein the silk fibroin fragments comprise one or more of low molecular weight silk fibroin fragments and medium molecular weight silk fibroin fragments.
The article of manufacture of any one of clauses 101-104, further comprising about 0.01% (w/w) to about 10% (w/w) of a sericin relative to the silk fibroin fragment.
The article of any one of clauses 101 to 105, wherein the fabric comprises one or more of the following: polyesters, polyamides, polyaramides, polytetrafluoroethylene, polyethylene, polypropylene, polyurethane, silicone, a mixture of polyurethane and polyethylene glycol, ultra high molecular weight polyethylene, high performance polyethylene, nylon, LYCRA (polyester-polyurethane copolymers, also known as span and elastomers), or mixtures thereof.
Clause 107 the article of any of clauses 101 to 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.
Clause 108. The article of any of clauses 101 to 107, wherein the w/w ratio of 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 59:42, about 58:57, about 46:43, about 44:45:45, about 45:45:54. 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 6:6, about 6:94, about 95:95, about 2:98, about 2:95.
Clause 109 the article of any of clauses 101 to 107, wherein the w/w ratio of the fibroin fragments to the surfactant in the coating is about 1:1.
The article of any one of clauses 101-109, wherein the surfactant is selected from the group consisting of cocoyl glucoside, decyl glucoside, lauryl glucoside, sucrose cocoate, octyl/octanoyl glucoside, and octanoyl/octyl glucoside.
Clause 111 the article of any of clauses 101 to 109, wherein the surfactant is selected from the group consisting of octyl/octanoyl glucoside and octanoyl/octyl glucoside.
The article of any one of clauses 101 to 111, wherein the article has improved moisture management compared to a similar article comprising a similar fabric but no coating.
Clause 113 the article of clause 112, wherein the moisture management is assessed by a absorbency test, a vertical wicking test, or a drying rate test.
Clause 114 a method of making a fibroin coated fabric, the method comprising: applying a solution comprising a surfactant to the fabric; applying a fibroin fragment solution to the fabric; and drying the fabric.
Clause 115. A method of making a fibroin coated fabric, the method comprising: applying a solution comprising a surfactant and a silk fibroin fragment to the fabric; and drying the fabric.
Clause 116 the method of clause 114 or clause 115, wherein the concentration of the silk fibroin fragments in the solution ranges from 0.01g/L to about 100g/L.
The method of any one of clauses 114 to 116, wherein the concentration of the surfactant in the solution ranges from 0.01g/L to about 100g/L.
Clause 118 the method of any of clauses 114 to 117, wherein the w/w ratio of 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, 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 59:42, about 57:43, about 55:45:45, about 46:44, about 45:44. 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 5:94, about 4:96, about 1:98, or about 1:99.
Clause 119 the method of any of clauses 114 to 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.
The method of any one of clauses 114 to 119, wherein the silk fibroin fragment has an average weight average molecular weight selected from the group consisting of about 1kDa to about 5kDa, about 5kDa to about 10kDa, about 6kDa 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, about 39kDa to about 54kDa, about 39kDa to about 80kDa, about 40kDa to about 45kDa, about 45kDa to about 50kDa, about 50kDa to about 55kDa, about 55kDa to about 60kDa, about 60kDa to about 100kDa, or about 80kDa to about 144kDa, and a polydispersity ranging from 1 to about 5.
Clause 121 the method of any of clauses 114 to 120, wherein the fibroin fragments have a polydispersity 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 of any one of clauses 114 to 120, wherein the polydispersity of the fibroin fragments is about 1.5 to about 3.0.
The method of any one of clauses 114 to 120, 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.
The method of any one of clauses 114 to 123, wherein the solution further comprises about 0.01% (w/w) to about 10% (w/w) of sericin relative to the silk fibroin fragment.
The method of any one of clauses 114 to 124, wherein the fabric comprises one or more of the following: polyesters, polyamides, polyaramides, polytetrafluoroethylene, polyethylene, polypropylene, polyurethane, silicone, a mixture of polyurethane and polyethylene glycol, ultra high molecular weight polyethylene, high performance polyethylene, nylon, LYCRA (polyester-polyurethane copolymers, also known as span and elastomers), or mixtures thereof.
Clause 126 the method of any of clauses 114 to 125, wherein the surfactant is selected from the group consisting of cocoyl glucoside, decyl glucoside, lauryl glucoside, sucrose cocoate, octyl/octanoyl glucoside, and octanoyl/octyl glucoside.
Clause 127 the method of any of clauses 114 to 125, wherein the surfactant is selected from the group consisting of octyl/octanoyl glucoside and octanoyl/octyl glucoside.
The method of any one of clauses 114 to 127, wherein the drying comprises heating.
Clause 129 the method of clause 128, wherein the heating does not substantially change the coating properties.
The method of any one of clauses 114 to 129, wherein the pH of the solution is acidic.
The method of any one of clauses 114 to 129, wherein the pH of the solution is about 4 to about 4.5.
Clause 132 an article of manufacture made by the method of any of clauses 114 to 131.
Clause 133 the article of clause 132, wherein the article has improved moisture management as compared to a similar article comprising a similar fabric but without the coating.
