CN116606402B - Preparation method of self-assembled antibacterial nano microsphere containing zwitterionic polyhaloamine - Google Patents
Preparation method of self-assembled antibacterial nano microsphere containing zwitterionic polyhaloamine Download PDFInfo
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 80
- 239000004005 microsphere Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 81
- 238000003756 stirring Methods 0.000 claims abstract description 31
- 239000003999 initiator Substances 0.000 claims abstract description 27
- 239000000243 solution Substances 0.000 claims abstract description 25
- 239000000178 monomer Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000012153 distilled water Substances 0.000 claims abstract description 19
- 229920001577 copolymer Polymers 0.000 claims abstract description 17
- 239000000839 emulsion Substances 0.000 claims abstract description 16
- -1 polyhexamethylene Polymers 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000002500 ions Chemical class 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 10
- 229920000249 biocompatible polymer Polymers 0.000 claims abstract description 10
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 10
- 230000002140 halogenating effect Effects 0.000 claims abstract description 10
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 18
- 230000002572 peristaltic effect Effects 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- HNMRXHKSSFYJBH-UHFFFAOYSA-N 3-[(4-ethenylphenyl)methyl]-5,5-dimethylimidazolidine-2,4-dione Chemical compound O=C1C(C)(C)NC(=O)N1CC1=CC=C(C=C)C=C1 HNMRXHKSSFYJBH-UHFFFAOYSA-N 0.000 claims description 7
- 241000588724 Escherichia coli Species 0.000 claims description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- 235000019441 ethanol Nutrition 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- 241000191967 Staphylococcus aureus Species 0.000 claims description 6
- BCAIDFOKQCVACE-UHFFFAOYSA-N 3-[dimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azaniumyl]propane-1-sulfonate Chemical compound CC(=C)C(=O)OCC[N+](C)(C)CCCS([O-])(=O)=O BCAIDFOKQCVACE-UHFFFAOYSA-N 0.000 claims description 5
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 claims description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical group COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical group [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 5
- HOJYCNSTMZLRCV-UHFFFAOYSA-N 5,5-dimethyl-3-prop-2-enylimidazolidine-2,4-dione Chemical compound CC1(C)NC(=O)N(CC=C)C1=O HOJYCNSTMZLRCV-UHFFFAOYSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 230000002401 inhibitory effect Effects 0.000 claims description 4
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 4
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 4
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 claims description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 21
- 241000894006 Bacteria Species 0.000 description 23
- 230000000845 anti-microbial effect Effects 0.000 description 13
- 238000010521 absorption reaction Methods 0.000 description 9
- 230000003373 anti-fouling effect Effects 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 239000000017 hydrogel Substances 0.000 description 8
- 150000004985 diamines Chemical class 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- 230000001954 sterilising effect Effects 0.000 description 5
- 238000004659 sterilization and disinfection Methods 0.000 description 5
- 239000004599 antimicrobial Substances 0.000 description 4
- 230000001580 bacterial effect Effects 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- QDHHCQZDFGDHMP-UHFFFAOYSA-N Chloramine Chemical compound ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000010065 bacterial adhesion Effects 0.000 description 2
- 239000003899 bactericide agent Substances 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000011161 development 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
- 230000000694 effects Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 description 2
- 239000011807 nanoball Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- PSBDWGZCVUAZQS-UHFFFAOYSA-N (dimethylsulfonio)acetate Chemical group C[S+](C)CC([O-])=O PSBDWGZCVUAZQS-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 208000035143 Bacterial infection Diseases 0.000 description 1
- 102000010834 Extracellular Matrix Proteins Human genes 0.000 description 1
- 108010037362 Extracellular Matrix Proteins Proteins 0.000 description 1
- 241000192125 Firmicutes Species 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 206010034133 Pathogen resistance Diseases 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 208000022362 bacterial infectious disease Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229960003638 dopamine Drugs 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 210000002744 extracellular matrix Anatomy 0.000 description 1
- 210000003495 flagella Anatomy 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000002439 hemostatic effect Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical group O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 1
- 229940091173 hydantoin Drugs 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 210000002540 macrophage Anatomy 0.000 description 1
