CN1379055A - Process for preparing Chemically cross-linked silk extract gel or spongy silk extract gel - Google Patents
Process for preparing Chemically cross-linked silk extract gel or spongy silk extract gel Download PDFInfo
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- CN1379055A CN1379055A CN 01112285 CN01112285A CN1379055A CN 1379055 A CN1379055 A CN 1379055A CN 01112285 CN01112285 CN 01112285 CN 01112285 A CN01112285 A CN 01112285A CN 1379055 A CN1379055 A CN 1379055A
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Abstract
A silk extract gel or spongy silk extract gel with chemical cross-linking structure is prepared from cocoon shell through refining in aqueous solution of Na2CO3, washing with distilled water, and drying to obtain silk extract fibres, dissolving in aqueous solution of CaCl2, dialyzing with cellulose dialysis membrane in flowing water, removing CaCl2, concentrating, regualting pH value, mixing with epoxy compound as cross-linking agent, laying aside for solidification to obtain the gel, immersing in distilled water, and removing unreacted substance. It has high compressive strength (greater than 100 g/sq.m) and high compression deforming rate (greater than or equal to 60%).
Description
The present invention relates to a kind of silk extract gel of chemically crosslinked structure, spongy silk extract gel material preparation method.
Well-known silk is natural fiber beautiful, excellent property, mainly is made into silk over the past thousands of years, beautifies people's life.Silk thread also is used as operating sutures since ancient times in fact, has shown the characteristics of silk to human safety, affinity for a long time, has shown that silk is used for the possibility in biomaterial for medical purpose field.Along with progress of modern technology, by from the further research to silk of the angle of biomaterial, clear now, the main component of silk--fibroin is made up of 18 seed amino acids, and to the human body nontoxicity, antigenicity is faint.The silk fibroin material that utilizes fibroin to make has good tissue affinity, and good water vapour permeability, oxygen-permeable are arranged, and can also decompose, and is a kind of to the human body safe material, green material.Aspect the biomaterials such as artificial skin, disposable Contact Lenses, slow releasing carrier of medication, cell cultures bed good application prospects is being arranged all.The material that is suitable for doing these biomaterials that directly contact with tissue at present is very few, and fibroin is that rare having utilizes one of material that is worth.Exploitation fibroin biomaterial is widened silk in the high-tech product Application for Field, promotes the development of silk industry to obtain common recognition, and national 863 Program, state natural sciences fund have all dropped into reasearch funds to this direction.
Realize the utilization of fibroin aspect biomaterial, it is crucial obtaining structural form, mechanical property, physicochemical property excellent material.Gel is the physical form between solid and liquid, it is polymer substance lyosorption in solvent, swelling, so crosslinked or tangle to form that three dimensional network order structure forms, be defined in undissolved polymer and swelling body thereof in the solvent with three-dimensional mesh structure.In recent years, very fast at the research and the application development of aspects such as food, medicine, building, biotechnology, sporting goods.Because gel has microvoid structure, lower-molecular substances such as medicine are passed through, the oxygen perviousness is better than general solid material, can make the same with human body soft tissue soft again, water ratio is very suitable for making medical materials such as artificial skin, contact lens, slow releasing carrier of medication near human body soft tissue.Therefore, be necessary to obtain the making method of intensity, silk extract gel material that snappiness is good.
The Tian Yiyu (1995 Japanese Patent) that chisels of Japan had once studied the making method of silk extract gel material with dissolving method that the fibroin aqueous solution that silkworm silk glands and fibroin fiber obtained freezes repeatedly-thaw, but the material that obtains still has deficiency in flexibility, and form is near porous material.
The purpose of this invention is to provide a kind of silk extract gel of chemically crosslinked structure, spongy silk extract gel material preparation method.
