CN113638221A - Polyacrylonitrile fiber with biological activity and preparation method thereof - Google Patents
Polyacrylonitrile fiber with biological activity and preparation method thereof Download PDFInfo
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- 229920002239 polyacrylonitrile Polymers 0.000 title claims abstract description 160
- 239000000835 fiber Substances 0.000 title claims abstract description 142
- 230000004071 biological effect Effects 0.000 title claims abstract description 7
- 238000002360 preparation method Methods 0.000 title claims description 7
- 102000008186 Collagen Human genes 0.000 claims abstract description 86
- 108010035532 Collagen Proteins 0.000 claims abstract description 86
- 229920001436 collagen Polymers 0.000 claims abstract description 86
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 86
- 239000000243 solution Substances 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 238000004132 cross linking Methods 0.000 claims abstract description 21
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000012670 alkaline solution Substances 0.000 claims abstract description 8
- 239000012928 buffer substance Substances 0.000 claims abstract description 8
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 5
- 230000007062 hydrolysis Effects 0.000 claims description 21
- 238000006460 hydrolysis reaction Methods 0.000 claims description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 230000004913 activation Effects 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical group [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 10
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 10
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 8
- 241000283690 Bos taurus Species 0.000 claims description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 6
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- 229910019142 PO4 Inorganic materials 0.000 claims description 3
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- 238000001035 drying Methods 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
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- 239000001103 potassium chloride Substances 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- AZKVWQKMDGGDSV-BCMRRPTOSA-N Genipin Chemical compound COC(=O)C1=CO[C@@H](O)[C@@H]2C(CO)=CC[C@H]12 AZKVWQKMDGGDSV-BCMRRPTOSA-N 0.000 claims description 2
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002131 composite material Substances 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- AZKVWQKMDGGDSV-UHFFFAOYSA-N genipin Natural products COC(=O)C1=COC(O)C2C(CO)=CCC12 AZKVWQKMDGGDSV-UHFFFAOYSA-N 0.000 claims description 2
- 230000020477 pH reduction Effects 0.000 claims description 2
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 18
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- 239000000463 material Substances 0.000 description 15
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- 239000003513 alkali Substances 0.000 description 10
- 238000004108 freeze drying Methods 0.000 description 10
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 8
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- 230000000844 anti-bacterial effect Effects 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
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- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
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- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
- D06M15/15—Proteins or derivatives thereof
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- 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
- D06M11/32—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 oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—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 oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/38—Oxides or hydroxides of elements of Groups 1 or 11 of the Periodic Table
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- D06M11/68—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 phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof
- D06M11/70—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 phosphorus or compounds thereof, e.g. with chlorophosphonic acid or salts thereof with oxides of phosphorus; with hypophosphorous, phosphorous or phosphoric acids or their salts
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- D06M11/73—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 carbon or compounds thereof
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- D06M2101/16—Synthetic fibres, other than mineral fibres
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Abstract
The invention discloses a polyacrylonitrile fiber with biological activity, which is prepared by the following method: hydrolyzing polyacrylonitrile fibers in an alkaline solution, mixing the hydrolyzed polyacrylonitrile fibers with a collagen aqueous solution and a crosslinking solution, adjusting the pH value, and carrying out chemical modification for 2-72 h; the raw material of the alkaline solution comprises NaHCO3NaOH and water; starting material for the crosslinking solutionComprises a cross-linking agent, a buffer substance and water; the collagen modified polyacrylonitrile fiber contains collagen and polyacrylonitrile. The polyacrylonitrile fiber prepared by the method maintains a good natural structure of collagen, can better promote adhesion and proliferation of fibroblasts, is beneficial to directional growth and functional expression of the fibroblasts, has good biocompatibility and mechanical properties, is beneficial to soft tissue repair, and is particularly suitable for mechanical strength requirements needed by abdominal wall defects and the like; the method has the advantages of simple process, mild reaction conditions, stable and efficient reaction system and green and environment-friendly reaction reagents.
Description
Technical Field
The invention relates to the field of tissue engineering, in particular to a polyacrylonitrile fiber with biological activity and a preparation method thereof.
