US20030183978A1 - Method of producing fiber and film of silk and silk-like material - Google Patents

Method of producing fiber and film of silk and silk-like material Download PDF

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US20030183978A1
US20030183978A1 US10/276,058 US27605802A US2003183978A1 US 20030183978 A1 US20030183978 A1 US 20030183978A1 US 27605802 A US27605802 A US 27605802A US 2003183978 A1 US2003183978 A1 US 2003183978A1
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silk
fibers
hfa
solution
film
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Tetsuo Asakura
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JAPAN AS REPRESENTED BY PRESIDENT OF TOKYO UNIVERSITY OF AGRICULTURE AND TECH
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
    • D01D5/0038—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion the fibre formed by solvent evaporation, i.e. dry electro-spinning
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F4/00—Monocomponent artificial filaments or the like of proteins; Manufacture thereof
    • D01F4/02—Monocomponent artificial filaments or the like of proteins; Manufacture thereof from fibroin
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4266—Natural fibres not provided for in group D04H1/425
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/54—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/02—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of forming fleeces or layers, e.g. reorientation of yarns or filaments
    • D04H3/03—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of forming fleeces or layers, e.g. reorientation of yarns or filaments at random
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
    • D04H3/08—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating
    • D04H3/16—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of strengthening or consolidating with bonds between thermoplastic filaments produced in association with filament formation, e.g. immediately following extrusion
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
    • Y10T442/608—Including strand or fiber material which is of specific structural definition
    • Y10T442/614—Strand or fiber material specified as having microdimensions [i.e., microfiber]