Clause 134 the article of clause 133, wherein the moisture management is assessed by a absorbency test, a vertical wicking test, or a drying rate test.
Clause 201 an article comprising a fabric and a coating, wherein the coating comprises a surfactant and/or an emulsifier and a fibroin fragment having an average weight average molecular weight selected from the group consisting of about 1kDa to about 5kDa, about 5kDa to about 10kDa, about 6kDa 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, about 39kDa to about 54kDa, about 39kDa to about 80kDa, about 40kDa to about 45kDa, about 45kDa to about 50kDa, about 50kDa to about 55kDa, about 55kDa to about 60kDa, about 60kDa to about 100kDa, or about 80kDa to about 144kDa, and a polydispersity ranging from 1 to about 5.
Clause 202. The article of clause 201, wherein the fibroin fragments have a polydispersity 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.
Clause 203 the article of clause 201, wherein the fibroin fragments have a polydispersity of about 1.5 to about 3.0.
Clause 204 the article of manufacture of clause 201, wherein the silk fibroin fragments comprise one or more of low molecular weight silk fibroin fragments and medium molecular weight silk fibroin fragments.
Clause 205 the article of any of clauses 201 to 204, further comprising about 0.01% (w/w) to about 10% (w/w) of sericin relative to the silk fibroin fragment.
The article of any one of clauses 201 to 205, wherein the fabric comprises one or more of the following: polyesters, polyamides, polyaramides, polytetrafluoroethylene, polyethylene, polypropylene, polyurethane, silicone, a mixture of polyurethane and polyethylene glycol, ultra high molecular weight polyethylene, high performance polyethylene, nylon, LYCRA (polyester-polyurethane copolymers, also known as span and elastomers), or mixtures thereof.
The article of any one of clauses 201 to 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.
Clause 208. The article of any of clauses 201 to 207, wherein the w/w ratio of fibroin fragments to surfactants and/or emulsifiers 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 69:32, 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, about 58:57, about 43:45:46:42, about 46:45:45:46, about 55:44. 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 6:6, about 6:94, about 95:95, about 2:98, about 2:95.
Clause 209 the article of any of clauses 201 to 207, wherein the w/w ratio of the 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.
The article of any one of clauses 201 to 209, wherein the emulsifier and/or surfactant is selected from the group consisting of polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, polyoxyethylene castor oil, and any combination thereof.
Clause 211 the article of any of clauses 201 to 209, wherein the emulsifier and/or surfactant is selected from the group consisting of polyoxyethylene (10-30) sorbitan monooleate, polyoxyethylene (10-30) sorbitan trioleate, polyoxyethylene (10-50) castor oil, and any combination thereof.
The article of any one of clauses 201 to 209, wherein the emulsifier and/or surfactant is selected from the group consisting of polyoxyethylene (20) sorbitan monooleate, polyoxyethylene (20) sorbitan trioleate, polyoxyethylene (29) castor oil, and any combination thereof.
Clause 213 the article of any of clauses 201 to 212, wherein the emulsifier and/or surfactant has an HLB of between 11 and 13.50.
The article of any one of clauses 201 to 213, wherein the article has improved moisture management compared to a similar article comprising a similar fabric but without the coating.
Clause 215 the article of clause 214, wherein the moisture management is assessed by a absorbency test, a vertical wicking test, or a drying rate test.
Clause 216 the article of any of clauses 201 to 213, wherein the article has improved drape as compared to a similar article comprising a similar fabric but without the coating.
Clause 217 the article of any of clauses 201 to 213, wherein the article has improved smoothness as compared to a similar article comprising a similar fabric but no coating.
Clause 218 the article of any of clauses 201 to 213, wherein the article has an improved hand as compared to a similar article comprising a similar fabric but without the coating.
Clause 219, a method of making a fibroin coated fabric, the method comprising: applying a solution comprising a surfactant and/or emulsifier system to the fabric; applying a fibroin fragment solution to the fabric; and drying the fabric.
Clause 220. A method of making a fibroin coated fabric, the method comprising: applying a solution comprising a surfactant and/or emulsifier system and a fibroin fragment to the fabric; and drying the fabric.
The method of clause 219 or 220, wherein the concentration of the fibroin fragments in the solution ranges from 0.01g/L to about 100g/L.
The method of any one of clauses 219 to 221, wherein the concentration of the surfactant and/or emulsifier system in solution ranges from 0.01g/L to about 100g/L.
Clause 223 the method of any of clauses 219 to 222, wherein the w/w ratio of 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, 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, about 58:57, about 43:42, about 45:44, about 45:42, about 46:44. 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 6:6, about 6:94, about 95:95, about 2:98, about 2:95.
The method of any one of clauses 219 to 222, wherein 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 clauses 219 to 224, wherein the emulsifier and/or surfactant system comprises one or more of the following: polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, polyoxyethylene castor oil, and any combination thereof.
The method of any one of clauses 219 to 224, wherein the emulsifier and/or surfactant system comprises one or more of the following: polyoxyethylene (10-30) sorbitan monooleate, polyoxyethylene (10-30) sorbitan trioleate, polyoxyethylene (10-50) castor oil, and any combination thereof.
