CN112715574B - Environment-friendly composite antibacterial agent and preparation method thereof - Google Patents
Environment-friendly composite antibacterial agent and preparation method thereof Download PDFInfo
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- CN112715574B CN112715574B CN202110072404.1A CN202110072404A CN112715574B CN 112715574 B CN112715574 B CN 112715574B CN 202110072404 A CN202110072404 A CN 202110072404A CN 112715574 B CN112715574 B CN 112715574B
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- 239000003242 anti bacterial agent Substances 0.000 title claims abstract description 50
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 29
- 239000003607 modifier Substances 0.000 claims abstract description 28
- 239000013078 crystal Substances 0.000 claims abstract description 25
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 24
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims abstract description 22
- 239000000243 solution Substances 0.000 claims abstract description 21
- YCKOAAUKSGOOJH-UHFFFAOYSA-N copper silver Chemical compound [Cu].[Ag].[Ag] YCKOAAUKSGOOJH-UHFFFAOYSA-N 0.000 claims abstract description 17
- 101710134784 Agnoprotein Proteins 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims description 38
- 229920001690 polydopamine Polymers 0.000 claims description 25
- NSIFOGPAKNSGNW-UHFFFAOYSA-M dodecyl(triphenyl)phosphonium bromide Chemical group [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCCCCCCCCCC)C1=CC=CC=C1 NSIFOGPAKNSGNW-UHFFFAOYSA-M 0.000 claims description 24
- 238000001816 cooling Methods 0.000 claims description 22
- 239000011734 sodium Substances 0.000 claims description 20
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 18
- 229910052708 sodium Inorganic materials 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 37
- 230000000694 effects Effects 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 229910052709 silver Inorganic materials 0.000 description 17
- 239000004332 silver Substances 0.000 description 17
- -1 silver ions Chemical class 0.000 description 13
- CBURRHVHYULQTG-UHFFFAOYSA-N bromo-dodecyl-triphenyl-lambda5-phosphane Chemical group CCCCCCCCCCCCP(Br)(c1ccccc1)(c1ccccc1)c1ccccc1 CBURRHVHYULQTG-UHFFFAOYSA-N 0.000 description 12
- 239000000706 filtrate Substances 0.000 description 12
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 10
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 10
- 239000010949 copper Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 9
- 229910052802 copper Inorganic materials 0.000 description 9
- IAQVXLYDDSQIRZ-UHFFFAOYSA-B dodecapotassium hexasulfate Chemical compound [K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IAQVXLYDDSQIRZ-UHFFFAOYSA-B 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 239000001963 growth medium Substances 0.000 description 8
- 239000002082 metal nanoparticle Substances 0.000 description 7
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 6
- 230000002776 aggregation Effects 0.000 description 6
- 229910001431 copper ion Inorganic materials 0.000 description 6
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 6
- 239000002609 medium Substances 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 229910052901 montmorillonite Inorganic materials 0.000 description 6
- 241000894006 Bacteria Species 0.000 description 5
- 229910017770 Cu—Ag Inorganic materials 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 229960005070 ascorbic acid Drugs 0.000 description 5
- 235000010323 ascorbic acid Nutrition 0.000 description 5
- 239000011668 ascorbic acid Substances 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000011591 potassium Substances 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- HEZHYQDYRPUXNJ-UHFFFAOYSA-L potassium dithionite Chemical compound [K+].[K+].[O-]S(=O)S([O-])=O HEZHYQDYRPUXNJ-UHFFFAOYSA-L 0.000 description 5
- 239000012279 sodium borohydride Substances 0.000 description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical group OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 4
- 239000001965 potato dextrose agar Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 229920001817 Agar Polymers 0.000 description 3
- 241000234435 Lilium Species 0.000 description 3
- 239000008272 agar Substances 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 238000005341 cation exchange Methods 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 230000001954 sterilising effect Effects 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 2
- 235000002595 Solanum tuberosum Nutrition 0.000 description 2
- 244000061456 Solanum tuberosum Species 0.000 description 2
- NEIHULKJZQTQKJ-UHFFFAOYSA-N [Cu].[Ag] Chemical compound [Cu].[Ag] NEIHULKJZQTQKJ-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 239000004599 antimicrobial Substances 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 239000010445 mica Substances 0.000 description 2
- 229910052618 mica group Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 125000005496 phosphonium group Chemical group 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000003828 vacuum filtration Methods 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241000222122 Candida albicans Species 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- 206010059866 Drug resistance Diseases 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 108091005804 Peptidases Proteins 0.000 description 1
