CN103484963A - Method for preparing all recycled alcohol soluble protein fiber by laccase - Google Patents
Method for preparing all recycled alcohol soluble protein fiber by laccase Download PDFInfo
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- CN103484963A CN103484963A CN201310465391.XA CN201310465391A CN103484963A CN 103484963 A CN103484963 A CN 103484963A CN 201310465391 A CN201310465391 A CN 201310465391A CN 103484963 A CN103484963 A CN 103484963A
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Abstract
Belonging to the field of textile raw materials, the invention discloses a method for preparing an all recycled alcohol soluble protein fiber by laccase. The cross-linking effect between protein molecules of alcohol soluble protein is catalyzed by laccase so as to generate a macromolecular polymer, and the physical and mechanical properties of the recycled alcohol soluble protein fiber are improved. The method provided in the invention enables the preparation of high quality whole protein recycled fiber by a biotechnology to replace traditional preparation of protein fiber by chemical crosslinking modification, thus providing far-reaching potential application value for application of recycled protein fiber in the textile industry and the biological medicine field.
Description
Technical field
The present invention relates to a kind of method of utilizing the full regeneration of laccase preparation alcohol soluble protein fiber, belong to the textile raw material field.
Background technology
Along with people's living standard improves constantly, people are more and more stricter to taking the fibre property requirement, and clothes have been exceeded to requirement warming, that cover body, also will meet the requirements such as environmental protection, health care simultaneously.The natural fabric good hygroscopicity, the fabric of making has excellent wearability, but is subject to the restriction of plantation and regional condition, and output can not be satisfied the demand.Seek novel natural fabric raw material and technology of preparing, become the problem to be solved of compeling.As far back as 19 end of the centurys, people just successfully utilize agriculture and forestry by-product to produce regenerated celulose fibre for raw material, 20th century, the '30s started to attempt preparing regenerated protein from agricultural byproducts as soybean, corn, milk and Extraction of Peanut albumen, the toxic and side effect caused due to the chemical reagent of the production process of complex and expensive, use and environmental pollution and the fiber quality obtained are low, protein content is lower, finally has to abandon the production of this type of regenerated fiber.Along with the demand to bio-fuel and the other biological energy constantly increases, caused a large amount of generations of the cereal byproduct such as zein, soybean protein and gluten protein and cheap, so scientists concentrates on research interest to utilize these agricultural byproducts to produce novel regenerated protein again.
Alcohol soluble protein is the important vegetable protein of a class, be soluble in the organic solvents such as ethanol, protein molecular is single chain polypeptide, without intermolecular disulfide bond, without subunit structure, single chain polypeptide relies on intramolecular disulfide bond and intermolecular hydrogen bond, Van der Waals force, electrostatic force and hydrophobic bond to link, form three-dimensional structure more closely, spherical in shape, its amino acid forms and mostly is nonpolar, and alcohol soluble protein has viscosity and is mainly dough ductility is provided.These character based on alcohol soluble protein, consider from the molecular structure performance, and the alcohol soluble protein albumen of his kind relatively is more applicable for the preparation of fiber.
Because the physicochemical properties of the regenerated protein obtained are compared and still had gap with natural azelon and synthetic fiber, limited the range of application of this fiber.To fiber, carrying out cross-linking modified is to improve the regenerated fiber physical and chemical performance to enlarge one of most popular method of its Application Areas.Yet, the toxic and side effect that chemical reagent causes, environmental pollution, severe reaction conditions and cause the low inferior problem of fiber quality largely to limit the use of chemical crosslink technique because chemical reaction causes the fiber yellowing.Therefore, utilize biotechnology to carry out to various materials the research interest that functional modification has caused people day by day, become a large focus in current investigation of materials field.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of method of utilizing the full regeneration of laccase preparation alcohol soluble protein fiber, the alcohol soluble protein of take prepares spinning solution as raw material, wet spinning obtains fiber, the recycling laccase is processed the gained fiber, obtains having the full regeneration alcohol soluble protein fiber of higher physical and mechanical properties.
Technical scheme of the present invention: alcohol soluble protein is scattered in and contains 0.5-1.5%(w/v), in anhydrous sodium sulfite, the aqueous solution of 7-9mol/L urea, be configured to 25-30%(w/v) albumen spinning solution.Spinning solution is placed in to room temperature (21 ℃) and places 20-30h, regularly stirring formation during this time has the certain viscosity spinning solution and carries out wet spinning, gained fibroblast fiber is placed in to coagulating bath 10min, and coagulating bath is for containing 10%(w/v) aqueous solution of anhydrous sodium sulfate and 10% acetic acid (v/v).The gained fiber is washed for several times with clear water, and room temperature is dried, and after the laccase solution that to be placed in enzyme concentration be the 0.1-1U/mg fiber is processed 1-8h, fiber is baked to 2h in 120 ℃ of baking ovens, then fiber is soaked in water and do physics and stretch, and draws to 2-3 times of fibrillation length.
