WO2024043926A1 - Matériau de base pour corps moulé de fibroïne de soie et procédé de fabrication - Google Patents

Matériau de base pour corps moulé de fibroïne de soie et procédé de fabrication Download PDF

Info

Publication number
WO2024043926A1
WO2024043926A1 PCT/US2022/075286 US2022075286W WO2024043926A1 WO 2024043926 A1 WO2024043926 A1 WO 2024043926A1 US 2022075286 W US2022075286 W US 2022075286W WO 2024043926 A1 WO2024043926 A1 WO 2024043926A1
Authority
WO
WIPO (PCT)
Prior art keywords
base material
molding
silk fibroin
measured
bulk density
Prior art date
Application number
PCT/US2022/075286
Other languages
English (en)
Inventor
Akira Yane
Yu Kameno
Toshiyuki Tomita
Kota YAGI
Koki Kodaira
Original Assignee
Canon Virginia, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Canon Virginia, Inc. filed Critical Canon Virginia, Inc.
Priority to PCT/US2022/075286 priority Critical patent/WO2024043926A1/fr
Publication of WO2024043926A1 publication Critical patent/WO2024043926A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L89/00—Compositions of proteins; Compositions of derivatives thereof

Definitions

  • the present disclosure relates to a base material for molding silk fibroin and to its manufacturing method.
  • International Patent Application Publication No. 2017/047503 provides a molded article obtained by filling a mold with a powder of a protein containing a natural spider silk protein which is silk fibroin or a polypeptide derived from a natural spider silk protein, and heating and pressurizing it.
  • the present disclosure provides a base material for silk fibroin molding which can be stably molded, and a method for producing a molded body of silk fibroin.
  • the present disclosure provides a base material for molding that contains silk fibroin as a main component, wherein the bulk density is from about 0.70 g/cm 3 to about 1.20 g/cm 3 .
  • the base material has a thickness of about 100 jum or more.
  • the base material has a P-sheet content of less than about 10%, and/or the moisture content is from about 2 to about 15%.
  • the base material can have a cylindrical shape, a polygonal columnar shape, a spherical shape, or a hemispherical shape.
  • a still further aspect provides a set of packaged base material for molding containing a plurality of pieces of the base material for molding that contains silk fibroin as a main component, and wherein the bulk density is from about 0.70g/cm 3 to about 1.20 g/cm 3 .
  • the set of the base material includes a packing body consisting of paper, resin, rubber and metal.
  • a method for molding silk fibroin which comprises dispensing an aqueous solution of silk fibroin containing less than 10g of silk fibroin, lyophilizing the solution, compressing the resulting lyophilized body until the bulk density becomes about 0.7 g/cm 3 to about 1.20 g/cm 3 , and heating and pressurizing the compressed body.
  • the solid content in the dispensed aqueous solution is equal to or 1/N of the molded body's weight.
  • the silk fibroin is compressed until the bulk density becomes about 0.70 g/cm 3 to about 1.20 g/cm 3 , compared to silk fibroin powder, scattering and adhering to the surroundings are suppressed, and the filling amount to the mold becomes consistent. Furthermore, since the filling amount is consistent, the dimensions of the molded body are consistent, the transferability of the mold shape of the molded body is improved, and the deterioration of the mechanical strength of the molded body is suppressed.
  • FIG. 1 is a schematic diagram of a mold for silk fibroin molding.
  • FIG. 2 is diagram depicting blocks for lyophilization.
  • FIG. 3A-B are diagrams showing cross-sections of the blocks for lyophilization in Fig. 2.
  • FIG. 4 is a diagram showing the components for a process for obtaining a base material for silk fibroin molding.
  • the same reference numerals and characters, unless otherwise stated, are used to denote like features, elements, components or portions of the illustrated embodiments.