Definitions

  • This invention relates to a method of manufacturing silk, silk fibers or film, and silk-like fibers or film. More specifically this invention relates to a method of manufacturing silk fibers or film, and silk-like fibers or film using hexafluoroacetone hydrate as a solvent.
  • hexafluoroisopropyl alcohol was often used to obtain regenerated B. mori silk fibers which did not induce decrease of molecular weight and had excellent mechanical properties (U.S. Pat. No. 5,252,285).
  • a salt such as lithium bromide
  • the silk fibroin prepared as a film form is dissolved in HFIP.
  • 8 days are required until complete dissolution of silk film in HFIP (U.S. Pat. No. 5,252,205).
  • HFA hexafluoroacetone hydrate
  • the solvent should not remain after the silk fibroins have solidified, that is, the solvent should be easily removable.
  • HFA satisfies all these conditions, and can also dissolve the silk fibers from wild silkworms.
  • the above objects of this invention are attained by a method wherein silk or silk fibers are manufactured by spinning them from a solution wherein silk fibroins and/or silk materials are dissolved in hexafluoroacetone hydrate or a solvent system having this as the main component, and extruded if necessary. They are also attained by a method wherein silk or a silk film is manufactured by developing on a support a solution wherein silk fibroins and/or silk materials are dissolved in hexafluoroacetone hydrate or a solvent system having this as its main component, drying, and extruding if necessary.
  • a in FIG. 1 is a formula of hexafluoroacetone used as a spinning solvent in this invention.
  • B in FIG. 1 is a formula of a diol from which reacted with a water molecule, and C is the reaction equation.
  • FIG. 2 is a solution 13 C NMR spectrum of B. mori fibroin in HFA hydrate.
  • FIG. 3 is a solid-state 13 C CP/MAS NMR spectrum of B. mori silk fibroin fibers regenerated from the HFA solution.
  • a in FIG. 4 is an X-ray diffraction pattern of silk fibroins regenerated from the HFA solution, and B is an X-ray diffraction pattern of the natural silk fibroin fibers.
  • a in FIG. 5 is a DSC diagram of a sample wherein silk fibroins regenerated from the HFA solution after heat-treating at 100° C.
  • B is a DSC diagram of the sample after heat-treating at 125° C.
  • a in FIG. 6 is a stress-strain curve of the natural silk fibroin fibers
  • B is a stress-strain curve of silk fibroin fibers regenerated from the HFA solution.
  • FIG. 7 is a diagram describing the regeneration of the silk fibroin fibers from the HFA solution.
  • the hexafluoroacetone used in this invention is the substance shown in A of FIG. 1, and is normally present in a stable state as a hydrate. Therefore, the hydrate is used also in this invention.
  • the HFA may also be diluted with water or with HFIP. In this case, it is also desirable that at least 80% of the mixture is HFA.
  • the solvent which is diluted in this way is referred to as a solvent having HFA as its main component.
  • the silk fibroins used in this invention refer to silk fibroins from silkworms such as B. mori, S. c. ricini, A. pernyi and A. yamamai.
  • Silk materials mean proteins as, for example, represented by the general formula -[GA 1 ] j -((GA 2 ) k -G-Y-(GA 3 ) 1 ) m ] n -, or [GGAGSGYGGGYGHGYGSDGG(GAGAGS) 3 ] n .
  • G is glycine
  • A is alanine
  • S is serine
  • Y tyrosine.
  • a 1 in the above general formula is alanine, and every third A 1 may be serine.
  • a 2 and A 3 are both alanine, and part thereof may be valine.
  • the silk fibroins and/or silk-like materials may be dissolved in exclusively HFA.
  • HFA hydrogen fluoride
  • the silk fibers may first be dissolved in LiBr, dialyzed to remove LiBr and developed on a support to form a film, and the film obtained may then be dissolved in HFA.
  • the solubility in this case is much better than those of HFIP.
  • the operability is largely improved, and the mechanical properties of the fibers are also better than those obtained with HFIP as a solvent.
  • a mixture of HFA and HFIP as a solvent in this invention. In this case, the relative proportion of the two may be determined according to the proteins which it is desired to dissolve.
  • the silk fibroin film is dissolved in hexafluoroacetone hydrate, so there is almost no possibility of the decomposition of the silk fibroin chain, and the silk solution can be obtained within a shorter time than in the previous case, HFIP. Further, if longer dissolution time is possible, B. mori fibers can be directly dissolved without preparing a film, wild silkworm fibers such as S. c. ricini and A. yamamai can be directly dissolved, and the regenerated silk fibers or films can be obtained.
  • a 0.5 wt % aqueous solution of a Marseille-soap (No. 1 Chemical Industries) was prepared, and heated to 100° C.
  • the cocoon layer mentioned above was introduced, and after manipulating the fibers, the solution was boiled with stirring. After boiling for 30 minutes, these fibers were rinsed in distilled water heated to 100° C. This operation was repeated 3 times. The fiber was boiled for a further 30 minutes with distilled water, rinsed and dried to give silk fibroins.
  • B. mori fibroins are soluble in HFA in the form of fibers. However, it requires at least 2 months for complete dissolution.
  • a permeable membrane made from cellulose (VISKASE SELES CORP, Seamless Cellulose Tubing, 36/32) was used for dialysis for four days against distilled water to remove LiBr.
  • aqueous solution of the silk fibroin was poured on a plastic plate (Eiken Equipment Inc., sterile, square No. 2 Petri dish), allowed to stand for two days at room temperature to obtain a regenerated B. mori fibroin film.
  • the thickness of the film was about 0.1 mm. HFA.3H 2 O tends to evaporate and therefore, the film was dissolved at 25° C. without heating.
  • the silk fibroin concentration which is suitable for spinning is 8 to 10 wt %. Moreover, it was found that at this concentration, the dissolution time was very short, e.g., 2 hours.
  • HFA has different hydrates.
  • the trihydrate and x hydrate were used, but no difference was found in the solubility.
  • B. mori silk fiber could be dissolved directly in HFA (silk fibroin concentration is 10 wt %) without forming as film, but the dissolution took two months or more.
  • the silk fibroin film was placed in HFA, stirred and allowed to stand at 25° C. to dissolve it. Then the solution was degassed to give a spinning stock solution. A cylinder was filled with the spinning stock solution, and this was spun into a bath from a nozzle of diameter 0.45 mm to coagulate it.
