CN109675096B - Preparation method of chitosan fiber hydrogel dressing - Google Patents
Preparation method of chitosan fiber hydrogel dressing Download PDFInfo
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- CN109675096B CN109675096B CN201910130786.1A CN201910130786A CN109675096B CN 109675096 B CN109675096 B CN 109675096B CN 201910130786 A CN201910130786 A CN 201910130786A CN 109675096 B CN109675096 B CN 109675096B
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- Prior art keywords
- chitosan
- chitosan fiber
- maleyl
- fiber cloth
- solution
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- 229920001661 Chitosan Polymers 0.000 title claims abstract description 275
- 239000000835 fiber Substances 0.000 title claims abstract description 172
- 239000000017 hydrogel Substances 0.000 title claims abstract description 105
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000004744 fabric Substances 0.000 claims abstract description 86
- 125000003099 maleoyl group Chemical group C(\C=C/C(=O)*)(=O)* 0.000 claims abstract description 24
- 125000000349 (Z)-3-carboxyprop-2-enoyl group Chemical group O=C([*])/C([H])=C([H])\C(O[H])=O 0.000 claims description 97
- 239000000243 solution Substances 0.000 claims description 62
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 51
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 43
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 42
- 239000011259 mixed solution Substances 0.000 claims description 39
- 238000006467 substitution reaction Methods 0.000 claims description 39
- 239000008367 deionised water Substances 0.000 claims description 35
- 229910021641 deionized water Inorganic materials 0.000 claims description 35
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 28
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- 239000002798 polar solvent Substances 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 238000000502 dialysis Methods 0.000 claims description 25
- 239000000843 powder Substances 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 19
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 238000004108 freeze drying Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 230000008961 swelling Effects 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 9
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 9
- 125000003277 amino group Chemical group 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 7
- 125000002252 acyl group Chemical group 0.000 claims description 7
- 229910001507 metal halide Inorganic materials 0.000 claims description 6
- 150000005309 metal halides Chemical class 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 claims description 5
- QCCDLTOVEPVEJK-UHFFFAOYSA-N phenylacetone Chemical compound CC(=O)CC1=CC=CC=C1 QCCDLTOVEPVEJK-UHFFFAOYSA-N 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- SWXQHJMEARSCRK-UHFFFAOYSA-N 1-(6,6-dimethoxycyclohexa-2,4-dien-1-yl)propan-1-one Chemical compound C(C)C(=O)C1C(C=CC=C1)(OC)OC SWXQHJMEARSCRK-UHFFFAOYSA-N 0.000 claims description 4
- 239000001110 calcium chloride Substances 0.000 claims description 4
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000010979 pH adjustment Methods 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 238000004132 cross linking Methods 0.000 abstract description 21
- 238000010382 chemical cross-linking Methods 0.000 abstract description 5
- 239000003431 cross linking reagent Substances 0.000 abstract description 5
- 230000035876 healing Effects 0.000 abstract description 5
- 231100000331 toxic Toxicity 0.000 abstract description 5
- 230000002588 toxic effect Effects 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 1
- 238000005303 weighing Methods 0.000 description 21
- 239000000463 material Substances 0.000 description 14
- 206010052428 Wound Diseases 0.000 description 12
- 208000027418 Wounds and injury Diseases 0.000 description 12
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 8
- 239000002585 base Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 239000000499 gel Substances 0.000 description 4
- 230000029663 wound healing Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000010668 complexation reaction Methods 0.000 description 3
- 231100000135 cytotoxicity Toxicity 0.000 description 3
- 230000003013 cytotoxicity Effects 0.000 description 3
- 231100000263 cytotoxicity test Toxicity 0.000 description 3
- 229920005615 natural polymer Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229920001059 synthetic polymer Polymers 0.000 description 2
- 210000001519 tissue Anatomy 0.000 description 2
- LNBMZFHIYRDKNS-UHFFFAOYSA-N 2,2-dimethoxy-1-phenylethanone Chemical compound COC(OC)C(=O)C1=CC=CC=C1 LNBMZFHIYRDKNS-UHFFFAOYSA-N 0.000 description 1
- 206010067484 Adverse reaction Diseases 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 230000006838 adverse reaction Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical group 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- 210000000172 cytosol Anatomy 0.000 description 1
- 238000001804 debridement Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 210000000416 exudates and transudate Anatomy 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 230000023597 hemostasis Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- -1 on one hand Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
Classifications
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L26/00—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
- A61L26/0009—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form containing macromolecular materials
- A61L26/0023—Polysaccharides
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- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L26/00—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
- A61L26/0061—Use of materials characterised by their function or physical properties
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- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L26/00—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
- A61L26/0061—Use of materials characterised by their function or physical properties
- A61L26/008—Hydrogels or hydrocolloids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/243—Two or more independent types of crosslinking for one or more polymers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/28—Treatment by wave energy or particle radiation
-
- 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
- D06M11/32—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 System
-
- 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
- D06M13/10—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 oxygen
- D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
- D06M13/203—Unsaturated carboxylic acids; Anhydrides, halides or salts thereof
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- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
- A61L2300/412—Tissue-regenerating or healing or proliferative agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
- C08K2003/162—Calcium, strontium or barium halides, e.g. calcium, strontium or barium chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K2003/168—Zinc halides
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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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
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
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Abstract
The invention relates to a preparation method of a hydrogel dressing, in particular to a preparation method of a chitosan fiber hydrogel dressing, belonging to the technical field of preparation of medical dressings. The preparation method of the invention compounds the maleoyl chitosan fiber cloth with the maleoyl chitosan, and adopts ultraviolet curing and ion crosslinking technology to form the chitosan fiber hydrogel dressing with a double-crosslinked network structure. The preparation method of the invention fully exerts the synergistic effect of chemical crosslinking and ionic crosslinking, and endows the dressing with high wet strength. Because no toxic cross-linking agent such as aldehyde is adopted, the prepared chitosan fiber hydrogel dressing has good biocompatibility, cannot cause any damage to the wound surface when being applied to the wound surface, and is beneficial to the healing of the wound surface.
