CN114702624B - Antibacterial material based on polysaccharide polymer and preparation method thereof - Google Patents
Antibacterial material based on polysaccharide polymer and preparation method thereof Download PDFInfo
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- CN114702624B CN114702624B CN202210067788.2A CN202210067788A CN114702624B CN 114702624 B CN114702624 B CN 114702624B CN 202210067788 A CN202210067788 A CN 202210067788A CN 114702624 B CN114702624 B CN 114702624B
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 53
- 239000000463 material Substances 0.000 title claims abstract description 38
- 229920000642 polymer Polymers 0.000 title claims abstract description 29
- 150000004676 glycans Chemical class 0.000 title claims abstract description 28
- 229920001282 polysaccharide Polymers 0.000 title claims abstract description 28
- 239000005017 polysaccharide Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 239000000178 monomer Substances 0.000 claims abstract description 59
- 125000003147 glycosyl group Chemical group 0.000 claims abstract description 32
- 238000004132 cross linking Methods 0.000 claims abstract description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 12
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 12
- 230000000845 anti-microbial effect Effects 0.000 claims description 12
- 239000003999 initiator Substances 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 230000005587 bubbling Effects 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 6
- 239000012467 final product Substances 0.000 claims description 6
- VFXXTYGQYWRHJP-UHFFFAOYSA-N 4,4'-azobis(4-cyanopentanoic acid) Chemical compound OC(=O)CCC(C)(C#N)N=NC(C)(CCC(O)=O)C#N VFXXTYGQYWRHJP-UHFFFAOYSA-N 0.000 claims description 5
- 101100490446 Penicillium chrysogenum PCBAB gene Proteins 0.000 claims description 5
- 238000011010 flushing procedure Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 claims description 4
- NQIMONOHVBBZKE-UHFFFAOYSA-N n-[2-(3,4-dihydroxyphenyl)ethyl]-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCCC1=CC=C(O)C(O)=C1 NQIMONOHVBBZKE-UHFFFAOYSA-N 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- XSHISXQEKIKSGC-UHFFFAOYSA-N 2-aminoethyl 2-methylprop-2-enoate;hydron;chloride Chemical compound Cl.CC(=C)C(=O)OCCN XSHISXQEKIKSGC-UHFFFAOYSA-N 0.000 claims description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 3
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 3
- 239000007983 Tris buffer Substances 0.000 claims description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 3
- ZQMHJBXHRFJKOT-UHFFFAOYSA-N methyl 2-[(1-methoxy-2-methyl-1-oxopropan-2-yl)diazenyl]-2-methylpropanoate Chemical compound COC(=O)C(C)(C)N=NC(C)(C)C(=O)OC ZQMHJBXHRFJKOT-UHFFFAOYSA-N 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 239000002953 phosphate buffered saline Substances 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 239000004599 antimicrobial Substances 0.000 claims 1
- 241000894006 Bacteria Species 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 6
- 229920000307 polymer substrate Polymers 0.000 description 6
- 239000003242 anti bacterial agent Substances 0.000 description 3
- 239000003899 bactericide agent Substances 0.000 description 3
- 150000001720 carbohydrates Chemical class 0.000 description 3
- 235000014633 carbohydrates Nutrition 0.000 description 3
- 238000001723 curing Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 2
- -1 2-lactamidoethyl methacrylamide Chemical compound 0.000 description 2
- 208000035143 Bacterial infection Diseases 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 2
- 208000022362 bacterial infectious disease Diseases 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000012567 medical material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 description 2
- IYHLUGVVUPPBEJ-UHFFFAOYSA-N 1-butyl-3-ethenyl-1,2-dihydroimidazol-1-ium;bromide Chemical compound [Br-].CCCC[NH+]1CN(C=C)C=C1 IYHLUGVVUPPBEJ-UHFFFAOYSA-N 0.000 description 1
- 208000034309 Bacterial disease carrier Diseases 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 102000010834 Extracellular Matrix Proteins Human genes 0.000 description 1
- 108010037362 Extracellular Matrix Proteins Proteins 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Chemical compound OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229930186217 Glycolipid Natural products 0.000 description 1
- 102000003886 Glycoproteins Human genes 0.000 description 1
- 108090000288 Glycoproteins Proteins 0.000 description 1
- 231100000002 MTT assay Toxicity 0.000 description 1
- 238000000134 MTT assay Methods 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 206010060872 Transplant failure Diseases 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 239000003519 biomedical and dental material Substances 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 230000003833 cell viability Effects 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 231100000135 cytotoxicity Toxicity 0.000 description 1
- 230000003013 cytotoxicity Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 210000002744 extracellular matrix Anatomy 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000005802 health problem Effects 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- ZOTWHNWBICCBPC-UHFFFAOYSA-N n-ethyl-n-methylprop-2-enamide Chemical compound CCN(C)C(=O)C=C ZOTWHNWBICCBPC-UHFFFAOYSA-N 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/24—Homopolymers or copolymers of amides or imides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials For Medical Uses (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention provides a polysaccharide polymer based antibacterial material and a preparation method thereof, wherein the material is prepared by copolymerizing double-bond-capped glycosyl-containing monomers, double-bond-capped antibacterial monomers and crosslinking monomers, the content of the double-bond-capped glycosyl-containing monomers is 10-70% by mole percent, the content of the antibacterial monomers is 10-30% by mole percent, and the balance is the molar content of the crosslinking monomers.
