CN115152750B - Long-acting antibacterial spray and preparation method thereof - Google Patents
Long-acting antibacterial spray and preparation method thereof Download PDFInfo
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- CN115152750B CN115152750B CN202210835087.9A CN202210835087A CN115152750B CN 115152750 B CN115152750 B CN 115152750B CN 202210835087 A CN202210835087 A CN 202210835087A CN 115152750 B CN115152750 B CN 115152750B
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- phase solution
- antibacterial
- nano silver
- spray
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 82
- 239000007921 spray Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title abstract description 41
- 229920001661 Chitosan Polymers 0.000 claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 claims abstract description 33
- 239000012071 phase Substances 0.000 claims abstract description 28
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical group O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000004132 cross linking Methods 0.000 claims abstract description 25
- 239000008346 aqueous phase Substances 0.000 claims abstract description 22
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 20
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 20
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 10
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 10
- 239000008213 purified water Substances 0.000 claims abstract description 8
- 239000002562 thickening agent Substances 0.000 claims abstract description 8
- 239000002270 dispersing agent Substances 0.000 claims abstract description 5
- 230000001804 emulsifying effect Effects 0.000 claims abstract description 4
- 239000004698 Polyethylene Substances 0.000 claims description 31
- 229920000573 polyethylene Polymers 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 23
- 230000000845 anti-microbial effect Effects 0.000 claims description 18
- 239000000839 emulsion Substances 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000006467 substitution reaction Methods 0.000 claims description 12
- -1 sorbitan fatty acid ester Chemical class 0.000 claims description 10
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 8
- 239000000194 fatty acid Substances 0.000 claims description 8
- 229930195729 fatty acid Natural products 0.000 claims description 8
- 229920002385 Sodium hyaluronate Polymers 0.000 claims description 7
- 238000004945 emulsification Methods 0.000 claims description 7
- 229940010747 sodium hyaluronate Drugs 0.000 claims description 7
- YWIVKILSMZOHHF-QJZPQSOGSA-N sodium;(2s,3s,4s,5r,6r)-6-[(2s,3r,4r,5s,6r)-3-acetamido-2-[(2s,3s,4r,5r,6r)-6-[(2r,3r,4r,5s,6r)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2- Chemical group [Na+].CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 YWIVKILSMZOHHF-QJZPQSOGSA-N 0.000 claims description 7
- 239000012295 chemical reaction liquid Substances 0.000 claims description 6
- 229920000289 Polyquaternium Polymers 0.000 claims description 3
- 150000002191 fatty alcohols Chemical class 0.000 claims description 3
- 229920000223 polyglycerol Polymers 0.000 claims description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 2
- 239000003899 bactericide agent Substances 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- LVWZTYCIRDMTEY-UHFFFAOYSA-N metamizole Chemical compound O=C1C(N(CS(O)(=O)=O)C)=C(C)N(C)N1C1=CC=CC=C1 LVWZTYCIRDMTEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims 6
- 230000002421 anti-septic effect Effects 0.000 claims 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 53
- 239000000243 solution Substances 0.000 description 39
- 238000012360 testing method Methods 0.000 description 17
- 230000000694 effects Effects 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000011148 porous material Substances 0.000 description 10
- 238000005507 spraying Methods 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 230000009471 action Effects 0.000 description 7
- 241000894006 Bacteria Species 0.000 description 6
- 239000003242 anti bacterial agent Substances 0.000 description 6
- 238000005266 casting Methods 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
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- 125000003396 thiol group Chemical group [H]S* 0.000 description 5
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 239000003973 paint Substances 0.000 description 4
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000012216 screening Methods 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- 238000009777 vacuum freeze-drying Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 108010025899 gelatin film Proteins 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000004659 sterilization and disinfection Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 2
- LOEUPVXIWVJADW-UHFFFAOYSA-N 2-aminoethanol;1h-pyridin-2-one Chemical compound NCCO.O=C1C=CC=CN1 LOEUPVXIWVJADW-UHFFFAOYSA-N 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- 241000222122 Candida albicans Species 0.000 description 2
- 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
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 241000191967 Staphylococcus aureus Species 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229940095731 candida albicans Drugs 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000012792 lyophilization process Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 239000007762 w/o emulsion Substances 0.000 description 2
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 1
- 241000228245 Aspergillus niger Species 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 1
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 1
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 1
