CN111704699A - Antibacterial hydrogel containing multi-arm unsaturated polyester and application thereof - Google Patents
Antibacterial hydrogel containing multi-arm unsaturated polyester and application thereof Download PDFInfo
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- CN111704699A CN111704699A CN202010497334.XA CN202010497334A CN111704699A CN 111704699 A CN111704699 A CN 111704699A CN 202010497334 A CN202010497334 A CN 202010497334A CN 111704699 A CN111704699 A CN 111704699A
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- antibacterial
- unsaturated polyester
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 249
- 229920006305 unsaturated polyester Polymers 0.000 title claims abstract description 79
- 239000000017 hydrogel Substances 0.000 title claims abstract description 73
- 239000000499 gel Substances 0.000 claims abstract description 150
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 claims abstract description 29
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims abstract description 16
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims abstract description 15
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 15
- 229940014800 succinic anhydride Drugs 0.000 claims abstract description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 45
- 238000000034 method Methods 0.000 claims description 39
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 32
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 235000005074 zinc chloride Nutrition 0.000 claims description 14
- 239000011592 zinc chloride Substances 0.000 claims description 14
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 238000001556 precipitation Methods 0.000 claims description 6
- 238000005286 illumination Methods 0.000 claims description 4
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical group 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 2
- 238000007711 solidification Methods 0.000 claims description 2
- 230000008023 solidification Effects 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000001514 detection method Methods 0.000 description 23
- 238000002791 soaking Methods 0.000 description 23
- 238000002360 preparation method Methods 0.000 description 21
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 16
- 241000191967 Staphylococcus aureus Species 0.000 description 15
- -1 polyethylene Polymers 0.000 description 15
- 239000007787 solid Substances 0.000 description 15
- 241000588724 Escherichia coli Species 0.000 description 14
- 238000004108 freeze drying Methods 0.000 description 14
- 238000001179 sorption measurement Methods 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 230000006835 compression Effects 0.000 description 13
- 238000007906 compression Methods 0.000 description 13
- 230000008961 swelling Effects 0.000 description 13
- 241000894006 Bacteria Species 0.000 description 12
- 239000012153 distilled water Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 230000001678 irradiating effect Effects 0.000 description 11
- 229920000728 polyester Polymers 0.000 description 11
- 238000005406 washing Methods 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 10
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 10
- 150000002148 esters Chemical class 0.000 description 10
- 238000002329 infrared spectrum Methods 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 8
- 230000000845 anti-microbial effect Effects 0.000 description 6
- 230000001376 precipitating effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 230000001351 cycling effect Effects 0.000 description 4
- 229910010272 inorganic material Inorganic materials 0.000 description 4
- 239000011147 inorganic material Substances 0.000 description 4
- 150000003242 quaternary ammonium salts Chemical group 0.000 description 4
- 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 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 230000002522 swelling effect Effects 0.000 description 2
- FTALTLPZDVFJSS-UHFFFAOYSA-N 2-(2-ethoxyethoxy)ethyl prop-2-enoate Chemical compound CCOCCOCCOC(=O)C=C FTALTLPZDVFJSS-UHFFFAOYSA-N 0.000 description 1
- 101100136092 Drosophila melanogaster peng gene Proteins 0.000 description 1
- QTANTQQOYSUMLC-UHFFFAOYSA-O Ethidium cation Chemical compound C12=CC(N)=CC=C2C2=CC=C(N)C=C2[N+](CC)=C1C1=CC=CC=C1 QTANTQQOYSUMLC-UHFFFAOYSA-O 0.000 description 1
- 206010034133 Pathogen resistance Diseases 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000013558 reference substance Substances 0.000 description 1
Classifications
-
- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
-
- 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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/14—Macromolecular materials
- A61L27/16—Macromolecular materials obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- 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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
-
- 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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/52—Hydrogels or hydrocolloids
-
- 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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/54—Biologically active materials, e.g. therapeutic substances
-
- 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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/56—Porous materials, e.g. foams or sponges
-
- 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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/58—Materials at least partially resorbable by the body
-
- 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
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/46—Polyesters chemically modified by esterification
- C08G63/47—Polyesters chemically modified by esterification by unsaturated monocarboxylic acids or unsaturated monohydric alcohols or reactive derivatives thereof
-
- 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
- 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
- A61L2300/404—Biocides, antimicrobial agents, antiseptic agents
Abstract
The invention relates to an antibacterial hydrogel containing multi-arm unsaturated polyester, which consists of the multi-arm unsaturated polyester, dimethyldiallylammonium chloride which is 0.1-0.5 time of the weight of the multi-arm unsaturated polyester and a photoinitiator which is 0.1-0.5 time of the weight of the unsaturated polyester according to the weight ratio, wherein the multi-arm unsaturated polyester is obtained by ring-opening polymerization of triethanolamine, succinic anhydride and glycidyl methacrylate. The antibacterial active gel prepared from the antibacterial hydrogel has good hydrophilicity and antibacterial performance, and is long in antibacterial time.
Description
Technical Field
The invention relates to a prosthesis material characterized by its function or physical properties, in particular to a high-molecular hydrogel having antibacterial properties.
Background
Bacteria seriously threaten the health of human body. The antibacterial material refers to a material having a function of inhibiting or killing microorganisms by itself. The antibacterial hydrogel is a polymer material with a three-dimensional network structure with antibacterial activity and capable of keeping a certain water amount, has the characteristics of viscoelasticity, hydrophilicity, porosity, biocompatibility and the like, and has potential application prospects in the fields of health, medical instruments, food industry, personal hygiene and the like.
The antibacterial hydrogel can be obtained by modifying the gel with the antibacterial active material, and the bulk antibacterial material has the advantages of no pollution, lasting effect, no bacterial resistance and the like, and has obvious advantages when being applied as a medical dressing. Peng et al (Carbohydr. Polym., 2016, 137:59-64) utilize quaternized cellulose and cellulose bulk to prepare antibacterial hydrogel through chemical crosslinking, and can effectively kill staphylococcus aureus.
