CN102133425A - Tussah silk fibroin film and preparation method thereof - Google Patents
Tussah silk fibroin film and preparation method thereof Download PDFInfo
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- CN102133425A CN102133425A CN2011100590607A CN201110059060A CN102133425A CN 102133425 A CN102133425 A CN 102133425A CN 2011100590607 A CN2011100590607 A CN 2011100590607A CN 201110059060 A CN201110059060 A CN 201110059060A CN 102133425 A CN102133425 A CN 102133425A
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Abstract
The invention relates to technology of medical biological material with natural polymer, and discloses a tussah silk fibroin film and a preparation method thereof. Nontoxic dihydric alcohol is added into tussah silk solution so as to be taken as a cross-linking agent which is injected into a mold, and the tussah silk fibroin film is formed after the mixture drying. According to weight, the tussah silk fibroin film contains 40-90% of tussah silk fibroin; the protein leaching loss of the film in water with the temperature 37 DEG C for 24 hours is less than 3%, the tensile strength at break is greater than 20Mpa, and the tensile elongation at the break is greater than 20%. As an extra chemical cross-linking agent or chemical denaturant does not need to be added in the preparation process, the biocompatibility of the tussah silk fibroin can not be reduced, and can be kept good. The tussah silk fibroin difficult to dissolve can be used for covering materials for artificial cornea, endocranium, gullet, heart valve, blood vessels and wound surfaces, and can be used for temporal covering, and isolating tissues, and can be taken as medicine releasing materials and the like.
Description
Technical field
The present invention relates to a kind of natural polymer biomaterial for medical purpose technology, particularly a kind of tussah silk fibroin film and preparation method thereof, prepared material can be applicable to cornea,artificial, cerebral dura mater, esophagus, cardiac valve, blood vessel and wound surface cladding material etc.
Technical background
Antherea pernyi Guerin-Meneville is a kind of in the Bombyx mandarina Moore, is food with the toothed oak leaf.Tussah silk is to be the natural silk fiber that raw material reel silk from cocoons system forms with the tussah cocoon.China produces tussah cocoon 3～40,000 ton per year, accounts for more than 90% of world's tussah cocoon total output, and this is that the world is rare, the distinctive precious resources of China, but tussah silk is mainly as common textile raw material at present, and the economic worth that is embodied is very limited.During the protein of tussah silk peptide is formed based on glycine, alanine and serine, has excellent biological compatibility, itself and catabolite pair cell thereof and body are nontoxic, not can or less causing inflammation and immunological rejection, the RGD tripeptide sequence that contains in its protein molecule.The recognition site that the RGD sequence combines with extracellular ligand as the cell membrane integrin receptor, interaction between mediated cell and extracellular matrix and the cell, can promote that killing of support pair cell is attached, make cell be much better than the adhesive rate and the rate of increase on the Bombyxmori Linnaeus fibroin membrane, so the tussah silk fibroin material can be considered novel desirable biology and the medical material that is used for human body at the adhesive rate on the tussah silk peptide film and the rate of increase.
Tussah silk is a kind of fibrous material, and tussah silk fibroin is made film material, generally is to be prepared into the tussah silk fibroin aqueous solution after earlier tussah silk being come unstuck, and adopts diverse ways to prepare fibroin protein film again.Chinese invention patent (CN101445546) " preparation of tussore silk fibroin solution and method for concentration thereof " discloses a kind of preparation and method for concentration thereof of tussah silk fibroin solution.Chinese invention patent (CN100551449) " Antheraea pernyi silk fibrion biology medicine material and preparation method thereof " adopts electrospinning process, obtains the three-D non-woven network structure that the tussah silk fibroin fiber constitutes.At present, the chemical treatment reagent of tussah silk peptide film is mainly contained methanol, ethanol, but hard and crisp through the tussah silk peptide film after methanol or the Ethanol Treatment, mechanical property is relatively poor.In order to improve these performances, bibliographical information the has been arranged technical scheme that adopts Polyethylene Glycol Bisglycidyl Ether the tussah silk peptide film to be carried out chemical crosslinking as cross-linking agent, this method can significantly improve water-resistance and toughness ([J] China YouSe Acta Metallurgica Sinica of film, 2004,14 (6), 414-419), but its cross-linking agent that uses is epoxide, it remains in the fibroin membrane, with the biocompatibility of the prepared material of influence.
