CN112715574A - Environment-friendly composite antibacterial agent and preparation method thereof - Google Patents
Environment-friendly composite antibacterial agent and preparation method thereof Download PDFInfo
- Publication number
- CN112715574A CN112715574A CN202110072404.1A CN202110072404A CN112715574A CN 112715574 A CN112715574 A CN 112715574A CN 202110072404 A CN202110072404 A CN 202110072404A CN 112715574 A CN112715574 A CN 112715574A
- Authority
- CN
- China
- Prior art keywords
- parts
- environment
- antibacterial agent
- weight
- copper
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003242 anti bacterial agent Substances 0.000 title claims abstract description 61
- 239000002131 composite material Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000011259 mixed solution Substances 0.000 claims abstract description 38
- 239000003607 modifier Substances 0.000 claims abstract description 31
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 29
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims abstract description 26
- 239000013078 crystal Substances 0.000 claims abstract description 24
- YCKOAAUKSGOOJH-UHFFFAOYSA-N copper silver Chemical compound [Cu].[Ag].[Ag] YCKOAAUKSGOOJH-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000243 solution Substances 0.000 claims abstract description 21
- 101710134784 Agnoprotein Proteins 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 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 10
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 51
- 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 33
- 229920001690 polydopamine Polymers 0.000 claims description 29
- 238000001816 cooling Methods 0.000 claims description 24
- 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 19
- 239000011734 sodium Substances 0.000 claims description 19
- 229910052708 sodium Inorganic materials 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 16
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 229960005070 ascorbic acid Drugs 0.000 claims description 7
- 235000010323 ascorbic acid Nutrition 0.000 claims description 7
- 239000011668 ascorbic acid Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000012279 sodium borohydride Substances 0.000 claims description 7
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- MIBZBDUKANAWKZ-UHFFFAOYSA-H hexapotassium hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[K+].[K+].[K+].[K+].[K+].[K+] MIBZBDUKANAWKZ-UHFFFAOYSA-H 0.000 claims description 3
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 34
- 230000000694 effects Effects 0.000 abstract description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 229910052709 silver Inorganic materials 0.000 description 21
- 239000004332 silver Substances 0.000 description 21
- -1 silver ions Chemical class 0.000 description 17
- 239000011591 potassium Substances 0.000 description 15
- 229910052700 potassium Inorganic materials 0.000 description 15
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 14
- 239000000706 filtrate Substances 0.000 description 12
- 239000010410 layer Substances 0.000 description 12
- 239000010949 copper Substances 0.000 description 11
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 10
- 238000001914 filtration Methods 0.000 description 10
- 239000001963 growth medium 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
- 239000002082 metal nanoparticle Substances 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 229910021645 metal ion Inorganic materials 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 241000894006 Bacteria Species 0.000 description 6
- 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
- 229910052901 montmorillonite Inorganic materials 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229910017770 Cu—Ag Inorganic materials 0.000 description 5
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical group OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 5
- 239000001965 potato dextrose agar Substances 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- STMIIPIFODONDC-UHFFFAOYSA-N 2-(2,4-dichlorophenyl)-1-(1H-1,2,4-triazol-1-yl)hexan-2-ol Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(O)(CCCC)CN1C=NC=N1 STMIIPIFODONDC-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- NEIHULKJZQTQKJ-UHFFFAOYSA-N [Cu].[Ag] Chemical group [Cu].[Ag] NEIHULKJZQTQKJ-UHFFFAOYSA-N 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 4
- 239000002609 medium Substances 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229920001817 Agar Polymers 0.000 description 3
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 3
- 239000008272 agar Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000005341 cation exchange Methods 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 230000002195 synergetic effect Effects 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
- 235000002595 Solanum tuberosum Nutrition 0.000 description 2
- 244000061456 Solanum tuberosum Species 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 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
- 230000000536 complexating effect Effects 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 238000004090 dissolution Methods 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
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 125000004437 phosphorous atom Chemical group 0.000 description 2
- NWQOAHGBQFKLNI-UHFFFAOYSA-M potassium;hexacosanoate Chemical compound [K+].CCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O NWQOAHGBQFKLNI-UHFFFAOYSA-M 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000003828 vacuum filtration Methods 0.000 description 2
- 238000005303 weighing 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
- 206010059866 Drug resistance Diseases 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
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 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
- 239000004599 antimicrobial Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000003115 biocidal effect Effects 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
- 238000004140 cleaning Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 238000005520 cutting process 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
- QTUOYBXDUHAXBB-UHFFFAOYSA-N diphosphanium sulfate Chemical group [PH4+].[PH4+].[O-]S([O-])(=O)=O QTUOYBXDUHAXBB-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- VZXRCMCRCZBKEZ-UHFFFAOYSA-N dodecyl(triphenyl)phosphonium Chemical compound C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCCCCCCCCCC)C1=CC=CC=C1 VZXRCMCRCZBKEZ-UHFFFAOYSA-N 0.000 description 1
- 229960003638 dopamine Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 230000005764 inhibitory process Effects 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
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 150000004714 phosphonium salts Chemical group 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
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 description 1
- 229940056910 silver sulfide Drugs 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
- 239000000725 suspension Substances 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- SWGJCIMEBVHMTA-UHFFFAOYSA-K trisodium;6-oxido-4-sulfo-5-[(4-sulfonatonaphthalen-1-yl)diazenyl]naphthalene-2-sulfonate Chemical compound [Na+].[Na+].[Na+].C1=CC=C2C(N=NC3=C4C(=CC(=CC4=CC=C3O)S([O-])(=O)=O)S([O-])(=O)=O)=CC=C(S([O-])(=O)=O)C2=C1 SWGJCIMEBVHMTA-UHFFFAOYSA-K 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
Abstract
The invention 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 and react to obtain seed crystal mixed liquid; (2) AgNO is added into the seed crystal mixed liquid3Reacting the oleylamine solution with a modifier to obtain a 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 high-efficiency antibacterial and long-acting antibacterial.