The method of any one of clauses 219 to 224, wherein the emulsifier and/or surfactant system comprises one or more of the following: polyoxyethylene (20) sorbitan monooleate, polyoxyethylene (20) sorbitan trioleate, polyoxyethylene (29) castor oil, and any combination thereof.
The method of any one of clauses 219 to 224, wherein the emulsifier and/or surfactant has an HLB of between 11 and 13.50.
The method of any one of clauses 219 to 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.
The method of any one of clauses 219 to 229, wherein the silk fibroin fragment has an average weight average molecular weight selected from the group consisting of about 1kDa to about 5kDa, about 5kDa to about 10kDa, about 6kDa 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, about 39kDa to about 54kDa, about 39kDa to about 80kDa, about 40kDa to about 45kDa, about 45kDa to about 50kDa, about 50kDa to about 55kDa, about 55kDa to about 60kDa, about 60kDa to about 100kDa, or about 80kDa to about 144kDa, and a polydispersity ranging from 1 to about 5.
The method of any one of clauses 219 to 230, wherein the fibroin fragments have a polydispersity 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 of any one of clauses 219 to 230, wherein the fibroin fragments have a polydispersity of about 1.5 to about 3.0.
The method of any one of clauses 219 to 232, wherein the silk fibroin fragments comprise one or more of low molecular weight silk fibroin fragments and medium molecular weight silk fibroin fragments.
The method of any one of clauses 219 to 233, wherein the solution further comprises about 0.01% (w/w) to about 10% (w/w) of sericin relative to the silk fibroin fragment.
The method of any one of clauses 219 to 234, wherein the fabric comprises one or more of the following: polyesters, polyamides, polyaramides, polytetrafluoroethylene, polyethylene, polypropylene, polyurethane, silicone, a mixture of polyurethane and polyethylene glycol, ultra high molecular weight polyethylene, high performance polyethylene, nylon, LYCRA (polyester-polyurethane copolymers, also known as span and elastomers), or mixtures thereof.
The method of any one of clauses 219 to 235, wherein the drying comprises heating.
The method of any one of clauses 219 to 236, wherein the pH of the solution is acidic.
The method of any one of clauses 219 to 236, wherein the solution has a pH of about 4 to about 4.5.
Clause 239 an article made by the method of any of clauses 219 to 238.
Clause 240. The article of clause 239, wherein the article has improved moisture management as compared to a similar article comprising a similar fabric but without the coating.
Clause 241 the article of clause 240, wherein the moisture management is assessed by a absorbency test, a vertical wicking test, or a drying rate test.
The article of clause 242, wherein the article has improved drape as compared to a similar article comprising a similar fabric but without the coating.
Clause 243 the article of clause 239, wherein the article has improved smoothness as compared to a similar article comprising a similar fabric but without the coating.
Clause 244 the article of clause 239, wherein the article has an improved hand as compared to a similar article comprising a similar fabric but without the coating.
Examples
Embodiments encompassed herein are now described with reference to the following examples. These embodiments are provided for illustrative purposes only, and the disclosure contained herein should not be construed as limited to these embodiments in any way, but rather as covering any and all variations that are understood as being due to the teachings provided herein.
The compositions of the present disclosure may be prepared by various methods known in the art. These methods include the methods of the following embodiments and the methods of the following specific examples. Modifications of such methods involving techniques commonly used in the art of textile products may also be used.
Example 1: use of fibroin and surfactant on synthetic fabrics
As described in this example, silk fibroin can be used with surfactants to synthesize fabrics.
The active filament TM molecules (derived from sugar) containing octyl/octanoyl glucoside provide enhanced moisture management properties to various types of nylon fabrics.
The comfort properties of garments, particularly sportswear and sportswear, are highly dependent on the moisture management properties. Moisture management is the ability of a textile fabric to absorb moisture (sweat) from the skin, transport the moisture to the outer surface and release it into the environment. With the continuing high demands of people for comfortable apparel, there is a tremendous growth potential in this area.
The water management properties can be enhanced by employing microfiber technology that increases the specific surface area of the fabric, thus allowing for higher liquid transfer rates, as well as by applying various chemical finishes. The cost of the former option is quite high, making the chemical finishing option more favored by most manufacturers.
Although there are a variety of moisture management treatments available for nylon, sustainable chemicals from natural derivatives and zero waste management issues have not been widely reported. Therefore, it is very important to find green chemicals for moisture management treatments that are friendly to end users, water supplies, the environment and manufacturing personnel.
Coating of nylon fabrics
The coating solution was prepared by adjusting the pH of water to 4-4.5 using acetic acid, then octyl/octanoyl glucoside was added to a desired concentration (0.1%), then activated silk TM was added, and the ratio of the amount of activated silk TM added to octyl/octanoyl glucoside was controlled at 1:1 (v/v). The pH of the final solution was checked and if it was outside the range of 4-4.5, an adjustment was made.
The coating solution was applied to the nylon fabric at a rate of 3 meters per minute through the pad and curing process using a pad roll. The moisture absorption rate was controlled to 60% ± 3% by adjusting the roll pressure.