The patent application with the publication number of CN109134767A discloses an antibacterial hydrogel material, which is prepared by grafting methacryloyloxyethyl trimethyl ammonium chloride on polyvinyl alcohol polycondensation hydrogel, and the bacteriostasis rate of the hydrogel to escherichia coli and staphylococcus aureus is more than 99.9%. However, the methacryloyloxyethyltrimethyl ammonium chloride in the above hydrogel is grafted to the branched chains of polyvinyl alcohol, and thus the following disadvantages are apparent: 1. the grafting rate of methacryloyloxyethyl trimethyl ammonium chloride with antibacterial activity fluctuates along with the fluctuation of process conditions, so that the antibacterial performance of products in different batches is different; 2. methacryloyloxyethyltrimethylammonium chloride having antibacterial activity easily falls off from the branched chain, resulting in a short duration of antibacterial activity.
Patent application with publication number CN110776599A discloses an antibacterial hydrogel, in which the polymer is polyethylene glycol-unsaturated polyester block copolymer, which is compounded with dimethyldiallylammonium chloride and ethoxyethoxyethyl acrylate, and photocured under the action of photoinitiator to obtain the antibacterial hydrogel. Although the hydrogel has the advantages of good hydrophilicity and long antibacterial time, the crosslinking degree is low, and the mechanical property is not ideal.
Disclosure of Invention
The invention aims to solve the technical problem of providing the antibacterial hydrogel containing the multi-arm unsaturated polyester, the antibacterial hydrogel has long antibacterial time and good stability, and the cell scaffold prepared from the antibacterial hydrogel has excellent mechanical properties.
The technical scheme for solving the problems is as follows:
an antibacterial hydrogel containing multi-arm unsaturated polyester, which consists of the multi-arm unsaturated polyester, dimethyldiallylammonium chloride which is 0.1 to 0.5 time of the weight of the multi-arm unsaturated polyester and a photoinitiator which is 0.1 to 0.5 time of the weight of the unsaturated polyester according to the weight ratio; wherein the multi-arm unsaturated polyester is prepared by the following method:
adding triethanolamine, succinic anhydride, glycidyl methacrylate and zinc chloride into DMF (dimethyl formamide) according to the molar ratio of the triethanolamine to the succinic anhydride to the glycidyl methacrylate to the zinc chloride of 1 to q to n to m, carrying out freeze-thaw cycle for three times, heating to 80-100 ℃ under the protection of nitrogen for ring-opening polymerization for 5-10 h, cooling to room temperature, and adding cold diethyl ether for precipitation to obtain the multi-arm unsaturated polyester; wherein the content of the first and second substances,
n is 50 to 80, q is 50 to 80, m is 0.5 to 0.8, and n ═ q.
The photoinitiator is 1-hydroxycyclohexyl phenyl ketone or/and (2,4, 6-trimethyl benzoyl) diphenyl phosphine oxide.
In the scheme, n is preferably 60-70, p is preferably 60-70, and m is preferably 0.6.
In the scheme, the ring-opening polymerization reaction temperature is preferably 90 ℃, and the reaction time is preferably 8 h.
The antibacterial hydrogel is prepared by the following method: and uniformly mixing the multi-arm unsaturated polyester, the dimethyl diallyl ammonium chloride and the photoinitiator to obtain the polyester.
The antibacterial hydrogel disclosed by the invention has good hydrophilicity, biocompatibility and biodegradability, and is suitable for preparing antibacterial active gel, and the preparation method of the antibacterial active gel comprises the following steps: adding the antibacterial hydrogel into a mold, and curing at a wavelength of 395nm and a light intensity of 300mW/cm2The antibacterial active gel is obtained by illumination and solidification under an LED lamp.
The antibacterial hydrogel contains multi-arm unsaturated polyester, the multi-arm unsaturated polyester takes triethanolamine as an initiator, glycidyl ether and acid anhydride are subjected to ring-opening copolymerization reaction to form a three-arm star polymer, the side chain on the arm is connected with unsaturated double bonds, the unsaturated polyester is endowed with chemical reaction activity, and the multi-arm unsaturated polyester and dimethyl diallyl ammonium chloride are subjected to photocuring reaction to form a net structure under the action of a photoinitiator. The antibacterial active gel prepared by the antibacterial hydrogel has the advantages of good hydrophilicity, good swelling property, high porosity, good biocompatibility and good mechanical property. In addition, the antibacterial hydrogel contains dimethyl diallyl ammonium chloride, and after the dimethyl diallyl ammonium chloride reacts with the multi-arm unsaturated polyester under the action of the photoinitiator, quaternary ammonium salt groups with positive charges are introduced into the hydrogel, so that the antibacterial hydrogel has good hydrophilicity, has remarkable inhibition and sterilization effects on bacteria, is solidified on a net structure, and has long antibacterial time and good stability.
Detailed Description
The production method and effects of the present invention will be described in further detail with specific examples.
Example 1
(a) Preparation of multi-arm unsaturated polyester
Adding 0.149g (0.001mol) of triethanolamine, 6g (0.06mol) of succinic anhydride, 6.84g (0.06mol) of glycidyl methacrylate and 81.6mg (0.6mmol) of zinc chloride into 10mL of DMF, carrying out freeze-thaw cycle for three times, heating to 100 ℃ under the protection of nitrogen, carrying out ring-opening polymerization for 10h, cooling to room temperature, adding cold diethyl ether, and precipitating to obtain the compound.
The infrared spectrum of the unsaturated polyester was measured by Shimadzu FTIR-8100 infrared spectrometer. Detecting and finding IR (v)-1 ，KBr) Is 3158, 2683, 1911, 1744, 1637, 1215, 947, 676cm-1. 3158 the absorption peak corresponds to the C-H stretching vibration peak on the methacrylate ester, 1744cm-1Corresponding to the stretching vibration peak of carbonyl in ester bond, 1637cm-1Corresponding to the double bond stretching vibration peak of methacrylate ester, 1215 corresponds to the stretching vibration peak of ether bond in ester. Thus, it was confirmed that the obtained polyester contained methacrylate.
(b) Preparation of antibacterial hydrogel and antibacterial active gel
The antibacterial hydrogel comprises the following components:
uniformly mixing 1g of the multi-arm unsaturated polyester prepared in the step (a), 0.1g of dimethyl diallyl ammonium chloride and 0.1g of photoinitiator to obtain the antibacterial hydrogel; wherein the photoinitiator consists of 0.05g of 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone and 0.05g of (2,4, 6-trimethylbenzoyl) diphenylphosphine oxide.