Background
The first synthesis of Polyacrylonitrile (PAN) was proposed by Moreau, a french chemist, 1894, and since it was influenced by world war ii, the industrial production of polyacrylonitrile fibers was realized by i.g. farbenindustrie, germany, which is the trade name beron, and DuPont, usa, which is the trade name Orlon (Orlon), until 1950. Since the introduction of the first polyacrylonitrile fiber production line in the 70 th century in China, the production research of polyacrylonitrile fibers is rapidly developed, and at present, China almost has all the technological routes for producing polyacrylonitrile fibers in the world. According to customs data, only various types of polyacrylonitrile fibers are imported in 2018 years in China to reach 14.95 million tons, the total amount of imported polyacrylonitrile fibers exceeds 4 hundred million dollars, and the domestic demand for differentiated polyacrylonitrile fibers is still very large. In addition, with the development of new applications of polyacrylonitrile, the application of polyacrylonitrile fiber is not limited to clothing, home decoration and industrial applications, and because polyacrylonitrile materials have good thermal stability and mechanical stability, and excellent plasticity and antibacterial performance, they have been researched and developed in the aspect of medical non-implants such as hemodialysis membranes, antibacterial dressings, artificial liver ultrafilters, etc. However, because of its poor biocompatibility, polyacrylonitrile material must be modified before being applied to the repair of soft tissues implanted into the body, so as to meet the requirement of the body on the biocompatibility of the implant.
At present, the modes of modifying polyacrylonitrile materials to enhance the biocompatibility of the polyacrylonitrile materials mainly include polymer blending modification, spinning solution addition and copolymerization modification, but the above acrylonitrile fiber modification technology is not suitable for preparing soft tissue repair materials, and the reasons mainly include the following points:
(1) the reaction temperature is too high, so that the structure of the collagen can be strongly damaged, and the application value of the collagen in the aspect of soft tissue repair can be influenced; (2) toxic and harmful chemical reagents are applied in a reaction system and are difficult to remove, so that potential toxic and side reactions are brought to the modified polyacrylonitrile fiber, and the application value of the modified polyacrylonitrile fiber in the biomedical field is limited; (3) the collagen grafting modification efficiency in part of polyacrylonitrile fiber modification processes is low, and the effect of improving the biocompatibility of the modified polyacrylonitrile fiber is limited; (4) the polyacrylonitrile modified material partially uses a biological inert material, cells cannot be adhered and regenerated, and the risk of the implant related complications is increased after the polyacrylonitrile modified material is left in a body for a long time.
Therefore, how to create a modacrylic fiber capable of being applied to the repair of body soft tissues so as to meet the huge demands in the aspects of biological medicine, tissue engineering and the like becomes a hotspot of research in the field of tissue engineering and a problem to be solved urgently.
Disclosure of Invention
Collagen is a protein with a high-grade structure, the molecular composition and structure of which largely determine the final properties, such as biocompatibility and bioactivity, and therefore, effective measures must be taken to protect the composition and structure from being significantly changed when the collagen is used as a raw material to construct a tissue engineering scaffold or an implantation device. Since the composition and structure of collagen are significantly affected by temperature, pH, enzyme preparation, chemical and physical factors, available technical means and methods are limited.
The invention mainly solves the technical problem of providing the polyacrylonitrile fiber with biological activity and the preparation method thereof, the method has stable reaction system, high efficiency and low toxicity, and the prepared polyacrylonitrile fiber has good biocompatibility and mechanical strength and can be applied to soft tissue repair materials.
The soft tissue repair material is used for repairing and/or replacing diseased or damaged soft tissues in an organism and restoring or partially restoring the original tissue form and function, and can be a tissue engineering scaffold material, for example.
In order to solve the technical problems, the invention adopts a technical scheme that:
provides a polyacrylonitrile fiber with biological activity, which is prepared by the following method:
mixing and activating hydrolyzed polyacrylonitrile fibers and a crosslinking solution, mixing and reacting with 1-10 mg/L collagen, adjusting the pH value to 6-9, and reacting for 2-72 hours to obtain the collagen-based composite material;
the activation conditions are as follows: the pH value is 3-6, the activation temperature is 18-40 ℃, and the activation time is 0.3-2 h.
