CN113249967B - Material of regenerated cellulose fiber grafted by cysteine-coupled protein and preparation method thereof - Google Patents
Material of regenerated cellulose fiber grafted by cysteine-coupled protein and preparation method thereof Download PDFInfo
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
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- 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
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- D06M13/342—Amino-carboxylic acids; Betaines; Aminosulfonic acids; Sulfo-betaines
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Abstract
The invention discloses a material for grafting regenerated cellulose fiber by cysteine-coupled protein and a preparation method thereof 2 O 2 The quaternary composite oxidation system is used for catalyzing and oxidizing agent to carry out C on regenerated cellulose fiber 6 And (3) carrying out site-selective oxidation, putting the fiber into a cysteine solution for reaction, putting the fiber into a protein solution for reaction, adding a proper amount of acid for catalysis, taking out the fiber, washing and drying to constant weight. The method for grafting the oxidized regenerated cellulose fiber and the protein on the surface by using cysteine as the coupling agent has the advantages of improving the mechanical property of the regenerated cellulose fiber, along with high grafting rate, endowing the regenerated cellulose fiber with good skin-friendly property of the protein fiber, and having good application prospect in the field of medical textile materials.
Description
Technical Field
The invention relates to the technical field of fiber material modification, in particular to a cysteine-coupled protein grafted regenerated cellulose fiber material and a preparation method thereof.
Background
The regenerated cellulose fiber is prepared by using natural cellulose (cotton, hemp, bamboo, trees and shrubs) as a raw material, and only changing the physical structure of the natural cellulose without changing the chemical structure of the natural cellulose. The structure and the composition are similar to those of cotton, except that the moisture absorption and the air permeability of the cotton fiber are better than those of cotton fiber, so that the cotton fiber is the best one of all chemical fibers in moisture absorption and air permeability. In addition, the thermal stability and the light stability are high, and static electricity is not generated; the strength and the elongation can meet the requirements of most textiles, and the textile has better spinnability. However, the skin-friendly property and biocompatibility of the regenerated cellulose fiber are still to be improved, and the application of the regenerated cellulose fiber in the fields of biomedical and medical functional dressings and the like is limited by the properties.
Cellulose has high crystallinity, is difficult to dissolve and is not beneficial to processing and utilization, and chemical oxidation is generally adoptedThe method introduces aldehyde group, carboxyl group and other active groups to further chemically modify the compound. The oxidation reaction of the fiber is divided into selective oxidation and nonselective oxidation according to the difference of reaction positions, and the selective oxidation is divided into secondary hydroxyl C 2 、C 3 Ring opening oxidation of the site and primary hydroxyl C 6 Oxidation of the sites. But C is 2 、C 3 The ring-opening oxidation of the sites can destroy the original structure of the cellulose and influence the performance of the fiber, such as biodegradability, high crystallization performance and the like.
As the protein which is rich in resources, nontoxic, harmless and stable in property in the nature, such as collagen, the reasonable addition can improve the hygroscopicity and the dyeing property of the synthetic fiber, and the synthetic fiber has better nourishing and protecting effects on the skin of a human body due to better biocompatibility of the protein. The modification of synthetic fibers with natural proteins has led to the development of a variety of modified fibers, which is the trend in the development of textile materials today, so-called "natural fiber synthesis" and "synthetic fiber naturalization".
Disclosure of Invention
The invention provides a material for grafting the regenerated cellulose fiber by cysteine-coupled protein and a preparation method thereof, which can effectively improve the mechanical property of the regenerated cellulose fiber and improve the skin-friendly property and biocompatibility.