Summary of the invention
In order to overcome the deficiency that prior art exists, the purpose of this invention is to provide a kind of pliability and good biocompatibility, and be insoluble in tussah silk fibroin film of water and preparation method thereof.
To achieve the above object of the invention, the technical solution adopted in the present invention is: a kind of tussah silk fibroin film is provided, and by weight, it contains tussah silk fibroin matter 40～90%, and all the other are dihydroxylic alcohols; 24 hours albumen dissolve-loss ratio is less than 3% in 37 ℃ water for it, and tensile break strength is greater than 20Mpa, and tension fracture elongation rate is greater than 20%.
A kind of method for preparing above-mentioned tussah silk fibroin film, tussah silk obtain mass concentration after coming unstuck, dissolve, dialyse, concentrating be 1～30% tussah silk fibroin solution, carries out the processing of following steps again:
(1) adding mass ratio in tussah silk fibroin solution is 10～60% dihydroxylic alcohols, makes mixed solution;
(2) above-mentioned mixed solution is placed the mould film forming, obtain a kind of tussah silk fibroin film after the drying.
Dihydroxylic alcohols of the present invention is an ethylene glycol, 1, ammediol, 2, ammediol, 1,4-butanediol, 1,2-butanediol, 1,3 butylene glycol, 2, a kind of in 3-butanediol, diglycol and the triethylene-glycol, or their combination in any.
The structure of tussah silk peptide is different with silkworm, and its silk fibroin protein solution easily precipitates, and the film forming difficulty adopts the made membrane material of prior art, and its flexibility is poor, and easily dissolving in water, can't satisfy the specification requirement of biomaterial for medical purpose.The principle of foundation of the present invention is: contain two hydroxyls in the structure of dihydroxylic alcohols, join in the tussah silk fibroin solution after, can be crosslinked with the intermolecular formation hydrogen bond of tussah silk fibroin, thus reach the effect of the hot water dissolve-loss ratio that reduces fibroin albumen; Simultaneously, dihydroxylic alcohols has also played the effect of plasticizer, makes the tussah silk fibroin film of formation keep certain pliability.
Compared with prior art, it is cross-linking agent that the present invention has adopted avirulent dihydroxylic alcohols, do not need to add in addition chemical cross-linking agent or use chemical denaturant, therefore, the tussah silk fibroin film that obtains not only is insoluble in water, flexibility is good, also have excellent biological compatibility, be suitable for cell growth, and can be in a period of time complete biodegradable, final catabolite is avirulent aminoacid, is suitable for as bio-medical material.
The specific embodiment
Below in conjunction with embodiment the present invention is further described.
Embodiment one
The tussah silk fibroin film preparation step that is insoluble in water that present embodiment provides is as follows:
1,0.1 kilogram of Antherea pernyi Guerin-Meneville raw silk being put into 3 mass per liter concentration is 0.15% aqueous sodium carbonate, handles 2 hours in 98～100 ℃, makes stripping, obtains pure silk element (being tussah silk fibroin) behind the thorough washing.Pure silk element after will drying, the lithium rhodanate solution with 1 liter of concentration is 15 mol obtains the tussah silk fibroin mixed solution 60 ± 5 ℃ of following heating for dissolving.
2, be the dialysis material with cellulose membrane, the tussah silk fibroin mixed solution of gained is dialysed with deionized water, remove impurity such as lithium rhodanate, obtain mass concentration and be 10% tussah silk fibroin solution.
3, in above-mentioned tussah silk fibroin solution, add ethylene glycol, press mass ratio, the addition of ethylene glycol be in the solution tussah silk fibroin solid content 40%.