- 239000000159 acid neutralizing agent Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000011482 antibacterial activity assay Methods 0.000 description 1
- 230000008952 bacterial invasion Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000006196 deacetylation Effects 0.000 description 1
- 238000003381 deacetylation reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 238000013095 identification testing Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000000787 lecithin Substances 0.000 description 1
- 235000010445 lecithin Nutrition 0.000 description 1
- 229940067606 lecithin Drugs 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- ONJQDTZCDSESIW-UHFFFAOYSA-N polidocanol Chemical compound CCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO ONJQDTZCDSESIW-UHFFFAOYSA-N 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- UBQKCCHYAOITMY-UHFFFAOYSA-N pyridin-2-ol Chemical class OC1=CC=CC=N1 UBQKCCHYAOITMY-UHFFFAOYSA-N 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 229940083025 silver preparation Drugs 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
- A01N25/06—Aerosols
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
- A01N25/10—Macromolecular compounds
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
- A01N33/02—Amines; Quaternary ammonium compounds
- A01N33/12—Quaternary ammonium compounds
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P3/00—Fungicides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Abstract
The application discloses a long-acting antibacterial spray and a preparation method thereof, wherein the antibacterial spray comprises the following raw materials in percentage by weight: microporous support: 2-5%; antibacterial composition: 0.3 to 2 percent; dispersing agent: 0.1 to 2 percent; and (3) a thickening agent: 1 to 5 percent; purified water: the balance; the microporous carrier is prepared by emulsifying, crosslinking and drying aqueous phase solution, oil phase solution and crosslinking agent, wherein the aqueous phase solution comprises the following raw materials: carboxymethyl chitosan; ammonium bicarbonate; water; the oil phase solution comprises the following raw materials: an organic solvent; an emulsifying agent; the weight ratio of the oil phase solution to the water phase solution is (2-4) 1, and the dosage of the ammonium bicarbonate is 10-50% of the weight of the carboxymethyl chitosan; the cross-linking agent is glutaraldehyde, and the dosage of glutaraldehyde is 0.5-1.5% of the weight of the carboxymethyl chitosan. The long-acting antibacterial spray prepared by the method has excellent antibacterial property and durability.
Description
Technical Field
The application relates to the field of antibacterial spraying, in particular to a long-acting antibacterial spraying agent and a preparation method thereof.
Background
The antibacterial spray can effectively inhibit and kill harmful bacteria on the surfaces of fabrics, toys, furniture and other objects, such as escherichia coli, staphylococcus aureus, candida albicans, aspergillus niger and the like, and effectively reduce the probability of bacterial invasion, thereby guaranteeing the health of human bodies.
The antibacterial spray on the market is prepared by mixing the antibacterial agents such as quaternary ammonium salt, hypochlorous acid, nano silver ions, pyridone derivatives, ethanol and the like serving as active ingredients with a solvent, and has the advantages of low toxicity, high efficiency, safety and the like, but also has the defects of short acting time and poor antibacterial durability.
Disclosure of Invention
The long-acting antibacterial spray and the preparation method thereof can effectively prolong the effective action duration of antibacterial spray and improve the antibacterial durability of the antibacterial spray.
In a first aspect, the present application provides a long-acting antimicrobial spray comprising the following raw materials in weight percent:
microporous support: 2-5%;
antibacterial composition: 0.3 to 2 percent;
dispersing agent: 0.1 to 2 percent;
and (3) a thickening agent: 1 to 5 percent;
purified water: the balance;
the microporous carrier is prepared by emulsifying, crosslinking and drying aqueous phase solution, oil phase solution and crosslinking agent, wherein the aqueous phase solution comprises the following raw materials:
carboxymethyl chitosan;
ammonium bicarbonate;
water;
the oil phase solution comprises the following raw materials:
an organic solvent;
an emulsifying agent;
the weight ratio of the oil phase solution to the water phase solution is (2-4) 1, and the dosage of the ammonium bicarbonate is 10-50% of the weight of the carboxymethyl chitosan; the cross-linking agent is glutaraldehyde, and the dosage of glutaraldehyde is 0.5-1.5% of the weight of the carboxymethyl chitosan.
In the technical scheme, the water-in-oil emulsion can be prepared by adding the aqueous phase solution into the oil phase solution, and fully mixing and emulsifying under the action of the emulsifier; and adding glutaraldehyde crosslinking agent into the emulsion, and performing crosslinking reaction on carboxymethyl chitosan contained in the water phase and glutaraldehyde to obtain chitosan gel coated with ammonium bicarbonate. And (3) heating and drying the chitosan gel to evaporate the water and the organic solvent, and decomposing sodium bicarbonate to form a stable pore structure on the gel to obtain the microporous carrier. The microporous carrier is mainly prepared from chitosan with broad-spectrum antibacterial effect, and meanwhile, the antibacterial composition can be effectively loaded in the pore structure of the microporous carrier to play a good slow-release role, so that the antibacterial spray can be remarkably prolonged in durability on the surface of an object while the excellent antibacterial effect is achieved.