In order to achieve the above object, the present invention takes following measures:
The silk extract gel of chemically crosslinked structure, spongy silk extract gel material preparation method is that silk cocoon is peelled off husks, remove pupa, obtain the cocoon shell, with the concise cocoon shell of 4～6g/L Na2CO3 aqueous solution 1～3 time, remove silk gum, each 20～40 minutes kinds, 95～100 ℃ of concise temperature; bath raio 1: 90～110, concise back is with the abundant cleaning, drying of distilled water; obtain fibroin fiber; with 900～1100g/L CaCl2 aqueous solution dissolving fibroin fiber, about 97～100 ℃ of solvent temperature, bath raio 1: 20～30; solution that will obtain after will dissolve pours in the Mierocrystalline cellulose dialysis membrane; dialysed in flowing water 2～4, and removed CaCl2, concentrates the solution after the dialysis; obtain the fibroin protein aqueous solution of 20～150g/L concentration; pH to pH8.5～10 of the adjustment fibroin protein aqueous solution, sneak into 0.5～10% epoxy compounds linking agent, leave standstill under 10～90 ℃ of temperature; treat that solution solidifies becomes gel; gel is soaked in distilled water, the removal unreacted reactant gets final product.
Perhaps obtain the fibroin aqueous solution in order to last method, adjust pH to pH7～8.5 of the fibroin protein aqueous solution, sneak into 0.5～10% epoxy compounds linking agent, under-150～-2 ℃ of temperature, leave standstill, natural temperature thaws after treating freezing solution, spongy silk extract gel is soaked in distilled water, remove unreacted reactant, get final product.
Perhaps obtain the fibroin aqueous solution in order to last method, adjust pH to pH7～8.5 of the fibroin protein aqueous solution, sneak into 0.5～10% epoxy compounds linking agent, under-150～-10 ℃ of temperature, stir, natural temperature thaws after treating freezing solution, spongy silk extract gel is soaked in distilled water, remove unreacted reactant, get final product.
The present invention is with having obtained intensity and the good silk fibroin material of snappiness with chemical cross-linking agent and the fibroin reactant aqueous solution that protein carries out chemically crosslinked.The silk extract gel material compressive strength＞100g/mm2 that obtains, compression deformation rate＞60% can stand tens bendings and not rupture.The gained silk extract gel seldom has fibroin protein stripping, good stability in neutral solution.Has application prospect aspect disposable Contact Lenses, artificial skin, cell cultures bed, enzyme immobilization material, gel-filtration, the packing material.On the basis of snappiness silk extract gel, in conjunction with the method for freezing, obtained having fine flexible spongy silk extract gel again.The size in the control apertures such as concentration of adjustment fibroin and linking agent can be passed through about 10-300 μ m in the aperture of spongy silk extract gel.Tensile strength reaches 11g/mm2, and degree of stretching reaches about 79%, and compressive recovery rate can reach 100%, and good elasticity and snappiness are arranged.Water-intake rate is up to 1500%.The cell culture experiments in vitro result shows that also it has excellent biological compatibility.Has application prospect aspect artificial skin, three-dimensional cell cultures bed, enzyme immobilization material, gel-filtration, the packing material.
Below in conjunction with embodiment the present invention is elaborated.
Embodiment 1
Silk cocoon is peelled off husks, remove pupa, obtain the cocoon shell.Use 5g/L Na
2CO
3The concise cocoon shell of the aqueous solution 2 times is removed silk gum, each 30 minutes kinds, 98 ℃ of concise temperature, bath raio 1: 100.Concise back obtains fibroin fiber with the abundant cleaning, drying of distilled water.Use 1000g/L CaCl
2Aqueous solution dissolving fibroin fiber, about 98 ℃ of solvent temperature, bath raio 1: 25.The solution that obtains after the dissolving is poured in the Mierocrystalline cellulose dialysis membrane, and dialysis is 3 in flowing water, removes CaCl
2Concentrate the solution after dialysing, obtain the fibroin protein aqueous solution of 20～150g/L concentration.Adjust pH to pH8.5～10 of the fibroin protein aqueous solution, sneak into 0.5～10% epoxy compounds linking agent, under 10～90 ℃ of temperature, leave standstill, treat that solution solidifies becomes gel.Gel is soaked in distilled water, remove unreacted reactant, obtain intensity, flexibility, various silk extract gel materials that decomposability is different.
