CN103819707A - Preparation method of enzymatic grafting based antioxidant silk fibroin membrane - Google Patents
Preparation method of enzymatic grafting based antioxidant silk fibroin membrane Download PDFInfo
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- CN103819707A CN103819707A CN201410056821.7A CN201410056821A CN103819707A CN 103819707 A CN103819707 A CN 103819707A CN 201410056821 A CN201410056821 A CN 201410056821A CN 103819707 A CN103819707 A CN 103819707A
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Abstract
The invention discloses a preparation method of an enzymatic grafting based antioxidant silk fibroin membrane, and belongs to the biological technical field of textiles. With the help of tyrosinase, antioxidant flavonoids compounds are grafted onto silk fibroin surface after catalytic oxidation; and by crosslinking of tyrosine and the flavonoids compounds in the enzymatic silk fibroin, the antioxidant properties of the silk fibroin membrane is enhanced. The specific processes include silk fibroin solution preparation, silk fibroin membrane preparation, grafting of the flavonoids compounds on the enzymatic silk fibroin and after treatment of the modified silk fibroin membrane. The silk fibroin membrane prepared by the preparation method has improved antioxidant and antimicrobial properties, and the membrane material mechanical properties also are improved. Compared with a silk fibroin membrane modification method based on chemical crosslinking, the enzymatic modification method is low in energy consumption, high in efficiency, less in pollution and in favour of environmental protection.
Description
Technical field
The present invention relates to a kind of anti-oxidant fibroin membrane preparation method based on enzymatic grafting, the flavonoid compound that particularly utilizes tyrosinase catalysis to have anti-oxidant activity is prepared a method for anti-oxidant fibroin membrane at silk fibroin surface grafting, belong to field of textile biotechnology.
Background technology
The silk fibroin that comes from mulberry silk has good biocompatibility, and the fibroin protein film take it as Raw material processing has purposes more widely in medical tissue engineering materials builds.For improving the application performance of silk fibroin mould material, need carry out modification and functionalization processing to silk fibroin material by means of chemistry or biological method.
The method of modifying that fibroin protein film is conventional comprises high temperature wet heat treatment method, chemical crosslinking modified method, with other polymer blended method modifications etc.In different fibroin membrane method of modifying, chemic modified method application is more extensive, its ultimate principle is to utilize in silk fibroin to contain compared with the feature of polyamino, hydroxyl isopolarity reactive group, make between fibroin macromole to occur by means of chemical cross-linking agent (as glutaraldehyde, polycarboxylic acid etc.) crosslinked, or with external source functional compound generation grafting.Also there is certain deficiency in these class methods, as the linking agent using, easily to produce objectionable impurities residual, produces environmental pollution etc. in improving fibroin membrane performance.In recent years, along with the research of biotechnology in polymer modification is increasingly deep, the research of carrying out silk fibroin material functional modification with biotechnology comes into one's own day by day.
In the modification of fibroin material biological process, the zymin with latent effect effect comprises proteolytic enzyme, transglutaminase, oxydo-reductase (as laccase, tyrosine oxidase, horseradish peroxidase) etc.Wherein, proteolytic enzyme is used for the degraded of silk fibroin material; Transglutaminase can catalysis fibroin Glutamic Acid and adjacent silk peptide or the grafting of external source aminocompound, but because fibroin Glutamic Acid content is less, therefore this enzyme is applied less in fibroin material bio-modification.Tyrosine oxidase is as a kind of cupric polyphenoloxidase, the multiple compounds such as energy catalyzed oxidation list phenol, adjacent diphenol, triphenol, the o-quinone structure intermediate that formation reaction is more active, can further react with primary amine, realizes the synthetic or macromolecular grafted modification of novel cpd.Amino higher with the tyrosine content with phenolic hydroxyl structure in silk fibroin, can, according to this feature, by means of the catalysed oxidn of tyrosine oxidase, by catalysis polyphenolic substance and silk fibroin grafting, realize silk fibroin functional modification.
In different fibroin protein film functional modification processing, there is fibroin membrane anti-oxidant, antibacterial and anti-inflammation functions and there is higher medical value and application prospect.In flavonoid compound (as flavonol, flavanone etc.), contain multiple phenolic hydroxyl structures similar to tyrosine, there is anti-inflammatory, the multiple efficacies such as anti-oxidant.If by means of the catalysed oxidn of tyrosine oxidase, by the oxidation of above-mentioned flavonoid compound, can be further with silk fibroin in amino react; Meanwhile, in silk fibroin, tyrosine also can be oxidized by tyrosine oxidase, then reacts with flavonoid compound, can realize the preparation of the anti-oxidant fibroin protein film based on enzymatic grafting.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of anti-oxidant fibroin membrane preparation method based on enzymatic grafting, and gained fibroin protein film has anti-oxidant and antibiotic effect preferably, has expanded the performance of fibroin membrane as medical engineering material.