Because covalent crosslinking of collagen with polyacrylonitrile is affected by many factors, such as the degree of hydrolysis of polyacrylonitrile (i.e., the amount of carboxyl groups on the polyacrylonitrile molecule and the degree of exposure thereto); the ratio of the amino group content in the collagen molecule to the carboxyl group content in polyacrylonitrile (i.e., the relative amount of collagen and the crimp state of the collagen molecule); the crosslinking agent, the catalyst, the reaction conditions (namely the dosage of EDC and NHS, the addition mode, the pH value, the reaction time) and other factors, so that the invention ensures the crosslinking reaction by limiting the parameters of the polyacrylonitrile such as hydrolysis condition, the dosage of collagen, the crosslinking agent, the catalyst, the reaction conditions and the like, and obtains the fiber material with excellent biocompatibility and bioactivity.
Furthermore, the dosage of the hydrolyzed polyacrylonitrile fiber is 1.000-1.100 g, preferably 1.001-1.066 g;
the dosage of the collagen is 50-200 mg, preferably 60-150 mg.
In the invention, the crosslinking solution comprises a crosslinking agent and a buffer substance;
further, the cross-linking agent is selected from one or more of glutaraldehyde, genipin and EDC/NHS, preferably EDC/NHS; furthermore, the concentration of EDC in the crosslinking solution is 10-200 mmol/L, preferably 60 mmol/L; the concentration of NHS is 10 mmol/L-100 mmol/L, preferably 40 mmol/L;
the buffer substance is selected from one of a phosphoric acid buffer system and a carbonic acid buffer system; the phosphoric acid buffer system is composed of two or more of phosphoric acid, phosphate, hydrogen phosphate, dihydrogen phosphate, sodium hydroxide, sodium chloride and potassium chloride, and the carbonic acid buffer system is composed of carbonate and hydrogen carbonate; the components of the buffer substance are a mixture capable of keeping the pH of the solution stable.
In a specific embodiment of the present invention, the buffer substance according to the present invention is selected from two or more of phosphoric acid, phosphate, hydrogen phosphate, dihydrogen phosphate, sodium hydroxide, sodium chloride, potassium chloride and/or their corresponding hydrates; further, the buffer substance is selected from Na2HPO4、NaH2PO4The mixed solution of (1).
Further, the activation conditions are: the pH value is 4.7, the activation temperature is 20-25 ℃, and the activation time is 0.5-1 hour.
The collagen is a natural protein extremely sensitive to temperature, and not only can lose secondary structures such as three-strand helix and the like at an over-high temperature, but also can generate molecular chain fracture or hydrolysis.
In a particular embodiment of the invention, the collagen is type I collagen, preferably bovine type I collagen;
further, the concentration of the collagen is 5 mg/mL;
further, after mixing with collagen, the pH was adjusted to 8, and the reaction was carried out for 48 hours.
In a specific embodiment of the present invention, the preparation method of the hydrolyzed polyacrylonitrile fiber is: mixing polyacrylonitrile fiber and alkaline solution for reaction, cooling after the reaction is finished, acidifying, and drying to obtain the final product.
The drying method of the present invention includes, but is not limited to, freeze drying, vacuum drying, and spray drying, and in the present embodiment, freeze drying is preferred.
Furthermore, the linear density of the polyacrylonitrile fiber is 1.67dtex to 6.67dtex, and preferably 2.22 dtex to 5.55 dtex.
Further, the alkaline solution is selected from NaHCO3、NaOH、(Na)2CO3Preferably is one or more of NaHCO3A mixed solution of NaOH; further preferred is 1% NaHCO3A mixed solution of NaOH;
further, polyacrylonitrile, NaOH, NaHCO3The mass ratio of (A) to (B) is 3:0.7: 0.3.