Description
Technical Field
The invention relates to a preparation method of a hydrogel dressing, in particular to a preparation method of a chitosan fiber hydrogel dressing, belonging to the technical field of preparation of medical dressings.
Background
The hydrogel dressing is a gel material with better performance than gauze, is mainly formed by crosslinking hydrophilic macromolecules through physical or chemical action, and has the functions of debridement, absorbing wound exudate and providing a moist healing environment to accelerate wound healing when acting on a wound surface. The chitosan hydrogel dressing is a hydrogel dressing formed on the basis of natural high-molecular chitosan, has the advantages of the hydrogel dressing, and also gives full play to the excellent characteristics of chitosan, such as natural non-toxicity, hemostasis, bacteriostasis, promotion of wound healing and the like.
At present, the chitosan hydrogel dressing is commonly prepared by a chemical crosslinking method, an irradiation crosslinking method and the like. The Chinese patent publication No. CN108992702A, the publication date of 2018, 12 and 14, the invention name of which is 'a preparation method of a porous nano-oxide modified chitosan medical hydrogel dressing' discloses a preparation method of the chitosan medical hydrogel dressing, wherein toxic reagents such as glutaraldehyde and the like are used as cross-linking agents, and even if trace residues of the toxic cross-linking agents exist, the toxic cross-linking agents still cause damage to human tissues to different degrees and affect the healing of wound surfaces. Chinese publication No. CN101502667B, published as 12 and 5 days 2012, entitled "medical chitosan transparent hydrogel wound dressing and preparation and application thereof", Chinese patent publication No. CN103480034A, published as 1 and 1 day 2014, entitled "irradiation crosslinking chitosan/gelatin/polyvinyl alcohol hydrogel dressing and preparation method and application thereof", Chinese patent publication No. CN1579559, published as 2 and 16 days 2005, entitled "polyvinyl alcohol hydrogel dressing containing drug and chitosan and preparation method thereof", and the like disclose natural polymer chitosan composite synthetic polymers, and a case of forming hydrogel dressing by using an irradiation crosslinking method, which can lead to the problem that the strength of hydrogel is poor due to the large amount of degradation of chitosan in the chitosan hydrogel dressing under the irradiation condition of high-energy rays on one hand, and on the other hand, more synthetic polymers are added in the hydrogel dressing, so that the biocompatibility of the hydrogel dressing is reduced, and the hydrogel dressing has certain influence on the healing of the wound surface.
Disclosure of Invention
Aiming at the problems, the invention aims to provide a preparation method of a chitosan fiber hydrogel dressing with high wet strength and good biocompatibility.
In order to achieve the purpose, the technical scheme is as follows, and the preparation method of the chitosan fiber hydrogel dressing is carried out according to the following steps:
a. preparation of maleyl chitosan fiber cloth
Dispersing chitosan fiber cloth in a polar solvent, wherein the mass volume ratio of the chitosan fiber cloth to the polar solvent is 1 g: 10-100 mL, adding maleic anhydride into a mixed solution of chitosan fiber cloth and a polar solvent, wherein the molar ratio of amino groups of the chitosan fiber cloth to the maleic anhydride is 1: 0.1-5, uniformly stirring at room temperature, reacting in a constant-temperature water bath at 35-80 ℃ for 6-18 h, and separating the reacted chitosan fiber cloth from a mixed liquid formed by a polar solvent and maleic anhydride to obtain a maleic acyl grafted chitosan fiber cloth primary product.
Dispersing the primary chitosan fiber cloth grafted with the maleyl in an ethanol-water mixed solution with a volume ratio of 80:20, dropwise adding 30% (w/v) of an inorganic strong alkali aqueous solution, adjusting the pH value of the ethanol-water mixed solution to 6-8, soaking for 30 minutes, separating the primary chitosan fiber cloth grafted with the maleyl from a mixed liquid of ethanol, inorganic strong alkali and water, washing for 2 times in 75% by volume of alcohol, dehydrating, and drying at 40 ℃ to obtain the maleyl chitosan fiber cloth with the molar substitution degree of the maleyl of 0.05-0.9.
b. Preparation of maleoyl chitosan
Placing chitosan powder and maleic anhydride in a polar solvent, wherein the weight volume ratio of the chitosan powder to the polar solvent is 1 g: 10-200 mL, wherein the molar ratio of amino groups on a chitosan molecular chain to maleic anhydride is 1: 5-10, stirring uniformly at room temperature, reacting at 35-80 ℃, wherein the reaction time is 12-48 hours, after the reaction is finished, adding 1mol/L of inorganic strong base aqueous solution into a mixed solution of chitosan, maleic anhydride and a polar solvent, adjusting the pH value of the mixed solution to 11-13, transferring the mixed solution after the pH adjustment into a dialysis bag, dialyzing in deionized water, intercepting the molecular weight of the dialysis bag to be 8000-14000Da, and the dialysis time to be 2 days to form a maleyl chitosan solution, and freeze-drying the maleyl chitosan solution for 48 hours at-50 ℃ to obtain the maleyl chitosan with the maleyl molar substitution degree of 1.0-2.5.
c. And c, mixing the maleyl chitosan fiber cloth obtained in the step a and the maleyl chitosan obtained in the step b with water according to the mass percentage:
d. And c, placing the chitosan fiber hydrogel obtained in the step c in a deionized water solution of 0.1-1 mol/L metal halide, standing for 0.1-5 hours at room temperature to form the chitosan fiber hydrogel with the equilibrium swelling degree of 0.02-0.1, and washing for 3-5 times by using deionized water to obtain the chitosan fiber hydrogel dressing.