Physical and mechanical properties to the gained fiber is tested, and fracture strength is 0.482cN/dtex, and elongation at break is 32.70%, with the fiber without enzymatic reaction, compares, and has improved respectively 13% and 81%.
The present invention utilizes the method for the full regeneration of laccase preparation alcohol soluble protein fiber, utilizes the biocatalyst laccase to replace traditional chemical catalysis cross-linking method, and preparation has the method for the full alcohol soluble protein fiber of regeneration of higher physical and mechanical properties.The operation of this method is efficient, mild condition, environmental protection and easily control, and has very strong practicality, and the gained fiber has the potential that is widely used in textile industry and biomedicine field.
The accompanying drawing explanation
The SDS-PAGE of Fig. 1 alcohol soluble protein fiber, 1 is the fiber through the laccase effect of inactivation, and 2 is the fiber through the laccase effect, and 3 is the fiber of processing without enzyme.
The mechanical performance of Fig. 2 alcohol soluble protein fiber, 1 is the alcohol soluble protein fiber, 2 is the alcohol soluble protein fiber after the laccase effect.
The specific embodiment
Utilize the SDS-PAGE gel electrophoresis can characterize the enzymatic oxidation cross-linking reaction of the albumen in regenerated protein, prove the catalytic action of laccase to alcohol soluble protein; Fracture strength and the elongation at break of fiber of take is index, can investigate the mechanical performance of fiber.
The ratio that is 1:40 in the solid-liquid mass ratio by wheat gluten flour joins containing 70%(v/v) ethanol water in, the room temperature lower magnetic force stirs 12h is evenly distributed it, then centrifugal 15min under the rotating speed of 4000r/min, get its supernatant concentration postlyophilization, finally pulverizes and obtain alcohol soluble protein.Alcohol soluble protein is dissolved in containing 1%(w/v) in the aqueous solution of anhydrous sodium sulfite, 8mol/L urea, configuration 30%(w/v) alcohol soluble protein solution, form spinning solution.The spinning solution that configures is placed to 24h in 21 ℃, regularly stir, wet spinning, the fibroblast fiber is placed in coagulating bath 10min, coagulating bath is for containing 10%(w/v) anhydrous sodium sulfate and 10%(v/v) aqueous solution of acetic acid, with clear water, to wash 3 times, room temperature is dried.(laccase that the present invention uses is fungal laccase at the 100mL laccase to get 50mg gained fiber, the laccase in any source can be realized identical effect in the present invention, the laccase of separate sources has catalysed oxidn to alcohol soluble protein) in the concentration enzyme liquid that is 0.4U/mg fiber pH5, after 50 ℃ of processing 2h, with clear water, wash 3 times, soak in water bake 2h in 120 ℃ of baking ovens after and carry out to fibrillation length 2～3 times of drawing-off, after drying, obtain finished fiber.The fiber of preparation is carried out to SDS-gel electrophoresis test, and result as shown in Figure 1, shows that in fiber, albumen, through the Laccase Catalyzed oxidation, cross-linking reaction generation macromolecule polyalcohol has occurred.
Alcohol soluble protein fiber after embodiment 2 modifications
Alcohol soluble protein is dissolved in containing 1%(w/v) in the aqueous solution of anhydrous sodium sulfite, 8mol/L urea, configuration is containing 30%(w/v) alcohol soluble protein, form spinning solution.The spinning solution that configures is placed to 24h in 21 ℃, regularly stir, wet spinning, the fibroblast fiber is placed in coagulating bath 10min, coagulating bath is for containing 10%(w/v) aqueous solution of anhydrous sodium sulfate and 10% acetic acid (v/v), with clear water, to wash 3 times, room temperature is dried.In the enzyme liquid of the pH5 that the fiber of getting 50mg is 0.2U/mL in 100mL laccase concentration, in 50 ℃ process 2h after, with clear water, wash 3 times, bake 2h in 120 ℃ of baking ovens, then in water, soak and carry out to fibrillation length 2～3 times of drawing-off, obtain fiber after drying.Physical and mechanical properties to fiber is tested, and fracture strength is 0.482cN/dtex, and elongation at break is 32.70%, with the fiber without enzymatic reaction, compares, and has improved respectively 13% and 81%, and result as shown in Figure 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, so protection scope of the present invention should be with being as the criterion that claims were defined.
Claims (4)
1. one kind is utilized the laccase preparation method of regeneration alcohol soluble protein fiber entirely, it is characterized in that, be to take alcohol soluble protein to prepare spinning solution as raw material, and wet spinning obtains fiber, the recycling laccase is processed the gained fiber, obtains having the full regeneration alcohol soluble protein fiber of higher physical and mechanical properties.