The alkaline solution can hydrolyze cyano polar groups of polyacrylonitrile fiber macromolecules to convert into carboxyl, so that the carboxyl reacts with amino in collagen to generate amido bonds to realize modification reaction, and in addition, NaOH and NaHCO are used3The alkaline solution prepared by adopting a specific mass ratio can remove wax on the surface of the polyacrylonitrile fiber and expose the fiber, so that the surface of the material is increased, and the surface modification is facilitated. However, the high-concentration and long-time hydrolysis causes excessive roughness on the surface of polyacrylonitrile fibers and reduces cell surface adhesion, so that alkaline hydrolysis is required under appropriate alkaline conditions and hydrolysis time.
Further, the reaction conditions are as follows: the temperature is 70-99 ℃, and the condensing reflux time is 40-75 h; the preferable temperature is 85-95 ℃, and the condensing reflux time is 48-72 h;
further, the reagent used for acidification is hydrochloric acid solution.
The polyacrylonitrile belongs to a hydrophobic material, and the collagen is hydrophilic, so that the two macromolecules are directly and physically mixed, and phase separation is easy to occur. The hydrolyzed polyacrylonitrile fiber and collagen are chemically cross-linked, so that the efficiency of generating amido bonds by the reaction of amino groups of the collagen and carboxyl groups in the hydrolyzed polyacrylonitrile fiber can be improved, the self-crosslinking reaction between the collagen can be promoted, and a fully uniform collagen layer is formed on the surface of the polyacrylonitrile fiber, so that the mechanical strength and the stability of the collagen layer on the surface of the polyacrylonitrile fiber are improved, and therefore, the hydrolysis rate of the polyacrylonitrile has an important role in improving the mechanical strength and the stability of the final polyacrylonitrile fiber. The method can ensure that the hydrolysis rate and the collagen content of the obtained polyacrylonitrile simultaneously meet the product requirements.
The hydrolysis rate of the polyacrylonitrile fiber is 1-20%, the content of the collagen is 1-20%, preferably the hydrolysis rate of the polyacrylonitrile fiber is 6-15%, and the content of the collagen is 1-20%.
The invention has the beneficial effects that:
(1) the method has the advantages of simple process, mild reaction conditions, reduction of damage to the collagen structure, stable and efficient reaction system, green and environment-friendly reaction reagent, low toxicity and reduction of the problem that the biocompatibility is influenced by toxic substance residues in the product.
(2) The collagen in the invention is hydrolyzed with polyacrylonitrile molecules through 'zero length' crosslinking to generate carboxyl covalent crosslinking, has good stability in aqueous solution or local microenvironment implanted into a body, and can play a role in an implanted part for a long time, thereby achieving the purpose of tissue repair.
(3) The hydrolysis rate of the polyacrylonitrile fiber obtained by the method is 6-15%, the collagen content in the modified polyacrylonitrile fiber is 1-20%, the hydrolysis rate of the polyacrylonitrile fiber and the collagen content in the modified polyacrylonitrile fiber can simultaneously meet the product requirements, the good natural structure of the collagen is maintained, the adhesion and proliferation of fibroblasts are well promoted, the matrix secreted by the fibroblasts is distributed along the fiber, the oriented growth and the functional expression of the fibroblasts are facilitated, and the biocompatibility is good; meanwhile, the material also has the mechanical strength capable of meeting the requirements of soft tissue repair, is particularly suitable for the mechanical strength requirements needed by abdominal wall defects and the like, and can be applied to weaving soft tissue repair materials.
