CN109077062B - Preparation method of modified MMT/ZnO/GQDs nano composite antibacterial agent - Google Patents
Preparation method of modified MMT/ZnO/GQDs nano composite antibacterial agent Download PDFInfo
- Publication number
- CN109077062B CN109077062B CN201810900240.5A CN201810900240A CN109077062B CN 109077062 B CN109077062 B CN 109077062B CN 201810900240 A CN201810900240 A CN 201810900240A CN 109077062 B CN109077062 B CN 109077062B
- Authority
- CN
- China
- Prior art keywords
- antibacterial agent
- gqds
- solution
- zno
- modified
- 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.)
- Active
Links
- 239000003242 anti bacterial agent Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 35
- 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 claims abstract description 64
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 47
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000003756 stirring Methods 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- 229910052901 montmorillonite Inorganic materials 0.000 claims abstract description 20
- 238000001816 cooling Methods 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 239000008367 deionised water Substances 0.000 claims abstract description 15
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 15
- 239000003607 modifier Substances 0.000 claims abstract description 10
- 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 abstract description 8
- 239000006185 dispersion Substances 0.000 claims abstract description 8
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 8
- 239000011734 sodium Substances 0.000 claims abstract description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 239000011701 zinc Substances 0.000 claims abstract description 7
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 64
- 238000000034 method Methods 0.000 claims description 18
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- PXRKCOCTEMYUEG-UHFFFAOYSA-N 5-aminoisoindole-1,3-dione Chemical compound NC1=CC=C2C(=O)NC(=O)C2=C1 PXRKCOCTEMYUEG-UHFFFAOYSA-N 0.000 claims description 7
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 238000002390 rotary evaporation Methods 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 3
- 238000000502 dialysis Methods 0.000 claims description 3
- 238000003828 vacuum filtration Methods 0.000 claims description 3
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical group OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 claims description 3
- 206010059866 Drug resistance Diseases 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000001704 evaporation Methods 0.000 abstract 1
- 238000000643 oven drying Methods 0.000 abstract 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 49
- 239000011787 zinc oxide Substances 0.000 description 24
- 239000002131 composite material Substances 0.000 description 20
- 230000003385 bacteriostatic effect Effects 0.000 description 11
- -1 modified montmorillonite (modified MMT Chemical class 0.000 description 8
- 238000000967 suction filtration Methods 0.000 description 8
- 230000000844 anti-bacterial effect Effects 0.000 description 7
- 241000894006 Bacteria Species 0.000 description 5
- 241000588724 Escherichia coli Species 0.000 description 5
- 230000010355 oscillation Effects 0.000 description 5
- 239000000843 powder Substances 0.000 description 4
- 239000002096 quantum dot Substances 0.000 description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000004246 zinc acetate Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- 208000035143 Bacterial infection Diseases 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- CQBLUJRVOKGWCF-UHFFFAOYSA-N [O].[AlH3] Chemical compound [O].[AlH3] CQBLUJRVOKGWCF-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 208000022362 bacterial infectious disease Diseases 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 244000053095 fungal pathogen Species 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- General Health & Medical Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- General Physics & Mathematics (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dentistry (AREA)
- Organic Chemistry (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Composite Materials (AREA)
- Biophysics (AREA)
- Manufacturing & Machinery (AREA)
- Optics & Photonics (AREA)
- Toxicology (AREA)
- Inorganic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention relates to a preparation method of a modified MMT/ZnO/GQDs nano composite antibacterial agent, which comprises the steps of dispersing sodium-based montmorillonite in deionized water, and stirring at a high speed; dispersing modifier in ionized water, adding into sodium montmorillonite dispersion liquid after completely dissolving, stirring at high speed, standing, cooling, filtering, oven drying, and grinding to obtain modified montmorillonite (modified MMT); heating citric acid to obtain orange liquid; adjusting pH with sodium hydroxide water solution, dialyzing, and rotary evaporating to obtain GQDs solution; adding an alkali source into ethanol, and magnetically stirring to obtain a solution A; adding a zinc source into an ethanol solution, magnetically stirring, adding the obtained GQDs, and carrying out ultrasonic treatment; adding modified MMT, and then carrying out water bath reaction; and finally, adding the solution A, reacting for 20min, heating for reaction, cooling, washing and centrifuging a product after the reaction is finished, thus obtaining the nano composite antibacterial agent. The prepared nano composite antibacterial agent has the advantages of safety, environmental protection, strong drug resistance and the like.
Description
Technical Field
The invention relates to research on a novel efficient antibacterial agent, in particular to a preparation method of a modified MMT/ZnO/GQDs nano composite antibacterial agent.
Background
In recent years, due to unreasonable resource exploitation, the resources are deficient, the natural environment is damaged, and diseases caused by various pathogenic bacteria, fungi and viruses threaten the health of human beings. The development of various antibacterial agents has been a focus of research, and inorganic antibacterial materials are favored because of their excellent safety, durability, chemical stability, and low cost.
