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WO2001036531A1 - Materiau polymere moleculairement composite en fibroine/cellulose et procede de production de ce materiau - Google Patents

Materiau polymere moleculairement composite en fibroine/cellulose et procede de production de ce materiau Download PDF

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Publication number
WO2001036531A1
WO2001036531A1 PCT/JP2000/008043 JP0008043W WO0136531A1 WO 2001036531 A1 WO2001036531 A1 WO 2001036531A1 JP 0008043 W JP0008043 W JP 0008043W WO 0136531 A1 WO0136531 A1 WO 0136531A1
Authority
WO
WIPO (PCT)
Prior art keywords
cellulose
polymer material
silk
molecular
composite polymer
Prior art date
Application number
PCT/JP2000/008043
Other languages
English (en)
Japanese (ja)
Inventor
Rensuke Kanekatsu
Kenji Kiguchi
Eisaku Iizuka
Akira Hachimori
Original Assignee
Zaidan-Houjin Ueda Sen-I Kagaku Shinkoukai
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 Zaidan-Houjin Ueda Sen-I Kagaku Shinkoukai filed Critical Zaidan-Houjin Ueda Sen-I Kagaku Shinkoukai
Priority to AU14122/01A priority Critical patent/AU1412201A/en
Publication of WO2001036531A1 publication Critical patent/WO2001036531A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H1/00—Macromolecular products derived from proteins
    • 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
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/02—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from solutions of cellulose in acids, bases or salts
    • D01F2/04—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from solutions of cellulose in acids, bases or salts from cuprammonium solutions
    • 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
    • D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/24—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from cellulose derivatives
    • 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