- NXPNPYNCKSWEHA-WDSKDSINSA-N methyl (2r)-2-amino-3-[[(2r)-2-amino-3-methoxy-3-oxopropyl]disulfanyl]propanoate Chemical compound COC(=O)[C@@H](N)CSSC[C@H](N)C(=O)OC NXPNPYNCKSWEHA-WDSKDSINSA-N 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000004714 phosphonium salts Chemical group 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- RRHXZLALVWBDKH-UHFFFAOYSA-M trimethyl-[2-(2-methylprop-2-enoyloxy)ethyl]azanium;chloride Chemical compound [Cl-].CC(=C)C(=O)OCC[N+](C)(C)C RRHXZLALVWBDKH-UHFFFAOYSA-M 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
-
- 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
- A01N25/12—Powders or granules
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
- A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/18—Introducing halogen atoms or halogen-containing groups
- C08F8/20—Halogenation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental Sciences (AREA)
- Zoology (AREA)
- Wood Science & Technology (AREA)
- General Health & Medical Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Agronomy & Crop Science (AREA)
- Dentistry (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
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Abstract
The invention relates to a preparation method of self-assembled antibacterial nano-microspheres containing zwitterionic polyhaloamine, which comprises the following steps: the preparation method comprises the steps that an N-halamine antibacterial unit precursor and a hydrophobic acrylate monomer are dissolved in an alcohol solution to prepare a mixed solution A; dissolving a zwitterionic monomer and a water-soluble initiator into distilled water to prepare a mixed solution B; mechanically stirring distilled water and a biocompatible polymer emulsifier to obtain a mixed solution C; the mixed solution A and the mixed solution B are simultaneously added into the mixed solution C in a dropwise manner, and the copolymer emulsion is obtained through stirring reaction; simultaneously dripping the mixed solution A and the water-soluble initiator solution into the copolymer emulsion to react to obtain the self-assembled polyhydantoin nano-microsphere containing the amphoteric ions; and fifthly, adding a halogenating reagent into the self-assembled polyhexamethylene oxide nano-microsphere containing the zwitterions, and separating and washing after stirring reaction to obtain the self-assembled polyhexamethylene oxide nano-microsphere containing the zwitterions. The preparation method is simple to operate, and the obtained material has excellent antibacterial performance.
Description
Technical Field
The invention relates to the field of material science and antibacterial technology, in particular to a preparation method of self-assembled antibacterial nano-microspheres containing zwitterionic polyhaloamines.
Background
In daily life, bacteria are ubiquitous, and endanger human health at all times. The most direct medium for the bacteria to contact with human body in life is the surface of the material. Bacteria can adsorb to the surface of the material through the action of coulomb force, van der waals force, hydrogen bonds, etc., the bacteria gradually gather, degenerate flagella, and begin to secrete extracellular matrix, so as to achieve irreversible adhesion to the surface. Thus, the surface of the material plays a decisive role in the bacterial infection of the human body.
Currently, researchers have developed methods for inhibiting bacterial adhesion and proliferation by chemically modifying the surface of materials. One approach is to reduce the adhesion of bacteria to the surface, typically by grafting a polymer (e.g., polyethylene glycol, polyphosphorylcholine, etc.) with an anti-fouling function onto the surface of the material, so that a hydrated layer forms on the surface of the material. Another approach is to combine antimicrobial agents (N-halamines, quaternary ammonium salts, quaternary phosphonium salts, etc.) with the surface, either by releasing active substances with bactericidal effects or by killing the bacteria in direct contact.
Among the many antimicrobial agents, N-halamine type antimicrobial agents are a class of antimicrobial agents having a broad spectrum and high efficacy against bacteria, and have the characteristics of good stability, low toxicity, low cost, reproducibility, and the like, with N-chloramine being the most stable. N-halamines have unique structural properties that enable the conversion of amino groups (N-H) to chloramine (N-Cl) by household disinfectants or bleach powders. Upon contact with bacteria, oxidative chlorine is released and attacks multiple targets of bacterial cells, killing the bacteria and not causing bacterial resistance. The invention patent CN 113896930A discloses an N-halamine type acrylamide/polyvinyl alcohol based antibacterial hydrogel and a preparation method thereof, wherein the N-isopropylacrylamide and the polyvinyl alcohol are crosslinked through the electrostatic complexation of amino groups of the N-isopropylacrylamide and hydroxyl groups of the polyvinyl alcohol to form a semi-interpenetrating network hydrogel with certain mechanical properties, and the semi-interpenetrating network hydrogel has excellent antibacterial property. Jing Z et al (Amide-based cationic polymeric N-halamines: synthesis, conjugation, and antimicrobial and biofilm-binding properties [ J ]. Ind. Eng. Chem. Res., 2019, 58, 16, 6218-6225.) prepared an Amide N-halamine (Cl-PVPT) by 3- (4-vinylbenzyl) -5, 5-dimethylhydantoin and trimethyl-2-methacryloyloxyethyl ammonium chloride, the Cl-PVPT copolymer being soluble in water and having excellent functions in killing gram-positive and gram-negative bacteria.