Adding antibacterial hydrogel into a mold, and irradiating at a wavelength of 395nm with a light intensity of 300mW/cm2And (3) irradiating under an LED lamp for 3min for curing to obtain the antibacterial active gel.
(c) Performance testing of antimicrobial hydrogels
1. Qualitative determination of quaternary ammonium salt
The method described in (journal of china disinfection, 2008,25(2), 117-119) was used to qualitatively analyze the quaternary ammonium salt in the antibacterial active gel synthesized in the examples. The coloration reaction was carried out using ethidium bromide-acid blue indicator and the antibacterial active gel prepared above, so that the aqueous layer was changed from blue to colorless and the chloroform layer was changed from colorless to blue. Therefore, the prepared antibacterial active gel contains quaternary ammonium salt obtained after dimethyl diallyl ammonium chloride reacts.
2. Swelling Properties
Preparing sample strips (40 mm in length, 10mm in width and 5mm in thickness) by the above method, freeze-drying to obtain solid, and accurately weighing to obtain Wo(ii) a Swelling the sample in sufficient distilled water, placing in a constant-temperature water bath at 37 ℃, taking out the sample every 24 hours, wiping off the surface moisture by using filter paper, weighing, and weighing to constant weight WeThe swelling degree of the antibacterial active gel was calculated as follows. Swelling degree ═ We/W0。
The swelling degree of the prepared antibacterial activity gel is 3241% by detection.
2. Mechanical Property test
The compressive strength and the compression modulus of the antibacterial active gel are tested by using a universal mechanical testing machine, the compression rate is 0.5mm/min, and the stability is kept. The upper surface and the lower surface of the antibacterial active gel are smooth without bending deformation before testing, the outline dimension of the antibacterial active gel is measured by using a vernier caliper, and 5 parallel samples are tested in each group.
The detection shows that the compression strength of the prepared antibacterial active gel reaches 2.27mPa, and the elastic modulus reaches 1.17 MPa.
3. Antibacterial property
Preparing a gel sample block (with the diameter of 12mm and the thickness of 5mm) by the method for preparing the antibacterial active gel, freezing and drying to obtain a solid, and detecting the antibacterial rate of the gel sample block on escherichia coli and staphylococcus aureus to be more than 99.9% according to the GB/T21510-2008 nanometer inorganic material antibacterial performance detection method.
4. Stability against bacteria
Preparing gel sample block (diameter 12mm, thickness 5mm) by above method, freeze drying to obtain solid, and accurately weighing to obtain Wo(ii) a Adding sufficient PBS solution into the gel sample, soaking at room temperature for 48h, taking out the antibacterial active gel sample, washing with distilled water for three times, freeze-drying to obtain solid, and accurately weighing to obtain W1
Stability of W1/W0.
The stability was calculated to be 99.4%.
Preparing gel sample block (diameter 12mm, thickness 5mm) by the above method, freeze drying to obtain solid, soaking in PBS solution for 48h, taking out cell scaffold, washing with distilled water for three times, and freeze drying to obtain solid. The antibacterial effect of the soaked antibacterial hydrogel on escherichia coli and staphylococcus aureus is detected according to the GB/T21510-2008 nanometer inorganic material antibacterial performance detection method, and the antibacterial rate is found to be more than 99.9%.
From the above results, it can be understood that the antibacterial active gel prepared in the present invention shows no decrease in mass after soaking for 48 hours, shows high stability, and has no influence on antibacterial performance. Therefore, the antibacterial active gel has good antibacterial stability.
Amount of BSA adsorbed
Taking 10mg of completely dried antibacterial active gel, sterilizing with 75% ethanol, soaking for 60min, soaking with PBS (0.1M, pH7.4) buffer solution for 2h, adding BSA solution, culturing at 37 deg.C for 24h, detecting BSA absorbance at 280nm by ultraviolet spectrophotometer, and calculating BSA adsorption amount by standard curve at 280 nm.
The BSA adsorption amounts of the antibacterial active gels were measured to be 276mg/g, respectively.
Example 2
(a) Preparation of multi-arm unsaturated polyester
Adding 0.149g (0.001mol) of triethanolamine, 5g (0.05mol) of succinic anhydride, 7.1g (0.05mol) of glycidyl methacrylate and 68mg (0.5mmol) of zinc chloride into 10mL of DMF, carrying out freeze-thaw cycling for three times, heating to 90 ℃ under the protection of nitrogen, carrying out ring-opening polymerization for 8h, cooling to room temperature, adding cold diethyl ether, and precipitating to obtain the compound.
The infrared spectrum of the unsaturated polyester obtained above was measured by Shimadzu FTIR-8100 infrared spectrometer. Detecting and finding IR (v)-1 ，KBr) Is 3218, 2764, 19371, 1700, 1672, 1243, 917, 647cm-1. 3218 absorption peak corresponds to C-H stretching vibration peak of methacrylate at 1700cm-1Corresponding to the stretching vibration peak of carbonyl in ester bond, 1672cm-1Corresponding to the double bond stretching vibration peak of methacrylate, 1243 to the stretching vibration peak of ether bond in ester. Thus, it was confirmed that the obtained polyester contained methacrylate.
(b) Preparation of antibacterial hydrogel and antibacterial active gel
Hydrogel composition:
and (b) uniformly mixing 1g of the multi-arm unsaturated polyester prepared in the step (a), 0.1g of dimethyl diallyl ammonium chloride and 0.1g of photoinitiator 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-acetone to obtain the compound.
Adding hydrogel into a mold, and irradiating at a wavelength of 395nm with a light intensity of 300mW/cm2The gel is cured for 3min under the LED lamp to obtain the antibacterial active gel.
(c) Detection of gel Performance of antibacterial Activity
The prepared antibacterial active gel was found to have a swelling degree of 3152% according to the method described in example 1.
The compression strength of the prepared antibacterial active gel reaches 2.38mPa and the elastic modulus reaches 1.23MPa according to the detection method of the example 1.
The BSA adsorption amounts of the antibacterial gels were found to be 347mg/g, respectively.