- 239000004365 Protease Substances 0.000 description 1
- 102100037486 Reverse transcriptase/ribonuclease H Human genes 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 229910052946 acanthite Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229940095731 candida albicans Drugs 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- JJCFRYNCJDLXIK-UHFFFAOYSA-N cyproheptadine Chemical compound C1CN(C)CCC1=C1C2=CC=CC=C2C=CC2=CC=CC=C21 JJCFRYNCJDLXIK-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- POXRUQZSBXFWGH-UHFFFAOYSA-L dipotassium dithionate Chemical compound [K+].[K+].[O-]S(=O)(=O)S([O-])(=O)=O POXRUQZSBXFWGH-UHFFFAOYSA-L 0.000 description 1
- FGRVOLIFQGXPCT-UHFFFAOYSA-L dipotassium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [K+].[K+].[O-]S([O-])(=O)=S FGRVOLIFQGXPCT-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 description 1
- 229960003638 dopamine Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229940056910 silver sulfide Drugs 0.000 description 1
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 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
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
- A01N59/20—Copper
-
- 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
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
Landscapes
- Life Sciences & Earth Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Dentistry (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Agronomy & Crop Science (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Toxicology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The application discloses an environment-friendly composite antibacterial agent and a preparation method thereof. The preparation method of the environment-friendly composite antibacterial agent comprises the following steps: (1) Copper nitrate, a reducing agent and oleylamine are mixed for reaction to obtain seed crystal mixed solution; (2) AgNO in the seed crystal mixed solution 3 The oleylamine solution and the modifier react to obtain copper-silver mixed solution; (3) Adding absolute ethyl alcohol into the copper-silver mixed solution, and centrifuging. The environment-friendly composite antibacterial agent has the technical effects of efficient antibacterial and long-acting antibacterial.
Description
Technical Field
The application relates to the technical field of antibacterial agents, in particular to an environment-friendly composite antibacterial agent and a preparation method thereof.
Background
The traditional antibacterial agents mainly comprise organic antibacterial agents and natural and high-molecular antibacterial agents, and although the organic antibacterial agents have the advantages of strong bactericidal power, wide sources, low price and the like, in the use process, the antibacterial agents are poor in thermal stability, easy to decompose, poor in durability and have certain toxicity; natural and polymeric antimicrobial agents have the advantages of non-toxicity, environmental protection, but have poor heat resistance and difficult processing, and most polymers have limited thermodynamic compatibility with each other. The inorganic antibacterial agent has long-acting, no drug resistance and slow release property.
The composite antibacterial agent has complementary advantages through synergistic effect, can improve the performance of the antibacterial agent, and gradually becomes a hotspot in the field of antibacterial agent research. Organic-inorganic composite antibacterial agents are broadly classified into three types: (1) an organic antimicrobial agent is added to an inorganic carrier; (2) A complex salt antibacterial agent formed by an inorganic antibacterial agent and an organic carrier; (3) rare earth composite antibacterial agent. However, in the compounding process, the selection of organic and inorganic reagents and the like are not deeply studied in the aspects of compounding performance and the like.
Disclosure of Invention
Aiming at the defects existing in the prior art, the application provides an environment-friendly composite antibacterial agent and a preparation method, the bimetallic composite antibacterial agent is synthesized by adopting a 2-step oxidation-reduction method, firstly, a reducing agent polydopamine is added into a copper-containing solution to prepare a copper seed crystal solution, and the copper nanoparticles coated with dopamine are obtained.
The technical scheme adopted by the application is realized as follows:
the application provides a preparation method of an environment-friendly composite antibacterial agent, which comprises the following steps:
(1) Copper nitrate, a reducing agent and oleylamine are mixed for reaction to obtain seed crystal mixed solution;
(2) AgNO in the seed crystal mixed solution 3 The oleylamine solution and the modifier react to obtain copper-silver mixed solution;
(3) Absolute ethyl alcohol is added into the copper-silver mixed solution, and the environment-friendly composite antibacterial agent is obtained after centrifugation.