4, above-mentioned tussah silk fibroin solution is injected the mould film forming, air blast dries up under 60 ℃ temperature conditions.
5, the environment of above-mentioned dried fibroin/ethylene glycol blend film being put into relative humidity 60% was handled 10 hours, obtained being insoluble in the transparent fibroin protein film of water.
The main performance index of tussah silk fibroin film of pressing present embodiment technical scheme preparation is referring to table one.
Table one
Embodiment two
It is 0.5% neutral soap solution that 0.5 kilogram of Antherea pernyi Guerin-Meneville raw silk is put into 25 mass per liter concentration, handles in 98～100 ℃ and comes unstuck in 2 hours, obtains pure silk element (being tussah silk fibroin) behind the thorough washing.Pure silk element after will drying with the lithium rhodanate aqueous solution of 2 liter of 16 mol, becomes the tussah silk fibroin mixed solution 60 ± 2 ℃ of stirring and dissolving.
With cellulose membrane is the dialysis material, and the tussah silk fibroin mixed solution of gained is dialysed with deionized water, removes impurity such as lithium rhodanate, obtains mass concentration and be 20% tussah silk fibroin solution.
In pure tussah silk fibroin solution, add 1, ammediol, 1, the addition of ammediol (pressing mass ratio) is 45% of solid content in the tussah silk fibroin solution.
Silk fibroin protein solution is injected mould make membranaceously, air blast at room temperature dries up.
Above-mentioned dried fibroin/propylene glycol blend film is put into the environment of relative humidity 50% and handled 20 hours, obtain being insoluble in the tussah silk fibroin film of water.
The main performance index of tussah silk fibroin film of pressing present embodiment technical scheme preparation is referring to table two.
Table two
Embodiment three
It is 0.05% aqueous sodium carbonate that 200 gram Antherea pernyi Guerin-Meneville raw silks are put into 8 mass per liter concentration, adds mass concentration and be 0.01% sodium lauryl sulphate, handles in 98～100 ℃ and comes unstuck in 0.5 hour, and reprocessing 3 times obtains the pure silk element behind the thorough washing.The plain lithium rhodanate aqueous solution with 1 liter of 14 mol of pure silk after will drying obtains the tussah silk fibroin mixed solution 65 ± 5 ℃ of following heating for dissolving.
With cellulose membrane is the dialysis material, and the tussah silk fibroin mixed solution of gained with deionized water dialysis 3 days, is obtained mass concentration and be 16% tussah silk fibroin solution.
In pure tussah silk fibroin solution, add 1, the 2-butanediol, the addition of 1 ,-2 butanediols (pressing mass ratio) is 50% of solid content in the tussah silk fibroin solution.
Silk fibroin protein solution is injected the mould film forming, dry up in the following air blast of 80 ℃ temperature.
Above-mentioned dried fibroin/butanediol blend film is put into the environment of relative humidity 70% and handled 30 hours, obtain being insoluble in the tussah silk fibroin film of water.
The main performance index of tussah silk fibroin film of pressing present embodiment technical scheme preparation is referring to table three.
Table three
By the result of table one, table two and table three as can be seen, tussah silk fibroin film provided by the present invention is insoluble in water, and its tensile property is good, and tensile break strength is greater than 20Mpa, and tension fracture elongation rate is greater than 20%.Especially the strength and elongation of hygrometric state, therefore, it has good flexibility, can be used as in cornea,artificial, cerebral dura mater, esophagus, cardiac valve, blood vessel and wound surface cladding material, and isolates and drug controlled release material etc. as temporary covering, tissue.
Claims (2)
1. tussah silk fibroin film, it is characterized in that: by weight, it contains tussah silk fibroin matter 40～90%, and all the other are dihydroxylic alcohols; 24 hours albumen dissolve-loss ratio is less than 3% in 37 ℃ water for it, and tensile break strength is greater than 20Mpa, and tension fracture elongation rate is greater than 20%; Described dihydroxylic alcohols is an ethylene glycol, 1, ammediol, 2, ammediol, 1,4-butanediol, 1,2-butanediol, 1,3 butylene glycol, 2, a kind of in 3-butanediol, diglycol and the triethylene-glycol, or their combination in any.
