CN109610180B - Method for improving wool keratin enzymatic modification efficiency - Google Patents

Method for improving wool keratin enzymatic modification efficiency Download PDF

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CN109610180B
CN109610180B CN201811452561.XA CN201811452561A CN109610180B CN 109610180 B CN109610180 B CN 109610180B CN 201811452561 A CN201811452561 A CN 201811452561A CN 109610180 B CN109610180 B CN 109610180B
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wool
keratin
wool keratin
regenerated material
reaction
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CN109610180A (en
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崔莉
王平
袁久刚
范雪荣
王强
孟剑英
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Jiangnan University
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Jiangnan University
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
    • D06M16/003—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic with enzymes or microorganisms
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/51—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof
    • D06M11/54—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with sulfur, selenium, tellurium, polonium or compounds thereof with sulfur dioxide; with sulfurous acid or its salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/325—Amines
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/10—Animal fibres
    • D06M2101/12—Keratin fibres or silk

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Biochemistry (AREA)
  • Microbiology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)

Abstract

The invention discloses a method for improving wool keratin enzymatic modification efficiency, and belongs to the technical field of biochemical modification of textile materials. The method aims to utilize the characteristic that the wool keratin structure is rich in disulfide bonds, and through the click chemical reaction between sulfydryl formed by reduction and propynylamine, amino is introduced into the keratin structure, so that the number of TGase enzymatic reaction action sites is increased, and the wool keratin enzymatic modification efficiency is improved. The method has the advantages of high operation reaction efficiency, no toxicity, easy control, no problems of byproduct residue, environmental pollution, fabric strength damage and the like caused by side reaction of chemical reaction, and very high practical value.