The polar solvent is one of dimethyl sulfoxide, dimethylformamide, acetonitrile or 1, 3-dimethyl-2-imidazolidinone.
The inorganic strong base is one of sodium hydroxide or potassium hydroxide.
The photoinitiator is one of 2-hydroxy-2-methyl-1-p-hydroxyethyl ether phenyl acetone or 1-hydroxycyclohexyl phenyl ketone or 2, 2-dimethoxy-phenyl ethyl ketone.
The metal halide is one of lithium chloride, calcium chloride, zinc chloride, copper chloride and ferric chloride.
Due to the adoption of the technical scheme, the preparation method of the chitosan fiber hydrogel dressing has the beneficial technical effects that:
(1) the preparation method disclosed by the invention combines ultraviolet curing and standing crosslinking technologies, and the chitosan fiber hydrogel dressing with the double-crosslinking network structure is formed through copolymerization crosslinking between carbon-carbon double bonds on a molecular chain on the surface of the maleoyl chitosan fiber and carbon-carbon double bonds on the molecular chain of the maleoyl chitosan fiber and complexation reaction between carboxyl on the molecular chain on the surface of the maleoyl chitosan fiber and carboxyl on the molecular chain of the maleoyl chitosan and metal ions, so that the synergistic effect of chemical crosslinking and ionic crosslinking is fully exerted, the wet strength of the hydrogel dressing is remarkably improved, and the universal defect of low strength of hydrogel formed by natural polymers is completely overcome.
(2) The preparation method of the invention does not adopt any toxic cross-linking agent such as aldehyde and the like, so that the prepared chitosan fiber hydrogel dressing has good biocompatibility, can not cause any damage to the wound surface when being applied to the wound surface, and is beneficial to the healing of the wound surface.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
A preparation method of a chitosan fiber hydrogel dressing comprises the following steps:
a. preparation of maleyl chitosan fiber cloth
Dispersing chitosan fiber cloth in a polar solvent, wherein the mass volume ratio of the chitosan fiber cloth to the polar solvent is 1 g: 10-100 mL, adding maleic anhydride into a mixed solution of chitosan fiber cloth and a polar solvent, wherein the molar ratio of amino groups of the chitosan fiber cloth to the maleic anhydride is 1: 0.1-5, uniformly stirring at room temperature, reacting in a constant-temperature water bath at 35-80 ℃ for 6-18 h, and separating the reacted chitosan fiber cloth from a mixed liquid formed by a polar solvent and maleic anhydride to obtain a maleic acyl grafted chitosan fiber cloth primary product.
Dispersing the primary chitosan fiber cloth grafted with the maleyl in an ethanol-water mixed solution with a volume ratio of 80:20, dropwise adding 30% (w/v) of an inorganic strong alkali aqueous solution, adjusting the pH value of the ethanol-water mixed solution to 6-8, soaking for 30 minutes, separating the primary chitosan fiber cloth grafted with the maleyl from a mixed liquid of ethanol, inorganic strong alkali and water, washing for 2 times in 75% by volume of alcohol, dehydrating, and drying at 40 ℃ to obtain the maleyl chitosan fiber cloth with the molar substitution degree of the maleyl of 0.05-0.9. The polar solvent is one of dimethyl sulfoxide, dimethylformamide, acetonitrile or 1, 3-dimethyl-2-imidazolidinone. The inorganic strong base is one of sodium hydroxide or potassium hydroxide.
Chitosan is a hydrophilic natural polymer and has many excellent properties, such as good biocompatibility, biodegradability, reproducibility, antibacterial property, and promotion of wound healing. Due to the characteristics, the chitosan has wide application prospects in the aspects of wound dressing, drug controlled release systems, tissue engineering and the like.
The chitosan fiber can be prepared by a wet spinning process, and the chitosan with the viscosity average molecular weight of more than 100 ten thousand can be easily spun into the fiber. Hydroxyl and amino groups on the surface of the chitosan fiber form a large amount of intermolecular and intramolecular hydrogen bonds due to drafting orientation in the spinning process, and are difficult to form effective acting force with groups on high molecular chains in a solution, so that when the chitosan fiber is used for enhancing the strength of hydrogel, enhancement failure is often caused by the problem of weak interface bonding force. If some reactive groups such as maleyl groups are grafted on the surface of the chitosan fiber and react with functional groups such as the maleyl groups on the macromolecular chains in the solution to form covalent crosslinking, the strength of the formed fiber hydrogel is obviously improved. Therefore, it is necessary to structurally modify chitosan fibers. But due to the existence of a large number of intermolecular/internal hydrogen bonds in the molecular structure of the chitosan, the molecules of the reaction reagent are difficult to enter the molecular chains of the chitosan fibers. In order to solve the problem, a micromolecular polar solvent is used as a reaction medium, and intermolecular/internal hydrogen bonds in a chitosan fiber structure can be effectively opened, so that a reaction reagent can react with amino and hydroxyl on a chitosan molecular chain. Here, we select maleic anhydride as the reactive agent, on one hand, carbon-carbon double bonds can be grafted to the surface of chitosan fibers to provide further reactive groups, and on the other hand, the grafted carboxyl groups can also undergo a complexation reaction with metal ions. In the step a, the positioned substitution on the amino N of the chitosan fiber is realized by controlling the molar ratio of the amino of the chitosan fiber cloth to the carbon-carbon double bond on the maleic anhydride molecule and the reaction conditions, and the molar substitution degree of the maleic acyl is in the range of 0.05-0.9. Thus, suitable molar ratios are chosen to be: 1: 0.1 to 5; suitable reaction conditions are selected as follows: the temperature is 35-80 ℃, and the reaction time is 6-18 h.