Zwitterionic polymers contain both anionic and cationic groups and have been widely studied for their stability in aqueous solutions. Yon HY et al (Double network hydrogels from polyzwitterions: high mechanical strength and excellent anti-biofouling properties [ J ]. J. Mater. Chem. B, 2013, 1, 3685-3693.) A novel single network hydrogel (PAMPS) and dual network (PAMPS/PCDMEDN) hydrogels were synthesized using N- (carboxymethyl) -N, N-dimethyl-2- (methacryloyloxy) ethylamine inner salt (CDME), and both PCDME hydrogels and PAMPS/PCDME DN hydrogels exhibited excellent anti-biocontamination properties through macrophage adhesion test. The excellent antifouling property of the zwitterionic polymer is a hydrated layer formed by solvation of charged groups, which can prevent bacteria from adhering to surfaces, and has excellent antifouling properties even in complex biological media. In addition, the zwitterionic polymer not only has excellent stain resistance, but also has adhesion properties to the substrate. The polymer chain contains a large amount of positive charges and negative charges, and adhesion can be achieved through dipole-dipole interaction or ion-dipole interaction at a contact interface.
However, the colonization of bacteria on the surface of the material is also a way for bacteria to invade the human body, and even though the antibacterial material has a remarkable effect of inactivating bacteria, a small amount of bacteria adheres to the surface of the material to proliferate. Therefore, development of a novel antibacterial material having both sterilization and antifouling functions is desired. Li LD et al (Synthesis of zwitterionic N-chlorohydantoins for antibacterial applications [ J ]. Bioorganic Med. Chem. Lett., 2018, 28, 3665-3669.) prepared two novel zwitterionic N-halamine bactericides containing an N-halamine unit and a sulfobetaine unit or carboxybetaine unit, both of which exhibit good antibacterial effects. However, the prepared zwitterionic N-halamine bactericide is small organic molecules, has high toxicity to human bodies, is easy to dissolve out, and causes the loss of antibacterial components. Therefore, the incorporation of an antibacterial material into a polymer material is the best solution to the above-mentioned problems. The invention patent CN 112012012A discloses a preparation method of betaine-halamine compound double antibacterial textile, and the prepared antibacterial textile has double antibacterial effects of halamine and betaine, improves antibacterial efficiency and has good antibacterial adhesion resistance. Zhang YD et al (Zwitterion and N-halamine functionalizedcotton wound dressing with enhanced antifouling, antimicrobial, and hemostatic properties [ J ]. Int. J. Biol. Macromol., 2023, 230, 123121.) polymerized N-halamine, zwitterionic and dopamine onto cotton fabric to prepare a wound dressing having antibacterial and antifouling properties, but both of the above antibacterial and antifouling materials are applied to cotton fabric in terms of antibacterial properties and limited fields of application.
In summary, most of the antibacterial materials developed can meet the requirement of sterilization, but the antibacterial materials are unsatisfactory in terms of the performance of preventing bacterial adhesion. The existing antibacterial antifouling material has better activity on bacteria, but has limited application fields. Moreover, the material only carries out simple polymerization reaction, and the active site of the material is not designed. Therefore, the development of the self-assembled antibacterial nano microsphere containing the amphoteric ion polyhexamethylene diamine has more application prospect.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of self-assembled antibacterial nano-microspheres containing zwitterionic polyhaloamine, which is simple to operate and has excellent antibacterial performance.
In order to solve the problems, the preparation method of the self-assembled antibacterial nano microsphere containing the zwitterionic polyhaloamine comprises the following steps of:
the method comprises the steps of dissolving an N-halamine antibacterial unit precursor and a hydrophobic acrylate monomer into an alcohol solution to prepare a mixed solution A with the concentration of 0.1-0.3 g/mL;
dissolving a zwitterionic monomer and a water-soluble initiator into distilled water to prepare a mixed solution B with the concentration of 0.09-0.17 g/mL; the dosage of the water-soluble initiator is 1.0-10% of the total mass of the monomer;
sequentially adding distilled water and a biocompatible polymer emulsifier into a container with a stirring and heating device at room temperature, and mechanically stirring at 70-80 ℃ for 15-60 min to obtain a mixed solution C of 4.5-10 mg/mL; then, dropwise adding the mixed solution A and the mixed solution B into the mixed solution C at the peristaltic pump speed of 0.1-3.0 mL/min, and stirring at 50-90 ℃ for reaction for 3-4 hr to obtain copolymer emulsion; the volume ratio of the mixed solution A to the mixed solution B to the mixed solution C is 1.0-3.0:1.0:2.0-5.0;
fourthly, the mixed solution A and the water-soluble initiator solution with the concentration of 3.0-8.0 mg/mL are added into the copolymer emulsion in a dropwise manner at the peristaltic pump speed of 0.5-5.0 mL/min; reacting at 60-85 ℃ for 2.5-5 hr to obtain the self-assembled polyhydantoin nano-microsphere containing the zwitterionic; the volume ratio of the mixed solution A to the water-soluble initiator solution is 1.0-3.5;
fifthly, adding a halogenating reagent into the self-assembled polyhexamethylene oxide nano-microsphere containing the zwitterions, stirring at 20-30 ℃ for reaction for 4-10 hr, centrifugally separating and washing for 3-5 times to obtain the self-assembled polyhexamethylene oxide nano-microsphere containing the zwitterions; the ratio of the self-assembled polyhydantoin microsphere containing the zwitterion to the halogenating agent is 3-5 g:10-30 mL.