Description

Method for improving wool keratin enzymatic modification efficiency
Technical Field
The invention relates to a method for improving wool keratin enzymatic modification efficiency, and belongs to the technical field of biochemical modification of textile materials.
Background
Wool as a basic raw material not only occupies an important position in the textile industry, but also has wide application in the field of regenerative materials. Wool products used as textile materials have their own disadvantages, such as tendency to felting, difficulty in care, poor dyeing properties, tendency to mildew, etc., and the regenerated materials containing wool keratin must also be suitably modified for use. Wool and its keratin-regenerating materials generally make use of the reactive groups-COOH, -NH-contained in wool keratin2The modification is carried out by a chemical method, however, a large amount of chemical reagents are needed in the chemical reaction process, the reaction conditions are harsh, and the damage to wool fibers is large; in addition, the residual and the discharge of chemical reagents have inevitable toxic and side effects and are easy to cause serious pollution to the environment.
At present, the problems of chemical reagent residue and emission existing in the chemical method can be solved by modifying wool and related materials by using a biological enzyme method, and the biological enzyme method modification of the wool and related materials is to hydrolyze wool keratin by using an enzyme preparation capable of acting on the wool keratin, such as protease, so that wool fabrics are endowed with good anti-felting property, and the dyeing property of the wool can be improved. However, the protease use process has the problems of difficult control of reaction, poor specificity of enzyme action and the like, so that the excessive damage of wool is easily caused.
Transglutaminase (TGase) catalyzes the intermolecular or intramolecular formation of a covalent bond between proteins and compounds containing a primary amine group, and the amino acid composition (14% glutamic acid content and 2.8% lysine content) of wool keratin makes it theoretically possible to serve as a substrate for TGase. The research results in recent years show that TGase can repair the strong damage of wool fibers caused by chemical or protease pretreatment, and improve the felting property, dyeing property, pilling resistance, hydrolysis resistance of protease, hydrophilicity, hand feeling and the like of fabrics to a certain extent; in addition, TGase can catalyze the graft reaction of wool keratin and active substances containing primary amine groups, so that the wool keratin material has the functional properties of flame retardance, antibiosis and the like. However, the solid state of wool fibers and the low lysine content in wool keratin make the enzymatic modification of wool by TGase inefficient.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for efficiently and simply introducing amino groups into keratin by utilizing a thiol click chemical reaction to improve the enzymatic modification efficiency of wool keratin TGase.
In order to solve the technical problems, the invention utilizes the property that the wool keratin is rich in disulfide bonds and forms sulfydryl after reduction, the sulfydryl can perform click chemical reaction with alkyne or alkene, and propynylamine is used as a reactant to introduce amino into the wool keratin structure, thereby improving the efficiency of TGase enzymatic modification of wool and related materials thereof.
In order to achieve the purpose, the technical scheme of the invention is as follows: a method for improving enzymatic modification efficiency of wool keratin by utilizing a thiol click chemical reaction is characterized in that disulfide bonds in the wool keratin are reduced to form thiol, and an alkynylamine compound is used as a reactant to perform the click chemical reaction with the thiol, so that amino groups can be introduced into the structure of the wool keratin, and the enzymatic modification efficiency of TGase is improved.
In one embodiment of the invention, the reducing agent used to reduce the disulfide bonds in the wool keratin to form sulfhydryl groups is any soluble reducing agent.
In one embodiment of the present invention, the reducing agent is any one of sodium bisulfite, sodium sulfite, mercaptoethanol, or cysteine.
In one embodiment of the invention, the alkynylamine compound is propynylamine.
In one embodiment of the invention, the click chemistry reaction occurs under the influence of a photoinitiator.
In one embodiment of the invention, when the raw material is wool, the method specifically comprises the following steps:
(1) amination modification of wool: weighing degreased wool, soaking in aqueous solution containing 15-25mg/L reducing agent at a bath ratio of 1:30-1:50, pretreating in 60-70 deg.C water bath for 0.5-1 hr, and mixing at a ratio of 40-60 μ L/100mgWoolAdding propynylamine, adding 10-20 mu L of photoinitiator, reacting for 1-2h with the initiation power of 80-90kJ, taking out the reacted wool, washing with water and drying to obtain aminated wool;
(2) TGase enzymatic reaction of aminated wool: immersing the aminated wool obtained by the above steps into a solution containing 20-30U/gWoolReacting in 10-50mM Tris-hydrochloric acid buffer solution of TGase enzyme at 37-45 deg.C for 10-12h, taking out wool after reaction, washing with water, and oven drying.
In one embodiment of the invention, when the starting material is a wool keratin-containing recycled material, the method comprises in particular the following steps:
(1) amination modification of regenerated material containing wool keratin: weighing regenerated material containing wool keratin, soaking in reducing agent water solution containing 15-25mg/L at bath ratio of 1:30-1:50, pretreating in water bath at 60-70 deg.C for 0.5-1 hr, and mixing at a ratio of 40-60 μ L/100mgRecycled materialAdding propynylamine, adding a photoinitiator of 10-20 mu L, reacting for 1-2h with the initiation power of 80-90kJ, taking out the reacted regenerated material containing the wool keratin, washing with water and drying to obtain the aminated regenerated material containing the wool keratin;