The primary chitosan fiber cloth product grafted with the maleyl is acidic, the pH value is adjusted to 6-8 in an ethanol-water mixed solution by using an inorganic strong base aqueous solution, the obtained primary chitosan fiber cloth product grafted with the maleyl is close to neutral, and adverse reactions such as wound surface stimulation and the like caused after the primary chitosan fiber cloth product is contacted with a wound surface are avoided. The maleyl chitosan fiber cloth with the molar substitution degree of the maleyl group of 0.05-0.9 can absorb a large amount of liquid, can still keep the basic form of the fiber after absorbing the liquid, has high tensile strength and cannot be dissolved. When the molar substitution degree is 0.9-1.0, the maleyl chitosan fiber cloth can be dispersed in an aqueous solution to form colloid, and the shape of the fiber is lost. When the molar substitution degree is more than 1.0, the maleoyl chitosan fiber cloth can be completely dissolved in the aqueous solution to form a solution. When the fiber morphology is lost, the effect of the fibers in enhancing the strength of the hydrogel is insignificant or absent at all.
b. Preparation of maleoyl chitosan
Placing chitosan powder and maleic anhydride in a polar solvent, wherein the weight volume ratio of the chitosan powder to the polar solvent is 1 g: 10-200 mL, wherein the molar ratio of amino groups on a chitosan molecular chain to maleic anhydride is 1: 5-10, stirring uniformly at room temperature, reacting at 35-80 ℃, wherein the reaction time is 12-48 hours, after the reaction is finished, adding 1mol/L of inorganic strong base aqueous solution into a mixed solution of chitosan, maleic anhydride and a polar solvent, adjusting the pH value of the mixed solution to 11-13, transferring the mixed solution after the pH adjustment into a dialysis bag, dialyzing in deionized water, intercepting the molecular weight of the dialysis bag to be 8000-14000Da, and the dialysis time to be 2 days to form a maleyl chitosan solution, and freeze-drying the maleyl chitosan solution for 48 hours at-50 ℃ to obtain the maleyl chitosan with the maleyl molar substitution degree of 1.0-2.5. The polar solvent is one of dimethyl sulfoxide, dimethylformamide, acetonitrile or 1, 3-dimethyl-2-imidazolidinone. The inorganic strong base is one of sodium hydroxide or potassium hydroxide.
Chitosan is only soluble in dilute aqueous acid and has very low solubility in most organic solvents, which greatly limits the processing and application of chitosan. The solubility problem of chitosan is caused because the chitosan has regular molecular structure, and has intermolecular and intramolecular hydrogen bonds, so that the chitosan is easy to crystallize. If this regularity is destroyed, intermolecular and intramolecular hydrogen bonds are weakened, and the crystallinity is lowered, so that the polymer has a certain solubility. Especially in biomedical applications, the water solubility of chitosan is of more interest, since only water-solubility allows it to enter the cytosol for its function.
The chitosan weakens or destroys the hydrogen bond acting force between chitosan molecules and in the chitosan molecules through acylation reaction with maleic anhydride, and simultaneously introduces carboxyl with higher hydrophilicity, thereby greatly improving the solubility of the neutral aqueous solution of the chitosan. In addition, the carbon-carbon double bond on the maleoyl group can be polymerized, copolymerized and crosslinked with the carbon-carbon double bond on the surface of the chitosan fiber cloth of the maleoyl group to form a structure formed by connecting macromolecular chains among fibers, so that the wet strength of the chitosan hydrogel is obviously improved. And finally, both carboxyl on the surface of the maleoyl chitosan fiber cloth and carboxyl on a molecular chain of the maleoyl chitosan are subjected to complexing crosslinking with metal ions, so that the wet strength of the chitosan hydrogel is further improved.
In the step b, the molar substitution degree of the maleic acyl is within the range of 1.0-2.5 by controlling the molar ratio of the amino group of the chitosan to the anhydride group of the maleic anhydride and reaction conditions, so that the maleylation chitosan has good water solubility, and meanwhile, the double bonds with enough content on the molecular chain can be subjected to the next polymerization reaction or crosslinking reaction. Thus, suitable molar ratios are chosen to be: 1: 5-10; suitable reaction conditions are selected as follows: the temperature is 35-80 ℃, and the reaction time is 12-48 hours. The chitosan powder adopts chitosan with viscosity average molecular weight of less than 90 ten thousand, and can prepare water-soluble maleyl chitosan with high degree of substitution of maleyl.
c. And c, mixing the maleyl chitosan fiber cloth obtained in the step a and the maleyl chitosan obtained in the step b with water according to the mass percentage:
The ultraviolet polymerization method adopted in the step c has the characteristics of mild reaction conditions, low released reaction heat, short crosslinking curing time and the like. The photo-active group maleic acyl on the molecular chain of the maleic acyl chitosan is subjected to photo-initiated self-polymerization under the irradiation of ultraviolet light to form hydrogel of a three-dimensional cross-linked network to a certain extent. Meanwhile, carbon-carbon double bonds on the molecular chain of the maleoyl chitosan and carbon-carbon double bonds on the surface of the chitosan fiber cloth of the maleoyl are polymerized, copolymerized and crosslinked to form a structure formed by connecting macromolecular chains among fibers. By controlling the ratio of the monomer to the initiator, the exposure time and the light intensity index, the carbon-carbon double bond in the system can be completely converted into the carbon-carbon single bond, and the problem of monomer residue is avoided. The introduction of the chitosan fiber cloth containing the maleyl groups can form a structure formed by connecting macromolecular chains among fibers through copolymerization and crosslinking with the maleyl groups in the solution, and can effectively transfer the external force applied to the hydrogel to the fibers with higher strength, so that the wet strength of the chitosan hydrogel containing the maleyl groups is improved. The photoinitiators used in the invention, 2-hydroxy-2-methyl-1-p-hydroxyethyl ether phenyl acetone or 1-hydroxycyclohexyl phenyl ketone or 2, 2-dimethoxy phenyl ethyl ketone, are all photoinitiators with good biocompatibility, and have been reported in the literature.
d. And c, placing the chitosan fiber hydrogel obtained in the step c in a deionized water solution of 0.1-1 mol/L metal halide, standing for 0.1-5 hours at room temperature to form the chitosan fiber hydrogel with the equilibrium swelling degree of 0.02-0.1, and washing for 3-5 times by using deionized water to obtain the chitosan fiber hydrogel dressing. The metal halide is one of lithium chloride, calcium chloride, zinc chloride, copper chloride and ferric chloride.