3. Antibacterial property
According to the GB/T21510-2008 nano inorganic material antibacterial performance detection method, the antibacterial rate of the antibacterial agent on escherichia coli and staphylococcus aureus is over 99.9%.
4. Stability against bacteria
The stability of the prepared gel-like mass of antibacterial activity was measured to be 99.6% according to the method described in example 1.
And (3) taking the completely molded antibacterial active gel sample block, soaking the completely molded antibacterial active gel sample block in a PBS solution for 48h, taking out the antibacterial active gel sample block, washing with distilled water for three times, and freeze-drying to obtain a solid. And (3) detecting the antibacterial effect of the soaked antibacterial active gel sample block on escherichia coli and staphylococcus aureus according to a GB/T21510-.
From the above results, it can be understood that the mass of the antibacterial active gel-like mass prepared in the present invention is not reduced after soaking for 48 hours, and high stability is exhibited without affecting antibacterial performance. Therefore, the antibacterial active gel has good antibacterial stability.
Example 3
(a) Preparation of multi-arm unsaturated polyester
Adding 0.149g (0.001mol) of triethanolamine, 8g (0.08mol) of succinic anhydride, 11.36g (0.08mol) of glycidyl methacrylate and 108.8mg (0.8mmol) of zinc chloride into 20mL of DMF, carrying out freeze-thaw cycle for three times, heating to 85 ℃ under the protection of nitrogen, reacting for 6h, cooling to room temperature, adding cold diethyl ether, and precipitating to obtain the compound.
The infrared spectrum of the obtained multi-arm unsaturated polyester is measured by a Shimadzu FTIR-8100 infrared spectrometer. Detecting and finding IR (v)-1 ，KBr) 3277, 2541, 1944, 1708, 1659, 1246, 992, 701cm-1. 3277 the absorption peak corresponds to the C-H stretching vibration peak on methacrylate, 1708cm-1Corresponds to the stretching vibration peak of carbonyl in ester bond, 1659cm-1Corresponds to the double bond stretching vibration peak of methacrylate, 1246 corresponds to the stretching vibration peak of ether bond in ester. Thus, it was confirmed that the obtained unsaturated polyester contained a methacrylate ester.
(b) Preparation of hydrogels
Hydrogel composition:
1g of multi-arm unsaturated polyester prepared in the step a, 0.5g of dimethyldiallylammonium chloride and 0.5g of photoinitiator (2,4, 6-trimethylbenzoyl) diphenylphosphine oxide.
The multi-arm unsaturated polyester, the dimethyl diallyl ammonium chloride and the photoinitiator are uniformly mixed to obtain the polyester.
Adding hydrogel into a mold, and irradiating at a wavelength of 395nm with a light intensity of 300mW/cm2The gel is cured for 3min under the LED lamp to obtain the antibacterial active gel.
(c) Antimicrobial hydrogel performance testing
The swelling degree of the prepared antibacterial active gel was 3045% as measured according to the method described in example 1.
The compression strength of the prepared antibacterial active gel reaches 2.33mPa and the elastic modulus reaches 1.14MPa according to the detection method of the example 1.
The BSA adsorption amounts of the antibacterial active gels were measured to be 273mg/g, respectively.
3. Antibacterial property
According to the method for detecting the antibacterial performance of GB/T21510-.
4. Stability against bacteria
The stability of the prepared antibacterial gel was 99.2% according to the method described in example 1.
And (3) taking the completely formed antibacterial active gel sample block, soaking the sample block in a PBS solution for 48h, taking out the antibacterial active gel, washing with distilled water for three times, and freeze-drying to obtain a solid. And (3) detecting the antibacterial effect of the soaked antibacterial active gel sample block on escherichia coli and staphylococcus aureus according to a GB/T21510-.
From the above results, it can be understood that the mass of the antibacterial active gel-like mass prepared in the present invention is not reduced after soaking for 48 hours, and high stability is exhibited without affecting antibacterial performance. Therefore, the antibacterial active gel has good antibacterial stability.
Example 4
(a) Preparation of multi-arm unsaturated polyester
Adding 0.149g (0.001mol) of triethanolamine, 7g (0.07mol) of succinic anhydride, 9.94g (0.07mol) of glycidyl methacrylate and 95.2mg (0.7mmol) of zinc chloride into 15mL of DMF, carrying out freeze-thaw cycle for three times, heating to 100 ℃ under the protection of nitrogen for ring-opening polymerization reaction for 10h, cooling to room temperature, adding cold diethyl ether for precipitation to obtain the product.
The infrared spectrum of the obtained multi-arm unsaturated polyester is measured by a Shimadzu FTIR-8100 infrared spectrometer. Detecting and finding IR (v)-1 ，KBr) Is 3331, 2577, 1947, 1761, 1622, 1198, 897, 621cm-1. 3331 the absorption peak corresponds to the C-H stretching vibration peak on methacrylate, 1761cm-1Corresponding to the stretching vibration peak of carbonyl in ester bond, 1622cm-1Corresponding to the double bond stretching vibration peak of methacrylate ester, 1198 corresponding to the stretching vibration peak of ether bond in ester. Thus, it was confirmed that the obtained unsaturated polyester contained a methacrylate ester.
(b) Preparation of hydrogels
Hydrogel composition:
1g of multi-arm unsaturated polyester prepared in the step a, 0.4g of dimethyl diallyl ammonium chloride and 0.4g of photoinitiator; wherein the photoinitiator consists of 0.1g of 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-acetone and 0.3g of (2,4, 6-trimethylbenzoyl) diphenyl phosphine oxide.
The multi-arm unsaturated polyester, the dimethyl diallyl ammonium chloride and the photoinitiator are uniformly mixed to obtain the polyester.
Adding hydrogel into a mold, and irradiating at a wavelength of 395nm with a light intensity of 300mW/cm2The gel is cured for 3min under the LED lamp to obtain the antibacterial active gel.
(c) Detection of gel Performance of antibacterial Activity
The swelling degree of the prepared antibacterial active gel was 2866% according to the method described in example 1.
The compression strength of the prepared antibacterial active gel reaches 2.10mPa and the elastic modulus reaches 1.09MPa according to the detection method of the example 1.