The N-halamine antibacterial unit precursor in the step (A) is 3-allyl-5, 5-dimethyl hydantoin or 3- (4-vinyl benzyl) -5, 5-dimethyl hydantoin; the hydrophobic acrylate monomer is methyl methacrylate or benzyl methacrylate.
In the step, the mass ratio (g/g) of the N-halamine antibacterial unit precursor to the hydrophobic acrylate monomer is 0.5-1.0:0.8-1.2.
The alcohol solution in the step (A) refers to absolute ethyl alcohol or absolute methyl alcohol.
The zwitterionic monomer in the step is [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide or 3- [ [2- (methacryloyloxy) ethyl ] dimethyl ammonium ] propionate.
And step two and step four, wherein the water-soluble initiator is potassium persulfate or ammonium persulfate.
The biocompatible polymer emulsifier in the step III is one of polyvinylpyrrolidone, polyvinyl alcohol or polyoxyethylene ether, and the dosage of the biocompatible polymer emulsifier is 0.1-0.5% of the volume of distilled water.
The halogenating reagent in the step II is sodium hypochlorite, calcium hypochlorite or potassium hypochlorite with the effective chlorine content of 5.0-15.0%.
The self-assembled antibacterial nano microsphere containing the amphoteric ion, which is prepared by the method, can be applied to inhibiting escherichia coli and staphylococcus aureus.
Compared with the prior art, the invention has the following advantages:
1. in the polymerization reaction process, the mixed solution of alcohol and water is used as a solvent of an N-halamine precursor polymerization system, and the self-assembled antibacterial polyhaloamine nano microsphere containing amphoteric ions is prepared through one-pot two-step emulsion polymerization and halogenation.
2. The self-assembled antibacterial nano microsphere containing the zwitterionic is a novel antibacterial functional material, a compact hydration layer can be formed between the zwitterions in the nano microsphere, bacteria adhesion is prevented, and a sterilization mechanism for defending and attacking bacteria is formed with halogen positive ions released by N-halamine.
3. The self-assembled antibacterial nano microsphere containing the zwitterionic is formed by self-assembling nano microsphere with smaller size, has larger surface area and more active sites, can fully release halogen positive ions, and further plays a role in fast and efficient antibacterial activity.
4. The preparation method is simple to operate, and the prepared self-assembled antibacterial nano microsphere containing the zwitterionic polyhexamethylene diamine shows excellent antibacterial activity, and the antibacterial rate of the self-assembled antibacterial nano microsphere containing the zwitterionic polyhexamethylene diamine on escherichia coli and staphylococcus aureus reaches more than 99%.
Drawings
The following describes the embodiments of the present invention in further detail with reference to the drawings.
FIG. 1 is a Scanning Electron Microscope (SEM) image of self-assembled antimicrobial nano-microspheres containing zwitterionic polyhaloamines obtained in example 1 of the present invention.
FIG. 2 is an elemental distribution surface scanning (EDS) diagram of a self-assembled antimicrobial nano-microsphere of a zwitterionic-containing polyhexamethylene amine obtained in example 1 of the present invention.
FIG. 3 is an infrared spectrum (FT-IR) of a self-assembled antimicrobial nano-microsphere containing a zwitterionic polyhaloamine obtained in example 1 of the present invention.
FIG. 4 is a photograph showing the antibacterial activity of the self-assembled, zwitterionic-containing polyhexamethylene diamine nano-microsphere obtained in example 1 of the present invention against E.coli and Staphylococcus aureus.
Detailed Description
A preparation method of a self-assembled antibacterial nano microsphere containing zwitterionic polyhaloamine comprises the following steps:
the method comprises the steps of dissolving an N-halamine antibacterial unit precursor and a hydrophobic acrylate monomer into an alcohol solution to prepare a mixed solution A with the concentration of 0.1-0.3 g/mL.
Wherein: the N-halamine antibacterial unit precursor is 3-allyl-5, 5-dimethyl hydantoin or 3- (4-vinyl benzyl) -5, 5-dimethyl hydantoin; the hydrophobic acrylate monomer is methyl methacrylate or benzyl methacrylate.
The mass ratio (g/g) of the N-halamine antibacterial unit precursor to the hydrophobic acrylate monomer is 0.5-1.0:0.8-1.2.