Montmorillonite (MMT), also known as montmorillonite and microcrystalline kaolinite, is a natural mineral of silicate, is a main mineral component of bentonite ore, and has the advantages of rich source, low price and the like. Montmorillonite is a nanomaterial with a layered structure of type 2:1, which comprises two silicon-oxygen tetrahedrons and one aluminum-oxygen octahedron, and the MMT with the layered structure has large specific surface area and high absorptivity, and can adsorb bacteria, thereby killing the bacteria. In addition, the MMT structural unit has a large amount of exchangeable cations with large radius, and the cations with antibacterial activity can be replaced with the exchangeable cations to prepare the antibacterial agent taking montmorillonite as a carrier. However, the antimicrobial activity of the modified MMT itself is not ideal. Relevant researches prove that the catalyst particles are embedded between MMT layers, and the negative charges carried between the MMT layers can promote the transfer of holes through the attraction of electrons, so that the separation rate of photo-generated charge carriers can be obviously improved, and the antibacterial property of the catalyst particles is further improved.
Disclosure of Invention
The invention aims to provide a preparation method of a novel high-efficiency modified MMT/ZnO/GQDs nano composite antibacterial agent, which solves the problem that various bacterial infections, especially the generation of some drug-resistant bacteria, threaten human health.
The technical scheme adopted by the invention is as follows:
a preparation method of a modified MMT/ZnO/GQDs nano composite antibacterial agent comprises the following steps:
the method comprises the following steps: preparation of modified montmorillonite (modified MMT):
weighing 5-20g of sodium-based montmorillonite, dispersing in 200ml of deionized water, and stirring at a high speed of 80 ℃ for 30 min; dispersing 2-14 g of modifier in 50ml of deionized water, adding into the sodium-based montmorillonite dispersion liquid after the modifier is completely dissolved, stirring at a high speed of 80 ℃ for 2h, standing for 2h, cooling, repeatedly filtering with a vacuum filtration device, drying, and grinding to obtain modified montmorillonite (modified MMT);
step two: preparation of GQDs solution:
putting 1-10g of Citric Acid (CA) into a beaker, and heating to obtain an orange liquid; then, adjusting the pH to be 7.0 by using a sodium hydroxide aqueous solution, dialyzing and carrying out rotary evaporation to obtain a GQDs solution;
step three: the preparation of the modified MMT/ZnO/GQDs nano composite antibacterial agent comprises the following steps:
adding 0.2-0.9g of alkali source into 50ml of ethanol solution, and magnetically stirring for 30min to obtain solution A; adding 0.3-2g of zinc source into 100ml of ethanol solution, magnetically stirring for 30min, adding the GQDs obtained in the second step, and carrying out ultrasonic treatment for 10 min; adding modified MMT, transferring into a three-neck flask, and performing water bath reaction at 60 ℃ for 30 min; finally, adding the solution A, reacting for 20min, heating for reaction, cooling, washing and centrifuging the product after the reaction is finished, thus obtaining the modified MMT/ZnO/GQDs nano composite antibacterial agent;
in the first step, the drying temperature and time are respectively 100 ℃ and 24 hours.
The modifier is cetyl trimethyl ammonium bromide or octadecyl trimethyl ammonium chloride.
In the second step, the heating reaction temperature and time are respectively 200 ℃ and 30 min.
In the second step, the dialysis time is 24 h.
The alkali source is potassium hydroxide, sodium hydroxide or lithium hydroxide.
The zinc source is zinc acetate dihydrate or zinc nitrate hexahydrate.
In the third step, the heating reaction is carried out at the temperature of 80-100 ℃ for 3-7 h.
In the third step, the dosage of the modified MMT is 2-20 wt%.
The invention has the following advantages:
the invention takes the modified MMT as a carrier, takes the novel photoelectric functional material ZnO/GQDs composite quantum dots as a main antibacterial component, adsorbs bacteria to the surface of the modified MMT by utilizing the huge specific surface area and high absorptivity of the modified MMT, then kills the bacteria by utilizing the photocatalysis of the ZnO/GQDs composite quantum dots, and finally designs and prepares the novel nano composite antibacterial agent with good biocompatibility and high antibacterial activity. Compared with the traditional antibacterial agent, the nano-composite antibacterial agent prepared by the invention has the advantages of safety, environmental protection, strong drug resistance and the like, and the minimum inhibitory concentration of the nano-composite antibacterial agent on escherichia coli prepared by the invention can reach 2 mg/ml.
Drawings
FIG. 1 is an SEM photograph of a modified MMT/ZnO/GQD composite prepared according to the present invention;
FIG. 2 shows the antibacterial effect of the modified MMT/ZnO/GQD composite material prepared by the invention on Escherichia coli;
FIG. 3 shows the result of the minimum inhibitory concentration test of the modified MMT/ZnO/GQD composite material prepared by the invention on Escherichia coli.
Detailed Description
The present invention will be described in detail with reference to specific embodiments.