The step d adopts a method of crosslinking metal ions with 1 to 3 valences. The metal ions can perform complexation with carboxyl on the surface of the maleoyl chitosan fiber cloth and carboxyl on a maleoyl chitosan molecular chain to form ionic crosslinking, so that the chemically crosslinked chitosan molecular chain is further crosslinked, the wet strength of the chitosan hydrogel dressing is further improved, and a three-dimensional network structure with double crosslinking of chemical crosslinking and ionic crosslinking is formed. In the invention, chemical crosslinking and physical crosslinking are combined to form the chitosan fiber hydrogel with a double-crosslinked three-dimensional network structure. The two crosslinking have synergistic effect, and the chitosan fiber hydrogel dressing has high wet strength.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Example 1
Weighing 1g of chitosan fiber cloth, dispersing the chitosan fiber cloth in 10mL of dimethyl sulfoxide, adding 0.05g of maleic anhydride, stirring uniformly at room temperature, reacting for 6h in a constant-temperature water bath at 35 ℃, separating the reacted chitosan fiber cloth from the reaction mixed solution, dispersing the chitosan fiber cloth in an ethanol-water mixed solution with a volume ratio of 80:20, dropwise adding 30% (w/v) of sodium hydroxide aqueous solution, adjusting the pH value of the ethanol-water mixed solution to 6.0, soaking for 30 min, separating the soaked fiber cloth from the mixed solution, washing for 2 times by using 75% by volume of alcohol, dehydrating, and drying at 40 ℃ to obtain the maleyl chitosan fiber cloth with the molar substitution degree of 0.05 of maleyl.
Weighing 1g of chitosan powder and 2.49g of maleic anhydride, adding the chitosan powder and the maleic anhydride into 10mL of dimethylformamide, uniformly stirring at room temperature, reacting for 12 hours at 35 ℃, adding 1mol/L of NaOH solution after the reaction is finished, adjusting the pH value of the solution to 11, transferring the solution into a dialysis bag, dialyzing for 2 days in deionized water, intercepting the solution with the molecular weight of 8000-14000D from the dialysis bag, and freeze-drying the solution for 48 hours at-50 ℃ to obtain the maleyl chitosan with the molar substitution degree of 1.0 of the maleyl.
Weighing 0.2g of maleyl chitosan fiber cloth with the molar substitution degree of the maleyl group of 0.05 and 2g of the maleyl chitosan with the molar substitution degree of the maleyl group of 1.0, placing the weighed materials in 97.75mL of deionized water, stirring the materials until the materials are completely dissolved, adding 0.05g of 2-hydroxy-2-methyl-1-p-hydroxyethyl ether phenyl acetone, and performing ion exchange at the wavelength of 320-400nm and the light intensity of 5mW/cm2Irradiating for 15min under ultraviolet light to obtain chitosan fiber hydrogel, placing the chitosan fiber hydrogel in 0.1mol/L LiCl solution, standing for 0.1h at room temperature to form chitosan fiber hydrogel with the equilibrium swelling degree of 0.1, and washing for 3 times by deionized water to obtain the chitosan fiber hydrogel dressing.
Example 2
Weighing 1g of chitosan fiber cloth, dispersing the chitosan fiber cloth in 100mL of dimethylformamide, adding 2.49g of maleic anhydride, stirring uniformly at room temperature, reacting for 18h in a thermostatic water bath at 80 ℃, separating the reacted chitosan fiber cloth from the reaction mixed solution, dispersing the chitosan fiber cloth in an ethanol-water mixed solution with a volume ratio of 80:20, dropwise adding 30% (w/v) potassium hydroxide aqueous solution, adjusting the pH value of the ethanol-water mixed solution to 8.0, soaking for 30 min, separating the soaked fiber cloth from the mixed solution, washing for 2 times by using 75% by volume of alcohol, dehydrating, and drying at 40 ℃ to obtain the maleyl chitosan fiber cloth with the molar substitution degree of maleyl of 0.9.
Weighing 1g of chitosan powder and 4.98g of maleic anhydride, adding the chitosan powder and the maleic anhydride into 200mL of acetonitrile, uniformly stirring at room temperature, reacting for 48 hours at 80 ℃, adding 1mol/L of KOH solution after the reaction is finished, adjusting the pH value of the solution to 13, transferring the solution into a dialysis bag, dialyzing for 2 days in deionized water, intercepting the solution with the molecular weight of 8000-14000D from the dialysis bag, and freeze-drying the solution for 48 hours at-50 ℃ to obtain the maleyl chitosan with the molar substitution degree of 2.5 of the maleyl.
Weighing 2g of maleyl chitosan fiber cloth with the molar substitution degree of the maleyl group of 0.9 and 12g of the maleyl chitosan with the molar substitution degree of the maleyl group of 2.5, placing the weighed materials in 85.9mL of deionized water, stirring the materials until the materials are completely dissolved, adding 0.1g of 1-hydroxycyclohexyl phenyl ketone, and adding the mixture into the deionized water at the wavelength of 320-400nm and the light intensity of 100mW/cm2Irradiating with ultraviolet light for 5min to obtain chitosan fiber hydrogel, placing the chitosan fiber hydrogel in 1mol/L CaCl2Standing the solution for 5 hours at room temperature to form chitosan fiber hydrogel with the equilibrium swelling degree of 0.03, and washing the chitosan fiber hydrogel dressing for 5 times by deionized water to obtain the chitosan fiber hydrogel dressing.