The reducing agent is one or more than two of sodium borohydride, ascorbic acid and polydopamine.
The modifier is dodecyl triphenyl phosphonium bromide and/or sodium-based rectorite.
Preferably, the preparation method of the environment-friendly composite antibacterial agent comprises the following steps:
(1) 8-20 parts by weight of copper nitrate, 15-30 parts by weight of reducing agent and 10-40 parts by weight of oleylamine are mixed, stirred for 20-50min at the temperature of 80-120 ℃ and the stirring speed of 400-800rpm, the stirring is kept at the speed of 5-15 ℃/min, the temperature is raised to 160-220 ℃, the stirring is continued for 2-4h, and the cooling at room temperature is carried out, so as to obtain seed crystal mixed solution;
(2) At normal temperature, adding 20-40 parts by weight of AgNO with mass fraction of 28-45% into the seed crystal mixture at stirring speed of 450-600rpm 3 Heating the oleylamine solution and 5-10 parts by weight of modifier to 70-90 ℃, continuously stirring for 1.5-3 hours, and cooling to room temperature to obtain copper-silver mixed solution;
(3) Adding 10-50 parts by weight of absolute ethyl alcohol into the copper-silver mixed solution, centrifuging for 10-30min at a centrifugal speed of 9000-12000rpm, and drying the obtained solid in a vacuum drying oven at 50-70 ℃ for 20-28h to obtain the environment-friendly composite antibacterial agent.
The reducing agent is one or a mixture of more than two of sodium borohydride, ascorbic acid and polydopamine; preferably, the reducing agent is polydopamine.
The modifier is dodecyl triphenyl phosphonium bromide and/or sodium-based rectorite; preferably, the modifier is dodecyl triphenyl phosphorus bromide and sodium-based rectorite, and the mass ratio is 1: (1-3).
One of the inventive concepts of the present application is to prepare a Cu-Ag composite antibacterial agent by a specific method, and to use polydopamine as a weak reducing agent and a binder, wherein a large amount of catechol groups and nitrogen-containing groups contained in the structure thereof make polydopamine have a strong adsorption force on metal ions, and these groups are also favorable for the grafting reaction and the next functionalization; the weak reducibility of the polydopamine can reduce metal ions to generate metal nano particles, and the metal nano particles can be attached to the surfaces of the metal nano particles due to strong adsorption force. Specifically, polydopamine and oleylamine are added into a copper solution, copper nanoparticles are obtained by reducing copper nanoparticles with the oleylamine under the heating condition, and polydopamine is adsorbed on the surface of copper ions through catechol groups and nitrogen-containing groups of the polydopamine.
The second concept of the application is that the modifier dodecyl triphenyl phosphorus bromide and/or sodium-based rectorite is added in the process of forming the silver-copper compound, so that the agglomeration of nano particles is effectively prevented, and the synergistic effect of the sodium-based rectorite and the dodecyl triphenyl phosphorus bromide modification is utilized, so that the prepared antibacterial compound has excellent antibacterial effect and can realize long-acting antibacterial effect. The reason is that the dodecyl triphenyl phosphonium bromide has an antibacterial effect, and phosphorus atoms in the molecular structure of the dodecyl triphenyl phosphonium bromide can form coordination bonds with silver to adsorb the dodecyl triphenyl phosphonium bromide, so that the release speed of silver ions is delayed, and aggregation of the dodecyl triphenyl phosphonium bromide is prevented. The sodium-based rectorite is an aqueous aluminosilicate, is an interlayer mineral formed by regularly and alternately stacking dioctahedral mica layers and dioctahedral montmorillonite layers, has good dispersibility and thermal stability, large specific surface area and strong adsorptivity, and contains exchangeable cations among montmorillonite layers, silver ions, copper ions, dodecyl triphenyl phosphorus bromide and dodecyl triphenyl phosphorus bromide adsorbed with silver particles can be intercalated into the montmorillonite interlayer through cation exchange, so that agglomeration is effectively prevented, antibacterial performance is improved, and a slow release effect is further realized. Specifically, due to the complexing action of catechol groups and nitrogen-containing groups in the polydopamine structure on metal ions, silver ions are adsorbed on the surfaces of nano Cu particles, the polydopamine has weak reducibility, and the adsorbed metal ions can be reduced to generate metal nano particles to become catalytic active centers of subsequent reduction reaction, and the added reducing agent enables the metal nano particles to continuously reduce and grow on the formed active centers to form shells, so that the silver-copper core-shell structure coated by the silver nano antibacterial agent is formed. The dodecyl triphenyl phosphonium bromide in the modifier is adsorbed on the surface of silver particles through forming a coordination bond with the active center of silver, and then intercalated into the rector Dan Jianceng through cation exchange, so that the environment-friendly composite antibacterial agent-Cu-Ag composite antibacterial agent is finally formed.