Description
Technical Field
The invention relates to the technical field of antibacterial agents, and particularly relates to an environment-friendly composite antibacterial agent and a preparation method thereof.
Background
Although the traditional antibacterial agents mainly comprise organic antibacterial agents and natural and high-molecular antibacterial agents, the organic antibacterial agents have the advantages of strong bactericidal power, wide sources, low price and the like, in the using process, the antibacterial agents have poor thermal stability, are easy to decompose and have poor durability and certain toxicity; natural and high molecular antibacterial agents have the advantages of non-toxicity and environmental protection, but have poor heat resistance and difficult processing, and most of the high polymers have limited thermodynamic compatibility with each other. The inorganic antibacterial agent has long-acting effect, no drug resistance and slow release.
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 research field of the antibacterial agent. The organic-inorganic composite antibacterial agents are roughly classified into three categories: (1) adding an organic antibacterial agent into an inorganic carrier; (2) a complex salt antibacterial agent formed by an inorganic antibacterial agent and an organic carrier; (3) a rare earth complex antimicrobial agent. However, there is no further study on the selection of organic and inorganic reagents and the complexing performance during the complexing process.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides an environment-friendly composite antibacterial agent and a preparation method thereof, the invention adopts a 2-step oxidation-reduction method to synthesize the bimetal composite antibacterial agent, firstly, polydopamine serving as a reducing agent is added into a copper-containing solution to prepare a copper seed solution so as to obtain dopamine-coated copper nanoparticles, silver ions are adsorbed on the surface of the nano Cu particles due to the complexation of catechol groups and nitrogen-containing groups in a polydopamine structure on the metal ions, the weak reducibility of the polydopamine can reduce the adsorbed metal ions to generate the metal nanoparticles to become catalytic active centers of the subsequent reduction reaction, the added reducing agent enables the metal nanoparticles to continue to reduce and grow on the formed active centers to form shells, and the silver-copper core-shell structure antibacterial agent coated by silver nanoparticles is formed, has good antibacterial property.
The technical scheme adopted by the invention is realized as follows:
the invention 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 and react to obtain seed crystal mixed liquid;
(2) AgNO is added into the seed crystal mixed liquid3Reacting the oleylamine solution with a modifier to obtain a copper-silver mixed solution;
(3) and adding absolute ethyl alcohol into the copper-silver mixed solution, and centrifuging 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.
The modifier is dodecyl triphenyl phosphonium bromide and/or sodium rectorite.
Preferably, the preparation method of the environment-friendly composite antibacterial agent comprises the following steps:
(1) mixing 8-20 parts by weight of copper nitrate, 15-30 parts by weight of reducing agent and 10-40 parts by weight of oleylamine, stirring at 80-120 ℃ for 20-50min at the stirring speed of 400-800rpm, keeping stirring, raising the temperature to 160-220 ℃ at the stirring speed of 5-15 ℃/min, continuing stirring for 2-4h, and cooling at room temperature to obtain a seed crystal mixed solution;
(2) at normal temperature and under the condition of stirring speed of 450-600rpm, adding 20-40 parts by weight of AgNO with mass fraction of (28-45)% into the seed crystal mixed solution3Heating the oleylamine solution and 5-10 parts by weight of modifier to 70-90 ℃, continuing 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 at the centrifugal rotation speed of 9000-12000rpm for 10-30min, and drying the obtained solid in a vacuum drying oven at the temperature of 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 rectorite; preferably, the modifier is dodecyl triphenyl phosphonium bromide and sodium rectorite according to a mass ratio of 1: (1-3).
One of the inventive concepts of the invention is that a specific method is adopted to prepare the Cu-Ag composite antibacterial agent, polydopamine is used as a weak reducing agent and a binder, and a large number of catechol groups and nitrogen-containing groups contained in the structure of the polydopamine make the polydopamine have strong adsorption capacity on metal ions, and the groups are also beneficial to the grafting reaction and the next step of functionalization; the weak reducibility of the polydopamine can reduce metal ions to generate metal nanoparticles, and the metal nanoparticles can be attached to the surfaces of the metal nanoparticles due to strong adsorption force. Specifically, polydopamine and oleylamine are added into a copper solution, copper nanoparticles are reduced by the oleylamine under a heating condition to obtain the copper nanoparticles, and the polydopamine is adsorbed on the surface of copper ions through catechol groups and nitrogen-containing groups of the polydopamine.