The fabric was dried and cured in an oven at 160 ℃ for 1.5 minutes, then allowed to stand overnight, and then performance tested.
Performance testing
Moisture management can be assessed by various test criteria, such as absorbency test, vertical wicking test, drying rate test, and the like. Although the results are presented in different ways by different test methods, characterization of the moisture management performance is relevant.
In this development, the modified AATCC 79-textile absorbency test method was used to determine the moisture management performance.
Test results
Fig. 3 and 4 are test results of reactive filaments having octyl/octanoyl glucoside coatings on various nylon fabrics, including interlocking fabrics, jerseys, warp knit, and cushion structures. The results show that the novel solution has general improvement on the water absorbability of various nylon fabrics, and the water management performance is generally improved.
Figure 3-absorbency of reactive filaments TM with octyl/octanoyl glucoside coating on various interlocking nylon fabrics. Unfinished nylon interlocking fabrics cannot absorb moisture due to poor absorbency. The absorbency of all nylon interlocking fabrics increases significantly after the reactive filaments TM are coated with an octyl/octanoyl glucoside coating.
Fig. 4 illustrates the absorbency of reactive filaments TM with octyl/octanoyl glucoside coating on various nylon fabrics in addition to the interlocking structure. The unfinished nylon fabrics do not absorb moisture or are less absorbent, and the absorbency of all nylon fabrics increases significantly after coating the active filaments TM with an octyl/octanoyl glucoside coating.
Example 2: use of fibroin and emulsifiers and/or surfactants on synthetic fabrics
As described in this example, silk fibroin can be used in combination with surfactants and/or emulsifiers to synthesize fabrics. In one non-limiting example, fibroin fragments are used with an emulsion of three ethoxylated fatty acids to impart smoothness and a hanging feel to nylon and polyester fabrics without inhibiting the moisture management properties imparted by the wicking agent. Wicking agents in textiles are commonly used to improve the comfort properties of casual and athletic garments by improving the moisture management properties of nylon and polyester fabrics. However, a common problem with many wicking agents is that they consist of hydrophilic surfactants or polymers that attract moisture between the fibers of the textile, resulting in the fabric feeling heavier and coarser than when not worn. With the widespread use of these surfactants as moisture management agents, there is a potential for new developments in the softener field that do not inhibit the moisture management properties while also imparting smoothness and a draping hand. Currently, most softeners suffer from two problems: (i) Since many of them are oil-based, the hydrophobic nature inhibits water absorption; (ii) Many softeners are derived from petrochemical sources, which can lead to waste and sustainability problems. While relatively many polymer and oil products can enhance the hand and moisture management capabilities of fabrics, the selection of 100% bio-based softeners is limited. Therefore, there is a need to develop 100% bio-based natural softeners that impart good hand feel when used in combination with a wicking agent, while not inhibiting the moisture management properties of the fabric.
Without wishing to be bound by any particular theory, the system described herein comprises a mixture of ethoxylated monooleate fatty acids and ethoxylated trioleate fatty acids and hydroxy fatty acids having an average HLB value between 12 and 12.1 (calculated using equation 1) as an emulsifier and softener, and the active filaments as a moisture wicking agent. In this system, the variation in fatty acid to hydroxy fatty acid ratio resulted in different HLB values (as shown in table 2). This in turn changes the wash resistance and softening ability of the coating.
Equation 1:
N i: the number of moles of surfactant molecule i in the solution; n: moles of all surfactants in the solution; m hi: the molar mass of the hydrophilic groups on the surfactant molecule i; m i: total molar mass of surfactant molecule i.
Coating of nylon fabrics
An emulsified mixture of surfactants was prepared as follows: polyoxyethylene (20) sorbitan monooleate, polyoxyethylene (20) sorbitan trioleate, polyoxyethylene (29) castor oil and water are combined in a ratio of 2:4:8:10 by mass. The mixture was then sonicated for 3 hours.
A solution of the wicking agent was then prepared as follows: active filament TM moisture management was added to water at a concentration of 1 g/L. The solution pH was then adjusted to 4.5-5 using acetic acid.
After the preparation of the wicking agent solution, the surfactant emulsion mixture was then added to the solution in the mass ratio defined in table 1.
The solution was applied to the fabric by padding and curing at a padding rate of 3 m/min, the moisture absorption was controlled to 50% by rolling
The fabric was then cured in a drying oven at 160 ℃ for 1.5 to 3 minutes, depending on the fabric, and allowed to equilibrate overnight.
Coating of polyester fabrics
An emulsified mixture of surfactants was prepared as follows: polyoxyethylene (20) sorbitan monooleate, polyoxyethylene (20) sorbitan trioleate, polyoxyethylene (29) castor oil and water are combined in a ratio of 2:4:8:10 by mass. The mixture was then sonicated for 3 hours.
A solution of the wicking agent was then prepared as follows: active filament TM moisture management was added to water at a concentration of 1 g/L. The solution pH was then adjusted to 4.5-5 using acetic acid.