Definitions

  • the present invention relates to a fibroin / cellulose molecular composite polymer material and a method for producing the same.
  • the present invention relates to a novel polymer material in which silk fiproin obtained from silkworm or wild silkworm and cellulose are complexed at a molecular level, and a method for producing the same.
  • Silk is an excellent natural fiber that has many sensual advantages, such as rich luster, good dyeing properties, and excellent touch, while cotton is another practical natural fiber that is vulnerable to friction and heat. Some aspects are inferior to.
  • a method for extruding a fibrous solution into a coagulating solution after extruding a fibrous solution having a low concentration in a concentrated neutral salt solution containing alcohol into an alcoholic coagulation solution after extruding into a gaseous phase has not been determined.
  • the regenerated fibers also had an unsatisfactory strength of about 1.8 g / d.
  • the problem of removing large amounts of neutral salts remains unresolved.
  • the present invention is not based on the method of combining the properties of different fiber materials at the level of weaving, knitting, and spinning as described above, but rather by combining the properties of silk fiber mouth-in material and the properties of natural cell mouth material. It is an object of the present invention to provide a polymer material having useful properties that is combined and utilized, and a polymer product such as a fiber or a film made of the polymer material. Another object of the present invention is to provide a method for producing the above-mentioned polymer material.
  • the inventors of the present invention have studied long-lasting fibroin, and found that when a certain amount of cellulose was mixed with silk fiproin of silkworm or wild silkworm in a copper ammonia solution under specific conditions, the binding of both at the molecular level As a result, a composite polymer material having spinnability and film-forming properties is obtained, and it is possible to manufacture recycled fibers and films with a composition close to pure fibroin, which has been considered difficult in practice. I found something. The present invention has been completed based on these findings.
  • a molecular composite polymer material in which a silk fiber mouth in-protein and cellulose are bound at a molecular level.
  • the molecular composite polymer material of the present invention is obtained by dissolving silk fiber mouth and cellulose in a copper ammonia solution and binding them.
  • the weight ratio of silk fiber mouth to cellulose is from 0.1: 1 to 3: 1, more preferably from 0.5: 1 to 2: 1.
  • the silk fibroin used in the present invention is silk fibroin obtained from domestic silkworm or wild silkworm.
  • a fiber comprising the above-described molecular composite polymer material according to the present invention, and a film comprising the above-described molecular composite polymer material according to the present invention.
  • a molecular complex wherein silk fiproin protein and cellulose are bound at a molecular level by dissolving and mixing silk fiproin and cellulose in a copper ammonia solution.
  • a method for producing a polymer material is provided.
  • the mixing ratio of silk fiber mouth to cellulose is 0.1: 1 to 3: 1 by weight, and more preferably 0.5: 1 to 2: 1.
  • the silk fiber mouth used in the present invention is silk fibroin obtained from silkworm or wild silkworm.
  • FIG. 1 shows an X-ray diffraction diagram.
  • 1 shows the result of cocoon thread or fiber mouth
  • 2 shows the result of regenerated cellulose
  • 3 shows the result of molecular complex polymer.
  • FIG. 2 shows the infrared absorption spectrum (IR spectrum).
  • 1 shows the result of cocoon thread or fiber mouth
  • 2 shows the result of regenerated cellulose
  • 3 shows the result of molecular complex polymer.
  • FIG. 3 shows a schematic diagram of a simple stringing device used for experimentally producing the molecular composite fiber of the present invention.
  • reference numeral 10 denotes a fiber mixture in a cellulose mixed solution
  • 12 denotes a peristaltic pump
  • 14 denotes a cylinder filled with water
  • 16 denotes an acid treatment bath filled with dilute sulfuric acid
  • 18 denotes a washing bath.
  • 20 indicate a winding device.
  • silk-fiber mouth-ins and cocoons obtained from silkworms and wild silkworms are used, and as the cellulose material, cotton, natural cellulosic regenerated fiber and the like are used.
  • the copper ammonia liquid for dissolving these materials the same liquid as that used in the production process of copper ammonia rayon is used. For example, a 10% ammonia containing supersaturated copper hydroxide is used. A liquid solution corresponds to this, and a viscous solution in which a cotton material is dissolved under the condition that the air is shut off at a low temperature (for example, about 4 C) is used.