The BSA adsorption amounts of the antibacterial active gels were measured to be 299mg/g, respectively.
3. Antibacterial property
According to the method for detecting the antibacterial performance of GB/T21510-.
4. Stability against bacteria
The stability of the prepared gel-like mass of antibacterial activity was measured to be 99.8% according to the method described in example 1.
And (3) taking the completely molded antibacterial active gel sample block, soaking the completely molded antibacterial active gel sample block in a PBS solution for 48h, taking out the antibacterial active gel sample block, washing with distilled water for three times, and freeze-drying to obtain a solid. And (3) detecting the antibacterial effect of the soaked antibacterial active gel on escherichia coli and staphylococcus aureus according to a GB/T21510-.
From the above results, it can be understood that the mass of the antibacterial active gel-like mass prepared in the present invention is not reduced after soaking for 48 hours, and high stability is exhibited without affecting antibacterial performance. Therefore, the antibacterial active gel has good antibacterial stability.
Example 5
(a) Preparation of multi-arm unsaturated polyester
Adding 0.149g (0.001mol) of triethanolamine, 6g (0.06mol) of succinic anhydride, 8.52g (0.06mol) of glycidyl methacrylate and 68mg (0.5mmol) of zinc chloride into 20mL of DMF, carrying out freeze-thaw cycling for three times, heating to 85 ℃ under the protection of nitrogen, carrying out ring-opening polymerization for 7h, cooling to room temperature, adding cold diethyl ether, and precipitating to obtain the compound.
The infrared spectrum of the obtained multi-arm unsaturated polyester is measured by a Shimadzu FTIR-8100 infrared spectrometer. Detecting and finding IR (v)-1 ，KBr) Is 3222, 2670, 1928, 1761, 1664, 1229, 977, 651cm-1. 3222 absorption peak corresponds to the C-H stretching vibration peak on methacrylate, 1761cm-1Corresponds to the stretching vibration peak of carbonyl in ester bond, 1664cm-1Corresponding to the double bond stretching vibration peak of methacrylate ester, 1229 corresponding to the ether bond stretching vibration peak in ester. Thus, it was confirmed that the obtained unsaturated polyester contained a methacrylate ester.
(b) Preparation of hydrogels
Hydrogel composition:
1g of multi-arm unsaturated polyester prepared in the step a, 0.2g of dimethyl diallyl ammonium chloride and 0.5g of photoinitiator; wherein the photoinitiator consists of 0.25g of 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone and 0.25g of (2,4, 6-trimethylbenzoyl) diphenylphosphine oxide.
The multi-arm unsaturated polyester, the dimethyl diallyl ammonium chloride and the photoinitiator are uniformly mixed to obtain the polyester.
Adding hydrogel into a mold, and irradiating at a wavelength of 395nm with a light intensity of 300mW/cm2The gel is cured for 3min under the LED lamp to obtain the antibacterial active gel.
(c) Detection of gel Performance of antibacterial Activity
The swelling degree of the prepared antibacterial active gel was 2936% according to the method described in example 1.
The compression strength of the prepared antibacterial active gel reaches 2.29MPa and the elastic modulus reaches 1.18MPa according to the detection method of the example 1.
The BSA adsorption amounts of the antibacterial active gels were measured to be 310mg/g, respectively.
3. Antibacterial property
According to the method for detecting the antibacterial performance of GB/T21510-.
4. Stability against bacteria
The stability of the prepared gel-like mass of antibacterial activity was measured to be 99.8% according to the method described in example 1.
And (3) taking the completely formed antibacterial active gel, soaking the completely formed antibacterial active gel in a PBS solution for 48h, taking out an antibacterial active gel sample block, washing with distilled water for three times, and freeze-drying to obtain a solid. And (3) detecting the antibacterial effect of the soaked antibacterial active gel on escherichia coli and staphylococcus aureus according to a GB/T21510-.
From the above results, it can be understood that the antibacterial active gel prepared in the present invention shows no decrease in mass after soaking for 48 hours, shows high stability, and has no influence on antibacterial performance. Therefore, the antibacterial active gel has good antibacterial stability.
Example 6
(a) Preparation of multi-arm unsaturated polyester
Adding 0.149g (0.001mol) of triethanolamine, 5.5g (0.055mol) of succinic anhydride, 7.81g (0.055mol) of glycidyl methacrylate and 74.8mg of zinc chloride (0.55mmol) into 15mL of DMF, carrying out freeze-thaw cycle for three times, heating to 80 ℃ under the protection of nitrogen for ring-opening polymerization reaction for 10h, cooling to room temperature, adding into cold diethyl ether, and precipitating to obtain the compound.
The infrared spectrum of the obtained multi-arm unsaturated polyester is measured by a Shimadzu FTIR-8100 infrared spectrometer. Detecting and finding IR (v)-1 ，KBr) Is 3156, 2867, 2017, 1844, 1623, 1210, 933, 618cm-1. 3156 the absorption peak corresponds to the C-H stretching vibration peak on the methacrylate, 1844cm-1Corresponding to the stretching vibration peak of carbonyl in ester bond, 1623cm-1Corresponding to the double bond stretching vibration peak of methacrylate, 1210 corresponding to the stretching vibration peak of ether bond in ester. Thus, it was confirmed that the obtained unsaturated polyester contained a methacrylate ester.
(b) Preparation of hydrogels
Hydrogel composition:
1g of multi-arm unsaturated polyester prepared in the step a, 0.4g of dimethyl diallyl ammonium chloride and 0.4g of photoinitiator; wherein the photoinitiator consists of 0.3g of 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone and 0.1g of (2,4, 6-trimethylbenzoyl) diphenylphosphine oxide.
The multi-arm unsaturated polyester, the dimethyl diallyl ammonium chloride and the photoinitiator are uniformly mixed to obtain the polyester.
Adding hydrogel into a mold, and irradiating at a wavelength of 395nm with a light intensity of 300mW/cm2The gel is cured for 3min under the LED lamp to obtain the antibacterial active gel.
(c) Detection of gel Performance of antibacterial Activity
The swelling degree of the prepared antibacterial active gel was 3144% according to the method described in example 1.
The compression strength of the prepared antibacterial active gel reaches 2.14MPa and the elastic modulus reaches 1.11MPa according to the detection method of the example 1.