The technical scheme of the invention is that the method for grafting the cysteine-coupled protein to the regenerated cellulose fiber comprises the following steps:
s1, washing regenerated cellulose fibers with deionized water, then putting the regenerated cellulose fibers into a sodium hydroxide solution for washing, then washing with an absolute ethyl alcohol solution, volatilizing surface ethyl alcohol after washing is finished, and finally drying to constant weight;
s2, preparing H with the mass fraction of 5-15% 2 O 2 Adding the fiber obtained in the step S1 into the solution, stirring the solution uniformly, reacting the solution for 10 to 30min in a constant-temperature water bath at the temperature of between 15 and 60 ℃, dissolving TEMPO and NaBr in deionized water, stirring the solution, and adding H into the solution 2 O 2 Adding 0.3 mmol/L-2.0 mmol/L NaClO solution to react, dropping NaOH solution to maintain the pH of the reaction system at 10-11, reacting in 15-60 deg.c constant temperature water bath for 3-6 hr,adding absolute ethyl alcohol to terminate the reaction, taking out the fiber, washing the fiber with deionized water to be neutral, and drying the fiber to constant weight;
s3, preparing a cysteine solution with the mass fraction of 2-8%, putting the dried fiber in the S2 into the solution, reacting for 1-3 h at the water bath temperature of 15-60 ℃, taking out, washing with deionized water to be neutral, and drying to constant weight;
s4, preparing a protein solution with the mass fraction of 2% -10%, putting the dried fiber in the S3 into the solution, reacting for 3-5 h at the water bath temperature of 15-60 ℃, taking out, washing with deionized water to be neutral, and drying to constant weight.
Further, the regenerated cellulose fiber in S1 is lyocell fiber.
Further, washing the product in S1 with deionized water for multiple times; when the sodium hydroxide solution is used for washing, the mass concentration of the solution is 2-8%, the washing temperature is 15-60 ℃, and the time is 10-20 min; the temperature is 15-60 ℃ and the time is 5-10 min when the absolute ethyl alcohol solution is used for washing.
Further, the usage amount of TEMPO and NaBr is 0.05-0.2 mmol/L and 0.8-3.2 mmol/L respectively; the dosage of NaClO is 0.3-2.0 mmol/g fiber.
Further, before the fiber is added into S3, sodium hydroxide is added to adjust the pH value of the cysteine solution to 6.5-8.5.
Further, before adding the fiber into S4, acid is added to adjust the pH of the protein solution to 4.5-6.5.
Further, the acid is one or a mixture of several of formic acid, acetic acid, hydrochloric acid and sulfuric acid.
Further, the protein is casein, collagen, silk fibroin or soybean protein.
The invention also relates to the cysteine coupled protein grafted regenerated cellulose fiber obtained by the method.
The invention also relates to application of the cysteine-coupled protein grafted regenerated cellulose fiber in the field of biomedical or medical functional dressing materials.
The invention provides a preparation method of a cysteine-coupled protein grafted regenerated cellulose fiberThe method comprises the steps of sequentially washing regenerated cellulose fibers with deionized water, a sodium hydroxide solution and an absolute ethyl alcohol solution for three times to wash away oil agents and impurities on the surfaces of the fibers, and then passing the washed and impurity-removed regenerated cellulose fibers through TEMPO/NaClO/NaBr/H 2 O 2 C with quaternary complex oxidation system 6 The site selective oxidation makes C be selectively oxidized under the condition of not destroying other partial structures of cellulose 6 Converting primary hydroxyl into carboxyl, reacting the oxidized regenerated cellulose fiber with cysteine as coupling agent to obtain amino (-NH) at one end of cysteine 2 ) The modified cellulose fiber is subjected to condensation reaction with carboxyl (-COOH) on the surface of oxidized regenerated cellulose fiber to form an amido bond, so that the length and flexibility of a grafting chain are increased, the protein grafting rate and the grafting fastness are improved, active groups such as carboxyl (-COOH), sulfydryl (-SH) and the like of cysteine can be continuously introduced into the surface of the regenerated cellulose fiber, finally the regenerated cellulose fiber is reacted with a protein solution, and the groups such as carboxyl (-COOH), sulfydryl (-SH) and the like on the cysteine are connected with the protein through covalent bonds. The modified regenerated cellulose fiber is grafted by cysteine coupled protein macromolecules, so that the mechanical property of the regenerated cellulose fiber is improved, and a composite structure of a stable protein film layer is formed on the surface of the regenerated cellulose fiber.
The reaction process of the invention is as follows:
the invention has the following beneficial effects:
(1) The invention provides a method for carrying out covalent bond surface grafting on oxidized regenerated cellulose fibers and protein by taking cysteine as a coupling agent. The main functions of cysteine as a coupling agent are as follows: i, increasing the carbon chain length of regenerated cellulose fiber molecules; and II, introducing active groups such as carboxyl (-COOH), sulfydryl (-SH) and the like through cysteine coupling to improve the grafting fastness. The method not only improves the mechanical property, but also uses natural materials (regenerated cellulose fiber, cysteine and protein) as raw materials, does not pollute the environment, and accords with the concept of green development.