Example 3
Weighing 1g of chitosan fiber cloth, dispersing the chitosan fiber cloth in 50mL of 1, 3-dimethyl-2-imidazolidinone, adding 1.25g of maleic anhydride, stirring uniformly at room temperature, reacting for 12h in a thermostatic water bath at 50 ℃, separating the reacted chitosan fiber cloth from the reaction mixed solution, dispersing the chitosan fiber cloth in an ethanol-water mixed solution with the volume ratio of 80:20, dropwise adding 30% (w/v) potassium hydroxide aqueous solution, adjusting the pH value of the ethanol-water mixed solution to 7.2, soaking for 30 min, separating the soaked fiber cloth from the mixed solution, washing for 2 times by using 75% alcohol by volume fraction, dehydrating, and drying at 40 ℃ to obtain the maleyl chitosan fiber cloth with the maleyl molar substitution degree of 0.4.
Weighing 1g of chitosan powder and 3.74g of maleic anhydride, adding the chitosan powder and the maleic anhydride into 100mL of acetonitrile, uniformly stirring at room temperature, reacting for 36 hours at 60 ℃, adding 1mol/L of KOH solution after the reaction is finished, adjusting the pH value of the solution to 12, transferring the solution into a dialysis bag, dialyzing for 2 days in deionized water, intercepting the solution with the molecular weight of 8000-14000D from the dialysis bag, and freeze-drying the solution at-50 ℃ for 48 hours to obtain the maleyl chitosan with the molar substitution degree of 1.6 of the maleyl.
Weighing 1g of maleyl chitosan fiber cloth with the molar substitution degree of the maleyl group of 0.4 and 5g of the maleyl chitosan with the molar substitution degree of the maleyl group of 1.6, placing the weighed materials in 93.92mL of deionized water,stirring until completely dissolved, adding 0.08g of 2, 2-dimethoxy-acetophenone at wavelength of 320-400nm and light intensity of 50mW/cm2Irradiating for 12min under ultraviolet light to obtain chitosan fiber hydrogel, and placing the chitosan fiber hydrogel in 0.5mol/L ZnCl2Standing the solution for 2 hours at room temperature to form chitosan fiber hydrogel with the equilibrium swelling degree of 0.05, and washing the chitosan fiber hydrogel dressing for 4 times by deionized water to obtain the chitosan fiber hydrogel dressing.
Example 4
Weighing 1g of chitosan fiber cloth, dispersing the chitosan fiber cloth in 100mL of dimethylformamide, adding 2.49g of maleic anhydride, stirring uniformly at room temperature, reacting for 18h in a thermostatic water bath at 80 ℃, separating the reacted chitosan fiber cloth from the reaction mixed solution, dispersing the chitosan fiber cloth in an ethanol-water mixed solution with a volume ratio of 80:20, dropwise adding 30% (w/v) potassium hydroxide aqueous solution, adjusting the pH value of the ethanol-water mixed solution to 8.0, soaking for 30 min, separating the soaked fiber cloth from the mixed solution, washing for 2 times by using 75% by volume of alcohol, dehydrating, and drying at 40 ℃ to obtain the maleyl chitosan fiber cloth with the molar substitution degree of maleyl of 0.9.
Weighing 1g of chitosan powder and 4.98g of maleic anhydride, adding the chitosan powder and the maleic anhydride into 200mL of acetonitrile, uniformly stirring at room temperature, reacting for 48 hours at 80 ℃, adding 1mol/L of KOH solution after the reaction is finished, adjusting the pH value of the solution to 13, transferring the solution into a dialysis bag, dialyzing for 2 days in deionized water, intercepting the solution with the molecular weight of 8000-14000D from the dialysis bag, and freeze-drying the solution for 48 hours at-50 ℃ to obtain the maleyl chitosan with the molar substitution degree of 2.5 of the maleyl.
Weighing 2g of maleyl chitosan fiber cloth with the molar substitution degree of the maleyl group of 0.9 and 12g of the maleyl chitosan with the molar substitution degree of the maleyl group of 2.5, placing the weighed materials in 85.9mL of deionized water, stirring the materials until the materials are completely dissolved, adding 0.1g of 1-hydroxycyclohexyl phenyl ketone, and adding the mixture into the deionized water at the wavelength of 320-400nm and the light intensity of 100mW/cm2Irradiating with ultraviolet light for 5min to obtain chitosan fiber hydrogel, and placing the chitosan fiber hydrogel in 0.4mol/L CuCl2Standing in the solution at room temperature for 5h to form chitosan fiber hydrogel with equilibrium swelling degree of 0.04And washing the gel for 5 times by using deionized water to obtain the chitosan fiber hydrogel dressing.
Example 5
Weighing 1g of chitosan fiber cloth, dispersing the chitosan fiber cloth in 100mL of dimethylformamide, adding 2.49g of maleic anhydride, stirring uniformly at room temperature, reacting for 18h in a thermostatic water bath at 80 ℃, separating the reacted chitosan fiber cloth from the reaction mixed solution, dispersing the chitosan fiber cloth in an ethanol-water mixed solution with a volume ratio of 80:20, dropwise adding 30% (w/v) potassium hydroxide aqueous solution, adjusting the pH value of the ethanol-water mixed solution to 8.0, soaking for 30 min, separating the soaked fiber cloth from the mixed solution, washing for 2 times by using 75% by volume of alcohol, dehydrating, and drying at 40 ℃ to obtain the maleyl chitosan fiber cloth with the molar substitution degree of maleyl of 0.9.