  • the subject disclosure will now be described in detail with reference to the figures, it is done so in connection with the illustrative exemplary embodiments. It is intended that changes and modifications can be made to the described exemplary embodiments without departing from the true scope and spirit of the subject disclosure as defined by the appended claims. Furthermore, each embodiment described can be made or used in combination with any other described embodiment.
  • the base material for the silk fibroin molded body of this embodiment contains silk fibroin and has a bulk density in a range from 0.70 g/cm 3 to 1.20 g/cm 3 .
  • the base material for molded body (base material for molding) is a base material used when a functional solid item having silk fibroin as the main material is molded into a desired shape.
  • the protein molded body of the present embodiment can be formed. Specifically, by adjusting the bulk density in the range from 0.70 g/cm 3 to 1.20 g/cm 3 , scattering and adhesion are suppressed, since the base material for the silk fibroin molded body has the appropriate strength and weight.
  • Silk fibroin is a fibrous protein that can be extracted from cocoons and/or nests.
  • the extraction of silk fibroin can be carried out, for example, by the method described in WO 2006/101223.
  • Silk fibroin is generally characterized by high ratios of glycine, alanine, serine, and tyrosine.
  • Silk fibroin can exemplify a silk fibroin derived from an organism classified into the orders of Lepidoptera, Hymenoptera, or Araneae. In addition, it may also be silk fibroin obtained via gene recombination technology.
  • additives may be added to silk fibroin to the extent that it does not impair its properties.
  • the bulk density is low, the tableting strength is low, and the tablet breaks up when loading it into a mold and easily scatters around, so it is necessary for the bulk density to be 0.70 g/cm 3 or more, 0.90 g/cm 3 or more, or 1.00 g/cm 3 or more.
  • the bulk density is high, the surface transferability becomes bad during molding, so it is necessary for the bulk density to be less than 1.20 g/cm 3 and desirably less than 1.10 g/cm 3 .
  • the method for adjusting the bulk density of silk fibroin it is possible to exemplify a method for adjusting the bulk density by crushing and compressing the silk fibroin powder, or a method for obtaining a base material for molding by drying an aqueous solution of the silk fibroin before it is formed as a powder or after the powder is redissolved, temporarily preparing a porous silk fibroin body having a low bulk density and then compressing the porous body to the bulk density as desired.
  • the bulk density of silk fibroin decreases when the particle size is reduced by crushing
  • the bulk density can be adjusted by controlling the crushed particle size.
  • a jet mill, a pin mill, a hammer mill or the like can be used for grinding.
  • the bulk density of silk fibroin increases by compressing it.
  • the bulk density can be adjusted by controlling the pressure during compression.
  • a compression molding machine or a tableting machine can be used for compression.
  • the method for drying the aqueous solution of silk fibroin is not particularly limited as long as the solvent can be removed without decomposing silk fibroin, and examples include air drying, heat drying, vacuum drying, spray drying, and lyophilization (freeze-drying), and the like.
  • An advantage of lyophilization is that because the solution is frozen at a low temperature and the solvent is removed using sublimation, decomposition of the silk fibroin is suppressed.
  • one method for molding silk fibroin comprises dispensing an aqueous solution of silk fibroin containing less than 10g of silk fibroin, lyophilizing the solution, compressing the resulting lyophilized body until the bulk density becomes about 0.7 g/cm 3 to about 1.20 g/cm 3 , and heating and pressurizing the compressed body.
  • the process can utilize a block 31, 32 as shown in FIG. 2.
  • Block 31 can be used to lyophilize one portion of aqueous fibroin solution
  • block 32 can be used to simultaneously lyophilize multiple portions of aqueous silk fibroin solution.
  • Through hole 33 in each of blocks 31, 32 is configured to receive the one or more portions of aqueous fibroin solution prior to freezing.