2. method according to claim 1, is characterized in that, concrete steps are:
(1) alcohol soluble protein is scattered in the aqueous solution that contains 0.5-1.5% anhydrous sodium sulfite, 7-9mol/L urea, is configured to the albumen spinning solution of 25-30%;
(2) spinning solution is placed in to room temperature and places 20-30h, regularly stir during this time to form and there is the certain viscosity spinning solution and carry out wet spinning and obtain the fibroblast fiber, the fibroblast fiber is placed in to coagulating bath 10min, and coagulating bath is the aqueous solution containing 10% anhydrous sodium sulfate and 10% acetic acid;
(3) the gained fiber is washed for several times with clear water, room temperature is dried, and the laccase solution that to be placed in enzyme concentration be the 0.1-1U/mg fiber is processed 1-8h, then fiber is baked to 2h in 120 ℃ of baking ovens, soak in water and do the physics stretching again, draw to 2～3 times of fibrillation length.
3. method according to claim 1, is characterized in that, the alcohol soluble protein that described alcohol soluble protein is any source, and in the alcohol soluble protein spinning solution of configuration, alcohol soluble protein concentration is 25-30%.
4. method according to claim 1, is characterized in that, described laccase is any microorganism or tissue-derived laccase, and enzyme dosage is the 0.1-1U/mg fibrin.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103789894A (en) * | 2014-02-14 | 2014-05-14 | 江苏新芳科技集团股份有限公司 | Chymotrypsin modified protein fiber and semi-worsted spun yarn modifying method through same |
| CN105925222A (en) * | 2016-05-25 | 2016-09-07 | 合肥东彩印刷科技有限公司 | Environment-friendly epoxy resin adhesive with good heat stability and long storage time |
| CN106047243A (en) * | 2016-05-25 | 2016-10-26 | 合肥东彩印刷科技有限公司 | High-toughness anti-stripping epoxy resin adhesive |
| CN109097870A (en) * | 2017-06-21 | 2018-12-28 | 中国科学院过程工程研究所 | Ionic liquid is the method that solvent wet spinning prepares Far-infrared carbon nano-conductive fiber |
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| US20030177589A1 (en) * | 2000-08-15 | 2003-09-25 | Johanna Buchert | Method for treating proteinaceous fibers |
| DE102009025190A1 (en) * | 2009-06-12 | 2010-12-16 | Call, Krimhild | Enzyme-based method for coupling- and/or crosslinking reactions of e.g. textiles, comprises coating surfaces of products, modifying suitable compounds, and coupling and/or crosslinking suitable compounds as coupling agents to the compounds |
| CN103266494A (en) * | 2013-05-25 | 2013-08-28 | 上海秋橙新材料科技有限公司 | Pretreatment method of soybean protein fabric bio-enzyme |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030177589A1 (en) * | 2000-08-15 | 2003-09-25 | Johanna Buchert | Method for treating proteinaceous fibers |
| DE102009025190A1 (en) * | 2009-06-12 | 2010-12-16 | Call, Krimhild | Enzyme-based method for coupling- and/or crosslinking reactions of e.g. textiles, comprises coating surfaces of products, modifying suitable compounds, and coupling and/or crosslinking suitable compounds as coupling agents to the compounds |
| CN103266494A (en) * | 2013-05-25 | 2013-08-28 | 上海秋橙新材料科技有限公司 | Pretreatment method of soybean protein fabric bio-enzyme |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103789894A (en) * | 2014-02-14 | 2014-05-14 | 江苏新芳科技集团股份有限公司 | Chymotrypsin modified protein fiber and semi-worsted spun yarn modifying method through same |
| CN105925222A (en) * | 2016-05-25 | 2016-09-07 | 合肥东彩印刷科技有限公司 | Environment-friendly epoxy resin adhesive with good heat stability and long storage time |
| CN106047243A (en) * | 2016-05-25 | 2016-10-26 | 合肥东彩印刷科技有限公司 | High-toughness anti-stripping epoxy resin adhesive |
| CN109097870A (en) * | 2017-06-21 | 2018-12-28 | 中国科学院过程工程研究所 | Ionic liquid is the method that solvent wet spinning prepares Far-infrared carbon nano-conductive fiber |
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Effective date of registration: 20181229 Address after: 261500 Room 101, Building 2, Yinying Garden Area A, 1216 Renmin Street, Gaomi City, Weifang City, Shandong Province Patentee after: Li Yong Address before: 214122 1800 Lihu Avenue, Binhu District, Wuxi, Jiangsu Patentee before: Jiangnan University |
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Effective date of registration: 20190125 Address after: 261500 Xingyuan Street 1169 Chaoyang Street, Gaomi City, Weifang City, Shandong Province Patentee after: Shandong Yinying Chemical Fibre Co., Ltd. Address before: 261500 Room 101, Building 2, Yinying Garden Area A, 1216 Renmin Street, Gaomi City, Weifang City, Shandong Province Patentee before: Li Yong |