The invention also discloses a method for preparing the silver-copper composite, which is characterized in that a modifier of dodecyl triphenyl phosphonium bromide and/or sodium-based rectorite is added in the process of forming the silver-copper composite, so that the agglomeration of nano particles is effectively prevented, and the prepared antibacterial composite has excellent antibacterial effect and can realize long-acting antibiosis by utilizing the synergistic effect of the modification of the sodium-based rectorite and the dodecyl triphenyl phosphonium bromide. 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 coordinate bonds with silver to adsorb the silver, so that the release speed of silver ions is delayed, and the aggregation of the silver ions is prevented. The sodium-based rectorite is aqueous aluminosilicate, is interlayer mineral regularly and alternately stacked by dioctahedral mica layers and dioctahedral montmorillonite layers, has good dispersibility and thermal stability, large specific surface area and strong adsorbability, and exchangeable cations are contained in the montmorillonite layers, and silver ions, copper ions, dodecyl triphenyl phosphonium bromide and dodecyl triphenyl phosphonium bromide adsorbing silver particles can be intercalated into the montmorillonite layers through cation exchange, so that agglomeration is effectively prevented, the antibacterial performance is improved, and a slow release effect is further realized. Specifically, due to the complexation of the catechol group and the nitrogen-containing group in the polydopamine structure on the metal ions, the silver ions are adsorbed on the surface of the nano Cu particles, the weak reducibility of the polydopamine can reduce the adsorbed metal ions to generate metal nanoparticles to become catalytic active centers of the subsequent reduction reaction, and the added reducing agent enables the metal nanoparticles to continue to reduce and grow on the formed active centers to form shells, so that the silver-copper core-shell structure coated with 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 an rectorite interlayer through cation exchange, and finally the environment-friendly composite antibacterial agent, namely the Cu-Ag composite antibacterial agent, is formed.
The sterilization mechanism is as follows: after the silver ions contact 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 loses activity, inherent components of the cells are damaged, the activity of the cells is damaged, and the bacteria are killed.
Still further preferably, the preparation method of the environment-friendly composite antibacterial agent comprises the following steps:
(1) mixing 8-20 parts by weight of copper nitrate, 15-30 parts by weight of reducing agent and 10-40 parts by weight of oleylamine, stirring at 80-120 ℃ for 20-50min at the stirring speed of 400-800rpm, keeping stirring, raising the temperature to 160-220 ℃ at the stirring speed of 5-15 ℃/min, continuing stirring for 2-4h, and cooling at room temperature to obtain a seed crystal mixed solution;
(2) at normal temperature and under the condition of stirring speed of 450-600rpm, adding 20-40 parts by weight of AgNO with mass fraction of (28-45)% into the seed crystal mixed solution3Heating oleylamine solution, 5-10 parts of modifier and 2-4 parts of potassium hexachloride to 70-90 ℃, continuing 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 at the centrifugal rotation speed of 9000-12000rpm for 10-30min, and drying the obtained solid in a vacuum drying oven at the temperature of 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 rectorite; preferably, the modifier is dodecyl triphenyl phosphonium bromide and sodium rectorite according to a mass ratio of 1: (1-3).
The preparation method of the potassium hemimellitate is disclosed in the following references: bacteria activities of multiple reactions enhanced by carbonates of Guofang Li, et al Med. chem. Commun.2015 (6) 1643-.
Will 8mLS2Cl2Dissolving in 50mLCCl4Cooling to-15 deg.C, adding 50g Na2S2O3·5H2O; 80mL of 6M HCl pre-cooled to-5 ℃ and 8mL of 0.6M FeCl pre-cooled to-5 ℃ were added3Reacting for 60min, and filtering to remove solids to obtain filtrate A; the aqueous phase is separated from the filtrate A and concentrated to 30mL at 40 ℃ under reduced pressure,filtering and removing the separated NaCl precipitate to obtain filtrate B; adjusting the pH value of the filtrate B to 1, cooling to 0 ℃, and dropwise adding 20mL of 0-DEG C methanol solution containing 4gKOH under the stirring condition of 800 rpm; carrying out vacuum filtration to obtain a white solid, washing with acetone for 2 times, wherein the amount of acetone used for washing each time is 20 mL; drying at room temperature to obtain crude potassium hexachlorosulfate. Preheating 30ml of 0.1M sulfuric acid to 60 ℃, adding 15g of the potassium hexacosanoate crude product for dissolution, then immediately filtering, and cooling the filtrate to-5 ℃; adding 30mL of methanol, aging for 12 hours, vacuum filtering to obtain crystals, washing with methanol twice, wherein the amount of methanol used in each washing is 20mL, and obtaining potassium hexaconazole.