(2) The protein applied by the invention contains active reaction group sulfydryl, and disulfide bonds are formed between the protein molecules or in the protein, the existence of the disulfide bonds endows the fabric with certain elasticity and toughness, and meanwhile, peptide chains in the protein molecules are regularly curled (such as an alpha-spiral structure) or folded (such as a beta-folding structure) to form a specific space structure, so that the material is endowed with a good mechanical space.
(3) The fiber material prepared by the invention is a composite fiber material which takes regenerated cellulose fiber as a base material and has the property of natural protein fiber, and has wide application prospect, such as: the natural protein film layer has good wearing comfort and biocompatibility, and the application space of the regenerated cellulose fiber in the fields of biomedical and medical functional dressings and the like is expanded. And the regenerated cellulose fiber material has good flexibility due to the excellent ductility and molecular elasticity of protein macromolecules, so that the regenerated cellulose fiber material can be used in the field of close-fitting household textiles.
(4) The preparation method is simple and convenient in preparation process, easy to implement, beneficial to industrial production and wide in development prospect.
(5) The cysteine-coupled protein grafted regenerated cellulose fiber prepared by the method not only improves the mechanical properties of the regenerated cellulose fiber, such as breaking strength, breaking elongation and the like, but also has the excellent characteristics of good fiber flexibility, protein biocompatibility, good dyeing property and the like; the application space of the dressing in the fields of biological medical treatment, medical functional dressing and the like is expanded.
Drawings
FIG. 1 is a graph comparing the infrared spectra (FTIR) of regenerated cellulose fiber as-received with the grafted protein sample of example 1.
FIG. 2 is a graph comparing the X-ray diffraction (XRD) of a regenerated cellulose fiber sample, a cysteine treated sample, and a grafted protein sample of example 1.
FIG. 3 is a Scanning Electron Microscope (SEM) comparison of regenerated cellulose fibers as such with a sample of grafted protein of example 1.
FIG. 4 is a graph comparing the breaking strength and elongation at break of regenerated cellulose fiber samples with those of the grafted protein sample of example 1.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention.
Example 1:
taking a representative protein, namely collagen, as an example, taking 2g of regenerated cellulose fiber (taking lyocell fiber as an example), washing the regenerated cellulose fiber for three times by using deionized water, preparing 100ml of a sodium hydroxide solution with the mass fraction of 2%, taking out the washed fiber, putting the fiber into the prepared sodium hydroxide solution, completely soaking the fiber by using a glass rod, putting the fiber into a constant-temperature water bath kettle at the temperature of 40 ℃, stirring and washing the fiber by using the glass rod for 10min, taking out the fiber, putting the fiber into 50ml of an absolute ethyl alcohol solution, completely soaking the fiber by using the glass rod, putting the fiber into the constant-temperature water bath kettle at the temperature of 40 ℃, stirring and washing the fiber by using the glass rod for 8min, taking out the fiber, volatilizing the ethyl alcohol, and putting the fiber into an oven for drying to constant weight.
Preparing H with the mass fraction of 8% 2 O 2 Adding impurity-removed regenerated cellulose fiber into the solution, stirring uniformly, reacting for 10min in a constant-temperature water bath at 30 ℃, dissolving TEMPO (0.05 mmol/L) and NaBr (0.8 mmol/L) in 100ml deionized water, stirring, and adding H 2 O 2 Adding 0.3mmol/L NaClO solution into the solution to react, dropwise adding 0.5mol/L NaOH solution to maintain the pH of the reaction system at 10.2, reacting in a constant-temperature water bath at 30 ℃ for 4h, adding 6ml of absolute ethyl alcohol to terminate the reaction, taking out the fiber, washing the fiber with deionized water to be neutral, and drying the fiber to constant weight;
preparing 100ml of cysteine solution with the mass fraction of 4%, adjusting the pH value of the cysteine solution to 7.0 by using sodium hydroxide, then putting the oxidized fiber into the prepared cysteine solution, completely soaking the fiber by using a glass rod, putting the fiber into a constant-temperature water bath kettle with the temperature of 30 ℃ for reaction for 3.5 hours, taking out the fiber, repeatedly washing the fiber by using deionized water until the fiber is neutral, and putting the fiber into an oven to be dried until the weight of the fiber is constant.