The alcohol solution refers to absolute ethanol or absolute methanol.
Dissolving a zwitterionic monomer and a water-soluble initiator into distilled water to prepare a mixed solution B with the concentration of 0.09-0.17 g/mL; the dosage of the water-soluble initiator is 1.0-10% of the total mass of the monomer.
Wherein: the zwitterionic monomer is [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide or 3- [ [2- (methacryloyloxy) ethyl ] dimethyl ammonium ] propionate.
The water-soluble initiator is potassium persulfate or ammonium persulfate.
Sequentially adding distilled water and a biocompatible polymer emulsifier into a container with a stirring and heating device at room temperature, and mechanically stirring at 70-80 ℃ for 15-60 min to fully disperse the materials to obtain a mixed solution C of 4.5-10 mg/mL; and then dropwise adding the mixed solution A and the mixed solution B into the mixed solution C at the peristaltic pump speed of 0.1-3.0 mL/min. The volume ratio (mL/mL) of the mixed solution A, the mixed solution B and the mixed solution C is 1.0-3.0:1.0:2.0-5.0. Stirring and reacting at 50-90 ℃ for 3-4 hr to obtain the copolymer emulsion.
Wherein: the biocompatible polymer emulsifier is one of polyvinylpyrrolidone, polyvinyl alcohol or polyoxyethylene ether, and the dosage of the biocompatible polymer emulsifier is 0.1-0.5% of the volume of distilled water.
And fourthly, mixing the solution A and a water-soluble initiator solution (the water-soluble initiator is the same as the former) with the concentration of 3.0-8.0 mg/mL, and dripping the mixed solution A and the water-soluble initiator solution into the copolymer emulsion at the peristaltic pump speed of 0.5-5.0 mL/min. The volume ratio (mL/mL) of the mixed solution A to the water solution of the water-soluble initiator is 1.0-3.5. Reacting at 60-85 ℃ for 2.5-5 hr to obtain the self-assembled polyhydantoin nano-microsphere containing the zwitterionic.
And fifthly, adding a halogenating reagent into the self-assembled polyhexamethylene oxide nano-microsphere containing the zwitterions, stirring at 20-30 ℃ for reaction for 4-10 hr, centrifugally separating and washing for 3-5 times to obtain the self-assembled polyhexamethylene oxide nano-microsphere containing the zwitterions.
Wherein: the halogenating reagent is one of sodium hypochlorite, calcium hypochlorite or potassium hypochlorite with the effective chlorine content of 5.0-15.0%.
The ratio of the self-assembled nano microsphere containing the zwitterionic to the halogenating agent is 3-5 g:10-30 mL.
The self-assembled antibacterial nano microsphere containing the amphoteric ion, which is prepared by the method, can be applied to inhibiting escherichia coli and staphylococcus aureus.
Example 1 a preparation method of a self-assembled antimicrobial nano microsphere of polyhaloamine containing zwitterion comprises the following steps:
dissolving 0.6 g of 3-allyl-5, 5-dimethyl hydantoin and 1.2 g of methyl methacrylate into 15 mL of absolute methanol to prepare 0.12 g/mL of mixed solution A;
dissolving 0.7 g of 3- [ [2- (methacryloyloxy) ethyl ] dimethyl ammonium ] propionate and 0.075 g of ammonium persulfate into 5.0 mL of distilled water to prepare 0.17 g/mL of mixed solution B;
sequentially adding 25 mL distilled water and 0.12 g polyvinyl alcohol into a container with a stirring and heating device at room temperature, and mechanically stirring at 70 ℃ for 30 min to obtain 4.8 mg/mL mixed solution C; then mixing the 15 mL mixed solution A and the 5 mL mixed solution B, and dripping the mixed solution A and the mixed solution B into the mixed solution C of 25 mL at the peristaltic pump speed of 1.0 mL/min; stirring and reacting at 75 ℃ for 3.5. 3.5 hr to obtain copolymer emulsion;
fourthly, mixing the mixed solution A of 5 mL and the water-soluble initiator solution with the concentration of 10 mL of 5.4 mg/mL, and dripping the mixed solution A and the water-soluble initiator solution into the copolymer emulsion at the peristaltic pump speed of 2.0 mL/min; reacting at 75 ℃ with 4 hr to obtain 3.6 g self-assembled nano-microsphere containing zwitterionic;
and fifthly, adding 25-mL mass percent of 12% potassium hypochlorite into the self-assembled polyhydantoin nano-microsphere containing the zwitterion, stirring at 25 ℃ for reaction of 8-hr, centrifugally separating and washing for 4 times to obtain the self-assembled polyhaloamine antibacterial nano-microsphere containing the zwitterion.