The gel formed by crosslinking the chitosan with glutaraldehyde has a stable network structure and high mechanical strength, is favorable for stabilizing the pore structure, and ensures the loading and sustained release effects.
In addition, in the drying procedure described in the present application, a vacuum freeze-drying process may be used, which has a high cost, but the pore structure of the obtained microporous carrier is relatively large, and the pore distribution is relatively uniform. Specifically, in the vacuum freeze-drying process, the gel obtained after cross-linking is frozen into ice crystal state at low temperature, the freezing temperature (cold trap temperature) is preferably-40-55 ℃, and the freeze dryer is vacuumized, and the vacuum degree is preferably 15-25 Pa; after the freezing is finished, carrying out one-section heating by a heating device, wherein the temperature after one-section heating is less than the eutectic point, preferably-10 ℃ to-15 ℃, so that ice crystals in the ice crystal state emulsion are fully sublimated, and the sublimation of the ice crystals enables pores to be generated on the particle structure; the second-stage heating is carried out after sublimation is finished, the temperature after the second-stage heating is usually more than 0 ℃, the temperature is preferably 40-60 ℃ in the application, so that the organic solvent volatilizes, meanwhile, ammonium bicarbonate is promoted to decompose, a pore-forming effect is generated, and the porosity of the microporous carrier is effectively improved.
The organic solvent of the application preferably adopts any one of dichloromethane, chloroform, carbon tetrachloride and cyclohexane, and has the advantages of low boiling point, easy evaporation and good environmental protection performance. The particle diameter of the microporous carrier is preferably 30-80 mu m, and the microporous carrier has high loading performance and is easy to disperse.
Preferably, the antibacterial composition comprises the following components in percentage by weight:
pyridone bactericides: 0.1 to 1 percent;
polyquaternium: 0.1 to 1 percent.
By adopting the technical scheme, the compounding of various antibacterial components is helpful for reducing the drug resistance of bacteria and guaranteeing the antibacterial activity of spraying.
Preferably, the aqueous phase solution also comprises nano silver, and the dosage of the nano silver is 10-20% of the weight of the chitosan.
The nano silver is beneficial to improving the antibacterial effect of antibacterial spraying, and meanwhile, the nano silver can be wrapped by the crosslinked chitosan gel after being added into the water phase, so that the slow release effect of the nano silver can be obviously improved, and the long-acting property of the antibacterial effect of spraying is improved.
Preferably, the substitution degree of the carboxymethyl chitosan is 0.2-0.3.
The carboxymethyl chitosan with the substitution degree range has better water solubility, and enough amino groups are reserved on chitosan molecules, so that reaction sites can be provided for the crosslinking bonding of glutaraldehyde and the amino groups on the chitosan. The molecular weight of the carboxymethyl chitosan is preferably 9000-50000, and the deacetylation degree is more than or equal to 85%.
Preferably, the emulsifier is one or more of fatty alcohol polyoxyethylene ether, sorbitan fatty acid ester, polyglycerol fatty acid ester and sucrose fatty acid ester.
The emulsifiers described above are all nonionic surfactants that aid in the formation of water-in-oil emulsions and homogeneous emulsion particles.
Preferably, the microporous carrier is prepared according to the following method:
emulsification: dissolving carboxymethyl chitosan, ammonium bicarbonate and polyquaternium in water to obtain an aqueous phase solution; adding an emulsifying agent into an organic solvent to obtain an oil phase solution; mixing the aqueous phase solution and the oil phase solution, and uniformly stirring to obtain emulsion;
crosslinking: glutaraldehyde is added into the emulsion to carry out a crosslinking reaction, so as to obtain a reaction solution;
and (3) freeze-drying: and (3) performing vacuum freeze drying on the reaction liquid to obtain freeze-dried blocks, and crushing to obtain the microporous carrier.
In the emulsification process, firstly, aqueous phase solution is used as a disperse phase, oil phase solution is used as a continuous phase, and water-in-oil emulsion is formed in a solution system through the emulsification of an emulsifier. And secondly, glutaraldehyde is added into the emulsion, so that the mutual crosslinking of chitosan molecules can be promoted, and the stability of the chitosan structure can be improved. Finally, heating and drying are carried out, water and solvent are evaporated, and ammonium bicarbonate is decomposed, so that the microporous carrier with a pore structure is obtained.