Drawings
FIG. 1 is a graph showing the effect of collagen dosage on collagen content;
FIG. 2 is a scanning electron microscope image of collagen-modified polyacrylonitrile fibers;
FIG. 3 is a FT-IR chart of collagen-modified polypropylene fibers with polypropylene fibers and hydrolyzed polypropylene fibers;
FIG. 4 is a graph of the effect of PAN hydrolysis rate on mechanical performance;
FIG. 5 is a graph showing the results of adhesion and proliferation of fibroblasts on collagen-modacrylic fibers;
wherein, in the graph 2, the content of the collagen is 4.90 percent in A, polyacrylonitrile fiber, B, hydrolyzed polyacrylonitrile fiber, C, collagen modified polyacrylonitrile fiber, and the content of the collagen is 9.03 percent in D, collagen modified polyacrylonitrile fiber;
in fig. 5, the content of collagen in the a-polyacrylonitrile fiber and the b-collagen-modified polyacrylonitrile is 4.8%, the content of collagen in the c-collagen-modified polyacrylonitrile is 7.9%, and the content of collagen in the d-collagen-modified polyacrylonitrile is 10.75%.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
(1) Using Polyacrylonitrile (PAN) fiber, NaOH and NaHCO3PAN fiber, NaOH and NaHCO were weighed in a mass ratio of 3:0.7:0.3, respectively3Weighing 3g of PAN fiber with the linear density of 2.22-5.55 dtex, placing the PAN fiber in a 500mL three-neck flask, weighing 0.7g of NaOH and 0.3g of NaHCO3Preparing an aqueous alkali with the concentration of 1%, adding the aqueous alkali into a PAN fiber three-neck flask, starting a stirrer, stirring at the speed of 60-100 r/min, heating to 85-95 ℃, condensing and refluxing for 48-72 h to fully swell, cooling a sample to room temperature after the reaction is finished, washing with a large amount of water, acidifying with a hydrochloric acid solution, washing with a large amount of water, and freeze-drying to obtain the hydrolyzed PAN fiber sample.
(2) Mixing Na2HPO4·2H2O、NaH2PO4Dissolving 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) and N-hydroxysuccinimide (NHS) in water, and uniformly mixing at the temperature of 20-25 ℃, wherein the concentration of each substance in the solution is as follows: 60mmol/L EDC, 40mmol/L NHS, 0.2mol/L Na2HPO4·2H2O and 0.2mol/L NaH2PO4And adjusting the pH value of the solution to 3.8-4.5 by using NaOH to obtain a cross-linking solution.
(3) And (2) placing the polyacrylonitrile fiber hydrolyzed and dried in the step (1) into a crosslinking solution at normal temperature, adjusting the pH value to 4.7, activating at 18 ℃ for 0.5-1 hour, slowly dropping 5mg/mL bovine I type collagen, adjusting the pH value of a reaction system to 8, and uniformly stirring for 24 hours at 60-100 r/min by using a magnetic stirrer. Washing the obtained collagen modified polyacrylonitrile fiber with a large amount of water, and freeze-drying to obtain the collagen modified polyacrylonitrile fiber.
Example 2
(1) Using Polyacrylonitrile (PAN) fiber, NaOH and NaHCO3PAN fiber, NaOH and NaHCO were weighed in a mass ratio of 3:0.7:0.3, respectively3Weighing 3g of PAN fiber with the linear density of 2.22-5.55 dtex, placing the PAN fiber in a 500mL three-neck flask, weighing 0.7g of NaOH and 0.3g of NaHCO3Preparing an aqueous alkali with the concentration of 1%, adding the aqueous alkali into a PAN fiber three-neck flask, starting a stirrer, stirring at the speed of 60-100 r/min, heating to 85-95 ℃, condensing and refluxing for 48-72 h to fully swell, cooling a sample to room temperature after the reaction is finished, washing with a large amount of water, acidifying with a hydrochloric acid solution, washing with a large amount of water, and freeze-drying to obtain the hydrolyzed PAN fiber sample.
(2) Mixing Na2HPO4·2H2O、NaH2PO4Dissolving 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) and N-hydroxysuccinimide (NHS) in water, and uniformly mixing at the temperature of 20-25 ℃, wherein the concentration of each substance in the solution is as follows: 60mmol/L EDC, 40mmol/L NHS, 0.2mol/L Na2HPO4·2H2O and 0.2mol/L NaH2PO4And adjusting the pH value of the solution to 3.8-4.5 by using NaOH to obtain a cross-linking solution.
(3) And (2) placing the polyacrylonitrile fiber hydrolyzed and dried in the step (1) into a crosslinking solution at normal temperature, adjusting the pH value to be 3, activating for 0.5-1 hour at 40 ℃, then slowly dripping 10mg/mL bovine I type collagen, adjusting the pH value of a reaction system to be 9, and uniformly stirring for 12 hours at 60-100 r/min by using a magnetic stirrer. Washing the obtained collagen modified polyacrylonitrile fiber with a large amount of water, and freeze-drying to obtain the collagen modified polyacrylonitrile fiber.