The BSA adsorption amounts of the antibacterial active gels were measured to be 255mg/g, respectively.
3. Antibacterial property
According to the method for detecting the antibacterial performance of GB/T21510-.
4. Stability against bacteria
The stability of the prepared gel-like mass of antibacterial activity was measured to be 99.7% according to the method described in example 1.
And (3) taking the completely molded antibacterial active gel sample block, soaking the completely molded antibacterial active gel sample block in a PBS solution for 48h, taking out the antibacterial active gel sample block, washing with distilled water for three times, and freeze-drying to obtain a solid. And (3) detecting the antibacterial effect of the soaked antibacterial active gel sample block on escherichia coli and staphylococcus aureus according to a GB/T21510-.
From the above results, it can be understood that the antibacterial active gel prepared in the present invention shows no decrease in mass after soaking for 48 hours, shows high stability, and has no influence on antibacterial performance. Therefore, the antibacterial active gel has good antibacterial stability.
Example 7
(a) Preparation of multi-arm unsaturated polyester
Adding 0.149g (0.001mol) of triethanolamine, 7.5g (0.075mol) of succinic anhydride, 2.84g (0.075mol) of glycidyl methacrylate and 102mg (0.75mmol) of zinc chloride into 20mL of DMF, carrying out freeze-thaw cycling for three times, heating to 100 ℃ under the protection of nitrogen for ring-opening polymerization for 5h, cooling to room temperature, adding cold diethyl ether for precipitation to obtain the product.
The infrared spectrum of the obtained multi-arm unsaturated polyester is measured by a Shimadzu FTIR-8100 infrared spectrometer. Detecting and finding IR (v)-1 ，KBr) Is 3186, 2839, 2152, 1871, 1682, 1210, 1138, 942, 650cm-1. 3186 the absorption peak corresponds to the C-H stretching vibration peak on the methacrylate, 2839cm-1Corresponding to saturated C-H stretching vibration peak, 1871cm-1Corresponding to the stretching vibration peak of carbonyl in ester bond, 1682cm-1Corresponding to the double bond stretching vibration peak of methacrylate, 1210 corresponding to the stretching vibration peak of ether bond in ester. Thus, it was confirmed that the obtained unsaturated polyester contained a methacrylate ester.
(b) Preparation of hydrogels
Hydrogel composition:
1g of multi-arm unsaturated polyester prepared in the step a, 0.3g of dimethyl diallyl ammonium chloride and 0.2g of photoinitiator; wherein the photoinitiator consists of 0.1g of 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone and 0.1g of (2,4, 6-trimethylbenzoyl) diphenylphosphine oxide.
The multi-arm unsaturated polyester, the dimethyl diallyl ammonium chloride and the photoinitiator are uniformly mixed to obtain the polyester.
Adding hydrogel into a mold, and irradiating at a wavelength of 395nm with a light intensity of 300mW/cm2Under the LED lampIrradiating with light for 3min to obtain antibacterial active gel.
(c) Detection of gel Performance of antibacterial Activity
The swelling degree of the antibacterial gel prepared according to the method described in example 1 was 3007%.
The compression strength of the prepared antibacterial active gel reaches 2.21mPa and the elastic modulus reaches 1.16MPa according to the detection method of the example 1.
The BSA adsorption amounts of the antibacterial active gels were measured to be 329mg/g, respectively.
3. Antibacterial property
According to the method for detecting the antibacterial performance of GB/T21510-.
4. Stability against bacteria
The stability of the prepared gel-like mass of antibacterial activity was measured to be 99.4% according to the method described in example 1.
And (3) taking the completely molded antibacterial active gel sample block, soaking the completely molded antibacterial active gel sample block in a PBS solution for 48h, taking out the antibacterial active gel sample block, washing with distilled water for three times, and freeze-drying to obtain a solid. And (3) detecting the antibacterial effect of the soaked antibacterial active gel sample block on escherichia coli and staphylococcus aureus according to a GB/T21510-.
From the above results, it can be understood that the antibacterial active gel prepared in the present invention shows no decrease in mass after soaking for 48 hours, shows high stability, and has no influence on antibacterial performance. Therefore, the antibacterial active gel has good antibacterial stability.
Example 8
(a) Preparation of multi-arm unsaturated polyester
Adding 0.149g (0.001mol) of triethanolamine, 6g (0.06mol) of succinic anhydride, 8.52g (0.06mol) of glycidyl methacrylate and 108.8mg (0.5mmol) of zinc chloride into 20mL of DMF, carrying out freeze-thaw cycle for three times, heating to 90 ℃ under the protection of nitrogen for ring-opening polymerization reaction for 6h, cooling to room temperature, adding cold diethyl ether for precipitation to obtain the compound.
Obtained as described aboveThe infrared spectrum of the multi-arm unsaturated polyester is measured by a Shimadzu FTIR-8100 infrared spectrometer. Detecting and finding IR (v)-1 ，KBr) 3134, 2883, 2002, 1867, 1633, 1227, 927, 655cm-1. 3134 the absorption peak corresponds to the C-H stretching vibration peak on methacrylate, 1867cm-1Corresponding to the stretching vibration peak of carbonyl in ester bond, 1633cm-1Corresponding to the double bond stretching vibration peak of methacrylate ester, 1227 corresponding to the ether bond stretching vibration peak in ester. Thus, it was confirmed that the obtained unsaturated polyester contained a methacrylate ester.
(b) Preparation of hydrogels
Hydrogel composition:
1g of multi-arm unsaturated polyester prepared in the step a, 0.3g of dimethyl diallyl ammonium chloride and 0.4g of photoinitiator; wherein the photoinitiator consists of 0.2g of 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone and 0.2g of (2,4, 6-trimethylbenzoyl) diphenylphosphine oxide.
The multi-arm unsaturated polyester, the dimethyl diallyl ammonium chloride and the photoinitiator are uniformly mixed to obtain the polyester.
Adding hydrogel into a mold, and irradiating at a wavelength of 395nm with a light intensity of 300mW/cm2The gel is cured for 3min under the LED lamp to obtain the antibacterial active gel.
(c) Detection of gel Performance of antibacterial Activity
The swelling degree of the antibacterial active gel prepared according to the method described in example 1 was 3105%.