Weighing 1g of chitosan powder and 4.98g of maleic anhydride, adding the chitosan powder and the maleic anhydride into 200mL of acetonitrile, uniformly stirring at room temperature, reacting for 48 hours at 80 ℃, adding 1mol/L of KOH solution after the reaction is finished, adjusting the pH value of the solution to 13, transferring the solution into a dialysis bag, dialyzing for 2 days in deionized water, intercepting the solution with the molecular weight of 8000-14000D from the dialysis bag, and freeze-drying the solution for 48 hours at-50 ℃ to obtain the maleyl chitosan with the molar substitution degree of 2.5 of the maleyl.
Weighing 2g of maleyl chitosan fiber cloth with the molar substitution degree of the maleyl group of 0.9 and 12g of the maleyl chitosan with the molar substitution degree of the maleyl group of 2.5, placing the weighed materials in 85.9mL of deionized water, stirring the materials until the materials are completely dissolved, adding 0.1g of 1-hydroxycyclohexyl phenyl ketone, and adding the mixture into the deionized water at the wavelength of 320-400nm and the light intensity of 100mW/cm2Irradiating for 5min under ultraviolet light to obtain chitosan fiber hydrogel, placing the chitosan fiber hydrogel in 1mol/L FeCl3Standing the solution for 5 hours at room temperature to form chitosan fiber hydrogel with the equilibrium swelling degree of 0.02, and washing the chitosan fiber hydrogel dressing for 5 times by deionized water to obtain the chitosan fiber hydrogel dressing.
Example 6
Weighing 1g of chitosan powder and 4.98g of maleic anhydride, adding the chitosan powder and the maleic anhydride into 200mL of acetonitrile, uniformly stirring at room temperature, reacting for 48 hours at 80 ℃, adding 1mol/L of KOH solution after the reaction is finished, adjusting the pH value of the solution to 13, transferring the solution into a dialysis bag, dialyzing for 2 days in deionized water, intercepting the solution with the molecular weight of 8000-14000D from the dialysis bag, and freeze-drying the solution for 48 hours at-50 ℃ to obtain the maleyl chitosan with the molar substitution degree of 2.5 of the maleyl.
Weighing 12g of maleyl chitosan with the molar substitution degree of the maleyl group of 2.5, placing the mixture into 85.9mL of deionized water, stirring the mixture until the mixture is completely dissolved, adding 0.1g of 1-hydroxycyclohexyl phenyl ketone, and adding the mixture into the mixture at a wavelength of 320-400nm and a light intensity of 100mW/cm2Irradiating for 5min under ultraviolet light to obtain chitosan hydrogel, placing the chitosan hydrogel in 1mol/L FeCl3Standing the solution for 5 hours at room temperature to form chitosan hydrogel with the equilibrium swelling degree of 0.05, and washing the chitosan hydrogel dressing for 5 times by deionized water to obtain the chitosan hydrogel dressing.
Example 7
Weighing 1g of chitosan powder and 2.1g of maleic anhydride, adding the chitosan powder and the maleic anhydride into 10mL of dimethylformamide, uniformly stirring at room temperature, reacting for 12 hours at 35 ℃, adding 1mol/L of NaOH solution after the reaction is finished, adjusting the pH value of the solution to 11, transferring the solution into a dialysis bag, dialyzing for 2 days in deionized water, intercepting the solution with the molecular weight of 8000-14000D from the dialysis bag, and freeze-drying the solution for 48 hours at-50 ℃ to obtain the maleyl chitosan with the molar substitution degree of 0.9 of the maleyl.
Weighing 12g of maleyl chitosan with the molar substitution degree of the maleyl group of 0.9, placing the weighed maleyl chitosan into 85.9mL of 1% acetic acid aqueous solution, stirring the mixture until the maleyl chitosan is completely dissolved, adding 2mL of 25% glutaraldehyde solution, stirring the mixture evenly, standing the mixture for 2 hours to obtain chitosan hydrogel, placing the chitosan hydrogel into 1mol/L FeCl3Standing the solution at room temperature for 5h to form chitosan hydrogel with the equilibrium swelling degree of 0.06, and washing the chitosan hydrogel dressing for 5 times by deionized water to obtain the chitosan hydrogel dressing.
Example 8
Weighing 1g of chitosan powder and 4.98g of maleic anhydride, adding the chitosan powder and the maleic anhydride into 200mL of acetonitrile, uniformly stirring at room temperature, reacting for 48 hours at 80 ℃, adding 1mol/L of KOH solution after the reaction is finished, adjusting the pH value of the solution to 13, transferring the solution into a dialysis bag, dialyzing for 2 days in deionized water, intercepting the solution with the molecular weight of 8000-14000D from the dialysis bag, and freeze-drying the solution for 48 hours at-50 ℃ to obtain the maleyl chitosan with the molar substitution degree of 2.5 of the maleyl.
Weighing 2g of chitosan fiber cloth and 12g of maleyl chitosan with the molar substitution degree of the maleyl group of 2.5, placing the chitosan fiber cloth and the maleyl chitosan into 85.9mL of deionized water, stirring the mixture until the chitosan fiber cloth and the maleyl chitosan are completely dissolved, adding 0.1g of 1-hydroxycyclohexyl phenyl ketone, and adding the mixture into the mixture at a wavelength of 320-400nm and a light intensity of 100mW/cm2Irradiating for 5min under ultraviolet light to obtain chitosan fiber hydrogel, placing the chitosan fiber hydrogel in 1mol/L FeCl3Standing the solution for 5 hours at room temperature to form chitosan fiber hydrogel with the equilibrium swelling degree of 0.07, and washing the chitosan fiber hydrogel dressing for 5 times by deionized water to obtain the chitosan fiber hydrogel dressing.
The prepared chitosan fiber hydrogel dressing is tested for wet strength and cytotoxicity as follows.