[ microcosmic topography ]
The microscopic morphology Scanning Electron Microscope (SEM) photograph of the self-assembled antimicrobial nano microsphere containing the zwitterionic polyhaloamine prepared by the invention is shown in figure 1. As can be seen from SEM pictures, the self-assembled antibacterial nano microsphere containing the zwitterionic polyhaloamine prepared by the invention has nano size (300-400 nm), and the microsphere is formed by self-assembling a plurality of microspheres with smaller sizes. This shows that the self-assembled antibacterial nano microsphere containing the zwitterionic polyhaloamine prepared by the invention has larger surface area, has more active sites and is more beneficial to release oxidative chloridion to kill bacteria. The zwitterionic monomer in the microsphere can form a compact hydration layer to prevent the adhesion of bacteria, and form an antibacterial mechanism with synergistic sterilization and defense. In conclusion, the self-assembled antibacterial nano-microsphere containing the zwitterionic polyhaloamine has been successfully prepared.
[ EDS elemental analysis ]
The distribution of each element in the selected area of the prepared self-assembled antimicrobial nano-microsphere containing the zwitterionic polyhaloamine is analyzed by EDS, and the result is shown in figure 2. It is evident that the nanospheres mainly contain C, O, N, S, cl, wherein S is derived from a zwitterionic monomer and wherein Cl is derived from N-halamine. Moreover, the elements can be uniformly distributed in the selected area, which indicates that the elements in the self-assembled antibacterial nano-microsphere containing the amphoteric ion polyhexamethylene diamine are uniformly distributed, and also indicates that the self-assembled antibacterial nano-microsphere containing the amphoteric ion polyhexamethylene diamine has been successfully prepared.
[ Infrared Spectrometry (FT-IR) analysis ]
FT-IR analysis was performed on the prepared self-assembled antimicrobial nano-microspheres containing zwitterionic polyhexamethylene amine, as shown in FIG. 3. At 3345 cm -1 The nearby absorption peak is attributed to the telescopic vibration absorption peak of-N-H on the hydantoin ring in N-halamine; at 2960 cm -1 And 2935 cm -1 The absorption peaks occurring nearby are attributed to saturated C-H and-CH on the main chain 2 Is stretched out and stretched out; at 1775 and 1775 cm -1 The nearby absorption peak is attributed to the characteristic absorption peak of hydantoin cyclic amide group (N-c=o) in N-halamine; at 1715 cm -1 The absorption peak at this point is assigned to the stretching vibration peak of the ester carbonyl c=o. 1270 cm -1 The nearby absorption peak is assigned to the C-N stretching vibration peak. 1180 cm -1 And 1040 cm -1 The absorption peak occurring nearby is attributed to-SO 3 - Is characterized by an absorption peak. In conclusion, the self-assembled antibacterial nano-microsphere containing the zwitterionic polyhaloamine has been successfully prepared.
[ antibacterial Properties ]
Gram negative bacteria (e.coli,E.coli) And gram positive bacteria (staphylococcus aureus,S.aureus) As bacterial strain, the antibacterial performance of the self-assembled antibacterial nano microsphere containing the polyhaloamine with amphoteric ions is researched from a control groupE.coliAndS.aureus) In the medium containing the bacteria, the formation of a large number of bacterial colonies is observedE.coli+ antimicrobial nanomicrospheresS.aureusThe bacterial colony is hardly observed in the sample group of the +antibacterial nanoball, so that the self-assembled antibacterial nanoball containing the zwitterionic polyhaloamine can kill and inhibit the growth of bacteria well, mainly because the sterilization of the N-haloamine and the antifouling function of the zwitterionic unit are cooperatedIs used.
Example 2 a method for preparing self-assembled antimicrobial nano-microspheres of polyhalide containing amphoteric ions, comprising the following steps:
dissolving 0.8 g of 3- (4-vinylbenzyl) -5, 5-dimethyl hydantoin and 1.4 g of methyl methacrylate into 10 mL of absolute ethyl alcohol to prepare 0.22 g/mL of mixed solution A;
dissolving 1.1 g [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide and 0.165 g potassium persulfate into 8.0 mL distilled water to prepare 0.16 g/mL mixed solution B;
sequentially adding 20 mL distilled water and 0.16 g polyvinylpyrrolidone into a container with a stirring and heating device at room temperature, and mechanically stirring at 75 ℃ for 30 min to obtain 8.0 mg/mL mixed solution C; then mixing the 10 mL mixed solution A and the 8 mL mixed solution B, and dripping the mixed solution A and the mixed solution B into the mixed solution C of 20 mL at the peristaltic pump speed of 1.5 mL/min; stirring and reacting at 80 ℃ for 3 hr to obtain copolymer emulsion;
mixing 10. 10 mL of the mixed solution A and 12. 12 mL of water-soluble initiator solution with the concentration of 4.5 mg/mL, and dripping the mixed solution A and the water-soluble initiator solution into the copolymer emulsion at the peristaltic pump speed of 1.0 mL/min; reacting at 80 ℃ for 3 hr to obtain 5.0 g self-assembled nano-microsphere containing zwitterionic;
and fifthly, adding 30-mL mass percent of calcium hypochlorite into the self-assembled polyhydantoin nano-microsphere containing the zwitterion, stirring at 30 ℃ for reaction of 6 hr, centrifugally separating and washing for 5 times to obtain the self-assembled polyhaloamine antibacterial nano-microsphere containing the zwitterion.