  • a method for recovering copper hydroxide and sulfuric acid used in the production process a method already established in the field of industrial production of copper ammonia rayon may be used.
  • the above-mentioned silk fiber mouth and cellulose are mixed at an appropriate ratio (preferably 0.1: 1 to 3: 1, more preferably 0.5: 1 to 2: 1, for example, 1: 1). Mix) ratio.
  • Cu (OH) 2 copper hydroxide
  • a 10% aqueous ammonia solution is added and mixed.
  • the amount of Cu (OH) 2 (copper hydroxide) used can be adjusted as appropriate, but is preferably 1.67 g or less, preferably 1 g or less (eg, about 0.4 g) per g of fibroin.
  • the amount is 0.1 g to 2 g, preferably 0.5 g to 1 g (for example, about 0.84 g) per cellulose lg.
  • the amount of the 10% ammonia aqueous solution to be used can be appropriately adjusted, but is preferably 10 to 50 ml, more preferably 15 to 30 ml, for example, about 24 ml per lg of cellulose.
  • a viscous solution can be obtained by dissolving the mixture obtained as described above in a sealed bag at 5 ° C.
  • Spinning (spinning) can be performed by a known method using the viscous solution obtained as described above.
  • an undiluted spinning solution is discharged from a spinneret of 0.1 to 2 mm at a discharge linear velocity of 0.1 to 200 m / min into a coagulation bath at 0 to 20% by weight of sulfuric acid and a temperature of 10 to 60 ° C
  • Sulfuric acid can be spun at a spinning speed of 50 to 1500 m / min through a regeneration bath at 0.1 to 20% by weight at a temperature of 0 to 60 ° C.
  • the spinning device a conventionally known device can be used.
  • Machine, drum type continuous spinning machine, net process type continuous spinning machine, industrial type continuous spinning machine, Oscar cophone type continuous spinning machine, Kurdish type continuous spinning machine and the like can be used.
  • For scouring, washing, and drying after spinning conventionally known devices and conditions can be applied as they are.
  • the fiber-in-cellulose composite material prepared in this manner was analyzed by a differential thermal analysis method, an X-ray diffraction method, and an infrared absorption spectrum method in the form of a fibrous film. It became clear that new structures were formed at the molecular level, rather than merely mixing (Fig. 1). In particular, X-ray diffraction showed that the fiber molecules had good orientation. In other words, it was clarified that “molecular composite polymers” such as “molecular composite fibers” and “molecular composite films” were formed.
  • bound at the molecular level means that silk fiproin protein and cellulose are simultaneously present in a molecular chain composed of a polymer.
  • the tensile strength, elongation, Young's modulus, dynamic viscoelasticity, etc. of this molecular composite fiber are both characteristics of silk fiber mouth and natural characteristics of cotton and cellulose-based regenerated fiber (rayon etc.). It was a composite that had useful properties.
  • Example 1 will explain the method for producing a molecular composite polymer material of the present invention in detail, taking production of a molecular composite fiber as an example.
  • the materials, reagents, ratios, operations, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention, and the scope of the present invention is not limited to the specific examples described below. .
  • Example 2 will explain the method for producing a molecular composite polymer material of the present invention in detail, taking production of a molecular composite fiber as an example.
  • the materials, reagents, ratios, operations, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention, and the scope of the present invention is not limited to the specific examples described below. .
  • the silk glands of the silkworm larva were removed by dissection, the skin tissue was peeled off, and the covering fission layer, which had been washed away with water, was dispersed in a small amount of water at a refrigeration temperature.
  • the solution was spread thinly on a styrene plate, and the film obtained by air-drying was used as a raw material for silkworm silk fibroin.
  • a refined cocoon can be used without any problem.
  • the silk glands of ⁇ ⁇ and ⁇ ⁇ have no thick and simple part like the silkworm, and it is impossible to directly obtain a fib-mouth solution therefrom. And it is sufficient.
  • / JP00 / 08043 Commercially available absorbent cotton was used as cellulose.
  • various cellulosic raw materials are used, so these cell-mouth raw materials can be used in the same manner.