(2) TGase enzymatic reaction of amination of regenerated material containing wool keratin: immersing the regenerated material containing the aminated wool keratin obtained in the above step into a solution containing 20-30U/gRecycled materialReacting in 10-50mM Tris-hydrochloric acid buffer solution of TGase enzyme at 37-45 deg.C for 10-12h, taking out regenerated material, washing with water, and oven drying.
The invention also provides wool prepared by the method, a regeneration material containing wool keratin, and wool fabric or mixed fabric prepared from the wool.
The invention has the following beneficial effects:
the method reduces disulfide groups in the wool keratin into sulfhydryl groups, introduces amino groups through click chemical reaction, thereby improving the enzymatic modification efficiency of the wool keratin glutamine transaminase, provides a new research idea for biological method functional modification of wool, and compared with the method which adopts a physical method or a chemical method to carry out proper pretreatment on wool in the traditional method and improves the enzymatic modification effect of keratin by destroying a scale structure, the method has the advantages of simple modification reaction conditions, strong reactivity, harmless side reactions, small strong influence on wool keratin materials, obviously improved enzymatic modification efficiency which can be improved by 28 percent, and strong practicability.
Detailed Description
Characterization of the extent of click chemistry reaction: the wool keratin is dissolved, and the change of the sulfhydryl content in the wool keratin is determined by using an Ellman's reagent method, so that the degree of the click chemical reaction of the wool keratin can be represented.
Efficiency of the enzymatic reaction: the efficiency of the wool enzymatic reaction was investigated by measuring the free ammonia content generated by the wool TGase enzymatic reaction.
Example 1
(1) Amination modification of wool: weighing degreased wool, soaking in 25mg/L sodium bisulfite water solution at a bath ratio of 1:30, pretreating in 70 deg.C water bath for 1 hr, and adding propargylamine 60 μ L/100mgWool10 mu L of photoinitiator, the initiation power is 90kJ, the reaction is carried out for 2h, and the mixture is taken out and washed by waterDrying to obtain aminated wool;
determination of the thiol content in keratin: cutting aminated wool, soaking in water solution containing 8M urea and 25mg/L sodium bisulfite, adjusting pH to 9.5 with 5mol/L sodium hydroxide reagent, dissolving in 90 deg.C oscillating water bath for 6 hr, filtering, dialyzing, and concentrating to obtain keratin solution. The content of sulfydryl in the keratin is reduced by 15.3 percent compared with that of unmodified raw wool keratin by using an Ellman's reagent method;
(2) TGase enzymatic reaction of aminated wool: immersing wool in a bath solution containing 30U/gWoolReacting in 50mM Tris-hydrochloric acid buffer solution of TGase at 37 deg.C for 12h, taking out wool, washing with water, and oven drying.
The concentration of ammonia gas released when TGase catalyzes keratin is determined by an indophenol blue method, and the content of free ammonia generated by enzymatic reaction of the aminated and modified wool is increased by 28.2 percent compared with that of unmodified wool.
Example 2
(1) Amination modification of wool: weighing degreased wool, soaking in 25mg/L mercaptoethanol water solution at a bath ratio of 1:50, pretreating in 70 deg.C water bath for 1 hr, and adding propynylamine 60 μ L/100mgWool10 mu L of photoinitiator, the initiation power is 90kJ, the reaction is carried out for 2h, and the aminated wool is obtained after the reaction is taken out, washed and dried; the content of sulfydryl in the keratin is reduced by 14.5 percent compared with that of unmodified raw wool keratin by using an Ellman's reagent method;
(2) TGase enzymatic reaction of aminated wool: immersing wool in a bath solution containing 20U/gWoolThe TGase enzyme is reacted in 50mM Tris-hydrochloric acid buffer solution at 37 ℃ for 12 hours, and after the reaction is finished, the wool is taken out and fully washed by water and dried.
The concentration of ammonia gas released when TGase catalyzes keratin is determined by an indophenol blue method, and the content of free ammonia generated by enzymatic reaction of the aminated and modified wool is increased by 27.0 percent compared with that of unmodified wool.
Example 3
(1) Amination modification of wool: weighing defatted wool, soaking in 15mg/L aqueous solution of sodium bisulfite at 70 deg.C at a bath ratio of 1:30After 0.5h of pretreatment in water bath condition, 40 mu L/100mg of propynylamine is addedWool20 mu L of photoinitiator, the initiation power is 90kJ, the reaction is carried out for 2h, and the aminated wool is obtained after the reaction is taken out, washed and dried; the content of sulfydryl in the keratin is reduced by 14.8 percent compared with that of unmodified raw wool keratin by using an Ellman's reagent method;
(2) TGase enzymatic reaction of aminated wool: soaking wool in 50mM Tris-hydrochloric acid buffer solution containing 25U/g wool TGase, reacting at 37 deg.C for 12 hr, taking out wool, washing with water, and oven drying.
The concentration of ammonia released when TGase catalyzes keratin is determined by an indophenol blue method, and the content of free ammonia generated by enzymatic reaction of the aminated and modified wool is increased by 27.2 percent compared with that of unmodified wool.
Comparative example 1 with other acetylenic amines
The alkynylamine used here was N-methylpropynylamine, and the remaining procedure and operation were the same as in example 1, and wool was prepared such that the free ammonia content produced by the enzymatic reaction did not change significantly from that of unmodified wool.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (9)

