CN102133425B - Tussah silk fibroin film and preparation method thereof - Google Patents
Tussah silk fibroin film and preparation method thereof Download PDFInfo
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- CN102133425B CN102133425B CN201110059060.7A CN201110059060A CN102133425B CN 102133425 B CN102133425 B CN 102133425B CN 201110059060 A CN201110059060 A CN 201110059060A CN 102133425 B CN102133425 B CN 102133425B
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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 the one in Bombyx mandarina Moore, take toothed oak leaf as food.Tussah silk is the natural silk fiber forming take tussah cocoon as raw material reel silk from cocoons system.China produces tussah cocoon 3～40,000 ton per year, accounts for the more than 90% of world's tussah cocoon total output, and the Zhe Shi 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 embodying is very limited.In the protein composition of tussah silk peptide take glycine, alanine and serine as main, there is good biocompatibility, itself and catabolite thereof are nontoxic to cell and body, not can or less causing inflammation and immunological rejection, the RGD tripeptide sequence containing in its protein molecule.The recognition site that RGD sequence combines with extracellular ligand as cell membrane integrin receptor, interaction between mediated cell and extracellular matrix and cell, can promote support attached to killing of cell, make adhesive rate and the rate of increase of cell on tussah silk peptide film be much better than adhesive rate and the rate of increase on Bombyx mori Silk Fibroin film, therefore tussah silk fibroin material can be considered the novel ideal biological for human body and medical material.
Tussah silk is a kind of fibrous material, and tussah silk fibroin is made to film material, is to be generally prepared into tussah silk fibroin aqueous solution after first tussah silk being come unstuck, then adopts diverse ways to prepare fibroin protein film.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 tussah silk fibroin fiber forms.At present, the chemical treatment reagent of tussah silk peptide film is mainly contained to methanol, ethanol, but the tussah silk peptide film after methanol or Ethanol Treatment is hard and crisp, mechanical property is poor.In order to improve these performances, there is bibliographical information and adopted the Polyethylene Glycol Bisglycidyl Ether technical scheme of as cross-linking agent, tussah silk peptide film being carried out chemical crosslinking, the method can significantly improve water-resistance and toughness ([J] China YouSe Acta Metallurgica Sinica of film, 2004,14 (6), 414-419), but the cross-linking agent of its use is epoxide, it remains in fibroin membrane, by the biocompatibility of the prepared material of impact.
Summary of the invention
The deficiency existing in order to overcome prior art, the object of this invention is to provide a kind of pliability and good biocompatibility, and is 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; Its albumen dissolve-loss ratio of 24 hours in the water of 37 ℃ is less than 3%, and tensile break strength is greater than 20Mpa, and tension fracture elongation rate is greater than 20%.
Prepare a method for above-mentioned tussah silk fibroin film, tussah silk obtains mass concentration through coming unstuck, dissolve, dialyse, after concentrated be 1～30% tussah silk fibroin solution, then carry out the processing of following steps:
(1) in tussah silk fibroin solution, adding mass ratio is 10～60% dihydroxylic alcohols, makes mixed solution;
(2) above-mentioned mixed solution is placed in to mould film forming, after being dried, obtains a kind of tussah silk fibroin film.
Dihydroxylic alcohols of the present invention is ethylene glycol, 1,3-PD, 2, ammediol, BDO, 1, the one in 2-butanediol, 1,3 butylene glycol, 2,3-butanediol, diglycol and triethylene-glycol, or their combination in any.
The structure of tussah silk peptide is different from silkworm, and its silk fibroin protein solution easily precipitates, and film forming difficulty adopts the made membrane material of prior art, and its flexibility is poor, and soluble in water, cannot meet the technical requirement of biomaterial for medical purpose.The principle of foundation of the present invention is: in the structure of dihydroxylic alcohols, contain two hydroxyls, and after joining in tussah silk fibroin solution, 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; Meanwhile, dihydroxylic alcohols has also played the effect of plasticizer, makes the tussah silk fibroin film forming 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 obtaining is not only insoluble in water, flexibility is good, also there is good biocompatibility, be suitable for Growth of Cells, and can be within 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 invention will be further described.
Embodiment mono-
The tussah silk fibroin film preparation process of what the present embodiment provided be insoluble in water is as follows:
1,0.1 kilogram of Antherea pernyi Guerin-Meneville raw silk is put into the aqueous sodium carbonate that 3 mass per liter concentration are 0.15%, in 98～100 ℃ of processing 2 hours, make stripping, fully after washing, obtain pure silk element (being tussah silk fibroin).By the pure silk element after drying, the lithium rhodanate solution that is 15 mol/L by 1 liter of concentration, at 60 ± 5 ℃, heating for dissolving obtains tussah silk fibroin mixed solution.
2, be dialysis material with cellulose membrane, the tussah silk fibroin mixed solution of gained is dialysed with deionized water, remove the 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, in mass ratio, the addition of ethylene glycol be in solution tussah silk fibroin solid content 40%.
4, above-mentioned tussah silk fibroin solution is injected to mould film forming, under the temperature conditions of 60 ℃, air blast dries up.
5, the environment of above-mentioned dried fibroin/ethylene glycol blend film being put into relative humidity 60% is processed 10 hours, obtains being insoluble in the transparent fibroin protein film of water.
The main performance index of the tussah silk fibroin film of preparing by the present embodiment technical scheme is referring to table one.