After the preparation of the wicking agent solution, the surfactant emulsion mixture was then added to the solution in the mass ratio defined in table 1.
The solution was applied to the fabric by padding and curing at a padding rate of 3 m/min, the moisture absorption was controlled to 50% by rolling
The fabric was then cured in a drying oven at 135 ℃ for 1 to 2 minutes, depending on the fabric, and allowed to equilibrate overnight.
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Table 1.1 list the ratio (in mass and final concentration) of silk to emulsified mixture of surfactant (emulsion) in aqueous solution.
POMO(g) POTO(g) EC(g) Water (g) HLB
a 2 4 0.5 10 12.56
b 2 4 1 10 12.5
c 2 4 2 10 12.39
d 2 4 4 10 12.25
e 2 4 8 10 12.09
f 2 4 16 10 11.94
Table 2. List of surfactants: polyoxyethylene (20) sorbitan monooleate (POMO), polyoxyethylene (20) sorbitan trioleate (POTO), polyoxyethylene (29) castor oil (EC), are mixed in different ratios, and their corresponding HLB values. Line e includes the ratios used in the emulsified mixture of surfactants of table 1.
Test method
Fabric properties
All samples were hand tested by a panel of n=3 panelists and compared against factors of drape (fabric easily deformed when handled by a user) and smoothness (apparent roughness of the fabric when rubbed by a user's hand). The test follows the method defined by the internal method. Inhibition of moisture management was also tested using the internal method defined water absorption test.
Silk wash fastness
UV/Vis absorbance was used to measure the quantification of filaments deposited on the surface. Standard curves were generated using different concentrations of filaments in water. The absorbance (tyrosine absorption peak) at the wavelength of 276 nm was then measured, yielding a linear curve of absorbance versus solution concentration.
The quality of the remaining filaments on the fabric was tested. The fabric was immersed in a 7.6M LiBr solution under sonication overnight. The fabric was then removed from the solution and the UV/Vis absorbance of the solution was measured to measure the filament concentration in the solution. Using the volume of the solution, the concentration of filaments in the solution, and the mass of the fabric, the mass of filaments remaining on the fabric can be calculated.
Test results
Surfactant system with light weight filaments
HLB-regulated concentration
According to the moisture management data, the optimal concentration for the shortest absorption time was 2g/L polyoxyethylene (29) castor oil (mixture HLB: 12.39). However, when the concentration was increased to 16g/L (mixture HLB: 11.94), the absorption time was only increased by 17% on average, and the fabrics all met the 2 second absorption time maximum criteria (FIG. 5). From the viewpoint of hand feel, generally, as the concentration of polyoxyethylene (29) castor oil increases, the hand feel improves (fig. 6).
Fig. 5 is a graph of unwashed water absorption produced by varying the concentration of polyoxyethylene (29) castor oil (and thus the HLB) in the emulsifier mixture prior to addition to the coating solution. Note that the silk concentration in the coating solution was 1g/L in all samples.
Fig. 6 is a plot of unwashed hand ratings produced by varying the concentration of polyoxyethylene (29) castor oil (and thus the HLB) in the emulsifier mixture prior to addition to the coating solution. Note that the silk concentration in the coating solution was 1g/L in all samples.
Surfactant system concentration study
As shown in fig. 5, the moisture management data shows that all the tested polyester and nylon fabrics coated with wicking and natural softening agents had negligible degradation in moisture management performance after 0 to 25 washes. The data show that all fabrics except Jintex Green had an absorbance time of less than 3 seconds after 0 to 25 washes (figures 7A-7D).
In terms of improvement of hand properties, as shown in fig. 6, there was a significant improvement in the hand of the fabric with increasing concentration of natural softener at 0 washes. Although the performance was slightly degraded after washing, there was still a hand after 5, 10 and 25 washes (fig. 8).
Fig. 7A-7D are graphs showing the moisture management data of unwashed (fig. 7A), 5 washes (fig. 7B), 10 washes (fig. 7C), and 25 washes (fig. 7D) produced by varying the concentration of the emulsion mixture (polyoxyethylene (20) sorbitan monooleate, polyoxyethylene (20) sorbitan trioleate, polyoxyethylene (29) castor oil, and water in a ratio of 2:4:8:10) in the final coating solution; the silk concentration in the coating solution was 1g/L in all samples.
Fig. 8A-8D are graphs showing the hand feel grade results of unwashed (fig. 8A), 5 washes (fig. 8B), 10 washes (fig. 8C), and 25 washes (fig. 8D) produced by varying the concentration of the emulsion mixture (polyoxyethylene (20) sorbitan monooleate, polyoxyethylene (20) sorbitan trioleate, polyoxyethylene (29) castor oil, and water in a ratio of 2:4:8:10) in the final coating solution; 1 is the best hand feel grade fraction, 8 is the worst hand feel grade fraction; the silk concentration in the solution was 1g/L in all samples.
Polyoxyethylene (20) sorbitan monooleate with medium weight filaments
According to the moisture management data, the absorption time was hardly changed with the increase of the medium weight silk. Without wishing to be bound by any particular theory, generally, medium weight filaments have a longer absorption time than their low weight filaments. For 20g/L of low molecular weight filaments, only one fabric exceeded the 2 second cut-off criteria. However, even though the number of washes is 0, there is still a fabric passing through this. This behavior only gets worse as the number of washes increases when comparing the same fabric between low weight and medium weight filaments (fig. 10A-10D).