1. A method for improving enzymatic modification efficiency of wool keratin is characterized in that disulfide bonds in the wool keratin are reduced to form sulfydryl, an alkynylamine compound is added, and the sulfydryl and the alkynylamine compound undergo a click chemical reaction, so that amino groups can be introduced into the wool keratin structure, and the enzymatic modification efficiency of TGase is improved; the alkynylamine compound is propargylamine.
2. The method of claim 1, wherein the reducing agent used for reducing the disulfide bonds in the wool keratin to form sulfhydryl groups is any one of sodium bisulfite, sodium sulfite, mercaptoethanol or cysteine.
3. The method according to claim 1 or 2, characterized in that it comprises, when the starting material is wool, the following steps:
(1) amination modification of wool: weighing degreased wool, immersing the degreased wool into a reducing agent water solution containing 15-25mg/L at a bath ratio of 1:30-1:50, pretreating in a water bath condition at 60-70 ℃ for 0.5-1h, adding propynylamine, adding 10-20 mu L of photoinitiator, reacting for 1-2h, taking out the reacted wool, washing with water and drying to obtain aminated wool;
(2) TGase enzymatic reaction of aminated wool: immersing the aminated wool obtained in the above steps into 10-50mM Tris-hydrochloric acid buffer solution containing TGase enzyme of 20-30U/g wool, reacting at 37-45 deg.C for 10-12h, taking out the wool after the reaction is finished, washing with water, and oven drying.
4. The method of claim 3, wherein propynylamine is added in an amount of 40-60 μ L/100mg of wool.
5. The method according to claim 1 or 2, characterized in that when the starting material is a regenerated material containing wool keratin, the method comprises the following steps:
(1) amination modification of regenerated material containing wool keratin: weighing a regenerated material containing wool keratin, immersing the regenerated material into a reducing agent aqueous solution containing 15-25mg/L at a bath ratio of 1:30-1:50, pretreating in a water bath condition at 60-70 ℃ for 0.5-1h, adding propynylamine into the regenerated material at a ratio of 40-60 mu L/100mg, adding a photoinitiator at a ratio of 10-20 mu L, wherein the initiation power is 80-90kJ, reacting for 1-2h, taking out the reacted regenerated material containing wool keratin, washing with water, and drying to obtain the aminated regenerated material containing wool keratin;
(2) TGase enzymatic reaction of amination of regenerated material containing wool keratin: immersing the regenerated material containing the aminated wool keratin obtained in the step into 10-50mM Tris-hydrochloric acid buffer solution containing TGase enzyme of 20-30U/g of the regenerated material, reacting at 37-45 ℃ for 10-12h, taking out the regenerated material after the reaction is finished, washing with water, and drying.
6. Wool produced by the method of claim 3 or 4 for increasing the efficiency of enzymatic modification of wool keratin.
7. A textile comprising the wool of claim 6.
8. The wool keratin-containing regenerated material prepared by the method for improving the wool keratin enzymatic modification efficiency of claim 5.
9. Use of a method according to any one of claims 1 to 5 for increasing the efficiency of the enzymatic modification of wool keratin in the textile sector or in the sector of regenerative materials.
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CN111549087A (en) * 2020-06-02 2020-08-18 江南大学 Preparation method and application of high molecular weight keratin

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JPH03213574A (en) * 1990-01-10 1991-09-18 Ajinomoto Co Inc Modification of zootic hair fiber
GB0016914D0 (en) * 2000-07-10 2000-08-30 Univ Nottingham Trent A method for enzymatic treatment of wool
EP2526121A4 (en) * 2010-01-19 2013-11-13 Organoclick Ab Heterogeneous thiol-ene click modifications of solid polysaccharide-based materials
CN104372613B (en) * 2014-09-29 2016-08-24 东华大学 A kind of method making wool fabric have felt proofing function
CN104404763B (en) * 2014-12-04 2016-10-12 东华大学 A kind of preparation method of the wool fabric of antistatic, felt proofing and good dyeability
CN105256556A (en) * 2015-10-23 2016-01-20 东华大学 Method for making wool fabric have antibacterial and anti-static functions

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