  • the fibrous mouth prepared above and cellulose were mixed at a ratio of 1: 1. Then, add and mix powder (11 (OH) 2 (copper hydroxide)) of less than 1.67 g, preferably 0.4 g, and 0.84 per g of cellulose as per 5 g of fiber mouth. Then add 24 ml of 10% aqueous ammonia solution (commercially-concentrated aqueous ammonia diluted to 1/3) per 1 g of cellulose, mix well, and dissolve in a seal bag at 5.C. Gave a viscous solution.
  • aqueous ammonia solution commercially-concentrated aqueous ammonia diluted to 1/3
  • the viscosity of the prepared solution was dominated by the amount of loose cellulose and was not significantly affected by the amount of coexisting fibrin.
  • This viscous solution was extruded from a nozzle with a diameter of 1 mm into water filled in a cylindrical container (14) using the apparatus shown in Fig. 3.
  • the non-oriented solution becomes thinner while growing in water under its own weight, and gradually acquires the orientation from a molecular viewpoint.
  • the elongating gel yarn was suspended until it reached the bottom of a cylindrical container having a height of about 55 cm so that the elongation and orientation proceeded as much as possible.
  • the gel yarn extracted from the water is then led to the next treatment tank (dilute sulfuric acid tank) (16), and then decoppered by passing it through a 5% dilute sulfuric acid bath with a stroke length of about 30 cm.
  • test thread described above was also manufactured by pulling the viscous solution extruded into water directly in the winding direction without suspending it, and replacing it with the method of orientation and fiberization.
  • the final winding speed was about 2 m / min. With this method, continuous continuous fibers could be obtained. When the tension conditions were changed in this method, the fibers could be reduced to about 4 d.
  • the mixing ratio of fiproin and cellulose is set to 1: 1. However, even if the mixing ratio of fiproin and cellulose is changed in the range of about 0.1: 1 to 3: 1, the same effect as described above is obtained. By using this method, a molecular composite polymer material having sufficiently excellent characteristics can be obtained.
  • FIGS. 1 and 2 show an X-ray photograph of the molecular composite fiber obtained in this example and a comparison of the IR spectrum with cocoon thread and regenerated cellulose.
  • the mechanical properties of the molecular composite fiber obtained in this example were as shown in Table 1. In the case of bicomponent fibers, the physical properties were sufficient for a garment material. Furthermore, the dyeability with the acid dye, which is not observed in the regenerated cellulose fibers, was good, and the dyeability of silk was maintained.
  • Table 1 Comparison of mechanical properties of fiber mouth-in-cellulose molecular composite fiber (1: 1) with fiber mouth and cellulose Fineness Tensile strength Elongation Static elastic modulus Dynamic elasticity Tan (5 (d)) (g / d) (3 ⁇ 4) (Gpa) (Gpa) Fibroin 1.0 4.8 20.0 14.10 19.4 0.013 Cellulose 43.6 0.55 5. 1 0.92 3.6 0.21 Molecular composite fiber 12.3 1.91 7.5 2.24 14.6 0.14 JP / 3
  • a composite polymer material, a composite fiber, a composite film, and the like can be created, in which the material components of different fibers are composited at the molecular level and both properties coexist, and also have new properties. That is, by mixing a certain amount of cellulose into the silk fiber mouth under conditions in a copper ammonia solution, the two are bound at the molecular level, resulting in a composite polymer material having spinnability and film-forming properties.
  • the molecular composite fiber of the present invention is characterized by its physical properties, that is, it is not too strong, does not damage tissue, and is a natural material whose constituent components have no antigenicity. Since it is expected to have degradability, it can be applied as a suture for surgical operation. Further, it can be used as a film material having various functions. That is, the present invention provides a novel molecular composite polymer material that can be expected not only as a clothing material but also as a functional material in various fields as described above.
  • the mechanism of fiberization of the composite material of the present invention is exactly the same as the mechanism of fiberizing copper ammonia solution-dissolved cellulose. Therefore, a large amount of water is flowed through a long, funnel-shaped channel that is held vertically, and the solution is stretched by the force of the water flow.
  • the method of converting the fibers into fibers can be applied as it is.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Biochemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Artificial Filaments (AREA)