The compression strength of the prepared antibacterial active gel reaches 2.22MPa and the elastic modulus reaches 1.15MPa according to the detection method of the example 1.
The BSA adsorption of the antibacterial active gel was measured to be 293mg/g, respectively.
3. Antibacterial property
According to the method for detecting the antibacterial performance of GB/T21510-.
4. Stability against bacteria
The stability of the prepared gel-like mass of antibacterial activity was measured to be 99.5% according to the method described in example 1.
And (3) taking the completely molded antibacterial active gel sample block, soaking the completely molded antibacterial active gel sample block in a PBS solution for 48h, taking out the antibacterial active gel sample block, washing with distilled water for three times, and freeze-drying to obtain a solid. And (3) detecting the antibacterial effect of the soaked antibacterial active gel sample block on escherichia coli and staphylococcus aureus according to a GB/T21510-.
From the above results, it can be understood that the antibacterial active gel prepared in the present invention shows no decrease in mass after soaking for 48 hours, shows high stability, and has no influence on antibacterial performance. Therefore, the antibacterial active gel has good antibacterial stability.
Example 9
(a) Preparation of multi-arm unsaturated polyester
Adding 0.149g (0.001mol) of triethanolamine, 5g (0.05mol) of succinic anhydride, 7.1g (0.05mol) of glycidyl methacrylate and 68mg (0.5mmol) of zinc chloride into 20mL of DMF, carrying out freeze-thaw cycling for three times, heating to 95 ℃ under the protection of nitrogen, carrying out ring-opening polymerization for 7h, cooling to room temperature, adding cold diethyl ether, and precipitating to obtain the compound.
The infrared spectrum of the obtained multi-arm unsaturated polyester is measured by a Shimadzu FTIR-8100 infrared spectrometer. Detecting and finding IR (v)-1 ，KBr) 3019, 2813, 2057, 1892, 1599, 1207, 921, 646cm-1. 3019 the absorption peak corresponds to the C-H stretching vibration peak on methacrylate, 1892cm-1Corresponding to the stretching vibration peak of carbonyl in ester bond of 1599cm-1Corresponding to the double bond stretching vibration peak of methacrylate ester, 1207 corresponding to the ether bond stretching vibration peak in ester. Thus, it was confirmed that the obtained unsaturated polyester contained a methacrylate ester.
(b) Preparation of hydrogels
Hydrogel composition:
1g of multi-arm unsaturated polyester prepared in the step a, 0.1g of dimethyl diallyl ammonium chloride and 0.1g of photoinitiator; wherein the photoinitiator is 0.1g of 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-acetone.
The multi-arm unsaturated polyester, the dimethyl diallyl ammonium chloride and the photoinitiator are uniformly mixed to obtain the polyester.
Adding hydrogel into a mold, and irradiating at a wavelength of 395nm with a light intensity of 300mW/cm2The gel is cured for 3min under the LED lamp to obtain the antibacterial active gel.
(c) Antimicrobial hydrogel performance testing
The swelling degree of the prepared antibacterial active gel was 2977% according to the method described in example 1.
The compression strength of the prepared antibacterial active gel reaches 2.14MPa and the elastic modulus reaches 1.13MPa according to the detection method of the example 1.
The BSA adsorption amounts of the antibacterial active gels were measured to be 354mg/g, respectively.
3. Antibacterial property
According to the method for detecting the antibacterial performance of GB/T21510-.
4. Stability against bacteria
The stability of the prepared gel-like mass of antibacterial activity was measured to be 99.2% according to the method described in example 1.
And (3) taking the completely molded antibacterial active gel sample block, soaking the completely molded antibacterial active gel sample block in a PBS solution for 48h, taking out the antibacterial active gel sample block, washing with distilled water for three times, and freeze-drying to obtain a solid. And (3) detecting the antibacterial effect of the soaked antibacterial active gel sample block on escherichia coli and staphylococcus aureus according to a GB/T21510-.
From the above results, it can be understood that the antibacterial active gel prepared in the present invention shows no decrease in mass after soaking for 48 hours, shows high stability, and has no influence on antibacterial performance. Therefore, the antibacterial active gel has good antibacterial stability.
Example 10
(a) Preparation of multi-arm unsaturated polyester
0.149g (0.001mol) of triethanolamine, 8g (0.08mol) of succinic anhydride, 11.36g (0.08mol) of glycidyl methacrylate and 108.8mg of zinc chloride (0.8mmol) are added into 20mL of DMF, after three freeze-thaw cycles, the mixture is heated to 90 ℃ under the protection of nitrogen for ring-opening polymerization reaction for 8h, cooled to room temperature and added into cold ether for precipitation to obtain the compound.
The infrared spectrum of the obtained multi-arm unsaturated polyester is measured by a Shimadzu FTIR-8100 infrared spectrometer. Detecting and finding IR (v)-1 ，KBr) 3278, 2680, 1922, 1833, 1657, 1210, 955, 646cm-1. 3278 the absorption peak corresponds to the C-H stretching vibration peak on methacrylate, 1833cm-1Corresponds to the stretching vibration peak of carbonyl in ester bond, 1657cm-1Corresponding to the double bond stretching vibration peak of methacrylate, 1210 corresponding to the stretching vibration peak of ether bond in ester. Thus, it was confirmed that the obtained unsaturated polyester contained a methacrylate ester.
(b) Preparation of hydrogels
Hydrogel composition:
1g of multi-arm unsaturated polyester prepared in the step a, 0.5g of dimethyl diallyl ammonium chloride and 0.5g of photoinitiator; wherein the photoinitiator consists of 0.2g of 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone and 0.3g of (2,4, 6-trimethylbenzoyl) diphenylphosphine oxide.
The multi-arm unsaturated polyester, the dimethyl diallyl ammonium chloride and the photoinitiator are uniformly mixed to obtain the polyester.
Adding hydrogel into a mold, and irradiating at a wavelength of 395nm with a light intensity of 300mW/cm2The gel is cured for 3min under the LED lamp to obtain the antibacterial active gel.
(c) Detection of gel Performance of antibacterial Activity
The swelling degree of the antibacterial active gel prepared according to the method described in example 1 was 2989%.