Sterilization mechanism: after the silver ions are contacted with bacteria, the silver ions can be combined with sulfhydryl groups of proteins in cell walls and cell membranes, so that protease of the cells is inactivated, inherent components of the cells are destroyed, and the activity of the cells is destroyed, thereby killing the bacteria.
Still further preferably, a method for preparing an environment-friendly composite antibacterial agent comprises the steps of:
(1) 8-20 parts by weight of copper nitrate, 15-30 parts by weight of reducing agent and 10-40 parts by weight of oleylamine are mixed, stirred for 20-50min at the temperature of 80-120 ℃ and the stirring speed of 400-800rpm, the stirring is kept at the speed of 5-15 ℃/min, the temperature is raised to 160-220 ℃, the stirring is continued for 2-4h, and the cooling at room temperature is carried out, so as to obtain seed crystal mixed solution;
(2) At normal temperature, adding 20-40 parts by weight of AgNO with mass fraction of 28-45% into the seed crystal mixture at stirring speed of 450-600rpm 3 The method comprises the steps of (1) heating the oleylamine solution, 5-10 parts by weight of modifier and 2-4 parts by weight of potassium hexasulfate to 70-90 ℃, continuously stirring for 1.5-3 hours, and cooling to room temperature to obtain copper-silver mixed solution;
(3) Adding 10-50 parts by weight of absolute ethyl alcohol into the copper-silver mixed solution, centrifuging for 10-30min at a centrifugal speed of 9000-12000rpm, and drying the obtained solid in a vacuum drying oven at 50-70 ℃ for 20-28h to obtain the environment-friendly composite antibacterial agent.
The reducing agent is one or a mixture of more than two of sodium borohydride, ascorbic acid and polydopamine; preferably, the reducing agent is polydopamine.
The modifier is dodecyl triphenyl phosphonium bromide and/or sodium-based rectorite; preferably, the modifier is dodecyl triphenyl phosphorus bromide and sodium-based rectorite, and the mass ratio is 1: (1-3).
The reference of the preparation method of the potassium dithionite is: antibacterial activities of polythionates enhanced by carbonatesAntibacterial activities of polythionates enhanced by carbonates, guofang Li, et al, med, chem, commun.,2015 (6): 1643-1648.
Will be 8mLS 2 Cl 2 Dissolved in 50mLCCl 4 Cooling to-15deg.C, adding 50g Na into the above solution 2 S 2 O 3 ·5H 2 O; continuing to add 80mL of 6M HCl pre-chilled to-5℃and 8mL of pre-chilled0.6M FeCl cooled to-5 DEG C 3 Reacting for 60min, filtering out solids, and obtaining filtrate A; separating to obtain an aqueous phase from the filtrate A, concentrating to 30mL under reduced pressure at 40 ℃, and filtering and removing the separated NaCl precipitate to obtain a filtrate B; adjusting the pH of the filtrate B to 1, cooling to 0 ℃, and dropwise adding 20mL of 0 ℃ methanol solution containing 4g KOH under the stirring condition of 800 rpm; vacuum filtering to obtain white solid, washing with acetone for 2 times, wherein the dosage of acetone for each washing is 20mL; drying at room temperature to obtain crude potassium hexasulfate. 30ml of 0.1M sulfuric acid was preheated to 60℃and 15g of the above crude potassium hexasulfate was added to dissolve, followed by immediate filtration and cooling of the filtrate to-5 ℃; 30mL of methanol was added, aged for 12 hours, and the crystals were obtained by vacuum filtration, washed twice with 20mL of methanol each time, to obtain potassium dithionite.