Embodiment 2
Obtain the fibroin aqueous solution with embodiment 1 with quadrat method, adjust pH to pH7～8.5 of the fibroin protein aqueous solution, sneak into 0.5～10% epoxy compounds linking agent, under-150～-2 ℃ of temperature, leave standstill, treat freezing solution after natural temperature thaw.Spongy silk extract gel is soaked in distilled water, remove unreacted reactant, obtain intensity, elasticity, flexibility, decomposability, aperture, the different various spongy silk extract gel material of water-intake rate.
Embodiment 3
Obtain the fibroin aqueous solution with embodiment 1 with quadrat method, adjust pH to pH7～8.5 of the fibroin protein aqueous solution, sneak into 0.5～10% epoxy compounds linking agent, under-150～-10 ℃ of temperature, stir, treat freezing solution after natural temperature thaw.Spongy silk extract gel is soaked in distilled water, remove unreacted reactant, obtain intensity, elasticity, flexibility, decomposability, aperture, the different various spongy silk extract gel material of water-intake rate.
The epoxy compounds linking agent is a class linking agent, and what the present invention was suitable for is that the agent of soluble epoxide compound crosslink is: polyethyleneglycol diglycidylether, polypropylene glycol diglycidyl ether, glycerol polyglycidylether.
Claims (3)
1. the silk extract gel material preparation method of a chemically crosslinked structure, it is characterized in that silk cocoon is peelled off husks, remove pupa, obtain the cocoon shell, with the concise cocoon shell of 4～6g/L Na2CO3 aqueous solution 1～3 time, remove silk gum, each 20～40 minutes kinds, 95～100 ℃ of concise temperature, bath raio 1: 90～110, concise back is fully clean with distilled water, drying obtains fibroin fiber, with 900～1100g/L CaCl2 aqueous solution dissolving fibroin fiber, 97～100 ℃ of solvent temperatures; bath raio 1: 20～30 pour into the solution that obtains after the dissolving in the Mierocrystalline cellulose dialysis membrane, dialyse in flowing water 2～4; remove CaCl2; concentrate the solution after the dialysis, obtain the fibroin protein aqueous solution of 20～150g/L concentration, adjust pH to pH8.5～10 of the fibroin protein aqueous solution; sneak into 0.5～10% epoxy compounds linking agent; leave standstill under 10～90 ℃ of temperature, treat that solution solidifies becomes gel, soaks gel in distilled water; remove unreacted reactant, get final product.
2. the spongy silk extract gel material preparation method of a chemically crosslinked structure, it is characterized in that silk cocoon is peelled off husks, remove pupa, obtain the cocoon shell, with the concise cocoon shell of 4～6g/L Na2CO3 aqueous solution 1～3 time, remove silk gum, each 20～40 minutes kinds, 95～100 ℃ of concise temperature, bath raio 1: 90～110, concise back is fully clean with distilled water, drying obtains fibroin fiber, with 900～1100g/L CaCl2 aqueous solution dissolving fibroin fiber, about 97～100 ℃ of solvent temperature; bath raio 1: 20～30 pours into the solution that obtains after the dissolving in the Mierocrystalline cellulose dialysis membrane, dialyses in flowing water 2～4; remove CaCl2; concentrate the solution after the dialysis, obtains the fibroin protein aqueous solution of 20～150g/L concentration, adjusts pH to pH7～8.5 of the fibroin protein aqueous solution; sneak into 0.5～10% epoxy compounds linking agent; leave standstill under-150～-2 ℃ of temperature, treat freezing solution after natural temperature thaw, spongy silk extract gel is soaked in distilled water; remove unreacted reactant, get final product.