After the potassium hexaconazole is added, the antibacterial effect of the obtained environment-friendly composite antibacterial agent is obviously improved. Polythionate is an unstable intermediate with similar molecular structure and physicochemical properties formed by dropwise addition of sulfur compounds during oxidation to sulfate. Potassium hexachlorosulfate, i.e. having S in the molecular structure6O6 2-Potassium polythionate. Potassium hexacontulfate is easily dissolved in water, and has antibacterial activity because elemental sulfur is easily decomposed and separated out. Potassium hexacontulfate and dodecyl triphenyl phosphonium bromide are combined to generate an inorganic organic composite antibacterial agent, namely, dodecyl triphenyl phosphonium hexacontulfate, which can slowly decompose quaternary phosphonium salt cations and active sulfur antibacterial components, has an antibacterial effect superior to the effect of simply adding the quaternary phosphonium salt cations and the active sulfur antibacterial components, and has long-acting antibacterial performance. In tests, the antibacterial effect of the environment-friendly composite antibacterial agent is reduced when the potassium hexachlorophnate is excessively added. The reason is that potassium hexacontulfate and dodecyl triphenyl phosphonium bromide are combined to generate a hexacontulfate quaternary phosphonium salt crystal, and excessive potassium hexacontulfate 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 and further influence the intercalation effect of the effective components on rectorite; and the excessive potassium and quaternary phosphonium sulfates contact with silver particles to generate gray black silver sulfide precipitate, thus reducing antibacterial effect.
The invention also provides an environment-friendly composite antibacterial agent prepared by the method.
The invention has the beneficial effects that: compared with the traditional method, the environment-friendly composite antibacterial agent prepared by the specific method has the advantages of simple steps, no toxicity of reagents and the like; the polydopamine is added, so that the reduction of copper ions can be accelerated, the reaction time is shortened, and the binding force between copper and silver can be improved, so that the prepared environment-friendly composite antibacterial agent has the technical effects of high-efficiency antibacterial and long-acting antibacterial; meanwhile, sodium-based rectorite and a dodecyl triphenyl phosphonium bromide modifier are added, so that the active ingredients enter a rectorite intercalation layer, the agglomeration of the active ingredients is avoided, the antibacterial effect is improved, and the slow release and protection effects are achieved; in addition, potassium hexaconazole is added to form an inorganic organic composite salt antibacterial component with dodecyl triphenyl phosphonium bromide, so that the antibacterial effect is further improved, and the application range is widened.
Detailed Description
The above summary of the present invention is described in further detail below with reference to specific embodiments, but it should not be understood that the scope of the above subject matter of the present invention is limited to the following examples.
Introduction of some raw materials in this application:
examples dodecyl triphenyl phosphonium bromide, CAS: 15510-55-1.
In the examples, sodium-based rectorite is purchased from Taixiang famous flow rectorite science and technology Limited, Hubei, and the content of the rectorite is as follows: 90 percent.
The oleylamine in the examples was purchased from manba commercial limited, texas, cat # stock: 112-90-3, CAS: 112-90-3.
The polydopamine in the examples is prepared according to example 5 of Chinese invention patent CN111004391A (patent application No. 201911147981.1), and the specific preparation method is as follows:
(1) weighing 0.0948g of DA & HCl, and dissolving in 5mL of Tris-buffer solution to obtain solution A; weighing 0.0990gK2FeO4Dissolved in 5mL of an aqueous ammonia solution (pH 8.5) to obtain a solution B; dropwise adding the solution B into the solution A, magnetically stirring, keeping the rotating speed at 5000r min < -1 >, keeping the reaction temperature at 70 ℃, gradually changing the reaction mixed solution from purple red to black in the reaction process, and stopping stirring after reacting for 40 minutes;
(2) and (3) filtering the reaction mixed solution under reduced pressure, washing the precipitate for 5 times by using distilled water, and freeze-drying the precipitate to constant weight to obtain a polydopamine product, wherein the yield is 94%, and the diameter of the polydopamine nano-particle is about 50 nm.
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 reducing agent and 20 parts by weight of oleylamine, stirring at the temperature of 100 ℃ and 500rpm for 30min, keeping stirring, increasing the temperature to 200 ℃ at the speed of 10 ℃/min, continuing stirring for 2.5h, and cooling at room temperature to obtain a seed crystal mixed solution;
(2) adding 30 parts by weight of AgNO containing 30 wt% into the seed crystal mixed solution at normal temperature and at the stirring speed of 500rpm3Heating the oleylamine solution and 8 parts by weight of modifier to 80 ℃, continuing stirring for 2 hours, and cooling to room temperature to obtain copper-silver mixed solution;
(3) and adding 30 parts by weight of absolute ethyl alcohol into the copper-silver mixed solution, centrifuging for 15min at the centrifugal rotation 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 rectorite.
Example 2
Essentially the same as example 1 except that the modifier was dodecyltriphenylphosphonium bromide.