(1) Wet strength test
A gel sample having a thickness of 2mm was cut into a dumbbell-shaped specimen having a middle length of 20mm and a width of 2mm by a cutter, and a tensile property test was conducted on a universal material testing machine with an effective initial length of the jig of 10mm and a uniaxial tension speed set to 10 mm/min. The test results are shown in Table 1.
(2) Cytotoxicity test
The gel samples were subjected to cytotoxicity tests according to the method in ISO 10993-5(2009) international standard. The test results are shown in Table 1.
| Strength in wet state (MPa) | Cytotoxicity | |
| Example 1 | 4.85±0.35 | Level 0 (none) |
| Example 2 | 5.06±0.13 | Grade 1 (slight) |
| Example 3 | 4.78±0.21 | Level 0 (none) |
| Example 4 | 5.25±0.19 | Level 0 (none) |
| Example 5 | 5.90±0.22 | Grade 1 (slight) |
| Example 6 | 0.18±0.05 | Grade 1 (slight) |
| Example 7 | 0.23±0.07 | Grade 3 (Severe) |
| Example 8 | 0.34±0.06 | Grade 1 (slight) |
The strength test results show that the wet strength of the chitosan fiber hydrogel dressings in examples 1-5 is significantly higher than that of the maleoyl chitosan hydrogel dressing (example 6) without the addition of the maleoyl chitosan fiber cloth, and is also significantly higher than that of the chitosan fiber hydrogel dressing (example 8) with the addition of the unmodified chitosan fiber cloth. The cytotoxicity test results show that the chitosan fiber hydrogel dressings in the examples 1-5 have better cytotoxicity than the chitosan hydrogel dressing crosslinked by glutaraldehyde (example 7).
The test results show that the chitosan fiber hydrogel dressing has the characteristics of high wet strength and good biocompatibility, and is favorable for wound healing when used for wound treatment.
Claims (5)
1. The preparation method of the chitosan fiber hydrogel dressing is characterized by comprising the following steps of:
a. preparation of maleyl chitosan fiber cloth
Dispersing chitosan fiber cloth in a polar solvent, wherein the mass volume ratio of the chitosan fiber cloth to the polar solvent is 1 g: 10-100 mL, adding maleic anhydride into a mixed solution of chitosan fiber cloth and a polar solvent, wherein the molar ratio of amino groups of the chitosan fiber cloth to the maleic anhydride is 1: 0.1-5, uniformly stirring at room temperature, reacting in a constant-temperature water bath at 35-80 ℃ for 6-18 h, and separating the reacted chitosan fiber cloth from a mixed liquid formed by a polar solvent and maleic anhydride to obtain a maleic acyl grafted chitosan fiber cloth primary product;
dispersing the primary chitosan fiber cloth product grafted with the maleyl in an ethanol-water mixed solution with a volume ratio of 80:20, dropwise adding 30% w/v inorganic strong base aqueous solution, adjusting the pH value of the ethanol-water mixed solution to 6-8, soaking for 30 minutes, separating the primary chitosan fiber cloth product grafted with the maleyl from a mixed liquid of ethanol, inorganic strong base and water, washing for 2 times in 75% ethanol by volume fraction, dehydrating, and drying at 40 ℃ to obtain the maleyl chitosan fiber cloth with the maleyl molar substitution degree of 0.05-0.9;
b. preparation of maleoyl chitosan
Placing chitosan powder and maleic anhydride in a polar solvent, wherein the weight volume ratio of the chitosan powder to the polar solvent is 1 g: 10-200 mL, wherein the molar ratio of amino groups on a chitosan molecular chain to maleic anhydride is 1: 5-10, uniformly stirring at room temperature, reacting at 35-80 ℃, wherein the reaction time is 12-48 hours, after the reaction is finished, adding 1mol/L of inorganic strong base aqueous solution into a mixed solution of chitosan, maleic anhydride and a polar solvent, adjusting the pH value of the mixed solution to 11-13, transferring the mixed solution after the pH adjustment into a dialysis bag, dialyzing in deionized water, intercepting the molecular weight of the dialysis bag to be 8000-14000Da, and the dialysis time to be 2 days to form a maleoyl chitosan solution, and freeze-drying the maleoyl chitosan solution for 48 hours at-50 ℃ to obtain the maleoyl chitosan with the maleoyl molar substitution degree of 1.0-2.5;
c. and c, mixing the maleyl chitosan fiber cloth obtained in the step a and the maleyl chitosan obtained in the step b with water according to the mass percentage:
d. And c, placing the chitosan fiber hydrogel obtained in the step c in a deionized water solution of 0.1-1 mol/L metal halide, standing for 0.1-5 hours at room temperature to form the chitosan fiber hydrogel with the equilibrium swelling degree of 0.02-0.1, and washing for 3-5 times by using deionized water to obtain the chitosan fiber hydrogel dressing.
2. The method for preparing the chitosan fiber hydrogel dressing according to claim 1, wherein: the polar solvent is one of dimethyl sulfoxide, dimethylformamide, acetonitrile or 1, 3-dimethyl-2-imidazolidinone.
3. The method for preparing the chitosan fiber hydrogel dressing according to claim 1, wherein: the inorganic strong base is one of sodium hydroxide or potassium hydroxide.
4. The method for preparing the chitosan fiber hydrogel dressing according to claim 1, wherein: the photoinitiator is one of 2-hydroxy-2-methyl-1-p-hydroxyethyl ether phenyl acetone or 1-hydroxycyclohexyl phenyl ketone or 2, 2-dimethoxy-phenyl ethyl ketone.
5. The method for preparing the chitosan fiber hydrogel dressing according to claim 1, wherein: the metal halide is one of lithium chloride, calcium chloride, zinc chloride, copper chloride and ferric chloride.
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