  • FIG. 3A and 3B Cross sections of blocks 31, 32 are provided in FIG. 3A and 3B.
  • block 31, 32 contains through hole 33, into which aqueous silk fibroin solution 21 is introduced.
  • Part 34 serves as a stopper on one end of through hole 33 to retain the aqueous silk fibroin solution within through hole 33.
  • FIG. 3B lyophilization has occurred, resulting in lyophilized silk fibroin 22which remains within the through hole 33 of blocks 31, 32.
  • Part 34 is still present as a stopper at one end of through hole 33.
  • Fig. 4 depicts a molding process for obtaining a base material for molding. Lyophilized silk fibroin 22is loaded into a mold 35, having a through hole and a part 36 to maintain the loaded material within the through hole. The bulk density of the loaded material is adjusted by compressing the lyophilized silk fibroin 22with a piston 37 to obtain the base material for molding 24.
  • the pressure at the compression can be, but is not limited to, for example, 30
  • the tablet hardness of the base material for silk fibroin molding can be from 10 or more to 130 or less. If it is in this range, it is possible to obtain the effect of the present disclosure without scattering around upon loading into the mold and the surface transferability also becomes good. In additional embodiments, the tablet hardness of the base material for molding silk fibroin is from 20 or more to 120 or less, or from 30 or more to 115 or less.
  • the moisture content after drying contains approximately 2 to 15% moisture content because this increases the fluidity during fibroin molding and improves the surface transferability.
  • 3-sheet ratio is less than 10%.
  • the solution is dried after being divided into a uniform amounts of liquid or divided into amounts of silk fibroin required for one molding or divided (dispensed) into amounts of silk fibroin equivalent to 1/N (N is an integer) in an aqueous solution, when drying it. Since it is generally more accurate to measure a liquid than to measure a powder, dividing the aqueous solution into fixed quantities and drying them, enables more accurate measuring than measuring after drying. For simplicity of weighing, N can typically be 2, 3, or 5 or less. And, silk fibroin weight in aqueous silk fibroin solution after dispensing can be approximately 10 g or less.
  • the base material for molding silk fibroin can be formed into a cylindrical, polygonal, spherical or hemispherical shape. This is because when obtaining the base material for silk fibroin molding by adjusting the bulk density by compression, pressure can be applied uniformly to the silk fibroin, and the hardness and the like of the base material for molding can be kept uniform within the base material for molding. If uniaxial compression is performed when obtaining base material for silk fibroin molding, the shape of the base material for molding can be cylindrical. When performing uniaxial compression, certain conditions provide that the height (thickness) of the base material for molding is 3 times or less and approximately 0.1 times or more of the diameter (or the width or the length) for uniform compression.
  • the height (thickness) of the base material for silk fibroin molding can be 1 mm or more. This is because if the base material for silk fibroin molding is too thin, restrictions may arise for the shape after the molding that used the base material for the molding.
  • the thickness of the base material can also be 1.5 mm or more, or 2.0 mm or more.
  • a silk fibroin molded body can be obtained by loading base material for silk fibroin molding of which the bulk density has been adjusted into a mold and heating and pressurizing it.
  • FIG. 1 is a schematic diagram of an example of a mold that can be used for molding silk fibroin.
  • the mold is composed of a part 3, of which the temperature can be adjusted, having a through-hole and an upper piston 1 and a lower piston 2, and the silk fibroin molded body can be obtained by loading the base material for silk fibroin molding into part 3 and compressing it by moving pistons 1 and 2 up and down.