Comparative example 1
Essentially the same as in example 1, except that no modifier was added. Namely, the step (2) is as follows: adding 30 parts by weight of AgNO containing 30 wt% into the seed crystal mixed solution at normal temperature and at the stirring speed of 500rpm3Heating the oleylamine solution to 80 ℃, continuing stirring for 2 hours, and cooling to room temperature to obtain a copper-silver mixed solution.
Example 3
Essentially the same as in example 1, except that the reducing agent is sodium borohydride.
Example 4
Essentially the same as in example 1, except that the reducing agent is 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 reducing agent and 20 parts by weight of oleylamine, stirring at the temperature of 100 ℃ and 500rpm for 30min, keeping stirring, increasing the temperature to 200 ℃ at the speed of 10 ℃/min, continuing stirring for 2.5h, and cooling at room temperature to obtain a seed crystal mixed solution;
(2) adding 30 parts by weight of AgNO containing 30 wt% into the seed crystal mixed solution at normal temperature and at the stirring speed of 500rpm3Heating the oleylamine solution and 8 parts by weight of modifier to 80 ℃, continuing stirring for 2 hours, and cooling to room temperature to obtain copper-silver mixed solution;
(3) and adding 30 parts by weight of absolute ethyl alcohol into the copper-silver mixed solution, centrifuging for 15min at the centrifugal rotation 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 rectorite according to the mass ratio of 1: 2, or a mixture thereof.
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 reducing agent and 20 parts by weight of oleylamine, stirring at the temperature of 100 ℃ and 500rpm for 30min, keeping stirring, increasing the temperature to 200 ℃ at the speed of 10 ℃/min, continuing stirring for 2.5h, and cooling at room temperature to obtain a seed crystal mixed solution;
(2) adding 30 parts by weight of AgNO containing 30 wt% into the seed crystal mixed solution at normal temperature and at the stirring speed of 500rpm3Heating the oleylamine solution, 8 parts of modifier and 3 parts of potassium hexachloride to 80 ℃, continuing stirring for 2 hours, and cooling to room temperature to obtain copper-silver mixed solution;
(3) and adding 30 parts by weight of absolute ethyl alcohol into the copper-silver mixed solution, centrifuging for 15min at the centrifugal rotation 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 rectorite according to the mass ratio of 1: 2;
the preparation method of the potassium hemimellitate is disclosed in the following references: bacteria activities of multiple reactions enhanced by carbonates of Guofang Li, et al Med. chem. Commun.2015 (6) 1643-.
Will 8mLS2Cl2Dissolving in 50mLCCl4Cooling to-15 deg.C, adding 50g Na2S2O3·5H2O; 80mL of 6M HCl pre-cooled to-5 ℃ and 8mL of 0.6M FeCl pre-cooled to-5 ℃ were added3Reacting for 60min, and filtering to remove solids to obtain filtrate A; separating the water phase from the filtrate A, concentrating the water phase at 40 ℃ under reduced pressure to 30mL, and filtering and removing the separated NaCl precipitate to obtain a filtrate B; adjusting the pH value of the filtrate B to 1, cooling to 0 ℃, and dropwise adding 20mL of 0-DEG C methanol solution containing 4gKOH under the stirring condition of 800 rpm; carrying out vacuum filtration to obtain a white solid, washing with acetone for 2 times, wherein the amount of acetone used for washing each time is 20 mL; drying at room temperature to obtain crude potassium hexachlorosulfate. Preheating 30ml of 0.1M sulfuric acid to 60 ℃, adding 15g of the potassium hexacosanoate crude product for dissolution, then immediately filtering, and cooling the filtrate to-5 ℃; adding 30mL of methanol, aging for 12 hours, vacuum filtering to obtain crystals, washing with methanol twice, wherein the amount of methanol used in each washing is 20mL, and obtaining potassium hexaconazole.
Test example 1
And (3) testing antibacterial performance:
strain: candida albicans ATCC 10231.
The Potato Dextrose Agar (PDA) culture medium comprises the following specific formula: 200g of potato, 20g of glucose, agar (20 g of upper medium and 7.5g of lower medium), and 1000mL of distilled water. A configuration step: 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 uniformly stirring; cooling to 80 deg.C, adding water to 1000mL, sterilizing at 121 deg.C for 20min, and cooling.
Testing the antibacterial performance by an oxford cup diffusion method:
1) the lower layer culture medium: heating and melting the PDA culture medium, pouring the PDA culture medium into a culture dish with the diameter of 9cm in a quantitative manner according to 20 mL/dish, and cooling and solidifying the PDA culture medium to be used as a lower-layer culture medium;
2) upper medium: 4mL of 109And adding the CFU/mL bacterial suspension into 100mL culture medium at 50 ℃, quickly shaking to obtain a bacterium-containing culture medium, sucking 5mL of the bacterium-containing culture medium by using a sterilized gun head, and uniformly distributing on the lower layer culture medium.