Preferably, the surface of the microporous carrier is modified with sulfhydryl-polyethylene glycol-amino, and the sulfhydryl-polyethylene glycol-amino has 8-16 carbon atoms.
The sulfhydryl-polyethylene glycol-amino is an oligomer of ethylene glycol, one end of the molecular chain of the oligomer contains sulfhydryl, and the other end contains amino. The sulfhydryl can generate coordination complexing action with nano silver so as to be attached to the surface of the nano silver, the amino group of the sulfhydryl can react and bond with glutaraldehyde, and the nano silver is connected to the chitosan gel through the crosslinking action of glutaraldehyde, so that on one hand, the slow release effect can be realized, and the action duration of antibacterial spraying can be effectively prolonged; on the other hand, the agglomeration of the nano metal ion antibacterial agent can be reduced, the precipitation phenomenon of antibacterial spraying is prevented, and the antibacterial performance and stability of the antibacterial spraying agent are ensured.
In addition, due to the existence of the peg spacer, the modification of the sulfhydryl-polyethylene glycol-amino group can promote the dispersion of the microporous carrier and the nano silver, thereby being beneficial to improving the antibacterial property of the spray. The molecular structure of the mercapto-polyethylene glycol-alcohol is shown below:
preferably, the mercapto-polyethylene glycol-amino is dissolved in water, the nano silver is added under the stirring condition, the nano silver with the surface modified by the mercapto-polyethylene glycol-amino is obtained, and the weight ratio of the mercapto-polyethylene glycol-amino to the nano silver is 1:4-7.
By adopting the technical scheme, in the aqueous solution, the sulfhydryl-polyethylene glycol-amino group can be effectively dissolved, so that the sulfhydryl-polyethylene glycol-amino group is fully contacted with the nano silver to form a complex, and the sulfhydryl-polyethylene glycol-amino group is promoted to be adsorbed on the surface of the nano silver.
Preferably, the thickener is sodium hyaluronate.
By adopting the technical scheme, the sodium hyaluronate contains a large number of polar groups such as carboxyl, amino, hydroxyl and the like, so that a network structure can be formed in an aqueous solution on one hand, and agglomeration and precipitation of a microporous carrier and nano silver are inhibited; on the other hand, hydrogen bonds can be formed between the antibacterial agent and the microporous carrier or nano silver, so that sedimentation of the antibacterial agent is inhibited, and the stability of antibacterial spraying is improved.
In a second aspect, the present application provides a method of preparing a long-acting antimicrobial spray comprising the steps of:
premixing the antibacterial composition and the microporous carrier to obtain a premix, adding the premix and the dispersing agent into purified water, uniformly stirring, adding the thickening agent, and continuously stirring to obtain the long-acting antibacterial spray.
By adopting the technical scheme, the antibacterial spray with long-acting antibacterial property is prepared, and has excellent stability and antibacterial property.
In summary, the application has the following beneficial effects:
1. according to the application, the microporous carrier prepared from the main raw materials of carboxymethyl chitosan and glutaraldehyde is adopted, so that the antibacterial spray is endowed with a slow release effect, the antibacterial durability and the long-acting performance of the antibacterial spray are improved, the loading area of antibacterial components and the contact area with bacteria are remarkably increased, and the sterilization effect is effectively improved.
2. According to the preparation method, the nano silver is added into the microporous carrier raw material, and the surface of the nano silver is modified by adopting the sulfhydryl-polyethylene glycol-amino group, so that the slow release effect of the antibacterial spray is improved, the sedimentation probability of the antibacterial spray is effectively reduced, and the stability of the antibacterial spray is improved.
3. According to the application, the sodium hyaluronate is used as the thickener, so that the dispersion of the microporous carrier and the nano silver antibacterial agent is effectively promoted, the tendency of suspension or agglomeration sedimentation of the microporous carrier and the nano silver antibacterial agent is inhibited, and the stability of the antibacterial spray is obviously improved.
Detailed Description
Modified nano silver preparation example
Preparation example 1-1, a modified nano silver, was prepared as follows:
1 kg of mercapto-polyethylene glycol-amino (the polymerization degree of polyethylene glycol is 5 and the carbon number is 10) is added into 10L of water, stirred and dissolved, then 5 kg of nano silver (30-50 nm) is added, filtered and dried, and the nano silver with the surface modified by the mercapto-polyethylene glycol-amino is obtained.
Preparation examples 1-2, a modified nano silver, were prepared as follows:
1 kg of mercapto-polyethylene glycol-amino (the polymerization degree of polyethylene glycol is 4 and the carbon number is 8) is added into 10L of water, stirred and dissolved, then 4 kg of nano silver (30-50 nm) is added, filtered and dried, and the nano silver with the surface modified by the mercapto-polyethylene glycol-amino is obtained.