Abstract

Cette invention se rapporte à un matériau polymère ayant des propriétés utiles que l'on a obtenu en tirant profit des protéines d'un matériau à base de fibroïne de soie associées aux propriétés d'un matériau cellulosique naturel; et à des produits polymères fabriqués à partir de ce matériau, tel que des fibres et des films. Ce matériau polymère moléculairement composite comprend une protéine de fibroïne de soie et de la cellulose qui sont liées l'une à l'autre à un niveau moléculaire.
PCT/JP2000/008043 1999-11-15 2000-11-15 Materiau polymere moleculairement composite en fibroine/cellulose et procede de production de ce materiau WO2001036531A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU14122/01A AU1412201A (en) 1999-11-15 2000-11-15 Molecularly composite polymeric material of fibroin/cellulose and process for producing the same

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP11/361468 1999-11-15
JP36146899 1999-11-15

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WO2001036531A1 true WO2001036531A1 (fr) 2001-05-25

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Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009280715A (ja) * 2008-05-23 2009-12-03 Gunma Univ 非結晶性フィブロインフィルム及びその製造方法
EP1558444A4 (fr) * 2002-06-24 2010-10-13 Univ Tufts Biomateriaux a base de soie et leurs methodes d'utilisation
US8501172B2 (en) 2008-09-26 2013-08-06 Trustees Of Tufts College pH-induced silk gels and uses thereof
US8614293B2 (en) 2003-04-10 2013-12-24 Trustees Of Tufts College Concentrated aqueous silk fibroin solution and use thereof
WO2014002605A1 (fr) * 2012-06-28 2014-01-03 スパイバー株式会社 Fibre de protéine teintée dans la masse et procédé pour produire celle-ci
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
US9040073B2 (en) 2008-05-15 2015-05-26 Trustees Of Tufts College Silk polymer-based adenosine release: therapeutic potential for epilepsy
US9074302B2 (en) 2009-09-28 2015-07-07 Trustees Of Tufts College Methods of making drawn silk fibers
US9102916B2 (en) 2007-02-27 2015-08-11 Trustees Of Tufts College Tissue-engineered silk organs
US9132197B2 (en) 2003-01-07 2015-09-15 Massachusetts Institute Of Technology Silk fibroin materials and use thereof
US9504575B2 (en) 2008-02-07 2016-11-29 Trustees Of Tufts College 3-dimensional silk hydroxyapatite compositions
US9539362B2 (en) 2003-06-06 2017-01-10 Trustees Of Tufts College Method for forming inorganic coatings
US9566365B2 (en) 2010-09-01 2017-02-14 Trustees Of Tufts College Silk fibroin and polyethylene glycol-based biomaterials
US9603971B2 (en) 2010-03-05 2017-03-28 Trustees Of Tufts College Silk-based ionomeric compositions
US9617315B2 (en) 2011-06-01 2017-04-11 Spiber Inc. Artificial polypeptide fiber and method for producing the same
US10335519B2 (en) 2011-04-20 2019-07-02 Trustees Of Tufts College Dynamic silk coatings for implantable devices
US10493179B2 (en) 2008-10-09 2019-12-03 Trustees Of Tufts College Modified silk films containing glycerol
US10912862B2 (en) 2012-02-06 2021-02-09 Children's Medical Center Corporation Multi-layer biomaterial for tissue regeneration and wound healing
US10933173B2 (en) 2010-10-19 2021-03-02 Trustees Of Tufts College Silk fibroin-based microneedles and methods of making the same
US10975206B2 (en) 2015-04-09 2021-04-13 Spiber Inc. Polar solvent solution and production method thereof
CN114958009A (zh) * 2022-05-24 2022-08-30 浙江理工大学 一种蚕丝基高强度离子凝胶柔性传感材料的制备方法
US11668024B2 (en) 2015-04-09 2023-06-06 Spiber, Inc. Polar solvent solution and production method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5496126A (en) * 1978-01-12 1979-07-30 Kanebo Ltd Preparation of fibroin dope
JPS6264841A (ja) * 1985-04-23 1987-03-23 Asahi Chem Ind Co Ltd 成形に適するド−プおよびその製造方法
JPH03131636A (ja) * 1989-10-18 1991-06-05 Agency Of Ind Science & Technol 新規な複合材料フィルム及びその製造方法
JPH03185183A (ja) * 1989-09-25 1991-08-13 Kanebo Ltd 絹フィブロイン―合成重合体加工布帛及びその製造方法
JPH04100975A (ja) * 1990-08-10 1992-04-02 Kanebo Ltd シルク風合を有する布帛及びその製造方法
JP2000027027A (ja) * 1998-07-02 2000-01-25 Omikenshi Co Ltd 高分子複合体とその製造法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5496126A (en) * 1978-01-12 1979-07-30 Kanebo Ltd Preparation of fibroin dope
JPS6264841A (ja) * 1985-04-23 1987-03-23 Asahi Chem Ind Co Ltd 成形に適するド−プおよびその製造方法
JPH03185183A (ja) * 1989-09-25 1991-08-13 Kanebo Ltd 絹フィブロイン―合成重合体加工布帛及びその製造方法
JPH03131636A (ja) * 1989-10-18 1991-06-05 Agency Of Ind Science & Technol 新規な複合材料フィルム及びその製造方法
JPH04100975A (ja) * 1990-08-10 1992-04-02 Kanebo Ltd シルク風合を有する布帛及びその製造方法
JP2000027027A (ja) * 1998-07-02 2000-01-25 Omikenshi Co Ltd 高分子複合体とその製造法