3) Measuring the diameter of the inhibition zone: 3 Oxford cups were placed on each dish at equal distances and lightly pressed to make contact with the medium without any gaps. And transferring 200 mu L of 1mg/mL distilled water dispersion of the environment-friendly composite antibacterial agent into an oxford cup, covering a culture dish, transferring the oxford cup into an incubator, culturing for 18h at 28 ℃, and measuring the diameter of a bacteriostatic circle around the oxford cup. 3 replicates were run for each sample.
The modifier in example 1 is sodium-based rectorite, the modifier in example 2 is dodecyl triphenyl phosphonium bromide, the modifier in comparative example 1 is not used, and the modifier in example 5 is dodecyl triphenyl phosphonium bromide and sodium-based rectorite according to the mass ratio of 1: 2, or a mixture thereof. The addition of the modifier effectively improves the antibacterial effect of the environment-friendly composite antibacterial agent, 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 phosphonium bromide and the sodium-based rectorite have a synergistic antibacterial effect. The dodecyl triphenyl phosphonium bromide has antibacterial performance, and phosphorus atoms in the molecular structure of the dodecyl triphenyl phosphonium bromide can form coordinate bonds with silver to adsorb the silver ions, so that the release speed of the silver ions is delayed, the aggregation of the silver ions is prevented, and the antibacterial performance is improved. The sodium-based rectorite is interlayer mineral regularly and alternately stacked by dioctahedral mica layers and dioctahedral montmorillonite layers, has good dispersibility and thermal stability, large specific surface area and strong adsorbability, and exchangeable cations are contained in the montmorillonite layers, so that silver ions, copper ions, dodecyl triphenyl phosphonium bromide and the dodecyl triphenyl phosphonium bromide adsorbed with silver particles can be intercalated into the montmorillonite interlayers through cation exchange, thereby effectively preventing agglomeration, improving antibacterial performance and further playing a role in slow release.
Examples 1, 3 and 4 adopt different substances as reducing agents, and the results show that the antibacterial effect of the environment-friendly composite antibacterial agent is the best when polydopamine is used as a reducing agent. Sodium borohydride and ascorbic acid are copper nano-composites which are formed by simply reducing copper ions and adsorbing silver nano-particles on the surfaces of the copper ions without bonding, and only simple copper and silver nano-particles are superposed. The polydopamine has weak reducibility and strong adsorption force to metal ions due to a large number of catechol groups and nitrogen-containing groups contained in the structure, and can reduce the adsorbed metal ions to generate metal nanoparticles to become catalytic active centers of subsequent reduction reaction. Therefore, the antibacterial effect is better.
The difference between example 5 and example 6 is that in example 6, potassium hexachlorophnate is added in a large amount, and the antibacterial performance is significantly improved. The potassium hexacosulfate and the dodecyl triphenyl phosphonium bromide are combined to generate an inorganic and organic composite antibacterial agent, namely the phosphonium hexacosulfate, can slowly decompose two antibacterial components, namely phosphonium sulfate cation and active sulfur, and has more excellent antibacterial performance.
Claims (8)
1. The preparation method of the environment-friendly composite antibacterial agent is characterized by comprising the following steps:
(1) copper nitrate, a reducing agent and oleylamine are mixed and react to obtain seed crystal mixed liquid;
(2) AgNO is added into the seed crystal mixed liquid3Reacting the oleylamine solution with a modifier to obtain a copper-silver mixed solution;
(3) and adding absolute ethyl alcohol into the copper-silver mixed solution, and centrifuging to obtain the environment-friendly composite antibacterial agent.
2. The method for preparing environment-friendly composite antibacterial agent according to claim 1, wherein the reducing agent is one or a mixture of more than two of sodium borohydride, ascorbic acid and polydopamine.
3. The method for preparing the environment-friendly composite antibacterial agent according to claim 1, wherein the modifier is dodecyl triphenyl phosphonium bromide and/or sodium-based rectorite.
4. The method for preparing the environment-friendly composite antibacterial agent according to claim 1, comprising the following steps:
(1) mixing 8-20 parts by weight of copper nitrate, 15-30 parts by weight of reducing agent and 10-40 parts by weight of oleylamine, stirring at 80-120 ℃ for 20-50min at the stirring speed of 400-800rpm, keeping stirring, raising the temperature to 160-220 ℃ at the stirring speed of 5-15 ℃/min, continuing stirring for 2-4h, and cooling at room temperature to obtain a seed crystal mixed solution;
(2) at normal temperature and under the condition of stirring speed of 450-600rpm, adding 20-40 parts by weight of AgNO with mass fraction of (28-45)% into the seed crystal mixed solution3Heating the oleylamine solution and 5-10 parts by weight of modifier to 70-90 ℃, continuing 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 at the centrifugal rotation speed of 9000-12000rpm for 10-30min, and drying the obtained solid in a vacuum drying oven at the temperature of 50-70 ℃ for 20-28 h.
5. The method for preparing environment-friendly composite antibacterial agent according to claim 4, wherein 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.