After the potassium hyposulfite is added, the antibacterial effect of the environment-friendly composite antibacterial agent is obviously improved. Dithionite is an unstable intermediate with similar molecular structure and physicochemical properties formed in the process of oxidizing a sulfur compound into sulfate. Potassium hypohexasulfate has S in molecular structure 6 O 6 2- Potassium dithionite salt of (c). Potassium hypohexasulfate is easy to dissolve in water, and has antibacterial activity due to easy decomposition of elemental sulfur. Potassium dithionate and dodecyl triphenyl phosphonium bromide are combined to generate an inorganic and organic composite antibacterial agent, namely dodecyl triphenyl phosphonium dithionate, which can slowly decompose quaternary phosphonium salt cations and active sulfur antibacterial components, has an antibacterial effect superior to the simple addition effect of the quaternary phosphonium salt cations and the active sulfur antibacterial components, and has long-acting antibacterial performance. In the test, when the addition amount of potassium hexasulfate is too large, the antibacterial effect of the environment-friendly composite antibacterial agent is reduced. The reason is that potassium Lily sulfate and dodecyl triphenyl phosphonium bromide are combined to generate a quaternary phosphonium Lily sulfate crystal, and too much potassium Lily sulfate consumes too much dodecyl triphenyl phosphonium bromide to influence the combination of the active center of the metal nano particle and the dodecyl triphenyl phosphonium bromide, so as to influence the intercalation effect of the effective components on rectorite; and the excessive active sulfur separated out by potassium hypohexasulfate and quaternary phosphonium hypohexasulfate is contacted with silver particles to generate gray black silver sulfide precipitate, so that the antibacterial effect is reduced.
The application also provides an environment-friendly composite antibacterial agent, which is prepared by adopting the method.
The application has the beneficial effects that: compared with the traditional method, the environment-friendly composite antibacterial agent prepared by adopting the specific method has the advantages of simple steps, non-toxic reagent and the like; the addition of polydopamine can not only accelerate the reduction of copper ions and shorten the reaction time, but also improve the binding force between copper and silver, so that the prepared environment-friendly composite antibacterial agent has the technical effects of efficient antibacterial and long-acting antibacterial; simultaneously adding sodium-based rectorite and dodecyl triphenyl phosphorus bromide modifier to enable the active ingredients to enter rectorite intercalation, so as to avoid aggregation of the active ingredients, improve antibacterial effect and play roles of slow release and protection; in addition, potassium hexasulfate and dodecyl triphenyl phosphonium bromide are added to form an inorganic and organic compound salt antibacterial component, so that the antibacterial effect is further improved, and the application range is widened.
Detailed Description
The above summary of the present application is described in further detail below in conjunction with the detailed description, but it should not be understood that the scope of the above-described subject matter of the present application is limited to the following examples.
Introduction of partial raw materials in the application:
dodecyl triphenyl phosphonium bromide, CAS:15510-55-1.
In the examples, sodium-based rectorite was purchased from the company rectorite technologies, inc. Of the auspicious name, hubei, rectorite Dan Hanliang: 90%.
The oleylamine was purchased from Manba, inc., texas, cat: 112-90-3, CAS:112-90-3.
The polydopamine of the examples was prepared according to example 5 of Chinese patent No. CN111004391A (patent application No. 201911147981.1), and the preparation method is as follows:
(1) 0.0948g of DA/HCl is weighed and dissolved in 5mL of Tris-buffer solution to obtain solution A; weighing 0.0990gK 2 FeO 4 Dissolving in 5mL of aqueous ammonia solution (ph=8.5) to obtain solution B; dropwise adding the solution B into the solution A, magnetically stirring, maintaining the rotation speed at 5000 r.min < -1 >, and reacting at 70 ℃ to reversely reactIn the reaction process, the reaction mixed solution is gradually changed from purple to black, and stirring is stopped after the reaction is carried out for 40 minutes;
(2) The reaction mixture was filtered under reduced pressure, the precipitate was washed 5 times with distilled water, and lyophilized to constant weight to give the polydopamine product in 94% yield with polydopamine nanoparticles about 50nm in diameter.