Example 3
(1) Using Polyacrylonitrile (PAN) fiber, NaOH and NaHCO3PAN fiber, NaOH and NaHCO were weighed in a mass ratio of 3:0.7:0.3, respectively3Weighing 3g of PAN fiber with the linear density of 2.22-5.55 dtex, placing the PAN fiber in a 500mL three-neck flask, weighing 0.7g of NaOH and 0.3g of NaHCO3Preparing an aqueous alkali with the concentration of 1%, adding the aqueous alkali into a PAN fiber three-neck flask, starting a stirrer, stirring at the speed of 60-100 r/min, heating to 85-95 ℃, condensing and refluxing for 48-72 h to fully swell, cooling a sample to room temperature after the reaction is finished, washing with a large amount of water, acidifying with a hydrochloric acid solution, washing with a large amount of water, and freeze-drying to obtain the hydrolyzed PAN fiber sample.
(2) Mixing Na2HPO4·2H2O、NaH2PO4Dissolving 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) and N-hydroxysuccinimide (NHS) in water, and uniformly mixing at the temperature of 20-25 ℃, wherein the concentration of each substance in the solution is as follows: 60mmol/L EDC, 40mmol/L NHS, 0.2mol/L Na2HPO4·2H2O and 0.2mol/L NaH2PO4And adjusting the pH value of the solution to 3.8-4.5 by using NaOH to obtain a cross-linking solution.
(3) And (2) placing the polyacrylonitrile fiber hydrolyzed and dried in the step (1) into a crosslinking solution at normal temperature, adjusting the pH value to be 5, activating the polyacrylonitrile fiber at 30 ℃ for 1.5 hours, slowly dripping 1mg/mL bovine I type collagen, adjusting the pH value of a reaction system to be 7, and uniformly stirring the polyacrylonitrile fiber for 72 hours at a constant speed of 60-100 r/min by using a magnetic stirrer. Washing the obtained collagen modified polyacrylonitrile fiber with a large amount of water, and freeze-drying to obtain the collagen modified polyacrylonitrile fiber.
Example 4
(1) Using Polyacrylonitrile (PAN) fiber, NaOH and NaHCO3PAN fiber, NaOH and NaHCO were weighed in a mass ratio of 3:0.7:0.3, respectively3Weighing 3g of PAN fiber with the linear density of 2.22-5.55 dtex, placing the PAN fiber in a 500mL three-neck flask, weighing 0.7g of NaOH and 0.3g of NaHCO3Preparing an aqueous alkali with the concentration of 1%, adding the aqueous alkali into a PAN fiber three-neck flask, starting a stirrer, stirring at the speed of 60-100 r/min, heating to 85-95 ℃, condensing and refluxing for 48-72 h to fully swell, cooling a sample to room temperature after the reaction is finished, washing with a large amount of water, acidifying with a hydrochloric acid solution, washing with a large amount of water, and freeze-drying to obtain the hydrolyzed PAN fiber sample.
(2) Mixing Na2HPO4·2H2O、NaH2PO4Dissolving 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) and N-hydroxysuccinimide (NHS) in water, and uniformly mixing at the temperature of 20-25 ℃, wherein the concentration of each substance in the solution is as follows: 60mmol/L EDC, 40mmol/L NHS, 0.2mol/L Na2HPO4·2H2O and 0.2mol/L NaH2PO4And adjusting the pH value of the solution to 3.8-4.5 by using NaOH to obtain a cross-linking solution.
(3) And (2) placing the polyacrylonitrile fiber hydrolyzed and dried in the step (1) into a crosslinking solution at normal temperature, adjusting the pH value to 6, activating for 2 hours at 25 ℃, then slowly dripping 8mg/mL bovine I type collagen, adjusting the pH value of a reaction system to 7.5, and uniformly stirring for 12 hours at 60-100 r/min by using a magnetic stirrer. Washing the obtained collagen modified polyacrylonitrile fiber with a large amount of water, and freeze-drying to obtain the collagen modified polyacrylonitrile fiber.