  • the heating in the heating and pressurizing process can be carried out from 70°C to 200°C, or from 100°C to 150°C. At less than 70°C, the protein does not sufficiently integrate, so the molded body does not become strong enough. On the other hand, at 200°C or higher, there is a concern that the protein may begin to decompose and the strength may decrease. Pressurization can be performed at 10 MPa or higher. At 10 MPa or lower, the protein does not sufficiently integrate, so the molded body will not be strong enough. Pressurization can also be performed at 50 MPa or higher.
  • the time for maintaining the pressure after the predetermined pressure is reached can be from 0 minutes to 60 minutes, or from 10 minutes to 30 minutes.
  • heat treatment may be performed from 70°C to 150°C. The heat treatment promotes crystallization and improves strength and shape stability.
  • the hardness of a prepared tablet was measured using a load cell type tablet hardness tester (PC-30, Okada Seiko Co., Ltd.).
  • the P-sheet ratio was measured using FT-IR (Frontier MIR N I R/Spotlight 400, Perkin Elmer). The absorbance was measured in the range from 1500 to 1800 cm 1 and the peak wavelength N at 1600 ⁇ 1650 cm 1 was read out, and the P-sheet ratio was calculated with the calculation formula of Equation 1.
  • Equation 1 To use Equation 1 is because the peak wavelength is 1641 cm 1 in the amorphous state and becomes 1621 cm 1 in the fully crystallization state.
  • the flexural modulus was measured using an Instron universal testing machine (Model 5582, Instron). The distance between the fulcrums of three-point bending was fixed at 27 mm, and the measurement speed was set at 1 mm/min. The flexural modulus was determined from the displacement (strain) of 0.05 up to 0.25%.
  • the surface roughness was measured using a surface roughness meter (SurfCorder SE3500, Kosaka Laboratory Co., Ltd.), and the ten-point average roughness Rzjis was measured in accordance with JIS B 0601-1994.
  • Silkworm cocoons were washed with water and then boiled in a 0.02 mol/L sodium carbonate aqueous solution for 30 minutes to degum cocoons. After drying, the degummed silk fibroin was put into a 9.3 mol/L Li Br aqueous solution and dissolved by agitating it at 60°C for 4 hours. Dialysis f las k30/32 (molecular weight cut off of 12000 ⁇ 14000) manufactured by Sekisui Chemical Co., Ltd. were used for desalination. The concentration of the fibroin aqueous solution after desalination was diluted with pure water so it became 5%.
  • the obtained 5% fibroin aqueous solution was divided into portions of 26.4 ml each into containers, as shown in FIG. 2.
  • the reference numerals 31 and 32 each denote blocks for lyophilization to be performed later.
  • Reference numeral 33 denotes a hole through which an aqueous solution of silk fibroin is injected.
  • FIG. 3A and 3B respectively show cross sections of the blocks for lyophilization shown in FIG. 2.
  • Reference numeral 21 denotes an aqueous solution of silk fibroin before lyophilization
  • reference numeral 22 denotes lyophilized silk fibroin.
  • reference numeral 34 denotes a part for holding the fibroin solution in place.
  • the lyophilization condition after freezing at -30°C, the atmosphere was depressurized, and then the temperature was raised to -6°C, and lyophilization was conducted for 100 hours. When the bulk density was measured, it was 0.03 g/cm 3 .
  • FIG. 4 a base material for molding
  • reference numerals 35 and 36 denote molds for obtaining base material for molding.
  • Reference numeral 37 denotes a piston for compression.
  • reference numeral 24 denotes a base material for molding of silk fibroin obtained through this process.
  • the same molds as the blocks 31, 32, and 34 for lyophilization may be used as the molds for obtaining the base material for molding.
  • the bulk density of the obtained base material for molding was measured, it was 1.02 g/cm 3 . Measuring the P-sheet formation rate, it was 5%. Measuring the moisture content, it was 7%.
  • the tablet hardness was measured, it was 103 N, and a base material for molding having a good hardness that did not disintegrate even when held with tweezers or the like was obtained.