Example 1
The preparation method of the environment-friendly composite antibacterial agent comprises the following steps:
(1) Mixing 12 parts by weight of copper nitrate, 20 parts by weight of a reducing agent and 20 parts by weight of oleylamine, stirring at 500rpm for 30min at 100 ℃, keeping stirring, heating to 200 ℃ at a speed of 10 ℃/min, continuing stirring for 2.5h, and cooling at room temperature to obtain seed crystal mixed solution;
(2) At normal temperature, 30 parts by weight of a seed crystal containing 30wt% AgNO was added to the seed crystal mixture at a stirring speed of 500rpm 3 Heating the oleylamine solution and 8 parts by weight of modifier to 80 ℃, continuously stirring for 2 hours, and cooling to room temperature to obtain copper-silver mixed solution;
(3) Adding 30 parts by weight of absolute ethyl alcohol into the copper-silver mixed solution, centrifuging for 15min at a centrifugal speed of 10000rpm, and drying the obtained solid in a vacuum drying oven at 60 ℃ for 24h to obtain the Cu-Ag composite antibacterial agent.
The reducing agent is polydopamine;
the modifier is sodium-based rectorite.
Example 2
Substantially the same as in example 1, except that the modifier was dodecyltriphenyl phosphonium bromide.
Comparative example 1
Substantially the same as in example 1, except that no modifier was added. Namely, the step (2) is as follows: at normal temperature, 30 parts by weight of a seed crystal containing 30wt% AgNO was added to the seed crystal mixture at a stirring speed of 500rpm 3 The temperature is raised to 80 ℃, stirring is continued for 2 hours, and cooling is carried out to room temperature, thus obtaining the copper-silver mixed solution.
Example 3
Substantially the same as in example 1, except that the reducing agent was sodium borohydride.
Example 4
Substantially the same as in example 1, except that the reducing agent was ascorbic acid.
Example 5
The preparation method of the environment-friendly composite antibacterial agent comprises the following steps:
(1) Mixing 12 parts by weight of copper nitrate, 20 parts by weight of a reducing agent and 20 parts by weight of oleylamine, stirring at 500rpm for 30min at 100 ℃, keeping stirring, heating to 200 ℃ at a speed of 10 ℃/min, continuing stirring for 2.5h, and cooling at room temperature to obtain seed crystal mixed solution;
(2) At normal temperature, 30 parts by weight of a seed crystal containing 30wt% AgNO was added to the seed crystal mixture at a stirring speed of 500rpm 3 Heating the oleylamine solution and 8 parts by weight of modifier to 80 ℃, continuously stirring for 2 hours, and cooling to room temperature to obtain copper-silver mixed solution;
(3) Adding 30 parts by weight of absolute ethyl alcohol into the copper-silver mixed solution, centrifuging for 15min at a centrifugal speed of 10000rpm, and drying the obtained solid in a vacuum drying oven at 60 ℃ for 24h to obtain the Cu-Ag composite antibacterial agent.
The reducing agent is polydopamine;
the modifier is dodecyl triphenyl phosphonium bromide and sodium-based rectorite, and the mass ratio is 1: 2.
Example 6
The preparation method of the environment-friendly composite antibacterial agent comprises the following steps:
(1) Mixing 12 parts by weight of copper nitrate, 20 parts by weight of a reducing agent and 20 parts by weight of oleylamine, stirring at 500rpm for 30min at 100 ℃, keeping stirring, heating to 200 ℃ at a speed of 10 ℃/min, continuing stirring for 2.5h, and cooling at room temperature to obtain seed crystal mixed solution;
(2) At normal temperature, 30 parts by weight of a seed crystal containing 30wt% AgNO was added to the seed crystal mixture at a stirring speed of 500rpm 3 Heating the oleylamine solution to 80 ℃, continuously stirring for 2 hours, and cooling to room temperature to obtain a copper-silver mixed solution, wherein the oleylamine solution comprises 8 parts by weight of modifier and 3 parts by weight of potassium hexasulfate;
(3) Adding 30 parts by weight of absolute ethyl alcohol into the copper-silver mixed solution, centrifuging for 15min at a centrifugal speed of 10000rpm, and drying the obtained solid in a vacuum drying oven at 60 ℃ for 24h to obtain the Cu-Ag composite antibacterial agent.