2. method for preparing the described tussah silk fibroin film of claim 1, tussah silk obtain mass concentration after coming unstuck, dissolve, dialyse, concentrating be 1～30% tussah silk fibroin solution, it is characterized in that carrying out the processing of following steps again:
(1) adding mass ratio in tussah silk fibroin solution is 10～60% dihydroxylic alcohols, makes mixed solution; Described dihydroxylic alcohols is an ethylene glycol, 1, ammediol, 2, ammediol, 1,4-butanediol, 1,2-butanediol, 1,3 butylene glycol, 2, a kind of in 3-butanediol, diglycol and the triethylene-glycol, or their combination in any;
(2) above-mentioned mixed solution is placed the molding of mould system film, obtain a kind of tussah silk fibroin film after the drying.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102304812A (en) * | 2011-09-07 | 2012-01-04 | 邱轶伟 | Preparation method of natural silk sericin-free silk fibroin cores |
| CN102327644A (en) * | 2011-09-07 | 2012-01-25 | 邱轶伟 | Natural silk sericin-free silk fibroin core and application thereof |
| CN104383598A (en) * | 2014-12-04 | 2015-03-04 | 湖北赛罗生物材料有限责任公司 | Bioactive material as well as preparation method and application thereof |
| CN108277204A (en) * | 2018-01-10 | 2018-07-13 | 山东麦德克斯生物科技有限公司 | A kind of method that bioengineering cultivates eye Full-thickness corneal |
| CN109007286A (en) * | 2018-09-03 | 2018-12-18 | 阜阳国安农业科技股份有限公司 | A kind of mixed feed improving meat quality |
| CN109090362A (en) * | 2018-09-03 | 2018-12-28 | 阜阳国安农业科技股份有限公司 | A kind of mixed feed improving pigling immunity |
| CN110279894A (en) * | 2019-06-27 | 2019-09-27 | 中国科学院金属研究所 | Composite material and heart valve prosthesis based on fibroin fiber |
| CN111821514A (en) * | 2020-08-06 | 2020-10-27 | 苏州大学 | Silk sericin composite membrane and preparation method thereof |
| EP4122948A4 (en) * | 2020-03-16 | 2024-05-01 | Spiber Inc. | Synthetic polymer and method for producing same, molding material, and molded body |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102304812A (en) * | 2011-09-07 | 2012-01-04 | 邱轶伟 | Preparation method of natural silk sericin-free silk fibroin cores |
| CN102327644A (en) * | 2011-09-07 | 2012-01-25 | 邱轶伟 | Natural silk sericin-free silk fibroin core and application thereof |
| CN104383598A (en) * | 2014-12-04 | 2015-03-04 | 湖北赛罗生物材料有限责任公司 | Bioactive material as well as preparation method and application thereof |
| CN108277204A (en) * | 2018-01-10 | 2018-07-13 | 山东麦德克斯生物科技有限公司 | A kind of method that bioengineering cultivates eye Full-thickness corneal |
| CN109007286A (en) * | 2018-09-03 | 2018-12-18 | 阜阳国安农业科技股份有限公司 | A kind of mixed feed improving meat quality |
| CN109090362A (en) * | 2018-09-03 | 2018-12-28 | 阜阳国安农业科技股份有限公司 | A kind of mixed feed improving pigling immunity |
| CN110279894A (en) * | 2019-06-27 | 2019-09-27 | 中国科学院金属研究所 | Composite material and heart valve prosthesis based on fibroin fiber |
| EP4122948A4 (en) * | 2020-03-16 | 2024-05-01 | Spiber Inc. | Synthetic polymer and method for producing same, molding material, and molded body |
| CN111821514A (en) * | 2020-08-06 | 2020-10-27 | 苏州大学 | Silk sericin composite membrane and preparation method thereof |
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