  • a plurality of the base material for molding thus obtained may be stored together in a package and transferred to the main molding process.
  • the package may be paper, resin, rubber, metal, or the like.
  • the base material for molding was molded by heating and pressurizing.
  • a mold having a square columnar through-hole with a length of 35 mm and a width of 15 mm was used.
  • a piston having a surface roughness Rz of 0.2 pm was used.
  • the base material for molding was loaded into a mold of which the temperature had been adjusted to 125°C in advance, pressurized with a pressure of 100 MPa for 30 seconds, and allowed to cool until the mold reached 25°C.
  • the silk fibroin molded body was taken out from the mold and the surface roughness of the surface contacted by the piston was measured, it was 2.3 pm, and good surface transfer was achieved.
  • a base material for molding silk fibroin was obtained with the same operation as Example 1, except that the lyophilized silk fibroin was pressurized at 20 MPa.
  • the bulk density of the obtained base material for molding was measured, it was 0.72 g/cm 3 .
  • the P-sheet ratio was measured, it was 5%.
  • the moisture content was measured, it was 7%.
  • the tablet hardness was measured, it was 34 N, and a base material for molding having a good hardness that did not disintegrate even when held with tweezers or the like was obtained.
  • a silk fibroin molded body was obtained with the same operation as in Example 1. When the surface roughness was measured, it was 2.2 pm, and good surface transfer was achieved.
  • a base material for molding silk fibroin was obtained with the same operation as Example 1, except that the lyophilized silk fibroin was pressurized at 2 MPa.
  • the bulk density of the obtained base material for molding was measured, it was 0.50 g/cm 3 .
  • the P-sheet formation rate was measured, it was 5%.
  • the moisture content was measured, it was 7%.
  • the tablet hardness was measured, it was 10 N or less. In addition, when it was held with tweezers, it broke into many pieces, so the handling performance was poor.
  • EXAMPLE 3 A base material for molding silk fibroin was obtained with the same operation as Example 1, except that the lyophilized silk fibroin was pressurized at 80 MPa. When the bulk density of the obtained base material for molding was measured, it was 1.20 g/cm 3 . When the P-sheet formation rate was measured, it was 5%. When the moisture content was measured, it was 7%. When the tablet hardness was measured, it was 114 N, and a base material for molding having a good hardness that did not disintegrate even when held with tweezers or the like was obtained.
  • a silk fibroin molded body was obtained with the same operation as in Example 1. When the surface roughness was measured, it was 2.3 pm, and good surface transfer was achieved.
  • a base material for molding silk fibroin was obtained with the same operation as Example 1, except that the lyophilized silk fibroin was pressurized at 120 MPa.
  • the bulk density of the obtained base material for molding was measured, it was 1.28 g/cm 3 .
  • the P-sheet formation rate was measured, it was 5%.
  • the moisture content was measured, it was 7%.
  • the tablet hardness was measured, it was 132 N, and a base material for molding having a good hardness that did not disintegrate even when held with tweezers or the like was obtained.
  • a silk fibroin molded body was obtained with the same operation as in Example 1. When the surface roughness was measured, it was 17.2 pm. It is thought that surface transfer did not take place sufficiently, because the bulk specific gravity of the base material for molding became high, and it became hard.
  • the lyophilized silk fibroin was kept in an environment at 100°C for 4 minutes, and then left at 23°C with a relative humidity of 50% for 48 hours. Thereafter, the base material for silk fibroin molding was obtained with the same operation as in Example 1, except that it was pressurized at 20 MPa.
  • the bulk density of the obtained base material for molding was measured, it was 1.03 g/cm 3 .