Cited By (42)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1558444A4 (fr) * 2002-06-24 2010-10-13 Univ Tufts Biomateriaux a base de soie et leurs methodes d'utilisation
US8071722B2 (en) 2002-06-24 2011-12-06 Trustees Of Tufts College Silk biomaterials and methods of use thereof
US11110148B2 (en) 2003-01-07 2021-09-07 Trustees Of Tufts College Silk fibroin materials and use thereof
US9993527B2 (en) 2003-01-07 2018-06-12 Trustees Of Tufts College Silk fibroin materials and use thereof
US9132197B2 (en) 2003-01-07 2015-09-15 Massachusetts Institute Of Technology Silk fibroin materials and use thereof
US10314938B2 (en) 2003-04-10 2019-06-11 Trustees Of Tufts College Concentrated aqueous silk fibroin solution and use thereof
US8614293B2 (en) 2003-04-10 2013-12-24 Trustees Of Tufts College Concentrated aqueous silk fibroin solution and use thereof
US11129921B2 (en) 2003-04-10 2021-09-28 Trustees Of Tufts College Concentrated aqueous silk fibroin solution and use thereof
US9623147B2 (en) 2003-04-10 2017-04-18 Trustees Of Tufts College Concentrated aqueous silk fibroin solution and use thereof
US9084840B2 (en) 2003-04-10 2015-07-21 Trustees Of Tufts College Concentrated aqueous silk fibroin solution and use thereof
US8742069B2 (en) 2003-04-10 2014-06-03 Trustees Of Tufts College Concentrated aqueous silk fibroin solution and use thereof
US9539362B2 (en) 2003-06-06 2017-01-10 Trustees Of Tufts College Method for forming inorganic coatings
US9102916B2 (en) 2007-02-27 2015-08-11 Trustees Of Tufts College Tissue-engineered silk organs
US10478524B2 (en) 2007-02-27 2019-11-19 Trustees Of Tufts College Tissue-engineered silk organs
US9655993B2 (en) 2007-02-27 2017-05-23 Trustees Of Tufts College Tissue-engineered silk organs
US8722067B2 (en) 2007-05-29 2014-05-13 Trustees Of Tufts College Method for silk fibroin gelation using sonication
US9504575B2 (en) 2008-02-07 2016-11-29 Trustees Of Tufts College 3-dimensional silk hydroxyapatite compositions
US9040073B2 (en) 2008-05-15 2015-05-26 Trustees Of Tufts College Silk polymer-based adenosine release: therapeutic potential for epilepsy
JP2009280715A (ja) * 2008-05-23 2009-12-03 Gunma Univ 非結晶性フィブロインフィルム及びその製造方法
US8501172B2 (en) 2008-09-26 2013-08-06 Trustees Of Tufts College pH-induced silk gels and uses thereof
US9694082B2 (en) 2008-09-26 2017-07-04 Trustees Of Tufts College pH induced silk gels and uses thereof
US10493179B2 (en) 2008-10-09 2019-12-03 Trustees Of Tufts College Modified silk films containing glycerol
US8728498B2 (en) 2009-07-14 2014-05-20 Trustees Of Tufts College Electrospun silk material systems for wound healing
US9074302B2 (en) 2009-09-28 2015-07-07 Trustees Of Tufts College Methods of making drawn silk fibers
US9381164B2 (en) 2009-09-29 2016-07-05 Trustees Of Tufts College Silk nanospheres and microspheres and methods of making same
US8715740B2 (en) 2009-09-29 2014-05-06 Trustees Of Tufts College Silk nanospheres and microspheres and methods of making same
US9603971B2 (en) 2010-03-05 2017-03-28 Trustees Of Tufts College Silk-based ionomeric compositions
US9566365B2 (en) 2010-09-01 2017-02-14 Trustees Of Tufts College Silk fibroin and polyethylene glycol-based biomaterials
US12194200B2 (en) 2010-10-19 2025-01-14 Trustees Of Tufts College Silk fibroin-based microneedles and methods of making the same
US10933173B2 (en) 2010-10-19 2021-03-02 Trustees Of Tufts College Silk fibroin-based microneedles and methods of making the same
US11266339B2 (en) 2011-04-20 2022-03-08 Trustees Of Tufts College Dynamic silk coatings for implantable devices
US10335519B2 (en) 2011-04-20 2019-07-02 Trustees Of Tufts College Dynamic silk coatings for implantable devices
US9617315B2 (en) 2011-06-01 2017-04-11 Spiber Inc. Artificial polypeptide fiber and method for producing the same
US10912862B2 (en) 2012-02-06 2021-02-09 Children's Medical Center Corporation Multi-layer biomaterial for tissue regeneration and wound healing
JP2014029054A (ja) * 2012-06-28 2014-02-13 Spiber Inc 原着タンパク質繊維及びその製造方法
JP5407009B1 (ja) * 2012-06-28 2014-02-05 スパイバー株式会社 原着タンパク質繊維の製造方法
WO2014002605A1 (fr) * 2012-06-28 2014-01-03 スパイバー株式会社 Fibre de protéine teintée dans la masse et procédé pour produire celle-ci
US9689089B2 (en) 2012-06-28 2017-06-27 Spiber Inc. Solution-dyed protein fiber and method for producing same
US10975206B2 (en) 2015-04-09 2021-04-13 Spiber Inc. Polar solvent solution and production method thereof
US11668024B2 (en) 2015-04-09 2023-06-06 Spiber, Inc. Polar solvent solution and production method thereof
CN114958009A (zh) * 2022-05-24 2022-08-30 浙江理工大学 一种蚕丝基高强度离子凝胶柔性传感材料的制备方法
CN114958009B (zh) * 2022-05-24 2024-01-16 浙江理工大学 一种蚕丝基高强度离子凝胶柔性传感材料的制备方法

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