From a hand perspective, similar to the moisture management data, there appears to be no significant trend to increase the medium weight filaments in the coating solution (fig. 9A-9D).
Fig. 9A-9D are graphs showing hand scale results for unwashed (fig. 9A), 5 washes (fig. 9B), 10 washes (fig. 9C), and 25 washes (fig. 9D) produced by varying the concentration of medium molecular weight filaments in the final coating solution; 1 is the best grade, 8 is the worst grade
Fig. 10A-10D are graphs showing the moisture management results of unwashed (fig. 10A), 5 washes (fig. 10B), 10 washes (fig. 10C), and 25 washes (fig. 10D) produced by varying the concentration of medium molecular weight filaments in the final coating solution.
Quantification of filaments on nylon fabrics
Using UV/Vis absorbance, the concentration of the filaments in the solution can be measured by measuring the absorbance of the 276nm peak of the filament spectrum. To quantify the amount of silk remaining on the fabric, a standard curve was generated by serial dilution of the stock solution. After measuring the absorbance of each solution, a linear curve was fitted to convert the solution absorbance to solution concentration. The filaments can be removed from the filament-coated fabric by sonicating the sample in a 9M LiBr solution for 3 hours. The remaining silk solution can then be measured to quantify the amount of silk removed from the fabric. To determine the fiber surface area, the filament cross-section of each fabric was microscopic examined to obtain the fabric denier and the surface area was then calculated.
As can be seen in fig. 11D, the filaments are still present on the fabric after washing, but the number is reduced. When comparing the percentage of filament mass loss for each sample, the increase in fiber surface area appears to increase the mass loss of filaments in the fabric (fig. 11A). However, it can be said that the inverse of the amount of silk absorbed on the fabric. The increase in fiber surface area appears to be associated with a decrease in the amount of silk absorbed on the fabric (fig. 11B). Without wishing to be bound by any particular theory, there appears to be a correlation between the adhesion of the filaments to the fabric and the surface of the fibers.
Fig. 11A-11D are graphs showing UV/Vis quantification experiments of fabrics coated with low molecular weight reactive filaments and polyoxyethylene (20) monooleate solution. Fig. 11A: a plot of percent silk loss after five washes relative to fiber surface area is shown. Fig. 11B: a graph showing the quantitative quality of the filaments on the fabric after coating relative to the fiber surface area. Fig. 11C: a plot of percent silk loss after five washes relative to fabric type is shown. Fig. 11D: a graph showing the quantitative quality of the filaments on each fabric before and after five washes according to the fabric type.
Fig. 12 is a graph showing UV/Vis quantification experiments of fabrics coated with low molecular weight reactive filaments and polyoxyethylene (20) monooleate solution. The figure shows the quantitative mass of filaments on the fabric after coating relative to the fabric mass in grams per square meter (GSM). The quality depends on the type of weave, fiber content and filament denier.
Silk surface charge study
Wire coated nylon fabrics, archroma RPU coated fabrics, and nylon fabric controls were potentiometric titrated. Different nylon fabrics were coated on a solution of active filaments (20 g/L) and polyoxyethylene (20) sorbitan monooleate (2 g/L) or a solution containing 2% Archroma RPU liquid. Samples of each fabric were washed five times in a pre-washer using AATCC non-softening non-brightening detergent. For the titration process, 0.1M sodium chloride was used as counter ion and hydrochloric acid or sodium hydroxide was used as titrant.
As shown in fig. 13A-13C, the resulting titration curves show that silk coated fabrics have more negative charge at pH 5 (Δc= -0.00316C g -1) than either the untreated fabric (Δc=0.00008C g -1) or the fabric coated in Archroma RPU liquid (Δc=0.00055C g -1). Without wishing to be bound by any particular theory, this suggests that the washed silk-coated surface has a more negative charge than the untreated control or positively charged Archroma RPU-coated fabric.
Fig. 13A-13C include a series of graphs showing potentiometric titration curves for charge density measured at pH 5 for an unfinished heavy double knit nylon fabric (fig. 13A), a reactive filament finished heavy double knit nylon fabric (fig. 13B), and Archroma RPU wet finished heavy double knit nylon fabric (fig. 13C). Each fabric had titration curves obtained at unwashed (fig. 13A-13C, left panels) and five launderings (fig. 13A-13C, right panels). The change in charge density at pH 5 after washing is indicated as deltac.

Claims (56)

1. An article comprising a fabric and a coating, wherein the coating comprises a surfactant and/or emulsifier system, and a fibroin fragment having an average weight average molecular weight selected from the group consisting of about 1kDa to about 5kDa, about 5kDa to about 10kDa, about 6kDa 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, about 39kDa to about 54kDa, about 39kDa to about 80kDa, about 40kDa to about 45kDa, about 45kDa to about 50kDa, about 50kDa to about 55kDa, about 55kDa to about 60kDa, about 60kDa to about 100kDa, or about 80kDa to about 144kDa, and a polydispersity ranging from 1 to about 5.