Example 3 a method for preparing self-assembled antimicrobial nano-microspheres of polyhaloamine containing zwitterions, comprising the steps of:
dissolving 0.65 g of 3- (4-vinylbenzyl) -5, 5-dimethylhydantoin and 0.94 g of benzyl methacrylate into 13 mL of absolute ethyl alcohol to prepare 0.12 g/mL of mixed solution A;
dissolving 0.72 g of [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide and 0.046 g of potassium persulfate into 6 mL of distilled water to prepare 0.13 g/mL of mixed solution B;
sequentially adding 24. 24 mL distilled water and 0.20. 0.20 g polyoxyethylene ether into a container with a stirring and heating device at room temperature, and mechanically stirring at 70 ℃ for 20 min to obtain 8.0. 8.0 mg/mL of mixed solution C; then mixing the 13 mL mixed solution A and the 6 mL mixed solution B, and dripping the mixed solution A and the mixed solution B into the mixed solution C of 24 mL at the peristaltic pump speed of 2.5 mL/min; stirring and reacting at 75 ℃ for 4 hr to obtain copolymer emulsion;
fourthly, mixing the mixed solution A of 7 mL and the water-soluble initiator solution of 10 mL with the concentration of 3.2 mg/mL, and dripping the mixed solution A and the water-soluble initiator solution into the copolymer emulsion at the peristaltic pump speed of 4.0 mL/min; reacting at 80 ℃ for 4 hr to obtain 3.4 g self-assembled nano-microsphere containing zwitterionic;
and fifthly, adding 30-mL mass percent of sodium hypochlorite into the self-assembled polyhydantoin nano-microsphere containing the zwitterions, stirring at 20 ℃ for reaction of 10 hr, centrifugally separating and washing for 5 times to obtain the self-assembled polyhaloamine antibacterial nano-microsphere containing the zwitterions.
Example 4 a method for preparing self-assembled antimicrobial nano-microspheres of polyhaloamine containing zwitterions, comprising the steps of:
the preparation method comprises the steps that 3- (4-vinylbenzyl) -5, 5-dimethyl hydantoin and benzyl methacrylate of 1.10 g of 0.75-g are dissolved in absolute ethyl alcohol of 10 mL to prepare a mixed solution A of 0.19 g/mL;
2- [ [2- (methacryloyloxy) ethyl ] dimethyl ammonium ] propionate of 0.80 g and ammonium persulfate of 0.106 g are dissolved in distilled water of 10 mL to prepare a mixed solution B of 0.09 g/mL;
sequentially adding 20 mL distilled water and 0.20 g polyvinylpyrrolidone into a container with a stirring and heating device at room temperature, and mechanically stirring at 60 ℃ for 40 min to obtain 10 mg/mL mixed solution C; then mixing the mixed solution A of 10 mL and the mixed solution B of 10 mL, and dripping the mixed solution A and the mixed solution B into the mixed solution C of 20 mL at the peristaltic pump speed of 2.5 mL/min; stirring and reacting at 80 ℃ for 3 hr to obtain copolymer emulsion;
fourthly, mixing the mixed solution A of 10 mL and the water-soluble initiator solution of 10 mL with the concentration of 7.4 mg/mL, and dripping the mixed solution A and the water-soluble initiator solution into the copolymer emulsion at the peristaltic pump speed of 5.0 mL/min; reacting at 80 ℃ for 3 hr to obtain 3.9 g self-assembled nano-microsphere containing zwitterionic;
and fifthly, adding 20-mL mass percent of calcium hypochlorite with the mass percent of 10% into the self-assembled polyhydantoin nano-microsphere containing the zwitterions, stirring at 25 ℃ for reaction of 8-hr, centrifugally separating and washing for 3 times to obtain the self-assembled polyhaloamine antibacterial nano-microsphere containing the zwitterions.