Preparation examples 1-3, a modified nano silver, were prepared as follows:
1 kg of mercapto-polyethylene glycol-amino (the polymerization degree of polyethylene glycol is 8 and the carbon number is 16) is added into 15L of water, stirred and dissolved, then 7 kg of nano silver (30-50 nm) is added, filtered and dried, and the nano silver with the surface modified by the mercapto-polyethylene glycol-amino is obtained.
Preparation of microporous Carrier
Preparation example 2-1, a microporous carrier, was prepared as follows:
emulsification: at 35 ℃, 1 kg of carboxymethyl chitosan (substitution degree 0.3, molecular weight 20000), 0.12 kg of modified nano silver prepared in preparation example 1-1 and 0.3 kg of ammonium bicarbonate are added into 18 kg of water, and stirred for 6 hours to obtain aqueous phase solution; adding span-80 (sorbitan fatty acid ester) into organic solvent, stirring for 30min to obtain oil phase solution; adding the obtained aqueous phase solution into the oil phase solution, and stirring for 4 hours to obtain emulsion.
Crosslinking: 40g glutaraldehyde solution (25 wt%) was added to the emulsion under stirring, and the mixture was stirred for 2 hours to carry out a crosslinking reaction, thereby obtaining a reaction solution containing carboxymethyl chitosan gel.
And (3) drying: removing the reaction liquid, casting to form a film, drying at 80 ℃, and then crushing and screening the casting dried gel film to obtain the microporous carrier with the granularity of 40-50 mu m.
Preparation example 2-2, a microporous carrier, was prepared as follows:
emulsification: 1 kg of carboxymethyl chitosan (substitution degree 0.2, molecular weight 9000), 0.1 kg of modified nano silver prepared in preparation examples 1-2 and 0.5 kg of ammonium bicarbonate are added into 20 kg of water at 35 ℃, and stirred for 8 hours to obtain an aqueous phase solution; adding AEO-7 (fatty alcohol polyoxyethylene ether) into an organic solvent, and stirring for 1h to obtain an oil phase solution; adding the obtained aqueous phase solution into the oil phase solution, and stirring for 3h to obtain emulsion.
Crosslinking: 20g glutaraldehyde solution (25 wt%) was added to the emulsion under stirring, and the mixture was stirred for 2 hours to carry out a crosslinking reaction, thereby obtaining a reaction solution containing carboxymethyl chitosan gel.
And (3) drying: removing the reaction liquid, casting to form a film, drying at 90 ℃, and then crushing and screening the casting dried gel film to obtain the microporous carrier with the granularity of 30-40 mu m.
Preparation examples 2-3, a microporous support, were prepared as follows:
emulsification: 1 kg of carboxymethyl chitosan (substitution degree 0.3, molecular weight 50000), 0.2 kg of modified nano silver prepared in preparation examples 1-3 and 0.1 kg of ammonium bicarbonate are added into 15 kg of water at 35 ℃, and stirred for 6 hours to obtain aqueous phase solution; adding polyglycerol fatty acid ester into an organic solvent, and stirring for 1h to obtain an oil phase solution; adding the obtained aqueous phase solution into the oil phase solution, and stirring for 3h to obtain emulsion.
Crosslinking: 60g glutaraldehyde solution (25 wt%) was added to the emulsion under stirring, and the mixture was stirred for 2 hours to carry out a crosslinking reaction, thereby obtaining a reaction solution containing carboxymethyl chitosan gel.
And (3) drying: removing the reaction liquid, casting to form a film, drying at 70 ℃, and then crushing and screening the casting dried gel film to obtain the microporous carrier with the granularity of 70-80 mu m.
Preparation examples 2-4, a microporous carrier, differ from preparation example 1 in that the drying step employs a vacuum lyophilization process, and the specific operations are as follows:
and (3) freeze-drying: the reaction liquid is flatly paved on a baffle plate in a vacuum freeze dryer, the vacuum freeze dryer is vacuumized until the absolute vacuum degree is 20+/-2 Pa, a refrigerating device is started, the temperature of a cold trap is reduced to minus 50+/-2 ℃ within 2 hours, and the temperature is kept constant for 45 minutes. Then heating the emulsion in the ice crystal state by a heating device under the partition board, wherein the temperature of the emulsion after heating is-12+/-2 ℃, and keeping for 12 hours; and then continuously heating to 50+/-2 ℃, maintaining for 10 hours to obtain freeze-dried blocks, and crushing and screening the freeze-dried blocks to obtain the microporous carrier with the granularity of 35-50 mu m.