3. the spongy silk extract gel material preparation method of a chemically crosslinked structure, it is characterized in that silk cocoon is peelled off husks, remove pupa, obtain the cocoon shell, with the concise cocoon shell of 4～6g/L Na2CO3 aqueous solution 1～3 time, remove silk gum, each 20～40 minutes kinds, 95～100 ℃ of concise temperature, bath raio 1: 90～110, concise back is fully clean with distilled water, drying obtains fibroin fiber, with 900～1100g/L CaCl2 aqueous solution dissolving fibroin fiber, about 97～100 ℃ of solvent temperature; bath raio 1: 20～30 pours into the solution that obtains after the dissolving in the Mierocrystalline cellulose dialysis membrane, dialyses in flowing water 2～4; remove CaCl2; concentrate the solution after the dialysis, obtains the fibroin protein aqueous solution of 20～150g/L concentration, adjusts pH to pH7～8.5 of the fibroin protein aqueous solution; sneak into 0.5～10% epoxy compounds linking agent; stir under-150～-10 ℃ of temperature, treat freezing solution after natural temperature thaw, spongy silk extract gel is soaked in distilled water; remove unreacted reactant, get final product.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1985791B (en) * | 2006-12-27 | 2010-05-19 | 浙江大学 | Preparing process of skin care silk protein gel cream |
| CN101397756B (en) * | 2008-11-03 | 2010-09-08 | 浙江理工大学 | Preparation and application of fibroin strengthening protecting agent |
| CN101531745B (en) * | 2009-04-13 | 2011-05-25 | 浙江大学 | Preparation of plural gel water absorbent material composed of silk fibroin/acrylic acid/acrylamide |
| CN104203292A (en) * | 2011-11-09 | 2014-12-10 | 塔夫茨大学信托人 | Injectable silk fibroin foams and uses thereof |
| CN107118359A (en) * | 2017-05-31 | 2017-09-01 | 南通纺织丝绸产业技术研究院 | Photocuring hydrogel and preparation method thereof |
| CN108272650A (en) * | 2018-04-04 | 2018-07-13 | 杭州万事利丝绸文化股份有限公司 | A kind of preparation method of water-soluble fibroin silk gum composite beauty treatment product |
| CN109232919A (en) * | 2018-09-11 | 2019-01-18 | 淮阴工学院 | A kind of preparation method of the recessed native composite aerogel of fibroin- |
| CN115490903A (en) * | 2022-04-21 | 2022-12-20 | 重庆大学 | Multifunctional silk fibroin colorful contact lens and preparation method thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP4122948A4 (en) * | 2020-03-16 | 2024-05-01 | Spiber Inc. | Synthetic polymer and method for producing same, molding material, and molded body |
-
2001
- 2001-04-06 CN CNB011122854A patent/CN1158338C/en not_active Expired - Fee Related
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1985791B (en) * | 2006-12-27 | 2010-05-19 | 浙江大学 | Preparing process of skin care silk protein gel cream |
| CN101397756B (en) * | 2008-11-03 | 2010-09-08 | 浙江理工大学 | Preparation and application of fibroin strengthening protecting agent |
| CN101531745B (en) * | 2009-04-13 | 2011-05-25 | 浙江大学 | Preparation of plural gel water absorbent material composed of silk fibroin/acrylic acid/acrylamide |
| CN104203292A (en) * | 2011-11-09 | 2014-12-10 | 塔夫茨大学信托人 | Injectable silk fibroin foams and uses thereof |
| CN107118359A (en) * | 2017-05-31 | 2017-09-01 | 南通纺织丝绸产业技术研究院 | Photocuring hydrogel and preparation method thereof |
| CN108272650A (en) * | 2018-04-04 | 2018-07-13 | 杭州万事利丝绸文化股份有限公司 | A kind of preparation method of water-soluble fibroin silk gum composite beauty treatment product |
| CN108272650B (en) * | 2018-04-04 | 2021-04-06 | 杭州万事利丝绸文化股份有限公司 | Preparation method of water-soluble silk fibroin sericin composite beauty product |
| CN109232919A (en) * | 2018-09-11 | 2019-01-18 | 淮阴工学院 | A kind of preparation method of the recessed native composite aerogel of fibroin- |
| CN115490903A (en) * | 2022-04-21 | 2022-12-20 | 重庆大学 | Multifunctional silk fibroin colorful contact lens and preparation method thereof |
| CN115490903B (en) * | 2022-04-21 | 2023-07-21 | 重庆大学 | Multifunctional silk fibroin color contact lens and preparation method thereof |
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| CN1158338C (en) | 2004-07-21 |
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