The reducing agent is polydopamine;
the modifier is dodecyl triphenyl phosphonium bromide and sodium-based rectorite, and the mass ratio is 1:2, a mixture of two or more of the above-mentioned materials;
the reference of the preparation method of the potassium dithionite is: antibacterial activities of polythionates enhanced by carbonatesAntibacterial activities of polythionates enhanced by carbonates, guofang Li, et al, med, chem, commun.,2015 (6): 1643-1648.
Will be 8mLS 2 Cl 2 Dissolved in 50mLCCl 4 Cooling to-15deg.C, adding 50g Na into the above solution 2 S 2 O 3 ·5H 2 O; continuing to add 80mL of 6M HCl pre-chilled to-5℃and 8mL of 0.6M FeCl pre-chilled to-5 ℃ 3 Reacting for 60min, filtering out solids, and obtaining filtrate A; separating to obtain an aqueous phase from the filtrate A, concentrating to 30mL under reduced pressure at 40 ℃, and filtering and removing the separated NaCl precipitate to obtain a filtrate B; adjusting the pH of the filtrate B to 1, cooling to 0 ℃, and dropwise adding 20mL of 0 ℃ methanol solution containing 4g KOH under the stirring condition of 800 rpm; vacuum filtering to obtain white solid, washing with acetone for 2 times, wherein the dosage of acetone for each washing is 20mL; drying at room temperature to obtain crude potassium hexasulfate. 30ml of 0.1M sulfuric acid was preheated to 60℃and 15g of the above crude potassium hexasulfate was added to dissolve, followed by immediate filtration and cooling of the filtrate to-5 ℃; 30mL of methanol was added, aged for 12 hours, and the crystals were obtained by vacuum filtration, washed twice with 20mL of methanol each time, to obtain potassium dithionite.
Test example 1
Antibacterial performance test:
and (3) strain: candida albicans ATCC10231.
Potato Dextrose Agar (PDA) medium, the specific formula is: 200g of potato, 20g of glucose and agar (20 g of upper medium and 7.5g of lower medium), and 1000mL of distilled water. Configuration: cleaning potato, peeling, cutting 200g into small pieces, adding water, boiling for 30min, and filtering with eight layers of gauze to obtain filtrate; heating the filtrate, adding 20g of agar, continuously heating and stirring until the agar is completely dissolved, adding 20g of glucose, and stirring uniformly; cooling to 80deg.C, supplementing water to 1000mL, sterilizing at 121deg.C for 20min, and cooling.
The oxford cup diffusion method is used for testing the antibacterial performance:
1) Lower medium: heating and melting the PDA culture medium, quantitatively pouring the PDA culture medium into a culture dish with the diameter of 9cm according to 20 mL/dish, and cooling and solidifying to obtain a lower culture medium;
2) Upper medium: 4mL was concentrated to 10 9 The CFU/mL bacterial suspension is added into 100mL culture medium at 50 ℃ and is rapidly and evenly shaken to obtain the bacteria-containing culture medium, 5mL of bacteria-containing culture medium is sucked by a sterilizing gun head, and the bacteria-containing culture medium is evenly distributed on the lower layer culture medium.
3) Measuring the diameter of the inhibition zone: 3 oxford cups were placed on each dish at equal distance and gently pressed to make contact with the medium without gaps. Transferring 200 mu L of distilled aqueous dispersion of 1mg/mL environment-friendly composite antibacterial agent into oxford cup, covering a culture dish, transferring into an incubator, culturing at 28 ℃ for 18h, and measuring the diameter of a bacteriostasis zone around the oxford cup. 3 replicates were run for each sample.