  • 3-sheet formation rate was measured, it was 8%.
  • the moisture content was measured, it was 7%.
  • a silk fibroin molded body was obtained with the same operation as in Example 1. When the surface roughness was measured, it was 2.3 pm, and good surface transfer was achieved.
  • the lyophilized silk fibroin was kept in an environment at 90°C for 3 minutes, and then left at 23°C with a relative humidity of 50% for 30 minutes. Thereafter, the base material for silk fibroin molding was obtained with the same operation as in Example 1, except that it was pressurized at 20 MPa.
  • the bulk density of the obtained base material for molding was measured, it was 1.09 g/cm 3 .
  • 3-sheet formation rate was measured, it was 5%.
  • the moisture content was measured, it was 2%.
  • a silk fibroin molded body was obtained with the same operation as in Example 1. When the surface roughness was measured, it was 2.3 pm, and good surface transfer was achieved.
  • the lyophilized silk fibroin was left at 23°C with a relative humidity of 80% for 12 hours. Thereafter, the base material for silk fibroin molding was obtained with the same operation as in Example 1, except that it was pressurized at 20 MPa.
  • the bulk density of the obtained base material for molding was measured, it was 1.12 g/cm 3 .
  • 3-sheet formation rate was measured, it was 5%.
  • the moisture content was measured, it was 15%.
  • the tablet hardness was measured, it was 89 N, and a base material for molding having a good hardness that did not disintegrate even when held with tweezers or the like was obtained.
  • a silk fibroin molded body was obtained with the same operation as in Example 1. When the surface roughness was measured, it was 2.4 pm, and good surface transfer was achieved.
  • a base material for silk fibroin molding was obtained with the same operation as in Example 4, except that keeping it in an environment of 100°C for 4 minutes was changed to keeping it in an environment of 100°C for 7 minutes.
  • the bulk density of the obtained base material for molding was measured, it was 1.02 g/cm 3 .
  • the P-sheet formation rate was measured, it was 13%.
  • the moisture content was measured, it was 7%.
  • the tablet hardness was measured, it was 68 N, and deformation was observed when the tablet was strongly pinched by the tweezers, but a base material for molding of a hardness which did not disintegrate was obtained.
  • a silk fibroin molded body was obtained with the same operation as in Example 1. When the surface roughness was measured, it was 2.9 pm, and good surface transfer was achieved.
  • a base material for silk fibroin molding was obtained with the same operation as in Example 5, except that the keeping it in an environment of 90°C for 3 minutes was changed to keeping it in an environment of 90°C for 5 minutes.
  • the bulk density of the obtained base material for molding was measured, it was 1.04 g/cm 3 .
  • the P-sheet formation rate was measured, it was 5%.
  • the moisture content was measured, it was 1%.
  • the tablet hardness was measured, it was 47 N, and deformation was observed when the tablet was strongly pinched by the tweezers, but a base material for molding of a hardness which did not disintegrate was obtained.
  • a silk fibroin molded body was obtained with the same operation as in Example 1. When the surface roughness was measured, it was 4.2 pm, and good surface transfer was achieved. [00090] EXAMPLE 9
  • the lyophilized silk fibroin was left at 23°C with a relative humidity of 80% for 24 hours. Thereafter, the base material for silk fibroin molding was obtained with the same operation as in Example 1, except that it was pressurized at 20 MPa.
  • the bulk density of the obtained base material for molding was measured, it was 1.02 g/cm 3 .
  • 3-sheet formation rate was measured, it was 5%.
  • the moisture content was measured, it was 17%.
  • a silk fibroin molded body was obtained with the same operation as in Example 1. When the surface roughness was measured, it was 3.6 pm, and good surface transfer was achieved.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)