6. The method for preparing the environment-friendly composite antibacterial agent according to claim 4, wherein the modifier is dodecyl triphenyl phosphonium bromide and/or sodium-based rectorite.
7. The method for preparing the environment-friendly composite antibacterial agent according to claim 1, comprising the following steps:
(1) mixing 8-20 parts by weight of copper nitrate, 15-30 parts by weight of reducing agent and 10-40 parts by weight of oleylamine, stirring at 80-120 ℃ for 20-50min at the stirring speed of 400-800rpm, keeping stirring, raising the temperature to 160-220 ℃ at the stirring speed of 5-15 ℃/min, continuing stirring for 2-4h, and cooling at room temperature to obtain a seed crystal mixed solution;
(2) at normal temperature and under the condition of stirring speed of 450-600rpm, adding 20-40 parts by weight of AgNO with mass fraction of (28-45)% into the seed crystal mixed solution3Heating oleylamine solution, 5-10 parts of modifier and 2-4 parts of potassium hexachloride to 70-90 ℃, continuing 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 at the centrifugal rotation speed of 9000-12000rpm for 10-30min, and drying the obtained solid in a vacuum drying oven at the temperature of 50-70 ℃ for 20-28h to obtain the environment-friendly composite antibacterial agent.
8. An environment-friendly composite antibacterial agent, which is characterized by being prepared by the method of any one of claims 1 to 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110072404.1A CN112715574B (en) | 2021-01-20 | 2021-01-20 | Environment-friendly composite antibacterial agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110072404.1A CN112715574B (en) | 2021-01-20 | 2021-01-20 | Environment-friendly composite antibacterial agent and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112715574A true CN112715574A (en) | 2021-04-30 |
| CN112715574B CN112715574B (en) | 2023-09-26 |
Family
ID=75592551
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110072404.1A Active CN112715574B (en) | 2021-01-20 | 2021-01-20 | Environment-friendly composite antibacterial agent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112715574B (en) |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1385474A (en) * | 2002-05-22 | 2002-12-18 | 湖北名流累托石科技股份有限公司 | Rectorite organic compound for synthesizing nano compound material and preparation method thereof |
| CN1789312A (en) * | 2005-12-16 | 2006-06-21 | 武汉大学 | Chitosan/rectorite nano composite materials and method for preparing the same |
| CN101347124A (en) * | 2008-06-20 | 2009-01-21 | 中国高岭土公司 | Method for preparing silver-carrying ion and copper ion kaolin anti-bacteria agent |
| CN102211200A (en) * | 2011-06-14 | 2011-10-12 | 东华大学 | Method for synthesizing eggplant-shaped Ag-Ag2S nano heterojunction in one-step |
| CN102585302A (en) * | 2012-02-21 | 2012-07-18 | 华南理工大学 | Silver-loaded chitosan-based phyllosilicate nanocomposite material and preparation method and application thereof |
| CN106179196A (en) * | 2016-07-15 | 2016-12-07 | 温州泓呈祥科技有限公司 | A kind of petrochemical wastewater process adsorbent and preparation method thereof |
| CN107096916A (en) * | 2017-05-14 | 2017-08-29 | 蒋春霞 | A kind of preparation method of silver-coated copper powder |
| CN107469410A (en) * | 2017-08-18 | 2017-12-15 | 华南理工大学 | A kind of durability super-hydrophobic coat for water-oil separating and preparation method thereof |
| WO2018093943A1 (en) * | 2016-11-16 | 2018-05-24 | The Regents Of The University Of California | Identification and optimization of carbon radicals on hydrated graphene oxide for ubiquitous antibacterial coatings |
| CN108997716A (en) * | 2018-08-29 | 2018-12-14 | 佛山市森昂生物科技有限公司 | A kind of antibacterial compound of environment-protection nano silver |
| CN109311662A (en) * | 2016-03-24 | 2019-02-05 | 南洋理工大学 | The nano structural material in nucleocapsid plasma nano gap |
-
2021
- 2021-01-20 CN CN202110072404.1A patent/CN112715574B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1385474A (en) * | 2002-05-22 | 2002-12-18 | 湖北名流累托石科技股份有限公司 | Rectorite organic compound for synthesizing nano compound material and preparation method thereof |
| CN1789312A (en) * | 2005-12-16 | 2006-06-21 | 武汉大学 | Chitosan/rectorite nano composite materials and method for preparing the same |
| CN101347124A (en) * | 2008-06-20 | 2009-01-21 | 中国高岭土公司 | Method for preparing silver-carrying ion and copper ion kaolin anti-bacteria agent |
| CN102211200A (en) * | 2011-06-14 | 2011-10-12 | 东华大学 | Method for synthesizing eggplant-shaped Ag-Ag2S nano heterojunction in one-step |
| CN102585302A (en) * | 2012-02-21 | 2012-07-18 | 华南理工大学 | Silver-loaded chitosan-based phyllosilicate nanocomposite material and preparation method and application thereof |
| CN109311662A (en) * | 2016-03-24 | 2019-02-05 | 南洋理工大学 | The nano structural material in nucleocapsid plasma nano gap |