Table one
Embodiment bis-
0.5 kilogram of Antherea pernyi Guerin-Meneville raw silk is put into the neutral soap solution that 25 mass per liter concentration are 0.5%, within 2 hours, come unstuck in 98～100 ℃ of processing, fully after washing, obtain pure silk element (being tussah silk fibroin).By the pure silk element after drying, with the lithium rhodanate aqueous solution of 2 liter of 16 mol/L, become tussah silk fibroin mixed solution 60 ± 2 ℃ of stirring and dissolving.
With cellulose membrane be dialysis material, the tussah silk fibroin mixed solution of gained is dialysed with deionized water, remove the impurity such as lithium rhodanate, obtain mass concentration and be 20% tussah silk fibroin solution.
In pure tussah silk fibroin solution, add 1,3-PD, the addition (in mass ratio) of 1,3-PD be in tussah silk fibroin solution solid content 45%.
Silk fibroin protein solution is injected to mould and make membranaceously, at room temperature air blast dries up.
The environment that above-mentioned dried fibroin/propylene glycol blend film is put into relative humidity 50% is processed 20 hours, obtains being insoluble in the tussah silk fibroin film of water.
The main performance index of the tussah silk fibroin film of preparing by the present embodiment technical scheme is referring to table two.
Table two
Embodiment tri-
200 grams of Antherea pernyi Guerin-Meneville raw silks are put into the aqueous sodium carbonate that 8 mass per liter concentration are 0.05%, and adding mass concentration is 0.01% sodium lauryl sulphate, within 0.5 hour, comes unstuck in 98～100 ℃ of processing, and reprocessing 3 times, fully obtains pure silk element after washing.Lithium rhodanate aqueous solution by the pure silk element after drying by 1 liter of 14 mol/L, at 65 ± 5 ℃, heating for dissolving obtains tussah silk fibroin mixed solution.
With cellulose membrane be dialysis material, by deionized water dialysis for the tussah silk fibroin mixed solution of gained 3 days, obtain mass concentration and be 16% tussah silk fibroin solution.
In pure tussah silk fibroin solution, add 1,2-butanediol, the addition (in mass ratio) of 1 ,-2 butanediols be in tussah silk fibroin solution solid content 50%.
Silk fibroin protein solution is injected to mould film forming, and at the temperature of 80 ℃, lower air blast dries up.
The environment that above-mentioned dried fibroin/butanediol blend film is put into relative humidity 70% is processed 30 hours, obtains being insoluble in the tussah silk fibroin film of water.
The main performance index of the tussah silk fibroin film of preparing by the present embodiment technical scheme is referring to table three.
Table three
Result by table one, table two and table three can find out, 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 as temporary covering, tissue isolation and drug controlled release material etc.
Claims (2)
1. a tussah silk fibroin film, is characterized in that: by weight, it contains tussah silk fibroin matter 40～90%, and all the other are dihydroxylic alcohols; Its albumen dissolve-loss ratio of 24 hours in the water of 37 ℃ is less than 3%, and tensile break strength is greater than 20Mpa, and tension fracture elongation rate is greater than 20%; Described dihydroxylic alcohols is ethylene glycol, 1,3-PD, 2, ammediol, BDO, 1, the one in 2-butanediol, 1,3 butylene glycol, 2,3-butanediol, diglycol and triethylene-glycol, or their combination in any.
2. prepare a method for tussah silk fibroin film claimed in claim 1, tussah silk obtains mass concentration through coming unstuck, dissolve, dialyse, after concentrated be 1～30% tussah silk fibroin solution, it is characterized in that carrying out the processing of following steps again:
(1) in tussah silk fibroin solution, adding mass ratio is 10～60% dihydroxylic alcohols, makes mixed solution; Described dihydroxylic alcohols is ethylene glycol, 1,3-PD, 2, ammediol, BDO, 1, the one in 2-butanediol, 1,3 butylene glycol, 2,3-butanediol, diglycol and triethylene-glycol, or their combination in any;
(2) above-mentioned mixed solution is placed in to the molding of mould masking, after being dried, obtains a kind of tussah silk fibroin film.
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| CN102327644A (en) * | 2011-09-07 | 2012-01-25 | 邱轶伟 | Natural silk sericin-free silk fibroin core and application thereof |
| CN104383598B (en) * | 2014-12-04 | 2016-02-17 | 湖北赛罗生物材料有限责任公司 | A kind of bioactive materials, its preparation method and application |
| 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 |
| JPWO2021187502A1 (en) * | 2020-03-16 | 2021-09-23 | ||
| CN111821514B (en) * | 2020-08-06 | 2021-12-24 | 苏州大学 | Silk sericin composite membrane and preparation method thereof |
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| CN1187098C (en) * | 2001-11-10 | 2005-02-02 | 苏州大学 | Coremia-resisting wound protecting film and its prepn |
| CN1179757C (en) * | 2002-08-14 | 2004-12-15 | 苏州大学 | Material for repairing defective tissue of body and its preparing process |
| CN100551449C (en) * | 2006-12-30 | 2009-10-21 | 苏州大学 | Antheraea pernyi silk fibrion biology medicine material and preparation method thereof |
| CN101824225B (en) * | 2010-03-03 | 2012-06-20 | 大连工业大学 | Tussah silk peptide-glutin blend film and preparation method |
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