For solving the problems of the technologies described above, the present invention utilizes the catalysed oxidn of tyrosine oxidase, and catalysis has flavonoid compound and the silk fibroin generation graft reaction of phenolic hydroxyl group, improves the application performance of fibroin protein film.
Concrete technology and step are as follows:
(1) silk fibroin solution preparation: dissolve fibroin fiber with lithiumbromide or calcium chloride, prepare silk fibroin solution.
Treatment process prescription and condition: silk is joined in the water solution system of lithiumbromide or calcium chloride, dissolve and make the silk fibroin protein solution that concentration is 10～50g/L at about 30～80 ℃; Pack silk fibroin solution into dialysis tubing, in deionized water, after dialysis, filter, make silk fibroin aqueous solution.
(2) fibroin membrane preparation: get silk fibroin solution and make its smooth sprawling by prolonging stream, fully lyophilize, obtains fibroin protein film under-50～-20 ℃ of conditions.
(3) enzymatic fibroin grafting flavonoid compound: add appropriate tyrosine oxidase in the flavonoid compound solution of phenolic hydroxy group, by fibroin protein film dip treating in above-mentioned solution, carry out enzymatic graft modification under aerobic conditions.
Treatment process prescription and condition: tyrosine oxidase is 1～200U/g fibroin protein film with respect to the consumption of fibroin membrane, fibroin protein film 50～200g/L, flavonoid compound 0.5～10g/L, 20～50 ℃ of temperature, pH scope 6.0～8.0, processes 1～24 hour.Preferred 6-12 hour of described treatment time.
(4) Modified silk fibroin film aftertreatment: after enzymatic grafting is white, fibroin membrane wash through 2～3 room temperatures ,-50～-20 ℃ obtain anti-oxidant fibroin protein film after being dried.
The preparation of described silk fibroin solution also can be selected lithium-bromide solution, lithiumbromide-aqueous ethanolic solution or the calcium chloride-aqueous ethanolic solution of different concns.
Described tyrosine oxidase has comprised the enzyme kind of the different sourcess such as animal, plant and microorganism.
Described flavonoid compound all contains the phenolic hydroxyl group of different quantities, specifically comprises the compounds such as flavonol, flavanone, flavanonol, isoflavones and isoflavanone.
The present invention utilizes the catalysed oxidn of tyrosine oxidase, makes flavonoid compound be grafted on silk fibroin surface, prepare functional type fibroin membrane with traditional chemical crosslinking compared with, the present invention has the following advantages:
(1) enzyme catalysis efficiency is high, utilizes in tyrosinase catalysis flavonoid compound and silk fibroin graft reaction catalytic efficiency high, and zymin consumption is less.
(2) enzyme treatment condition relax, under low temperature and nearly neutrallty condition, carry out the preparation of anti-oxidant fibroin membrane, have advantages of that energy consumption is low, treatment process is safe, avoided chemical crosslink technique reaction easily to cause all many-sided defects such as environmental pollution, fibroin membrane biological safety be low.
(3) fibroin membrane improved performance is obvious, utilizes the flavonoid compound of tyrosinase catalysis oxidation phenolic hydroxy group to react with fibroin, has not only improved the antioxidant property of fibroin membrane, has strengthened fibroin membrane germ resistance, has also promoted the mechanical property of mould material.
Embodiment
Adopt tyrosinase catalysis flavonoid compound and silk fibroin grafting, preparation has fibroin membrane better anti-oxidant and anti-microbial property, and specific embodiment is as follows:
Embodiment 1
(1) silk fibroin solution is prepared: the domestic silkworm silk after coming unstuck is joined in lithiumbromide-alcohol-water (mass ratio 45:45:10) solution, make 50g/L silk fibroin protein solution 60 ℃ of dissolvings.Pack silk fibroin solution into dialysis tubing, dialyse 36 hours in deionized water, the water that changes 1 time per hour during this time, filters and obtains silk fibroin aqueous solution after dialysis.