Description
Technical Field
The invention belongs to the field of polymer antibacterial materials, and particularly relates to a polysaccharide-based polymer antibacterial material and a preparation method thereof.
Background
Bacterial infection remains a serious health problem in biomedical material applications. Bacterial colonization and proliferation on the surface of medical materials can lead to graft failure and even pose a serious threat to patient health. A common strategy to prevent bacterial infection is to build a coating on the surface that contains a bactericide, which can be killed before the bacteria pose a threat to the material. Wherein antibiotics are able to kill bacteria on the surface quickly and effectively, but the probability of developing drug resistance is high. Although some bactericides can kill bacteria effectively, the problems of high cost, high cytotoxicity, complex operation and the like are not ignored, so that the use of the bactericides in biomedical materials is limited, and an antibacterial surface with good biocompatibility is needed.
Carbohydrates are one of the most abundant and important biological macromolecules in nature. Carbohydrates are present in large amounts as substances in the extracellular matrix of animals and in the cell walls of various plants, bacteria, fungi etc., acting as scaffolds. Carbohydrate macromolecule-based resources and chemical structures, including naturally occurring polysaccharides, naturally synthesized polysaccharides, glycocopolymers/glycodendrimers, supramolecular glycocopolymers, and synthetic glycolipids/glycoproteins, and the like. Some common polysaccharides have the characteristics of rigidity and controllable functions and are biocompatible, and can form high-molecular biological materials, so that the polysaccharide can be widely applied to the fields of drug delivery, tissue engineering and the like. The glycosyl polymer has unique performance, and the glycosyl polymer fixed on the surface of the material can greatly change physical and chemical properties and improve biocompatibility. Therefore, the copolymer containing the glycosyl unit and the antibacterial monomer is coated on the surface of the medical material, and the copolymer has important significance for improving the biocompatibility of the antibacterial coating.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides an antibacterial material based on a polysaccharide polymer and a preparation method thereof, and utilizes the hydrophilicity and biosafety of glycosyl monomers and the sterilization effect of antibacterial agents to prepare a biocompatible antibacterial surface, thereby being applicable to biomedical materials and instruments.
The invention adopts the technical scheme for solving the technical problems that: the antibacterial material based on polysaccharide polymer is prepared by copolymerizing double-bond end-capped glycosyl-containing monomers, double-bond end-capped antibacterial monomers and crosslinking monomers, wherein the content of the double-bond end-capped glycosyl-containing monomers is 10-70% by mole percent, the content of the antibacterial monomers is 10-30% by mole percent, and the balance of the crosslinking monomers is mole percent.
Further, the structural formula of the double bond terminated glycosyl-containing monomer is as follows:
any one of the following.
Further, R1 is
In any one of the above-mentioned items,
r2 isAny one of the following.
Further, the structural formula of the double bond end capped antibacterial monomer is
Further, the crosslinking monomer is any one of glycidyl methacrylate, hydroxyethyl acrylate, methacrylic acid, acrylic acid, methacrylamide, acrylamide, 2-aminoethyl methacrylate hydrochloride, N- (3, 4-dihydroxyphenethyl) methacrylamide or 3- (methacryloyloxy) propyl trimethoxysilane.
A method for preparing an antibacterial material based on a polysaccharide polymer, comprising the following steps:
step one, dissolving a double-bond-terminated glycosyl-containing monomer, a double-bond-terminated antibacterial monomer, a crosslinking monomer and an initiator in a mixed solvent of N, N-dimethylformamide and methanol or water; the volume ratio of N, N-dimethylformamide to methanol or water is (1-10): 1;
and step two, nitrogen bubbling is carried out in the mixed solution in the step one, the bubbling is carried out for 25-40 min, the mixed solution is raised to 65-75 ℃ and reacts for 12-30 h, the product is obtained, the product is dialyzed in deionized water for 2-3 days, and the dialyzed product is freeze-dried, so that the final product is obtained.