In examples 1 to 4, the hydrolysis rate of polyacrylonitrile fibers was 6% to 15%, and the obtained collagen-modified polyacrylonitrile fibers had a diameter of 20 to 100 μm and a collagen content of 1 to 20%.
Example 5 control of collagen content in collagen-modified Polyacrylonitrile fibers
By adopting the PAN fiber with the same hydrolysis rate and the collagen grafting modification method with the same hydrolysis rate, the collagen content in the final collagen-modified polyacrylonitrile fiber can be changed only by adjusting the addition amount of the collagen, and as can be seen from fig. 1, the higher the proportion of the added collagen is, the higher the collagen content in the modified product is.
Surface topography
The collagen modified polyacrylonitrile fiber obtained by the method of the invention is subjected to electron microscope examination, and the surface appearance result is shown in figure 2.
As can be seen from fig. 2, the unmodified PAN fibers have uniform diameter and relatively obvious fiber stripes (a) on the surface; and the PAN is hydrolyzed by alkali, and the fibers on the surface begin to be locally broken and damaged (B); after further collagen surface modification, the fiber surface can be seen to have a relatively complete and smooth collagen coating (C); after the collagen grafting rate is increased, the thickness of the coating is obviously increased, the roughness is increased, and the surface area is increased (D).
PAN hydrolysis and collagen grafting validity verification
Furthermore, the polyacrylonitrile fiber, the hydrolyzed polyacrylonitrile fiber and the collagen-modified polyacrylonitrile fiber obtained by the method of the present invention were scanned by a fourier infrared spectrometer, and the results are shown in fig. 3. As can be seen from the results in FIG. 3, compared with polyacrylonitrile fiber, polyacrylonitrile fiber after alkaline hydrolysis has a large number of hydroxyl peaks (2500-3500 cm)-1) And 2250cm-1The left and right nitrile group peaks are obviously reduced, which shows the effectiveness of the alkaline hydrolysis; furthermore, compared with polyacrylonitrile fibers and hydrolyzed polyacrylonitrile fibers, the polyacrylonitrile fibers modified by the collagen have a new characteristic absorption peak at the amide band position of 1600-1700 cm, which shows that the collagen is effectively grafted to the surface of the polyacrylonitrile fibers.
Mechanical property detection
When PAN is just hydrolyzed under the action of alkali, the stress originally existing in the PAN fiber is released, so that the extensibility of the fiber is improved; with the increase of the hydrolysis rate of PAN, the rate of the occurrence of cracks on the surface of the fiber is increased, the degree is gradually increased, and the mechanical properties such as load and elongation at break, which are macroscopically shown, are gradually reduced. As can be seen from fig. 4A, B, when the PAN hydrolysis rate was lower than 8.7%, both the load and the tensile shift of the fiber were higher than those of the unhydrolyzed PAN, but when the hydrolysis rate reached 10.05%, both the load and the tensile shift were decreased.
Biocompatibility testing
The modified polyacrylonitrile fiber and the unmodified polyacrylonitrile fiber with different collagen contents obtained by the method are soaked in 75 percent ethanol overnight, cleaned by sterile PBS solution and sterilized by ultraviolet rays. Then counting and centrifuging the prepared fibroblasts, and preparing a cell suspension with a certain amount by using a cell culture solution. Uniformly inoculating the cell suspension on sterilized collagen modified polyacrylonitrile fiber and polyacrylonitrile fiber with different collagen concentrations, wherein the inoculation density is 1 × 104And (4) performing subsequent culture by using a cell culture solution (alpha-MEM culture medium containing 10% fetal bovine serum and 1% double antibody). When the sample was taken at 7d and observed by a laser confocal microscope, as shown in fig. 5, the adhesion and proliferation of cells of the collagen-modified polyacrylonitrile fiber were better than those of the polyacrylonitrile fiber, but the growth of cells on the collagen-modified polyacrylonitrile fiber having a collagen content of 10.75% was better than that of the modified polyacrylonitrile fiber having a collagen content of 4.8% and 7.9%.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. The polyacrylonitrile fiber with biological activity is characterized by being prepared by the following method:
mixing and activating hydrolyzed polyacrylonitrile fibers and a crosslinking solution, mixing and reacting with 1-10 mg/mL collagen, adjusting the pH value to 6-9, and reacting for 2-72 hours to obtain the collagen-based composite material;
the activation conditions are as follows: the pH value is 3-6, the activation temperature is 18-40 ℃, and the activation time is 0.3-2 h.