(2) fibroin membrane preparation: get quantitative silk fibroin solution and pour in polytetrafluoroethylene (PTFE) mould, by prolonging stream film forming, abundant drying and forming-film under-50 ℃ of conditions.
(3) enzymatic fibroin grafting flavonoid compound: add Mushroom Tyrosinase in epigallocatechin solution, continuing to carry out fibroin protein film modification under logical oxygen condition, wherein, the consumption of fibroin protein film is 100g/L, tyrosine oxidase is 100U/g fibroin protein film with respect to the consumption of fibroin membrane, epigallocatechin 2g/L, 30 ℃ of temperature, pH scope 6.8, processes 6 hours.
(4) Modified silk fibroin film aftertreatment: after enzymatic graft reaction, fibroin membrane is washed through 3 room temperatures, dry under-50 ℃ of conditions, obtain anti-oxidant fibroin protein film.
Sample 1: only add epigallocatechin when fibroin membrane dipping;
Sample 2: fibroin membrane is through tyrosine oxidase, epigallocatechin combined treatment;
After above-mentioned art breading, it is 2.4% that sample 1 adopts the oxidation-resistance of the fibroin membrane that ABTS method records, and adopting GB15979-2002 to record fibroin membrane is 8.0% to streptococcus aureus bacteriostasis rate, fibroin membrane breaking tenacity 15.5N/cm
2; The oxidation-resistance that sample 2 records is 56.1%, and bacteriostasis rate is 36.6%, fibroin membrane breaking tenacity 21.0N/cm
2.
Embodiment 2
(1) silk fibroin solution is prepared: the domestic silkworm silk after coming unstuck is joined in calcium chloride-alcohol-water (mol ratio 1:1:7) solution, make 25g/L silk fibroin protein solution 70 ℃ of dissolvings.Pack silk fibroin solution into dialysis tubing, the 24h that dialyses in deionized water, the water that changes 1 time per hour during this time, filters and obtains silk fibroin aqueous solution after dialysis.
(2) fibroin membrane preparation: get quantitative silk fibroin solution and pour in polytetrafluoroethylene (PTFE) mould, make its smooth sprawling by prolonging stream, dry under-50 ℃ of conditions.
(3) enzymatic fibroin grafting flavonoid compound: add tyrosine oxidase in catechin solution, continuing to carry out fibroin protein film modification under logical oxygen condition, wherein, the consumption of fibroin protein film is 100g/L, tyrosine oxidase is 150U/g fibroin with respect to fibroin membrane consumption, catechin 2g/L, 30 ℃ of temperature, pH scope 7.0, processes 12 hours.
(4) Modified silk fibroin film aftertreatment: after enzymatic graft reaction, fibroin membrane-50 ℃ of condition cryodryings, obtains antibacterial fibroin protein film after 2 room temperature washings.
Sample 3: only add catechin processing when fibroin membrane dipping;
Sample 4: fibroin membrane is through tyrosine oxidase, catechin processing;
After above-mentioned art breading, the performance test methods that adopts sample 1 to address, recording sample 3 oxidation-resistances is 4.4%, bacteriostasis rate is 3.8%, fibroin membrane breaking tenacity 17.0N/cm
2; Sample 4 oxidation-resistances are 49.0%, and bacteriostasis rate is 37.5%, fibroin membrane breaking tenacity 22.5N/cm
2.
Although the present invention with preferred embodiment openly as above; but it is not in order to limit the present invention, any person skilled in the art, without departing from the spirit and scope of the present invention; all can do various changes and modification, therefore protection scope of the present invention should be with being as the criterion that claims were defined.
Claims (9)
1. a preparation method for anti-oxidant fibroin protein film, is characterized in that, utilizes tyrosinase catalysis to be oxidized flavonoid compound and the silk fibroin generation graft reaction with phenolic hydroxyl group, improves the application performance of fibroin protein film.
2. preparation method according to claim 1, is characterized in that, concrete technology step is as follows:
(1) prepare silk fibroin solution: dissolve fibroin fiber with lithiumbromide or calcium chloride, prepare silk fibroin solution;
(2) prepare fibroin membrane: get silk fibroin solution and make its smooth sprawling by prolonging stream, fully lyophilize, obtains fibroin protein film under-50～-20 ℃ of conditions;
(3) enzymatic fibroin grafting flavonoid compound: add appropriate tyrosine oxidase in the flavonoid compound solution of phenolic hydroxy group, by fibroin protein film dip treating in above-mentioned solution, carry out enzymatic graft modification under aerobic conditions;
(4) Modified silk fibroin film aftertreatment: after enzymatic grafting, fibroin membrane is washed through 2～3 room temperatures ,-50～-20 ℃ obtain anti-oxidant fibroin protein film after dry.