The compression strength of the prepared antibacterial active gel reaches 2.17MPa and the elastic modulus reaches 1.12MPa according to the detection method of the example 1.
The BSA adsorption amounts of the antibacterial active gels were measured to be 312mg/g, respectively.
3. Antibacterial property
The antibacterial rate of the antibacterial activity gel on escherichia coli and staphylococcus aureus is detected to be more than 99.9% according to the GB/T21510-2008 nano inorganic material antibacterial performance detection method.
4. Stability against bacteria
The stability of the prepared gel-like mass of antibacterial activity was measured to be 99.7% according to the method described in example 1.
And (3) taking the completely molded antibacterial active gel sample block, soaking the completely molded antibacterial active gel sample block in a PBS solution for 48h, taking out the antibacterial active gel sample block, washing with distilled water for three times, and freeze-drying to obtain a solid. And (3) detecting the antibacterial effect of the soaked antibacterial active gel sample block on escherichia coli and staphylococcus aureus according to a GB/T21510-.
From the above results, it can be understood that the antibacterial active gel prepared in the present invention shows no decrease in mass after soaking for 48 hours, shows high stability, and has no influence on antibacterial performance. Therefore, the antibacterial active gel has good antibacterial stability.
Comparative example 1
(a)
The invention relates to an antibacterial active gel prepared from multi-arm unsaturated polyester, which comprises the following components in percentage by weight:
2g of the multi-arm unsaturated polyester prepared in example 1, 0.6g of dimethyldiallylammonium chloride, 0.3g of 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone and 0.3g of (2,4, 6-trimethylbenzoyl) diphenylphosphine oxide were uniformly mixed and cured under illumination for 3min with an LED lamp having a wavelength of 395nm and a light intensity of 300mW/cm2 to obtain an antibacterial gel.
Control antibacterial active gel prepared with control unsaturated polyester:
2g of unsaturated polyester prepared by the method described in example 1 of patent (201911049657.6), 0.6g of dimethyldiallylammonium chloride, 0.3g of 2-methyl-2- (4-morpholinyl) -1- [4- (methylthio) phenyl ] -1-propanone and 0.3g of (2,4, 6-trimethylbenzoyl) diphenylphosphine oxide were mixed uniformly and cured under the illumination of an LED lamp with a light intensity of 300mW/cm2 and a wavelength of 395nm for 3min to obtain a control antibacterial active gel.
(b) Performance detection
5 samples of antimicrobially active gel and 5 samples of control antimicrobially active gel were prepared according to the procedure described in step a of comparative example 1.
The compressive strength, elastic modulus and BSA adsorption performance of 5 samples of the antibacterial active gel and 5 samples of the control antibacterial active gel were measured according to the method described in example 1. The results are shown in tables 1, 2 and 3 below.
TABLE 1 compression Strength (MPa) of antibacterial active gel and control antibacterial active gel
| First sample | Second sample | Third sample | Fourth sample | Fifth sample | Statistical results | |
| Antibacterial hydrogel | 2.33 | 2.32 | 2.28 | 2.29 | 2.31 | 2.306±0.0207 |
| Control antimicrobial hydrogel | 1.92 | 1.90 | 1.93 | 1.92 | 1.91 | 1.916±0.0114 |
TABLE 2 elastic modulus (MPa) of antibacterial hydrogel of antibacterial active gel and control antibacterial active gel
| First sample | Second sample | Third sample | Fourth sample | Fifth sample | Statistical results | |
| Antibacterial hydrogel | 1.18 | 1.20 | 1.19 | 1.16 | 1.17 | 1.18±0.0158 |
| Control antimicrobial hydrogel | 1.11 | 1.09 | 1.10 | 1.10 | 1.12 | 1.10±0.0158 |
TABLE 3 BSA adsorption (mg/g) of the antibacterial active gels and the control antibacterial active gel
| For the first time | For the second time | The third time | Fourth time | Fifth time | Statistical results | |
| Antibacterial hydrogel | 285 | 287 | 283 | 283 | 286 | 284.8±1.789 |
| Control antimicrobial hydrogel | 235 | 233 | 234 | 236 | 237 | 235±1.581 |
From the above table, it can be seen that the antibacterial active gel of the present invention has better compressive strength and elastic modulus. The BSA adsorption performance is better than that of a reference substance. Therefore, the antibacterial active gel has good mechanical properties.
Claims (4)
1. An antibacterial hydrogel containing multi-arm unsaturated polyester, which consists of the multi-arm unsaturated polyester, dimethyldiallylammonium chloride which is 0.1 to 0.5 time of the weight of the multi-arm unsaturated polyester and a photoinitiator which is 0.1 to 0.5 time of the weight of the unsaturated polyester according to the weight ratio; wherein the multi-arm unsaturated polyester is prepared by the following method:
adding triethanolamine, succinic anhydride, glycidyl methacrylate and zinc chloride into DMF (dimethyl formamide) according to the molar ratio of the triethanolamine to the succinic anhydride to the glycidyl methacrylate to the zinc chloride of 1 to q to n to m, carrying out freeze-thaw cycle for three times, heating to 80-100 ℃ under the protection of nitrogen for ring-opening polymerization for 5-10 h, cooling to room temperature, and adding cold diethyl ether for precipitation to obtain the multi-arm unsaturated polyester; wherein the content of the first and second substances,
n is 50 to 80, q is 50 to 80, m is 0.5 to 0.8, and n ═ q.
The photoinitiator is 1-hydroxycyclohexyl phenyl ketone or/and (2,4, 6-trimethyl benzoyl) diphenyl phosphine oxide.
2. The multi-arm unsaturated polyester-containing antibacterial hydrogel according to claim 1, wherein n is 60 to 70, q is 60 to 70, and m is 0.6 to 0.7.
3. The multi-arm unsaturated polyester-containing antibacterial hydrogel according to claim 1, wherein the ring-opening polymerization reaction temperature is 90 ℃ and the time is 8 hours.
4. A method for preparing an antibacterial active gel, which comprises the following steps: the method of adding the antibacterial hydrogel according to any one of claims 1 to 3 to a mold at 395nm light intensity of 300mW/cm2The antibacterial active gel is obtained by illumination and solidification under an LED lamp.
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