2. The polyacrylonitrile fiber according to claim 1, wherein the dosage of the hydrolyzed polyacrylonitrile fiber is 1.000-1.100 g, preferably 1.001-1.066 g;
the dosage of the collagen is 50-200 mg, preferably 60-150 mg.
3. The polyacrylonitrile fiber according to the claim 1, wherein the crosslinking solution comprises a crosslinking agent and a buffering substance;
further, the cross-linking agent is selected from one or more of glutaraldehyde, genipin and EDC/NHS, preferably EDC/NHS; furthermore, the concentration of EDC in the crosslinking solution is 10-200 mmol/L, preferably 60 mmol/L; the concentration of NHS is 10 mmol/L-100 mmol/L, preferably 40 mmol/L;
the buffer substance is selected from two or more of phosphoric acid, phosphate, hydrogen phosphate, dihydrogen phosphate, sodium hydroxide, sodium chloride, potassium chloride and/or corresponding hydrate thereof; further, the buffer substance is selected from Na2HPO4、NaH2PO4The mixed solution of (1).
4. Polyacrylonitrile fibers according to claim 1, characterized in that the activation conditions are: the pH value is 4.7, the activation temperature is 20-25 ℃, and the activation time is 0.5-1 hour.
5. Polyacrylonitrile fibers according to claim 1, characterized in that the collagen is type I collagen, preferably bovine type I collagen;
further, the concentration of the collagen is 5 mg/mL;
further, after mixing with collagen, adjusting the pH value to 8, and reacting for 48 hours to obtain the collagen.
6. The polyacrylonitrile fiber according to claim 1, wherein the preparation method of the hydrolyzed polyacrylonitrile fiber is as follows: mixing polyacrylonitrile fiber and alkaline solution for reaction, cooling after the reaction is finished, acidifying, and drying to obtain the final product.
7. The polyacrylonitrile fiber according to the claim 6, characterized in that the linear density of the polyacrylonitrile fiber is 1.67dtex to 6.67dtex, preferably 2.22 dtex to 5.55 dtex.
8. Polyacrylonitrile fiber according to claim 6, characterised in that the alkaline solution is selected from NaHCO3、NaOH、(Na)2CO3Preferably is one or more of NaHCO3A mixed solution of NaOH; further preferred is 1% NaHCO3A mixed solution of NaOH;
further, polyacrylonitrile: NaOH NaHCO3The mass ratio of (A) to (B) is 3:0.7: 0.3.
9. Polyacrylonitrile fibers according to claim 6, characterized in that the reaction conditions are: the temperature is 70-99 ℃, and the condensing reflux time is 40-75 h; the preferable temperature is 85-95 ℃, and the condensing reflux time is 48-72 h;
the reagent used for acidification is hydrochloric acid solution.
10. The polyacrylonitrile fiber according to any one of claims 1 to 9, wherein the hydrolysis rate of polyacrylonitrile fiber in the modified polyacrylonitrile fiber is 1% to 20%, the collagen content is 1% to 20%, preferably the hydrolysis rate of polyacrylonitrile fiber is 6% to 15%, and the collagen content is 1% to 20%.
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| PL312996A1 (en) * | 1996-02-27 | 1997-09-01 | Politechnika Lodzka | Method of obtaining filament spinning protein-polyacrylonitrile solutions |
| CN1590609A (en) * | 2003-09-03 | 2005-03-09 | 中国皮革和制鞋工业研究院 | Collagen protein-polyacrylonitrile composite fiber and its preparation method |
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