Abstract

La présente divulgation concerne un matériau de base pour moulage de fibroïne qui peut être facilement moulé sans le travail de stratification, et un procédé de production d'un corps moulé de fibroïne, le matériau de base pour moulage comportant de la fibroïne de soie en tant que composant principal, le matériau de base pour moulage ayant une masse volumique apparente comprise entre 0,7 g/cm3 et 1,2 g/cm3.
PCT/US2022/075286 2022-08-22 2022-08-22 Matériau de base pour corps moulé de fibroïne de soie et procédé de fabrication WO2024043926A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/US2022/075286 WO2024043926A1 (fr) 2022-08-22 2022-08-22 Matériau de base pour corps moulé de fibroïne de soie et procédé de fabrication

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US2022/075286 WO2024043926A1 (fr) 2022-08-22 2022-08-22 Matériau de base pour corps moulé de fibroïne de soie et procédé de fabrication

Publications (1)

Publication Number Publication Date
WO2024043926A1 true WO2024043926A1 (fr) 2024-02-29

Family

ID=90013783

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2022/075286 WO2024043926A1 (fr) 2022-08-22 2022-08-22 Matériau de base pour corps moulé de fibroïne de soie et procédé de fabrication

Country Status (1)

Country Link
WO (1) WO2024043926A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130158131A1 (en) * 2003-01-07 2013-06-20 Massachusetts Institute Of Technology Silk fibroin materials and use thereof
US20150272903A1 (en) * 2009-02-12 2015-10-01 Tufts University Nanoimprinting of silk fibroin structures for biomedical and biophotonic applications
US20210101946A1 (en) * 2012-07-09 2021-04-08 Trustees Of Tufts College High molecular weight silk fibroin and uses thereof
JP2021054994A (ja) * 2019-09-30 2021-04-08 Ｓｐｉｂｅｒ株式会社 繊維強化樹脂成形体及びその製造方法
US20210381129A1 (en) * 2018-10-10 2021-12-09 Trustees Of Tufts College Compression and heat-assisted production of silk-based materials

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130158131A1 (en) * 2003-01-07 2013-06-20 Massachusetts Institute Of Technology Silk fibroin materials and use thereof
US20150272903A1 (en) * 2009-02-12 2015-10-01 Tufts University Nanoimprinting of silk fibroin structures for biomedical and biophotonic applications
US20210101946A1 (en) * 2012-07-09 2021-04-08 Trustees Of Tufts College High molecular weight silk fibroin and uses thereof
US20210381129A1 (en) * 2018-10-10 2021-12-09 Trustees Of Tufts College Compression and heat-assisted production of silk-based materials
JP2021054994A (ja) * 2019-09-30 2021-04-08 Ｓｐｉｂｅｒ株式会社 繊維強化樹脂成形体及びその製造方法

Similar Documents

Publication Publication Date Title
Wang et al. Impacts of nanowhisker on formation kinetics and properties of all-cellulose composite gels
Ogale et al. Viscoelastic, thermal, and microstructural characterization of soy protein isolate films
EP2956184B1 (fr) Échafaudages poreux à base de soie et leur procédé de préparation
Stuer et al. Freeze granulation: Powder processing for transparent alumina applications
EP2418239B1 (fr) Procédé pour produire un matériau poreux de fibroïne de soie
CN106661474A (zh) 用于型煤的粘合剂
JP2024040230A (ja) 細胞担体粒子の凝集体およびその製造方法
Nangare et al. Silk industry waste protein: isolation, purification and fabrication of electrospun silk protein nanofibers as a possible nanocarrier for floating drug delivery
CN113412308A (zh) 基于丝的材料的压缩和热辅助制造
WO2024043926A1 (fr) Matériau de base pour corps moulé de fibroïne de soie et procédé de fabrication
CN104529497A (zh) 一种采用真空冷冻干燥技术提高陶瓷铸型精度的方法
CN106421902B (zh) 一种快速凝胶化丝素蛋白溶液及其制备方法
Wang et al. Development of binder-free CMG abrasive pellet and finishing performance on mono-crystal sapphire
Yamaguchi et al. Mechanism of densification of calcium carbonate by cold sintering process
KR102110860B1 (ko) 다공질 복합체, 골 재생 재료, 및 다공질 복합체의 제조 방법
Li et al. Autonomous ultrafast-self-healing hydrogel for application in multiple environments
CN111278422A (zh) 化妆用品用成形物和其制造方法
RU2006126051A (ru) Способы получения партии активного фармацевтического ингредиента, контейнер, содержащий криогранулы аллергенного продукта, и криогранула аллергенного продукта
CN114805535A (zh) 一种rh-bFGF冻干方法
WO2024043927A1 (fr) Matériau de base pour corps moulé de fibroïne de soie et procédé de fabrication
Jaya et al. Compressive characteristics of cellular solids produced using vacuum-microwave, freeze, vacuum and hot air dehydration methods
JPH07503678A (ja) ポリベンゾアゾール含有材料の圧縮及び成形
KR101797465B1 (ko) 물성이 개선된 알긴산 폼 및 그의 제조방법
CN110279122A (zh) 一种通过添加磷脂囊泡改善高蛋白营养棒内聚性的方法
RU2366637C1 (ru) Способ получения высокоплотных водных шликеров на основе литийалюмосиликатного стекла

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22956667

Country of ref document: EP

Kind code of ref document: A1