Preparing 100ml of collagen solution with the mass fraction of 5%, using a proper amount of dilute hydrochloric acid to catalyze and adjust the pH value to 5.0, putting the fiber into the prepared collagen solution, completely soaking the fiber by using a glass rod, putting the fiber into a constant-temperature water bath kettle with the temperature of 30 ℃ to react for 3.5 hours, taking out the fiber, repeatedly washing the fiber by using deionized water until the fiber is neutral, putting the fiber into an oven to dry the fiber to constant weight, and obtaining the cysteine-coupled protein grafted regenerated cellulose fiber material.
Example 2:
taking a representative protein, namely collagen, as an example, taking 2g of regenerated cellulose fiber (taking lyocell fiber as an example), washing the regenerated cellulose fiber for three times by using deionized water, preparing 100ml of a sodium hydroxide solution with the mass fraction of 2%, taking out the washed fiber, putting the fiber into the prepared sodium hydroxide solution, completely soaking the fiber by using a glass rod, putting the fiber into a constant-temperature water bath kettle at the temperature of 40 ℃, stirring and washing the fiber by using the glass rod for 10min, taking out the fiber, putting the fiber into 50ml of an absolute ethyl alcohol solution, completely soaking the fiber by using the glass rod, putting the fiber into the constant-temperature water bath kettle at the temperature of 40 ℃, stirring and washing the fiber by using the glass rod for 8min, taking out the fiber, volatilizing the ethyl alcohol, and putting the fiber into an oven for drying to constant weight.
Preparing H with the mass fraction of 10% 2 O 2 Adding impurity-removed regenerated cellulose fiber into the solution, stirring the solution uniformly, reacting the solution for 20min in a constant-temperature water bath at 45 ℃, dissolving TEMPO (0.1 mmol/L) and NaBr (1.6 mmol/L) TEMPO and NaBr in 100ml deionized water, and then stirring the solution and adding H 2 O 2 Adding 1.5mmol/L NaClO solution into the solution to react, dropwise adding 0.5mol/L NaOH solution to maintain the pH of the reaction system at 10.2, reacting for 5 hours in a constant-temperature water bath at 45 ℃, adding 8ml of absolute ethyl alcohol to terminate the reaction, taking out the fiber, washing the fiber with deionized water to be neutral, and drying the fiber to constant weight;
preparing 100ml of cysteine solution with the mass fraction of 6%, adjusting the pH value of the cysteine solution to 8.0 by using sodium hydroxide, then putting the oxidized fiber into the prepared cysteine solution, completely soaking the fiber by using a glass rod, putting the fiber into a constant-temperature water bath kettle with the temperature of 45 ℃ for reaction for 4.5 hours, taking out the fiber, repeatedly washing the fiber by using deionized water until the fiber is neutral, and putting the fiber into an oven to be dried until the weight of the fiber is constant.
Preparing 100ml of collagen solution with the mass fraction of 8%, using a proper amount of dilute hydrochloric acid to catalyze and adjust the pH value to 6.0, putting the fiber into the prepared collagen solution, completely soaking the fiber by using a glass rod, putting the fiber into a constant-temperature water bath kettle with the temperature of 45 ℃ to react for 4.5 hours, taking out the fiber, repeatedly washing the fiber by using deionized water until the fiber is neutral, putting the fiber into an oven to dry the fiber to constant weight, and obtaining the cysteine-coupled protein grafted regenerated cellulose fiber material.
Example 3:
taking a representative protein, namely collagen as an example, taking 2g of regenerated cellulose fiber (taking lyocell as an example), washing the regenerated cellulose fiber for three times by deionized water, preparing 100ml of a sodium hydroxide solution with the mass fraction of 2%, taking out the washed fiber, putting the fiber into the prepared sodium hydroxide solution, completely soaking the fiber by a glass rod, putting the fiber into a constant-temperature water bath kettle with the temperature of 40 ℃, stirring and washing the fiber by the glass rod for 10min, taking out the fiber, putting the fiber into 50ml of an absolute ethyl alcohol solution, completely soaking the fiber by the glass rod, putting the fiber into the constant-temperature water bath kettle with the temperature of 40 ℃, stirring and washing the fiber by the glass rod for 8min, taking out the fiber to volatilize the ethyl alcohol, and putting the fiber into an oven to be dried to constant weight.