Further, the initiator is any one of Azobisisobutyronitrile (AIBN), azobisisoheptonitrile (ABVN), dimethyl Azobisisobutyrate (AIBME), 4' -azobis (4-cyanovaleric acid) (ACVA), potassium persulfate (KPS), ammonium Persulfate (APS) or Benzoyl Peroxide (BPO), and the addition amount of the initiator is 1/1000-1/100 of the total molar amount of the glycosyl-containing monomer, the antibacterial monomer and the crosslinking monomer.
A method of using a polysaccharide-based polymeric antimicrobial material, comprising the steps of:
s1, dissolving a polysaccharide polymer antibacterial material in a solvent;
s2, immersing the pre-cleaned substrate in the solution of the S1 for 5-30 min;
s3, taking out the substrate lightly, naturally leveling, placing in an oven, thermally curing at 60-140 ℃ for 20-120min, and lightly flushing with the solvent in the step S1 to obtain the final product.
Further, the solvent in S1 is any one of ethanol, water, PBS or Tris buffer solution.
Further, the mass fraction of the polysaccharide polymer antibacterial material in the mixed solution is 5-30wt%.
The beneficial effects of the invention are as follows: the polysaccharide antibacterial polymer is prepared by polymerizing double-bond-terminated glycosyl-containing monomers, double-bond-terminated antibacterial monomers and crosslinking monomers through free radicals or through reversible addition-fragmentation chain transfer copolymerization; the hydrophilic and biosafety of the glycosyl monomer is utilized, and the sterilization effect of the antibacterial agent is combined to prepare the biocompatible antibacterial surface, so that the antibacterial surface is suitable for biomedical materials and instruments.
Drawings
FIG. 1 is a graph comparing antimicrobial properties of an uncoated antimicrobial glycosyl polymer substrate and a surface coated antimicrobial glycosyl polymer substrate of example 1 of the invention;
FIG. 2 is a graph of the evaluation of biocompatibility of the surface of the material according to example 1 of the present invention;
FIG. 3 is a graph comparing antimicrobial properties of an uncoated antimicrobial glycosyl polymer substrate and a surface coated antimicrobial glycosyl polymer substrate of example 2 of the invention;
FIG. 4 is a graph of the evaluation of biocompatibility of the surface of the material according to example 2 of the present invention;
Detailed Description
The embodiments of the present invention will be described in detail with reference to specific embodiments, and the present embodiment provides detailed embodiments and specific operation procedures on the premise of the technical solution of the present invention, but the scope of protection of the present invention is not limited to the following embodiments.
The antibacterial material based on polysaccharide polymer is prepared by copolymerizing double-bond end-capped glycosyl-containing monomers, double-bond end-capped antibacterial monomers and crosslinking monomers, wherein the content of the double-bond end-capped glycosyl-containing monomers is 10-70% by mole percent, the content of the antibacterial monomers is 10-30% by mole percent, and the balance of the crosslinking monomers is mole percent.
Further, the structural formula of the double bond terminated glycosyl-containing monomer is as follows:
any one of the following.
Further, R1 is
In any one of the above-mentioned items,
r2 isAny one of the following.
Further, the structural formula of the double bond end capped antibacterial monomer is
Further, the crosslinking monomer is any one of glycidyl methacrylate, hydroxyethyl acrylate, methacrylic acid, acrylic acid, methacrylamide, acrylamide, 2-aminoethyl methacrylate hydrochloride, N- (3, 4-dihydroxyphenethyl) methacrylamide or 3- (methacryloyloxy) propyl trimethoxysilane.
A method for preparing an antibacterial material based on a polysaccharide polymer, comprising the following steps:
step one, dissolving a double-bond-terminated glycosyl-containing monomer, a double-bond-terminated antibacterial monomer, a crosslinking monomer and an initiator in a mixed solvent of N, N-dimethylformamide and methanol or water; the volume ratio of N, N-dimethylformamide to methanol or water is (1-10): 1;
and step two, nitrogen bubbling is carried out in the mixed solution in the step one, the bubbling is carried out for 25-40 min, the mixed solution is raised to 65-75 ℃ and reacts for 12-30 h, the product is obtained, the product is dialyzed in deionized water for 2-3 days, and the dialyzed product is freeze-dried, so that the final product is obtained.