2. The article of claim 1, wherein the fibroin fragments have a polydispersity 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.
3. The article of claim 1, wherein the fibroin fragments have a polydispersity of about 1.5 to about 3.0.
4. The article of claim 1, wherein the fibroin fragments comprise one or more of low molecular weight fibroin fragments and medium molecular weight fibroin fragments.
5. The article of any one of claims 1-4, further comprising about 0.01% (w/w) to about 10% (w/w) sericin relative to the silk fibroin fragment.
6. The article of any one of claims 1 to 5, wherein the fabric comprises one or more of the following: polyesters, polyamides, polyaramides, polytetrafluoroethylene, polyethylene, polypropylene, polyurethane, silicone, a mixture of polyurethane and polyethylene glycol, ultra high molecular weight polyethylene, high performance polyethylene, nylon, LYCRA (polyester-polyurethane copolymers, also known as span and elastomers), or mixtures thereof.
7. The article of any one of claims 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.
8. The article according to any one of claim 1 to 7, wherein the w/w ratio of fibroin fragments in the coating 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, 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 58:58, about 55:42:45, about 44:45:45, about 45:43:44. 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 92, about 7:94, about 6:94, about 1:98, about 2:95, about 2:96, about 1:98, about 2:96.
9. The article of any one of claims 1-7, wherein the w/w ratio of fibroin fragments in the coating to the surfactant and/or emulsifier is about 1:1, about 1:2, about 1:4, about 1:8, about 1:16, or about 1:32.
10. The article of any one of claims 1-7, wherein the w/w ratio of fibroin fragments in the coating 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, 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.
11. The article of any one of claims 1 to 10, wherein the surfactant and/or emulsifier system comprises one or more of the following: polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, polyoxyethylene castor oil, and any combination thereof.
12. The article of any one of claims 1 to 10, wherein the surfactant and/or emulsifier system comprises one or more of the following: polyoxyethylene (10-30) sorbitan monooleate, polyoxyethylene (10-30) sorbitan trioleate, polyoxyethylene (10-50) castor oil, and any combination thereof.
13. The article of any one of claims 1 to 10, wherein the surfactant and/or emulsifier system comprises one or more of the following: polyoxyethylene (20) sorbitan monooleate, polyoxyethylene (20) sorbitan trioleate, polyoxyethylene (29) castor oil, and any combination thereof.
14. The article of any one of claims 1 to 10, wherein the surfactant and/or emulsifier system comprises one or more of the following: polyoxyethylene (20) sorbitan monolaurate, polyoxyethylene (20) sorbitan monopalmitate, polyoxyethylene (20) sorbitan monostearate, polyoxyethylene (20) sorbitan tristearate, and any combination thereof.
15. The article of any one of claims 1 to 10, wherein the surfactant and/or emulsifier system comprises one or more of the following: sorbitan mono fatty acid, sorbitan tri fatty acid, castor oil, and any combination thereof.
16. The article of any one of claims 1 to 15, wherein the surfactant and/or emulsifier system comprises one or more of the following: cocoyl glucoside, decyl glucoside, lauryl glucoside, sucrose cocoate, octyl/octanoyl glucoside, octanoyl/octyl glucoside, and any combination thereof.
17. The article of any one of claims 1 to 16, wherein the surfactant and/or emulsifier system has an HLB of from about 11 to about 13.50.
18. The article of any one of claims 1 to 16, wherein the surfactant and/or emulsifier system has an HLB of from about 11 to about 11.50, from about 11.50 to about 12, from about 12 to about 12.50, from about 12.50 to about 13, or from about 13 to about 13.50.
19. The article of any one of claims 1 to 18, wherein the article has improved moisture management compared to a similar article comprising a similar fabric but without a coating.
20. The article of claim 19, wherein moisture management is assessed by a water absorption test, a vertical wicking test, or a drying rate test.
21. The article of any one of claims 1 to 20, wherein the article has improved drape compared to a similar article comprising a similar fabric but without a coating.
22. The article of any one of claims 1 to 21, wherein the article has improved smoothness compared to a similar article comprising a similar fabric but without a coating.
23. The article of any one of claims 1 to 22, wherein the article has an improved hand as compared to a similar article comprising a similar fabric but without a coating.
24. The article of any one of claims 1 to 23, wherein the article has a lower charge density at a given pH value than a similar article comprising a similar fabric but without the coating.
25. A method of making a fibroin coated fabric, the method comprising:
applying a solution comprising a surfactant and/or emulsifier system to the fabric;
Applying a fibroin fragment solution to the fabric; and
Drying the fabric.
26. A method of making a fibroin coated fabric, the method comprising:
applying a solution comprising a surfactant and/or emulsifier system and a fibroin fragment to the fabric; and
Drying the fabric.
27. The method of claim 25 or claim 26, wherein the concentration of the silk fibroin fragments in solution ranges from 0.01g/L to about 100g/L.
28. The method of any one of claims 25 to 27, wherein the concentration of the surfactant and/or emulsifier system in solution ranges from 0.01g/L to about 100g/L.