Preparation examples 2 to 5, a microporous carrier, are different from preparation example 1 in that nano silver which is not subjected to surface modification of mercapto-polyethylene glycol-amino group is added to the aqueous phase solution.
Preparation examples 2 to 6, a microporous support, differ from preparation example 1 in that no nanosilver was added to the aqueous solution.
Preparation examples 2 to 7, a microporous support, differ from preparation example 1 in that carboxymethyl chitosan having a degree of substitution of 0.1 was used.
Preparation examples 2 to 8, a microporous support, differ from preparation example 1 in that carboxymethyl chitosan having a degree of substitution of 0.4 was used.
Preparation example 3-1, a microporous carrier, differs from preparation example 1 in that no ammonium bicarbonate was added to the starting material of the aqueous phase solution.
Preparation example 3-2, a microporous support, was different from preparation example 1 in that a crosslinking agent was not used and a crosslinking process was not performed, and an emulsion was obtained and then directly subjected to a drying process.
Examples
Example 1, a long-acting antimicrobial spray, was prepared as follows:
premixing 0.6 kg of polyquaternium-10, 0.6 kg of pyridone ethanolamine salt and 3.5 kg of the microporous carrier obtained in preparation example 2-1, and stirring for 1h to obtain a premix; premix and 1 kg of polyvinylpyrrolidone are added into purified water, and the mixture is stirred uniformly, then 3 kg of sodium hyaluronate is added, and stirring is continued, so that the long-acting antibacterial spray is obtained.
Example 2, a long-acting antimicrobial spray, was prepared as follows:
premixing 2 kg of polyquaternium-10 and 2 kg of microporous carrier obtained in preparation example 2-2, and stirring for 1h to obtain premix; the premix and 2 kg of hydroxyethyl cellulose are added into purified water, the mixture is stirred uniformly, then 5 kg of sodium polyacrylate is added, and the mixture is stirred continuously, so that the long-acting antibacterial spray is obtained.
Example 3, a long-acting antimicrobial spray, was prepared as follows:
premixing 0.1 kg of polyquaternium-10, 0.7 kg of pyridone ethanolamine salt and 5 kg of the microporous carrier obtained in preparation examples 2-3, and stirring for 1h to obtain a premix; adding the premix and 0.1 kg of AEO-9 into purified water, uniformly stirring, then adding 1 kg of sodium hyaluronate, and continuously stirring to obtain the long-acting antibacterial spray.
Table 1, long-acting antibacterial spray raw material ratio (kg)
Example 4, a long-acting antimicrobial spray, differs from example 1 in that the microporous support prepared in preparation examples 2-4 was used.
Example 5, a long-acting antimicrobial spray, differs from example 1 in that the microporous support prepared in preparation examples 2-5 was used.
Example 6, a long-acting antimicrobial spray, differs from example 1 in that the microporous support prepared in preparation examples 2-6 was used.
Example 7, a long-acting antimicrobial spray, differs from example 1 in that the microporous support prepared in preparation examples 2-7 was used.
Example 8, a long-acting antimicrobial spray, differs from example 1 in that the microporous support prepared in preparation examples 2-8 was used.
Example 9, a long-acting antimicrobial spray, was different from example 1 in that the microporous support prepared in preparation examples 2-6 was used and the antimicrobial composition contained 0.4 kg of nano silver.
Example 10, a long-acting antimicrobial spray, differs from example 1 in that an equivalent amount of polyacrylamide is used instead of sodium hyaluronate.
Comparative example
Comparative example 1, a long-acting antibacterial spray, was different from example 6 in that the microporous carrier prepared in preparation example 3-1 was used.
Comparative example 2, a long-acting antibacterial spray, was different from example 6 in that the microporous carrier prepared in preparation example 3-2 was used.
Comparative example 3, a long-acting antimicrobial spray, differs from example 6 in that carboxymethyl chitosan with an equivalent degree of substitution of 0.3 was used instead of the microporous carrier in the raw material.
Performance test
Test 1: test of antibacterial Rate and antibacterial durability of spray
The test method comprises the following steps: (1) The antibacterial rate of the test panels after 24 hours and 48 hours of incubation was measured with reference to the regulations and steps in GB/T21866-2008 "antibacterial paint (paint film) antibacterial assay and antibacterial Effect", and the detection results are shown in Table 2.