| CN106179196A (en) * | 2016-07-15 | 2016-12-07 | 温州泓呈祥科技有限公司 | A kind of petrochemical wastewater process adsorbent and preparation method thereof |
| WO2018093943A1 (en) * | 2016-11-16 | 2018-05-24 | The Regents Of The University Of California | Identification and optimization of carbon radicals on hydrated graphene oxide for ubiquitous antibacterial coatings |
| CN107096916A (en) * | 2017-05-14 | 2017-08-29 | 蒋春霞 | A kind of preparation method of silver-coated copper powder |
| CN107469410A (en) * | 2017-08-18 | 2017-12-15 | 华南理工大学 | A kind of durability super-hydrophobic coat for water-oil separating and preparation method thereof |
| CN108997716A (en) * | 2018-08-29 | 2018-12-14 | 佛山市森昂生物科技有限公司 | A kind of antibacterial compound of environment-protection nano silver |
Non-Patent Citations (5)
| Title |
|---|
| GIL YEROSLAVSKY: "Sonochemically-Produced Metal-Containing Polydopamine Nanoparticles and Their Antibacterial and Antibiofilm Activity", 《LANGMUIR》 * |
| 张泽强等: "载银累托石的抗菌作用", 《武汉科技大学学报（自然科学版）》 * |
| 李国防: "连多硫酸盐抗菌剂的制备、抗菌活性与机理", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 王洁冰: "核壳结构铜银双金属复合纳米粒子的新型制备方法的研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 谭绍早等: "含季鏻阳离子的抗菌改性蒙脱土的制备及表征", 《无机材料学报》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112715574B (en) | 2023-09-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Qi et al. | Preparation and antibacterial activity of chitosan nanoparticles | |
| Sureshkumar et al. | Magnetic antimicrobial nanocomposite based on bacterial cellulose and silver nanoparticles | |
| CN111202091A (en) | Nano-silver loaded mesoporous silica antibacterial material and preparation method and application thereof | |
| Sacourbaravi et al. | Fabrication of Ag NPs/Zn-MOF nanocomposites and their application as antibacterial agents | |
| CN105776179B (en) | A kind of water soluble quaternary ammonium salinization Nano carbon balls and preparation method and application | |
| CN110506741B (en) | Novel nano composite antibacterial material and preparation method and application thereof | |
| CN102939961B (en) | Pesticide microparticle preparation having core-shell structure and preparation method thereof | |
| JPWO2003053565A1 (en) | Phosphate adsorbent | |
| WO2010010569A1 (en) | A process for forming a rice husk ash composition | |
| CN112931530A (en) | Nano-silver loaded Cu-MOF antibacterial material and preparation method and application thereof | |
| Xue et al. | Influence of Ca2+ on phosphate removal from water using a non-core-shell Fe3O4@ ZIF-67 composites | |
| CN112715574A (en) | Environment-friendly composite antibacterial agent and preparation method thereof | |
| Puthalath et al. | Synthesis and antibacterial activity of silver-copper nano-composites formed by microwave assisted chemical reduction | |
| CN112913856B (en) | Anti-agglomeration slow-release inorganic antibacterial material and preparation method thereof | |
| Aly et al. | Chemical, microbial and biological studies on fresh mango juice in presence of nanoparticles of zirconium molybdate embedded chitosan and alginate | |
| CN112841191A (en) | Preparation method of chitosan antibacterial agent | |
| CN116584480A (en) | Preparation method and application of metal organic framework nano pesticide controlled release agent | |
| CN102190904A (en) | Production method of antibacterial high-water-absorbability resin | |
| CN113304275B (en) | Dihydromyricetin modified DNA drug delivery system, nano drug-loading system, preparation method and application | |
| Ma et al. | A facile one‐pot route to fabricate clothianidin‐loaded ZIF‐8 nanoparticles with biocompatibility and long‐term efficacy | |
| CN114734032A (en) | Method for preparing nano-silver based on kapok extract | |
| CN112168809A (en) | Novel nano-silver antibacterial material and preparation method and application thereof | |
| Parsa et al. | Loading and release study of ciprofloxacin from silica-coated magnetite modified by iron-based metal-organic framework (MOF) as a nonocarrier in targeted drug delivery system | |
| Nguyen et al. | Effects of synthetic procedures and postsynthesis incubation pH on size, shape, and antibacterial activity of copper (I) oxide nanoparticles | |
| CN113383787A (en) | Multivalent silver composite nano antibacterial agent and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231114 Address after: 430000, No. 201, Building 5, Longjing Environmental Protection Industrial Park, No. 9 Fozuling Third Road, Fozuling Street, Donghu New Technology Development Zone, Wuhan City, Hubei Province (Wuhan Free Trade Zone) Patentee after: Hubei Yueyi Chemical Industry Co.,Ltd. Address before: No. 52, group 1, Lingjiao village, Anzhou street, Xianju County, Taizhou City, Zhejiang Province, 317300 Patentee before: Zhang Chengbang |