29. The method of any one of claims 25-28, wherein the silk fibroin fragment has an average weight average molecular weight selected from the group consisting of about 1kDa to about 5kDa, about 5kDa to about 10kDa, about 6kDa 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, about 39kDa to about 54kDa, about 39kDa to about 80kDa, about 40kDa to about 45kDa, about 45kDa to about 50kDa, about 50kDa to about 55kDa, about 55kDa to about 60kDa, about 60kDa to about 100kDa, or about 80kDa to about 144kDa, and a polydispersity ranging from 1 to about 5.
30. The method of any one of claims 25 to 29, wherein the fibroin fragments have a polydispersity 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.
31. The method of any one of claims 25-29, wherein the fibroin fragments have a polydispersity of about 1.5 to about 3.0.
32. 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 solution further comprises about 0.01% (w/w) to about 10% (w/w) sericin relative to the silk fibroin fragment.
34. The method of any one of claims 25 to 33, wherein the fabric comprises one or more of the following: polyesters, polyamides, polyaramides, polytetrafluoroethylene, polyethylene, polypropylene, polyurethane, silicone, a mixture of polyurethane and polyethylene glycol, ultra high molecular weight polyethylene, high performance polyethylene, nylon, LYCRA (polyester-polyurethane copolymers, also known as span and elastomers), or mixtures thereof.
35. The method of any one of claims 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.
36. The method according to any one of claim 25 to 35, wherein the w/w ratio of 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, 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, about 58:57, about 43:42, about 45:44, about 45:42, about 46:44. 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 6:6, about 6:94, about 95:95, about 2:98, about 2:95.
37. The method of any one of claims 25-35, wherein 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.
38. The method of any one of claims 25 to 35, wherein the w/w ratio of 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, 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.
39. The method of any one of claims 25 to 38, wherein the surfactant and/or emulsifier system comprises one or more of the following: polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, polyoxyethylene castor oil, and any combination thereof.
40. The method of any one of claims 25 to 38, wherein the surfactant and/or emulsifier system comprises one or more of the following: polyoxyethylene (10-30) sorbitan monooleate, polyoxyethylene (10-30) sorbitan trioleate, polyoxyethylene (10-50) castor oil, and any combination thereof.
41. The method of any one of claims 25 to 38, wherein the surfactant and/or emulsifier system comprises one or more of the following: polyoxyethylene (20) sorbitan monooleate, polyoxyethylene (20) sorbitan trioleate, polyoxyethylene (29) castor oil, and any combination thereof.
42. The method of any one of claims 25 to 38, wherein the surfactant and/or emulsifier system comprises one or more of the following: polyoxyethylene (20) sorbitan monolaurate, polyoxyethylene (20) sorbitan monopalmitate, polyoxyethylene (20) sorbitan monostearate, polyoxyethylene (20) sorbitan tristearate, and any combination thereof.
43. The method of any one of claims 25 to 38, wherein the surfactant and/or emulsifier system comprises one or more of the following: sorbitan mono fatty acid, sorbitan tri fatty acid, castor oil, and any combination thereof.
44. The method of any one of claims 25 to 43, wherein the surfactant and/or emulsifier system comprises one or more of the following: cocoyl glucoside, decyl glucoside, lauryl glucoside, sucrose cocoate, octyl/octanoyl glucoside, octanoyl/octyl glucoside, and any combination thereof.
45. The method of any one of claims 25 to 44, wherein the surfactant and/or emulsifier system has an HLB of from about 11 to about 13.50.
46. The method of any one of claims 25 to 44, wherein the surfactant and/or emulsifier system has an HLB of from about 11 to about 11.50, from about 11.50 to about 12, from about 12 to about 12.50, from about 12.50 to about 13, or from about 13 to about 13.50.
47. The method of any one of claims 25 to 46, wherein the drying comprises heating.
48. The method of any one of claims 25 to 47, wherein the pH of the solution is acidic.
49. The method of any one of claims 25 to 47, wherein 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.
50. An article made by the method of 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 a similar fabric but without the coating.
52. The article of claim 51, wherein moisture management is assessed by a absorbency test, a vertical wicking test, or a dry rate test.
53. The article of any one of claims 50 to 52, wherein the article has improved drape compared to a similar article comprising a similar fabric but without a coating.
54. The article of any one of claims 50 to 53, wherein the article has improved smoothness compared to a similar article comprising a similar fabric but no coating.
55. The article of any one of claims 50 to 54, wherein the article has an improved hand as compared to a similar article comprising a similar fabric but without a coating.
56. The article of any one of claims 50 to 55, wherein the article has a lower charge density at a given pH value than a similar article comprising a similar fabric but without the coating.
CN202280035273.2A 2021-03-16 2022-03-16 Silk-coated synthetic fabric Pending CN118076776A (en)

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US63/161929 2021-03-16
US202263319765P 2022-03-14 2022-03-14
US63/319765 2022-03-14
PCT/US2022/020651 WO2022197871A1 (en) 2021-03-16 2022-03-16 Silk coated synthetic fabrics

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