(2) Referring to the regulations and steps in GB/T21866-2008 "antibacterial paint (paint film) antibacterial property determination method and antibacterial effect", 1 ultraviolet lamp with 30W and 253.7nm wavelength is adopted, the ultraviolet lamp accords with the regulations of GB19258, a test plate is irradiated for 100 hours at a position 0.8 m-1.0 m away from the ultraviolet lamp, antibacterial durability of the test plate is characterized by antibacterial rate of the test plate after irradiation, the antibacterial rate determination method is the same as that in the above (1), and the detection results are shown in Table 2.
TABLE 2 results of spray antibacterial Rate and antibacterial durability test
Analysis of test results:
(1) As can be seen from the combination of examples 1 to 10 and comparative examples 1 to 3 and table 2, the antimicrobial properties of the antimicrobial spray in examples 1 to 10 of the present application are remarkably improved by using the microporous carrier prepared from carboxymethyl chitosan, ammonium bicarbonate and a crosslinking agent as main raw materials, as compared with comparative examples 1 to 3. The reason for this may be that after the carboxymethyl chitosan is dissolved, a chitosan gel is formed by the action of glutaraldehyde, and a pore structure is generated due to the decomposition of ammonium bicarbonate in the drying process, so that a microporous carrier with a pore structure is obtained, which has a broad-spectrum antibacterial effect on one hand, and can effectively load other antibacterial components through micropores on the other hand, thereby playing a slow-release role and effectively improving the long-acting antibacterial effect of the spray.
The lack of glutaraldehyde crosslinking agent in its raw material will not form gel (comparative example 2), and therefore, the chitosan carrier will not be formed either; in the absence of ammonium bicarbonate (comparative example 1), the pore-forming effect cannot be generated during drying, and sufficient pores cannot be provided for the loading of the antibacterial ingredient, so that the slow release effect and durability thereof are drastically reduced.
(2) As can be seen in combination with examples 1 and 4 and table 2, the use of a vacuum lyophilization process helps to improve the durability of the spray. The reason for this may be that the microporous carrier obtained by vacuum freeze-drying has high porosity and good loading rate of the antibacterial component.
(3) It can be seen from the combination of examples 1 and examples 5 to 6 and example 9 and the combination of table 2 that when the microporous carrier is prepared, the antibacterial durability and long-acting performance can be effectively improved by adding nano silver, especially nano silver modified by mercapto-polyethylene glycol-amino group, into the aqueous phase solution. The reason for this may be that part of the nano silver can be wrapped in the gel formed by the crosslinking to finally form the microporous carrier doped with the nano silver, thereby improving the slow release performance of the nano silver and promoting the improvement of the durability and the long-acting performance of the spray.
The thiol-polyethylene glycol-amino modified nano silver has one end with thiol and the other end with amino as the thiol-polyethylene glycol-amino is the oligomer of ethylene glycol. Wherein, the sulfhydryl can generate coordination complexing action with the nano silver so as to lead the nano silver to be combined and attached to the surface of the nano silver, the amino can generate reaction bonding with glutaraldehyde, and the nano silver is connected with the chitosan gel through the crosslinking action of the glutaraldehyde to form a stable composite structure. The microporous carrier obtained by the composite structure contains more nano silver, and has more outstanding slow release effect, so that the durability and the long-acting property are further improved.
(4) It can be seen from the combination of examples 1 and examples 7 to 8 and Table 2 that the use of carboxymethyl chitosan having a substitution degree of 0.2 to 0.3 as a raw material for the microporous carrier is advantageous for improving the durability of the spray. The reason for this may be that the carboxymethyl chitosan has a substitution degree of less than 0.16, and is poorly water-soluble, which is unfavorable for the formation of gel and microporous carrier; the substitution degree is higher than 0.3, the amino content is reduced, the crosslinking between chitosan and mercapto-polyethylene glycol-amino surface modified nano silver is not facilitated, the slow release effect is not facilitated to be improved, and the durability of the antibacterial spray is reduced.
Test 2: neutralization agent identification test
The test method comprises the following steps: the staphylococcus aureus and candida albicans are used as indicator bacteria, a suspension quantitative method is adopted for testing, and the result judgment is carried out according to the standard specified in the disinfection technical Specification.
Test results: PBS containing 2g/L sodium thiosulfate plus 10g/L Tween 80 plus 3g/L lecithin is used as a neutralizer, so that the residual effect of the disinfectant on the test bacteria in the embodiment can be effectively neutralized, and the neutralization product of the neutralizer has no obvious influence on the growth of the test bacteria.