Preparing 100ml of cysteine solution with the mass fraction of 4%, adjusting the pH value of the cysteine solution to 7.0 by using sodium hydroxide, then putting the oxidized fiber into the prepared cysteine solution, completely soaking the fiber by using a glass rod, putting the fiber into a constant-temperature water bath kettle with the temperature of 30 ℃ for reaction for 3.5 hours, taking out the fiber, repeatedly washing the fiber by using deionized water until the fiber is neutral, and putting the fiber into an oven to be dried until the weight of the fiber is constant.
Preparing 100ml of collagen solution with the mass fraction of 5%, using a proper amount of dilute hydrochloric acid to catalyze and adjust the pH value to 5.0, putting the fiber into the prepared collagen solution, completely soaking the fiber by using a glass rod, putting the fiber into a constant-temperature water bath kettle with the temperature of 30 ℃ to react for 3.5 hours, taking out the fiber, repeatedly washing the fiber by using deionized water until the fiber is neutral, putting the fiber into an oven to dry the fiber to constant weight, and obtaining the cysteine-coupled protein grafted regenerated cellulose fiber material.
Infrared spectroscopy test (FTIR) and conclusion: as shown in FIG. 1, the sample of the regenerated cellulose fiber as it is and the protein-grafted modified regenerated cellulose fiber are still 2893.9cm -1 Has a stretching vibration absorption band of-CH at 1641.1cm -1 Symmetric and asymmetric stretching vibration peaks of H-O-H generated by the water absorption of the cellulose fiber exist, and the characteristic structure of the regenerated cellulose fiber is not changed by the grafting modification. In addition, the grafted modified regenerated cellulose fiber is 3300cm -1 A new absorption peak appears, which is an-NH stretching vibration peak. Moreover, as can be seen in the figure, 1221.3cm -1 And is 1004.3cm -1 The peak at-OH disappeared because-OH reacted to form other groups. This indicates that the experiment of protein grafting to regenerated cellulose fiber was successful.
XRD testing and conclusions: as shown in fig. 2, the XRD patterns of the regenerated cellulose fiber raw, cysteine-treated and grafted protein samples are compared in the figure: the sample after cysteine treatment and protein grafting has double peaks of diffraction peaks at 2 theta = 20-22 degrees, which is caused by that non-cellulose components in the fiber structure are removed by alkali treatment, the network structure of hydrogen bonds is destroyed, and the chemical composition, the polymerization degree and the molecular orientation of cellulose microcrystals are changed. Therefore, the X-ray diffraction curves of the regenerated cellulose fiber sample and the grafted protein modified regenerated cellulose fiber sample show partial crystallinity changes after being subjected to alkali treatment, but basically coincide with each other, and the regenerated cellulose fiber sample shows a strong diffraction peak at 2 theta =20.5 degrees and has a relatively weak diffraction peak at 2 theta =41.2 degrees, which indicates that the internal sequence state structure of the regenerated cellulose fiber is not obviously changed after being subjected to the protein grafting modification process.
TABLE 1 elemental Change analysis
EDS (electron spectrometer) testing and conclusions: by the elemental change analysis of table 1, it can be found that: amino groups (-NH) on the surface of cysteine due to radical changes caused by modification 2 ) Performing condensation reaction with carboxyl (-COOH) on the surface of oxidized regenerated cellulose fiber to form amide bond, and reacting carboxyl (-COOH) and sulfhydryl (-SH) on the other end with amino (-NH) of protein 2 ) And sulfhydryl (-SH) to generate amido bond and disulfide bond, so that the content of nitrogen (N) and oxygen (O) elements in the protein graft sample is relatively increased; meanwhile, since the sulfur (S) element exists only in a small number of disulfide bonds formed between thiol (-SH) groups of cysteines and proteins, its relative content is small and the change is not significant compared to other elements. This test quantitatively analyzes and demonstrates that the method of graft modification of cysteine-coupled proteins of the present invention is successful.