The modifier of the example 1 is sodium-based rectorite, the modifier of the example 2 is dodecyl triphenyl phosphorus bromide, the comparative example 1 is free of modifier, the modifier of the example 5 is dodecyl triphenyl phosphorus bromide and sodium-based rectorite, and the mass ratio is 1: 2. The addition of the modifier effectively improves the antibacterial effect of the environment-friendly composite antibacterial agent, and the antibacterial effect of the environment-friendly composite antibacterial agent is greatly improved when the mixture is used as the modifier, and the dodecyl triphenyl phosphorus bromide and the sodium-based rectorite have synergistic antibacterial effect. The dodecyl triphenyl phosphonium bromide has antibacterial property, and phosphorus atoms in the molecular structure of the dodecyl triphenyl phosphonium bromide can form coordination bonds with silver to adsorb the dodecyl triphenyl phosphonium bromide, so that the release speed of silver ions is delayed, aggregation of the dodecyl triphenyl phosphonium bromide is prevented, and the antibacterial property is improved. The sodium-based rectorite is an interlayer mineral formed by regularly and alternately stacking dioctahedral mica layers and dioctahedral montmorillonite layers, has good dispersibility and thermal stability, large specific surface area and strong adsorptivity, and contains exchangeable cations among montmorillonite layers, silver ions, copper ions, dodecyl triphenyl phosphorus bromide and dodecyl triphenyl phosphorus bromide adsorbed with silver particles can be intercalated into the montmorillonite layers through cation exchange, so that agglomeration is effectively prevented, antibacterial performance is improved, and a slow release effect is further achieved.
In examples 1, 3 and 4, different substances are selected as reducing agents, and the results show that the environment-friendly composite antibacterial agent has the best antibacterial effect when polydopamine is used as the reducing agent. Sodium borohydride and ascorbic acid simply play a role in reducing copper ions, and silver nano particles are not adsorbed on the surface of the copper ions through bonding to form a silver-coated copper nano composite, but only simple copper and silver nano particles are overlapped. The plurality of catechol groups and nitrogen-containing groups contained in the polydopamine structure enable polydopamine to have weak reducibility and strong adsorption force on metal ions, and the adsorbed metal ions can be reduced to generate metal nano particles which become catalytic active centers of subsequent reduction reactions. Therefore, the antibacterial effect is better.
The difference between the embodiment 5 and the embodiment 6 is that the embodiment 6 is added with more potassium hexasulfate, so that the antibacterial performance is obviously improved. Potassium dithionite and dodecyl triphenyl phosphonium bromide are combined to generate an inorganic and organic composite antibacterial agent, namely quaternary phosphonium dithionite, which can slowly decompose two antibacterial components, namely quaternary phosphonium salt cations and active sulfur, and has more excellent antibacterial performance.
Claims (2)
1. The preparation method of the environment-friendly composite antibacterial agent is characterized by comprising the following steps of:
(1) 8-20 parts by weight of copper nitrate, 15-30 parts by weight of reducing agent and 10-40 parts by weight of oleylamine are mixed, stirred for 20-50min at the temperature of 80-120 ℃ and the stirring speed of 400-800rpm, the stirring is kept at the speed of 5-15 ℃/min, the temperature is raised to 160-220 ℃, the stirring is continued for 2-4h, and the cooling at room temperature is carried out, so as to obtain seed crystal mixed solution;
（2）at normal temperature, adding 20-40 parts by weight of AgNO with mass fraction of 28-45% into the seed crystal mixed solution at stirring speed of 450-600rpm 3 Heating the oleylamine solution and 5-10 parts by weight of modifier to 70-90 ℃, continuously stirring for 1.5-3 hours, and cooling to room temperature to obtain copper-silver mixed solution;
(3) Adding 10-50 parts by weight of absolute ethyl alcohol into the copper-silver mixed solution, centrifuging for 10-30min at a centrifugal speed of 9000-12000rpm, and drying the obtained solid in a vacuum drying oven at 50-70 ℃ for 20-28h;
the reducing agent is polydopamine;
the modifier is dodecyl triphenyl phosphonium bromide and sodium-based rectorite, and the mass ratio is 1:1-3.
2. An environment-friendly composite antibacterial agent, which is characterized by being prepared by the method of claim 1.
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