  • a mechanical spectrometer (Rheometric Far East. Ltd., RMS-800) was used for the measurement. The frequency dependence was measured when the distortion was rad 50%. The viscosity was measured by changing the frequency. This shear rate was extrapolated to 0, and the 0 shear viscosity was calculated. As a result, the viscosity of the spinning stock solution was 18.32 poise.
  • the silk fibroin has a different structure in solution from that in HFIP which is also a fluorinated alcohol.
  • a Chemagnetic CMX400 spectrometer was used for the 3 C CP/MAS NMR measurements.
  • the C alpha and C beta regions are expanded in FIG. 3. It was clear that an alpha helix was formed in the regenerated film from the spinning stock solution, and a beta sheet was formed in the regenerated B. mori silk fibers. This shows that a structural transition occurred due to spinning.
  • HFA-xH 2 O was added to B. mori silk fiber to dissolve it. Subsequently, C alpha and C beta peaks were observed in the dried material and the film from the spinning stock solution. From this, it is seen that HFA remains in B. mori fibroin sample, and that it cannot be removed only by drying. Further, although the strength is less than that of the former material, the peaks from HFA were observed even in a non-stretched regenerated silk fiber which had only been spun. This shows that HFA is not completely eliminated merely by spinning out into the coagulate solvent like the case of the reproduced silk fiber from the HFIP solution.
  • a regenerated silk fiber (3 times stretching ratio) obtained by continuous spinning was used for observation with wide-angle X-ray diffraction.
  • FIG. 4 shows that the peak due to the orientation in the azimuth angle direction at 19.8 degrees was observed together with the case of B. mori silk fibers.
  • FIG. A shows regenerated silk fibroin fibers and FIG. B shows natural silk fibroin fibers.
  • the sample for DSC measurement was prepared by filling the regenerated silk fibers in an aluminium pan, and filling with N 2 gas. The samples were cut to approximately 5 mm.
  • the apparatus was a Rigaku Denki THERMOFLEX (DCS 83 230D). The temperature range was 30-350° C., and the rate of temperature rise was 10° C./minute.
  • the DSC curve of the regenerated silk fibers from the HFA solution is shown in FIG. 5. The heat absorption peak appearing in the vicinity of 70-80° C. is probably due to the vaporization of moisture absorbed in the sample.
  • FIG. 5 shows the curve of regenerated silk fibers at a different high humidity and heat processing temperature.
  • An exothermic peak appears at 123° C. in the curve of a specimen manufactured at a processing temperature of 100° C. (FIG. 5A).
  • HFA acts strongly on the silk fibroins, and crystallization does not go to completion during the period from solidification to stretching.
  • This exothermic peak was in a low temperature region which does not appear in previous peaks from B. mori silk fibroins.
  • the peak pattern is substantially identical to that for B. mori silk fibers, so it is seen that crystallinity improves due to the strong action of HFA. Also, it is postulated that, in B. mori silk fibers, crystallization occurs in the crystalline region.
  • the sample was a specimen piece of 70 mm, sandpaper grip 10 mm and grip interval 50 mm.
  • a Tensilon (Shimazu Labs. Inc, AGS-10 kng) was used. The rate of elongation was fixed, and the cell was a 10 Newton cell. Measurement was performed at a crosshead speed of 50 mm/min referring to JIS L-0105, L-1069, L-1095 and ASTM D 2101, D 2258.
  • mori silk fibers regenerated from the HFA solution Measurement of tensile strength and elongation Elongation maximum factor maximum tensile tensile strength Sample (times) diameter ( ⁇ m) elongation (%) Young's modulus B. mori silk fibers produced 3.00* 1 43 2.18(2.02-2.31)(cN/dTex) 15.6 74.0(68.4-78.9)(cN/dTex) from the HFA solution 0.29(Gpa) (12.8-16.6) 1.92(1.78-2.04)(gf/d) 65.3(60.4-69.6)(gf/d) B. mori silk fibers 3.00* 2 — 1.63(cN/dTex) ⁇ 0.19 17.3 ⁇ 4.3 1.44(gf/d) ⁇ 0.19 — approx. 15 0.39(Gpa) 16.5
  • Cocoons produced at 1997 year were used as the starting material. This was carefully disentangled with tweezers.
  • the sericin proteins and other lipids covering the fibroins were removed by degumming to obtain the silk fibroins.
  • the degumming method was as follows.
  • a 0.5 wt % aqueous solution of sodium bicarbonate (NaHCO 3 ) (Wako Pure Chemical Industries, Inc., special grade) was prepared and heated to 100° C. The cocoon was introduced and the solution was boiled with stirring. After 30 minutes, the cocoons were rinsed in distilled water at 100° C. This operation was repeated 5 times and the cocoons were boiled again for 30 minutes in distilled water, rinsed, and then dried to give the silk fibroins.
  • NaHCO 3 sodium bicarbonate
  • FIG. 6 shows the results of examining the coagulation. From this, it is seen that it was difficult to obtain fibers of identical transparency to those of B. mori . This difference seems due to the primary structure.
  • 30% ethanol/acetone as the coagulation bath, which has a comparatively high fiber-forming capacity, the spun fibers were left in the coagulation bath overnight and were used as a non-stretched sample.
  • Optimum component conditions for coagulant solvent Coagulant solvent Result 100% methanol ⁇ /whitening 90% methanol/water ⁇ /whitening 80% methanol/water ⁇ /whitening 75% methanol/water x/low coagulation properties 70% methanol/water x/low coagulation properties 85% methanol/ethanol ⁇ /low coagulation properties 70% methanol/ethanol ⁇ /low coagulation properties 10% methanol/ethanol ⁇ /whitening 5% methanol/ethanol ⁇ /low coagulation properties 2% methanol/ethanol ⁇ /low coagulation properties 100% ethanol ⁇ /low coagulation properties 90% ethanol/water ⁇ /low coagulation properties 90% ethanol/acetone ⁇ /low coagulation properties 40% ethanol/acetone ⁇ /whitening 30% ethanol/acetone ⁇ /whitening 17% ethanol/acetone ⁇ /whitening 100% acetone ⁇ /whitening
  • the silk concentration which gave a suitable viscosity for spinning was 10 wt %.
  • the non-stretched fibers did not have good stretching stability, and breaks of the fibers occurred.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Artificial Filaments (AREA)
  • Nonwoven Fabrics (AREA)
US10/276,058 2001-03-14 2001-03-14 Method of producing fiber and film of silk and silk-like material Abandoned US20030183978A1 (en)