Claims (9)
1. A preparation method of a self-assembled antibacterial nano microsphere containing zwitterionic polyhaloamine comprises the following steps:
the method comprises the steps of dissolving an N-halamine antibacterial unit precursor and a hydrophobic acrylate monomer into an alcohol solution to prepare a mixed solution A with the concentration of 0.1-0.3 g/mL;
dissolving a zwitterionic monomer and a water-soluble initiator into distilled water to prepare a mixed solution B with the concentration of 0.09-0.17 g/mL; the dosage of the water-soluble initiator is 1.0-10% of the total mass of the monomer;
sequentially adding distilled water and a biocompatible polymer emulsifier into a container with a stirring and heating device at room temperature, and mechanically stirring at 70-80 ℃ for 15-60 min to obtain a mixed solution C of 4.5-10 mg/mL; then dripping the mixed solution A and the mixed solution B into the mixed solution C at the peristaltic pump speed of 0.1-3.0 mL/min; stirring and reacting at 50-90 ℃ for 3-4 hr to obtain copolymer emulsion; the volume ratio of the mixed solution A to the mixed solution B to the mixed solution C is 1.0-3.0:1.0:2.0-5.0;
fourthly, the mixed solution A and the water-soluble initiator solution with the concentration of 3.0-8.0 mg/mL are added into the copolymer emulsion in a dropwise manner at the peristaltic pump speed of 0.5-5.0 mL/min; reacting at 60-85 ℃ for 2.5-5 hr to obtain the self-assembled polyhydantoin nano-microsphere containing the zwitterionic; the volume ratio of the mixed solution A to the water-soluble initiator solution is 1.0-3.5;
fifthly, adding a halogenating reagent into the self-assembled polyhexamethylene oxide nano-microsphere containing the zwitterions, stirring at 20-30 ℃ for reaction for 4-10 hr, centrifugally separating and washing for 3-5 times to obtain the self-assembled polyhexamethylene oxide nano-microsphere containing the zwitterions; the ratio of the self-assembled polyhydantoin microsphere containing the zwitterion to the halogenating agent is 3-5 g:10-30 mL.
2. The method for preparing the self-assembled antibacterial nano-microsphere containing the zwitterionic polyhaloamine according to claim 1, which is characterized in that: the N-halamine antibacterial unit precursor in the step (A) is 3-allyl-5, 5-dimethyl hydantoin or 3- (4-vinyl benzyl) -5, 5-dimethyl hydantoin; the hydrophobic acrylate monomer is methyl methacrylate or benzyl methacrylate.
3. The method for preparing the self-assembled antibacterial nano-microsphere containing the zwitterionic polyhaloamine according to claim 1, which is characterized in that: in the step, the mass ratio of the N-halamine antibacterial unit precursor to the hydrophobic acrylate monomer is 0.5-1.0 g:0.8-1.2 g.
4. The method for preparing the self-assembled antibacterial nano-microsphere containing the zwitterionic polyhaloamine according to claim 1, which is characterized in that: the alcohol solution in the step (A) refers to absolute ethyl alcohol or absolute methyl alcohol.
5. The method for preparing the self-assembled antibacterial nano-microsphere containing the zwitterionic polyhaloamine according to claim 1, which is characterized in that: the zwitterionic monomer in the step is [2- (methacryloyloxy) ethyl ] dimethyl- (3-sulfopropyl) ammonium hydroxide or 3- [ [2- (methacryloyloxy) ethyl ] dimethyl ammonium ] propionate.
6. The method for preparing the self-assembled antibacterial nano-microsphere containing the zwitterionic polyhaloamine according to claim 1, which is characterized in that: and step two and step four, wherein the water-soluble initiator is potassium persulfate or ammonium persulfate.
7. The method for preparing the self-assembled antibacterial nano-microsphere containing the zwitterionic polyhaloamine according to claim 1, which is characterized in that: the biocompatible polymer emulsifier in the step III is one of polyvinylpyrrolidone, polyvinyl alcohol or polyoxyethylene ether, and the dosage of the biocompatible polymer emulsifier is 0.1-0.5% of the volume of distilled water.
8. The method for preparing the self-assembled antibacterial nano-microsphere containing the zwitterionic polyhaloamine according to claim 1, which is characterized in that: the halogenating reagent in the step II is sodium hypochlorite, calcium hypochlorite or potassium hypochlorite with the effective chlorine content of 5.0-15.0%.
9. The application of the self-assembled antibacterial nano microsphere containing amphoteric ion, which is prepared by the method of one of claims 1 to 8, in inhibiting escherichia coli and staphylococcus aureus.
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| CN115160485A (en) * | 2022-08-15 | 2022-10-11 | 西北师范大学 | Preparation method of double-activity-center thiazole acrylate copolymer nano-microspheres |
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| CN108378039A (en) * | 2018-04-18 | 2018-08-10 | 大连理工大学 | Betaine type chloramines antiseptic and its synthetic method |
| CN115160485A (en) * | 2022-08-15 | 2022-10-11 | 西北师范大学 | Preparation method of double-activity-center thiazole acrylate copolymer nano-microspheres |
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