Further, the initiator is any one of Azobisisobutyronitrile (AIBN), azobisisoheptonitrile (ABVN), dimethyl Azobisisobutyrate (AIBME), 4' -azobis (4-cyanovaleric acid) (ACVA), potassium persulfate (KPS), ammonium Persulfate (APS) or Benzoyl Peroxide (BPO), and the addition amount of the initiator is 1/1000-1/100 of the total molar amount of the glycosyl-containing monomer, the antibacterial monomer and the crosslinking monomer.
A method of using a polysaccharide-based polymeric antimicrobial material, comprising the steps of:
s1, dissolving a polysaccharide polymer antibacterial material in a solvent;
s2, immersing the pre-cleaned substrate in the solution of the S1 for 5-30 min;
s3, taking out the substrate lightly, naturally leveling, placing in an oven, thermally curing at 60-140 ℃ for 20-120min, and lightly flushing with the solvent in the step S1 to obtain the final product.
Further, the solvent in S1 is any one of ethanol, water, PBS or Tris buffer solution.
Further, the mass fraction of the polysaccharide polymer antibacterial material in the mixed solution is 5-30wt%.
Example 1:
30.5g of 2-lactamidoethyl methacrylamide (LAEMA), 6.23g of methacryloyloxyethyl trimethyl ammonium chloride (META), 2.21g N- (3, 4-Dihydroxyphenethyl) Methacrylamide (DMA) and 0.28g of initiator ACVA were dissolved in 85.0ml of a mixed solution of n, n-dimethylformamide and methanol (v/v=1:1). After nitrogen bubbling for 30min, the temperature was raised to 70℃for polymerization for 24h. The mixed solution was dialyzed against deionized water for 2 days and then freeze-dried to obtain a glycosyl-containing copolymer p (LAEMA-co-META-co-DMA). The free radical polymerization reaction proceeds as follows:
dispersing the obtained glycosyl antibacterial polymer in deionized water at 5.0-30wt%, and then pre-cleaning the substrate, and soaking the substrate in the solution for 5-30 min or spraying the substrate on the surface of the substrate; slowly taking out, standing and naturally leveling; and (3) thermally curing for 20-120min at the temperature of 60-140 ℃ and lightly flushing to obtain the product.
Gram negative bacteria, such as E.coli, were selected as model bacteria and the antibacterial effect of the material was evaluated by plate colony counting. The non-coated antibacterial glycosyl polymer substrate is used as a blank control group, the experimental result is shown in figure 1, and bacteria collected on the surface of the blank group are far more than those on the surface of the experimental group (p is less than 0.05), so that the modified surface has good antibacterial performance.
The biocompatibility of the material surface is evaluated by using an MTT method, and the determination method adopts GB/T16886.5-2017. The experimental result is shown in figure 2, and the activity of the surface cell modified by LAEMA is obviously increased, so that the polymer p (META-co-DMA) without monomer 2-lactamide ethyl methyl acrylamide is used as a control group, and has good biocompatibility.
Example 2:
17.4g of 2- (methacrylamide) glucopyranose (MG), 4.06g of 1-vinyl-3-butylimidazole bromide (VBMB), 1.30g of hydroxyethyl methacrylate (HEMA) and 0.20g of initiator ACVA are dissolved in 60.0mL of a mixed solution of N, N-dimethylformamide and deionized water (v/v=2:1). After bubbling nitrogen for 30min, the system was heated to 70℃and polymerized for 24h. After the reaction was completed, the copolymer was dialyzed against deionized water for 2 days to remove unreacted monomers, and then freeze-dried to obtain a glycosyl-containing copolymer p (MG-co-VBMB-co-HEMA). The polymerization reaction proceeds as follows:
dispersing the obtained copolymer in ethanol in an amount of 5.0-30wt%, and then pre-cleaning the base material, and immersing the base material in the solution for 5-30 min or spin-coating the base material surface; slowly taking out, standing and naturally leveling; heat curing at 60-140 deg.c for 20-120min and light flushing.
The bactericidal effect of the polymer surface is tested by adopting escherichia coli (gram-negative bacteria), an uncoated antibacterial glycosyl polymer substrate is used as a blank control group, the experimental result is shown in figure 3, and the number of plate colonies on the surface of the blank group is far more than that of the experimental group (p < 0.05), so that the modified surface has good antibacterial effect.
The results of the MTT assay are shown in FIG. 4. In contrast to the polymer p (VBMB-co-HEMA) without monomeric 2-lactamidoethyl methacrylamide, the cell viability of the experimental group was significantly increased.