3. preparation method according to claim 2, is characterized in that, the preparation technology of described silk fibroin solution and condition are: silk is joined in the water solution system of lithiumbromide or calcium chloride, be stirred to dissolving at 30～80 ℃, make 10～50g/L silk fibroin solution; Pack silk fibroin solution into dialysis tubing, in deionized water, after dialysis, filter, make silk fibroin aqueous solution.
4. preparation method according to claim 2, it is characterized in that, described enzymatic reaction condition is: the consumption of tyrosine oxidase is 1～200U/g fibroin protein film, flavonoid compound 0.5～10g/L, fibroin protein film 50～200g/L, 20～50 ℃ of temperature, pH scope 6.0～8.0, processes 1～24 hour.
5. preparation method according to claim 4, is characterized in that, the described enzymatic reaction treatment time is 6-12 hour.
6. preparation method according to claim 2, is characterized in that, the preparation of described silk fibroin solution also can be selected lithiumbromide-aqueous ethanolic solution or calcium chloride-aqueous ethanolic solution.
7. preparation method according to claim 1, is characterized in that, described tyrosine oxidase is animal, plant or microbe-derived enzyme kind.
8. preparation method according to claim 1, is characterized in that, described flavonoid compound all contains the phenolic hydroxyl group of different quantities.
9. preparation method according to claim 1, is characterized in that, described flavonoid compound is flavonol, flavanone, flavanonol, isoflavones or isoflavanone.
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Cited By (6)
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| CN105088540A (en) * | 2015-09-25 | 2015-11-25 | 江南大学 | Method for preparing nano fibroin material on basis of tyrosinase/polyphenol medium |
| CN105218842A (en) * | 2015-09-25 | 2016-01-06 | 江南大学 | A kind of enzyme process prepares the method for fibroin/elastin composite film material |
| CN105801771A (en) * | 2016-05-13 | 2016-07-27 | 江南大学 | Method for preparing fibroin-based composite water absorbing material based on enzymatic graft copolymerization |
| CN105924596A (en) * | 2016-07-11 | 2016-09-07 | 江南大学 | Method for preparing silk-fibroin-based water-absorbing material by grafting vinyl monomer |
| CN107099046A (en) * | 2017-04-25 | 2017-08-29 | 江南大学 | A kind of method that fibroin base biomimetic mineralization material is prepared by grafting vinyl monomers |
| CN112679680A (en) * | 2020-12-17 | 2021-04-20 | 苏州经贸职业技术学院 | Bionic piezoresistive material, preparation method thereof and wearable bionic piezoresistive sensor |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105088540A (en) * | 2015-09-25 | 2015-11-25 | 江南大学 | Method for preparing nano fibroin material on basis of tyrosinase/polyphenol medium |
| CN105218842A (en) * | 2015-09-25 | 2016-01-06 | 江南大学 | A kind of enzyme process prepares the method for fibroin/elastin composite film material |
| CN105088540B (en) * | 2015-09-25 | 2017-03-29 | 江南大学 | A kind of method that nanometer silk fibroin material is prepared based on tryrosinase/polyphenol amboceptoid |
| CN105218842B (en) * | 2015-09-25 | 2017-11-03 | 江南大学 | A kind of method that enzyme process prepares fibroin/elastin laminin composite film material |
| CN105801771A (en) * | 2016-05-13 | 2016-07-27 | 江南大学 | Method for preparing fibroin-based composite water absorbing material based on enzymatic graft copolymerization |
| CN105801771B (en) * | 2016-05-13 | 2018-05-25 | 江南大学 | A kind of method that fibroin base composite absorbent material is prepared based on enzymatic graft copolymerization |
| CN105924596A (en) * | 2016-07-11 | 2016-09-07 | 江南大学 | Method for preparing silk-fibroin-based water-absorbing material by grafting vinyl monomer |
| CN107099046A (en) * | 2017-04-25 | 2017-08-29 | 江南大学 | A kind of method that fibroin base biomimetic mineralization material is prepared by grafting vinyl monomers |
| CN112679680A (en) * | 2020-12-17 | 2021-04-20 | 苏州经贸职业技术学院 | Bionic piezoresistive material, preparation method thereof and wearable bionic piezoresistive sensor |
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