SEM (electron microscopy) testing and conclusions: as can be seen from fig. 3, the surface of the washed and decontaminated regenerated cellulose fiber is smooth, slight ravines are generated on the surface of the regenerated cellulose fiber modified by cysteine, and the diameter of the regenerated cellulose fiber is reduced to a certain extent relative to the original fiber after washing and decontaminated. The regenerated cellulose fiber modified by protein grafting forms a layer of relatively obvious protein film on the surface, which indicates that the protein not only fills cracks and ravines on the surface of the fiber, but also covers an obvious protein film layer, and the fiber diameter is recovered to a certain extent, which indicates that the effect of the regenerated cellulose fiber grafted and modified protein is obvious, and also indicates that the surface modification of the protein is obvious for improving the skin-friendly property of the cellulose fiber.
Mechanical property test and conclusion: by comparing the breaking strength and elongation at break histograms in fig. 4 it can be found that: the breaking strength and the breaking elongation of the regenerated cellulose fiber modified by cysteine are relatively reduced, and the mechanical property of the regenerated cellulose fiber modified by grafted protein is improved to a certain extent, because the original structural integrity among macromolecular chains of the regenerated cellulose fiber is damaged due to sulfhydrylation, but the main body part of the regenerated cellulose fiber is not damaged, so that the interaction among polymer macromolecules is reduced, and after the regenerated cellulose fiber is modified by grafted protein, the surface of the oxidized fiber is covered and repaired by a protein film layer, so that the mechanical property of the modified fiber is improved to a certain extent compared with the fiber before modification.
Claims (7)
1. A method for grafting lyocell fibers by cysteine-coupled protein is characterized by comprising the following steps:
s1, washing lyocell fibers with deionized water, then putting the lyocell fibers into a sodium hydroxide solution for washing, then washing with an absolute ethyl alcohol solution, volatilizing surface ethyl alcohol after washing, and finally drying to constant weight;
s2, preparing H with the mass fraction of 5-15% 2 O 2 Adding the fiber obtained in the step S1 into the solution, stirring the solution uniformly, reacting the solution for 10 to 30min in a constant-temperature water bath at the temperature of between 15 and 60 ℃, dissolving TEMPO and NaBr in deionized water, stirring the solution, and adding H into the solution 2 O 2 Adding 0.3 mmol/L-2.0 mmol/L NaClO solution into the solution to react, dropwise adding NaOH solution to maintain the pH value of a reaction system to be 10-11, reacting for 3-6 h in a constant-temperature water bath at 15-60 ℃, adding absolute ethyl alcohol to terminate the reaction, taking out the fiber, washing the fiber with deionized water to be neutral, and drying the fiber to constant weight;
s3, preparing a cysteine solution with the mass fraction of 2-8%, adding sodium hydroxide to adjust the pH value of the cysteine solution to 6.5-8.5, putting the dried fiber in the S2 into the solution, reacting for 1-3 h at the water bath temperature of 15-60 ℃, taking out, washing with deionized water to be neutral, and drying to constant weight;
s4, preparing a protein solution with the mass fraction of 2% -10%, adding acid to adjust the pH value of the protein solution to 4.5-6.5, putting the dried fiber in the S3 into the solution, reacting for 3-5 h at the water bath temperature of 15-60 ℃, taking out, washing with deionized water to be neutral, and drying to constant weight.
2. The method of claim 1, wherein: s1, washing with deionized water for multiple times; when the sodium hydroxide solution is used for washing, the mass concentration of the solution is 2-8%, the washing temperature is 15-60 ℃, and the time is 10-20 min; the temperature is 15-60 ℃ and the time is 5-10 min when the absolute ethyl alcohol solution is used for washing.
3. The method of claim 1, wherein: wherein the usage amount of TEMPO and NaBr is 0.05-0.2 mmol/L and 0.8-3.2 mmol/L respectively; the dosage of NaClO is 0.3-2.0 mmol/g fiber.
4. The method of claim 1, wherein: the acid in the S4 is one or a mixture of several of formic acid, acetic acid, hydrochloric acid and sulfuric acid.
5. The method of claim 1, wherein: the protein is casein, collagen, silk fibroin or soybean protein.
6. Cysteine-coupled protein-grafted lyocell fibre obtainable by the process of any one of claims 1 to 5.
7. The use of cysteine-coupled protein-grafted lyocell fibre according to claim 6 in the field of biomedical or medical functional dressing materials.
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