Test 3: spray stability test
The test method comprises the following steps: 300ml of each of the sprays prepared in the above examples and comparative examples was packed into 3 PP sealed containers of the same standard to prepare samples. Referring to "sterilization Specification", the test pieces were placed in an oven at 54℃for standing, the number of days for which the solutions were allowed to stand for delamination (stabilization period) was observed, and the test results are shown in Table 3.
TABLE 3 stability test results of spray
Analysis of test results:
(1) It can be seen from the combination of example 1 and example 5 and the combination of table 3 that the use of the mercapto-polyethylene glycol-amino surface modified nano silver helps to improve the stability of the spray compared to the common nano silver. The reason for this is probably that nano silver has a large specific surface area and the surface contains more active groups, so that the agglomeration and precipitation phenomena are very easy to occur. The surface of the modified nano silver is combined with sulfhydryl-polyethylene glycol-amino, and the modified nano silver and carboxymethyl chitosan gel are subjected to crosslinking reaction under the action of glutaraldehyde, so that a relatively stable microporous carrier is formed, and sedimentation is not easy to occur.
(2) It can be seen from the combination of example 1 and comparative examples 2 to 3 and the combination of table 3 that glutaraldehyde and ammonium bicarbonate are used in the microporous carrier, which is advantageous for improving the stability of the spray, probably because glutaraldehyde contributes to the cross-linking of thiol-polyethylene glycol-amino surface-modified nano silver with carboxymethyl chitosan gel to form a stable microporous carrier. And the ammonium bicarbonate can promote the formation of a microporous structure, improve the loading rate of uncrosslinked nano silver and other antibacterial components, and reduce coalescence and precipitation.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.
Claims (6)
1. The long-acting antibacterial spray is characterized by comprising the following raw materials in percentage by weight:
microporous support: 2-5%;
antibacterial composition: 0.3 to 2 percent;
dispersing agent: 0.1 to 2 percent;
and (3) a thickening agent: 1 to 5 percent;
purified water: the balance;
the microporous carrier is prepared by emulsifying, crosslinking and drying aqueous phase solution, oil phase solution and crosslinking agent, wherein the aqueous phase solution comprises the following raw materials:
carboxymethyl chitosan;
ammonium bicarbonate;
nano silver;
water;
the oil phase solution comprises the following raw materials:
an organic solvent;
an emulsifying agent;
1, the weight ratio of the oil phase solution to the water phase solution is (2-4), the dosage of ammonium bicarbonate is 10-50% of the weight of carboxymethyl chitosan, the dosage of nano silver is 10-20% of the weight of carboxymethyl chitosan, the substitution degree of carboxymethyl chitosan is 0.2-0.3, the surface of nano silver is modified with sulfhydryl-polyethylene glycol-amino, and the number of carbon atoms of sulfhydryl-polyethylene glycol-amino is 8-16; the cross-linking agent is glutaraldehyde, and the dosage of glutaraldehyde is 0.5-1.5% of the weight of the carboxymethyl chitosan;
the antibacterial composition comprises the following components in percentage by weight:
pyridone bactericides: 0.1 to 1 percent;
polyquaternium: 0.1 to 1 percent.
2. The long-acting antibacterial spray of claim 1, wherein the emulsifier is one or more of fatty alcohol polyoxyethylene ether, sorbitan fatty acid ester, polyglycerol fatty acid ester, and sucrose fatty acid ester.
3. The long-acting antimicrobial spray of claim 1, wherein the microporous carrier is prepared by the following method:
emulsification: dissolving carboxymethyl chitosan and ammonium bicarbonate in water to obtain an aqueous phase solution; adding an emulsifying agent into an organic solvent to obtain an oil phase solution; adding the aqueous phase solution into the oil phase solution, and uniformly stirring to obtain emulsion;
crosslinking: glutaraldehyde is added into the emulsion to carry out a crosslinking reaction, so as to obtain a reaction solution;
and (3) drying: and drying and crushing the reaction liquid to obtain the microporous carrier.
4. A long-acting antibacterial spray according to claim 3, wherein the thiol-polyethylene glycol-amino group is dissolved in water, the nano silver is added under stirring condition, the nano silver with the surface modified with thiol-polyethylene glycol-amino group is obtained, and the weight ratio of the thiol-polyethylene glycol-amino group to the nano silver is 1:4-7.
5. The antiseptic spray of claim 1 wherein the thickener is sodium hyaluronate.
6. A method of preparing a long-acting antimicrobial spray according to any one of claims 1 to 5, comprising the steps of:
premixing the antibacterial composition and the microporous carrier to obtain a premix, adding the premix and the dispersing agent into purified water, uniformly stirring, adding the thickening agent, and continuously stirring to obtain the long-acting antibacterial spray.
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