It should be noted that while the above describes the invention in terms of embodiments, many other embodiments of the invention are possible. Various modifications and variations of this invention may be apparent to those skilled in the art without departing from the spirit and scope of this invention, and it is intended to cover in the appended claims all such modifications and variations as fall within the true scope of this invention.
Claims (6)
1. An antimicrobial material based on a polysaccharide polymer, characterized in that: the material is prepared by copolymerizing double-bond-capped glycosyl-containing monomers, double-bond-capped antibacterial monomers and crosslinking monomers, wherein the double-bond-capped glycosyl-containing monomers account for 10 to 70 percent of the molar percentage, the antibacterial monomers account for 10 to 30 percent of the molar percentage, and the balance is the crosslinking monomers;
the structural formula of the double-bond terminated glycosyl-containing monomer is
Any one of them;
the structural formula of the double bond end capped antibacterial monomer is
The crosslinking monomer is any one of glycidyl methacrylate, hydroxyethyl acrylate, methacrylic acid, acrylic acid, methacrylamide, acrylamide, 2-aminoethyl methacrylate hydrochloride, N- (3, 4-dihydroxyphenethyl) methacrylamide or 3- (methacryloyloxy) propyl trimethoxysilane;
r1 isAny one of R2 isAny one of the following.
2. The method for preparing the antibacterial material based on the polysaccharide polymer according to claim 1, wherein the method comprises the following steps: the method comprises the following steps:
step one, dissolving a double-bond-terminated glycosyl-containing monomer, a double-bond-terminated antibacterial monomer, a crosslinking monomer and an initiator in a mixed solvent of N, N-dimethylformamide and methanol or water; the volume ratio of N, N-dimethylformamide to methanol or water is (1-10): 1;
and step two, nitrogen bubbling is carried out in the mixed solution in the step one, the bubbling is carried out for 25-40 min, the mixed solution is raised to 65-75 ℃, the reaction is carried out for 12-30 h, the product is obtained, the product is dialyzed in deionized water for 2-3 days, and the dialyzed product is freeze-dried, so that the final product is obtained.
3. The method for preparing the antibacterial material based on the polysaccharide polymer according to claim 2, wherein the method comprises the following steps: the initiator is any one of Azobisisobutyronitrile (AIBN), azobisisoheptonitrile (ABVN), dimethyl Azobisisobutyrate (AIBME), 4' -azobis (4-cyanovaleric acid) (ACVA), potassium persulfate (KPS), ammonium Persulfate (APS) or Benzoyl Peroxide (BPO), and the addition amount of the initiator is 1/1000-1/100 of the total molar amount of the glycosyl-containing monomer, the antibacterial monomer and the crosslinking monomer.
4. The method of using a polysaccharide polymer based antimicrobial material according to claim 1, wherein: the method comprises the following steps:
s1, dissolving a polysaccharide polymer antibacterial material in a solvent;
s2, immersing the pre-cleaned substrate in the solution of the S1 for 5-30 min;
s3, taking out the substrate lightly, naturally leveling, placing in an oven, thermally curing at 60-140 ℃ for 20-120min, and lightly flushing with the solvent in the step S1 to obtain the final product.
5. The method of using a polysaccharide polymer based antimicrobial material according to claim 4, wherein: the solvent in S1 is any one of ethanol, water, PBS or Tris buffer solution.
6. The method of using a polysaccharide polymer based antimicrobial material according to claim 4, wherein: the mass fraction of the polysaccharide polymer antibacterial material in the solvent is 5-30wt%.
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| CN107652393A (en) * | 2017-10-20 | 2018-02-02 | 苏州大学 | Adsorption antibacterial sugar-containing polymer and preparation method thereof |
| CN108003740A (en) * | 2017-12-14 | 2018-05-08 | 浙江大学 | A kind of antibacterial polymer of blood compatibility and its preparation method and application |
| WO2018126796A1 (en) * | 2017-01-05 | 2018-07-12 | 华南理工大学 | Method for preparing anti-bacterial surface on medical material surface |
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| WO2018126796A1 (en) * | 2017-01-05 | 2018-07-12 | 华南理工大学 | Method for preparing anti-bacterial surface on medical material surface |
| CN107652393A (en) * | 2017-10-20 | 2018-02-02 | 苏州大学 | Adsorption antibacterial sugar-containing polymer and preparation method thereof |
| CN108003740A (en) * | 2017-12-14 | 2018-05-08 | 浙江大学 | A kind of antibacterial polymer of blood compatibility and its preparation method and application |
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