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PCT/JP2001/002026 WO2002072931A1 (fr) 2001-03-14 2001-03-14 Procede de production d'une fibre ou d'une bande de soie et de matiere de type soie

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US10/471,587 Abandoned US20040185737A1 (en) 2001-03-14 2002-03-14 Non-woven fabric comprising ultra-fine fiber of silk fibroin and/or silk-like material, and method for production thereof

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EP (2) EP1277857A4 (zh)
JP (1) JPWO2002072931A1 (zh)
KR (2) KR20020091244A (zh)
CN (2) CN1247837C (zh)
CA (2) CA2405850A1 (zh)
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Cited By (36)

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US20040224406A1 (en) * 2001-11-16 2004-11-11 Tissue Regeneration, Inc. Immunoneutral silk-fiber-based medical devices
US20090030454A1 (en) * 2005-04-08 2009-01-29 David Philip Knight Resorbable implantable devices
US20090234026A1 (en) * 2003-04-10 2009-09-17 Trustees Of Tufts College Concentrated aqueous silk fibroin solution and use thereof
US20090318963A1 (en) * 2006-07-04 2009-12-24 Nat Univ Corp Tokyo Univ Of Agrigulture And Tech Spinning solution composition, process for producing regenerated silk fiber using the composition, and regenerated silk fiber produced by the process
US20100191328A1 (en) * 2007-02-27 2010-07-29 Trustees Of Tufts College Tissue-engineered silk organs
US20100203226A1 (en) * 2003-06-06 2010-08-12 Trustees Of Tufts College Method for forming inorganic coatings
US20110009960A1 (en) * 2001-11-16 2011-01-13 Allergan, Inc. Prosthetic fabric structure
US20110014263A1 (en) * 2009-04-20 2011-01-20 Altman Gregory H Silk Fibroin Hydrogels and Uses Thereof
US20110046686A1 (en) * 2008-02-07 2011-02-24 Trustees Of Tufts College 3-dimensional silk hydroxyapatite compositions
US20110052695A1 (en) * 2009-04-20 2011-03-03 Allergan, Inc. Drug delivery platforms comprising silk fibroin hydrogels and uses thereof
US20110111031A1 (en) * 2009-04-20 2011-05-12 Guang-Liang Jiang Drug Delivery Platforms Comprising Silk Fibroin Hydrogels and Uses Thereof
US20110121485A1 (en) * 2006-10-30 2011-05-26 Spintec Engineering Gmbh Method and apparatus for the manufacture of a fiber
US20110129531A1 (en) * 2009-04-20 2011-06-02 Allergan, Inc. Dermal Fillers Comprising Silk Fibroin Hydrogels and Uses Thereof
US20110152214A1 (en) * 2008-05-15 2011-06-23 Trustees Of Tufts College Silk polymer-based adenosine release: therapeutic potential for epilepsy
US20110171239A1 (en) * 2008-09-26 2011-07-14 Trustees Of Tufts College pH INDUCED SILK GELS AND USES THEREOF
US20110184227A1 (en) * 2009-09-11 2011-07-28 Allergan, Inc. Prosthetic device and method of manufacturing the same
US20110224703A1 (en) * 2008-12-15 2011-09-15 Allergan, Inc. Prosthetic device having diagonal yarns and method of manufacturing the same
US20110223153A1 (en) * 2008-10-09 2011-09-15 Trustees Of Tufts College Modified silk films containing glycerol
US8715740B2 (en) 2009-09-29 2014-05-06 Trustees Of Tufts College Silk nanospheres and microspheres and methods of making same
US8722067B2 (en) 2007-05-29 2014-05-13 Trustees Of Tufts College Method for silk fibroin gelation using sonication
US8728498B2 (en) 2009-07-14 2014-05-20 Trustees Of Tufts College Electrospun silk material systems for wound healing
US8746014B2 (en) 2008-12-15 2014-06-10 Allergan, Inc. Method for making a knitted mesh
US20150148823A1 (en) * 2008-12-15 2015-05-28 Allergan, Inc. Pliable silk medical device
US9074302B2 (en) 2009-09-28 2015-07-07 Trustees Of Tufts College Methods of making drawn silk fibers
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