A preparation method of a modified MMT/ZnO/GQDs nano composite antibacterial agent comprises the following steps:
the method comprises the following steps: preparation of modified montmorillonite (modified MMT):
weighing 5-20g of sodium-based montmorillonite, dispersing in 200ml of deionized water, and stirring at a high speed of 80 ℃ for 30 min; dispersing 2-14 g of modifier in 50ml of deionized water, adding into the sodium-based montmorillonite dispersion liquid after the modifier is completely dissolved, stirring at a high speed of 80 ℃ for 2h, standing for 2h, cooling, repeatedly filtering with a vacuum filtration device, drying, and grinding to obtain modified montmorillonite (modified MMT);
step two: preparation of GQDs solution:
putting 1-10g of Citric Acid (CA) into a 50ml beaker, and heating and reacting to obtain an orange liquid; then, adjusting the pH to be =7.0 by using a sodium hydroxide aqueous solution, dialyzing for 24h, and performing rotary evaporation to obtain a GQDs solution;
step three: the preparation of the modified MMT/ZnO/GQDs nano composite antibacterial agent comprises the following steps:
adding 0.2-0.9g of alkali source into 50ml of ethanol solution, and magnetically stirring for 30min to obtain solution A; adding 0.3-2g of zinc source into 100ml of ethanol solution, magnetically stirring for 30min, adding the GQDs obtained in the second step, and carrying out ultrasonic treatment for 10 min; adding modified MMT, transferring into a three-neck flask, and reacting in water bath at 60 ℃ for 30 min; finally adding the solution A, reacting for 20min, heating to 80-100 ℃, reacting for 3-7h, cooling, washing and centrifuging to obtain the modified MMT/ZnO/GQDs nano composite antibacterial agent; and (3) determining the minimum bacteriostatic concentration of the composite antibacterial agent by using a microplate reader, and calculating the bacteriostatic rate of the composite antibacterial agent by using an oscillation method and a flat plate counting method.
In the first step, the drying temperature and time are respectively 100 ℃ and 24 hours.
The modifier is cetyl trimethyl ammonium bromide or octadecyl trimethyl ammonium chloride.
In the second step, the reaction temperature and the reaction time of the heating reaction are respectively 200 ℃ and 30 min.
In the second step, the dialysis time is 24 h.
The alkali source is potassium hydroxide, sodium hydroxide or lithium hydroxide.
The zinc source is zinc acetate dihydrate or zinc nitrate hexahydrate.
In the third step, the heating reaction is carried out at the temperature of 80-100 ℃ for 3-7 h.
In the third step, the dosage of the modified MMT is 2-20 wt%.
Example 1:
the method comprises the following steps: preparation of modified montmorillonite (modified MMT):
weighing 8.5g of sodium montmorillonite, dispersing in 200ml of deionized water, and stirring at a high speed of 80 ℃ for 30 min; dispersing 9.0g of octadecyl trimethyl ammonium chloride in 50ml of deionized water, adding the obtained solution into sodium montmorillonite dispersion liquid after the solution is completely dissolved, stirring the solution at a high speed of 80 ℃ for 2 hours, standing the solution for 2 hours, cooling the solution, repeatedly performing suction filtration on the solution by using a vacuum suction filtration device, drying the solution at 100 ℃ for 24 hours, and grinding the solution into fine powder to obtain modified montmorillonite;
step two: preparation of GQDs solution:
putting 4g of Citric Acid (CA) into a 50ml beaker, heating to 200 ℃ and reacting for 30min to obtain orange liquid; then, adjusting the pH to be =7.0 by using a sodium hydroxide aqueous solution, dialyzing for 24h, and performing rotary evaporation to obtain a GQDs solution;
step three: the preparation of the modified MMT/ZnO/GQDs composite nano-composite antibacterial agent comprises the following steps:
adding 0.65g of sodium hydroxide into 50ml of ethanol solution, and magnetically stirring for 30min to obtain solution A; adding 0.90g of zinc acetate into 100ml of ethanol solution, magnetically stirring for 30min, adding the GQDs obtained in the second step, carrying out ultrasonic treatment for 10min, adding 8% of modified MMT, pouring the solution into a three-neck flask, and carrying out water bath reaction at 60 ℃ for 30 min; adding the solution A to react for 20min, heating to 95 ℃ to react for 5h, cooling to room temperature after the reaction is finished, and repeatedly and alternately centrifuging for 3 times by using alcohol and water to obtain the modified MMT/ZnO/GQDs nano composite antibacterial agent; and (3) determining the minimum bacteriostatic concentration of the composite antibacterial agent by using a microplate reader, and calculating the bacteriostatic rate of the composite antibacterial agent by using an oscillation method and a flat plate counting method.
Example 2:
the method comprises the following steps: preparation of modified montmorillonite (modified MMT):
weighing 12.0g of sodium montmorillonite, dispersing in 200ml of deionized water, and stirring at a high speed of 80 ℃ for 30 min; dispersing 8.6g of hexadecyl trimethyl ammonium bromide in 50ml of deionized water, adding the obtained solution into sodium-based montmorillonite dispersion liquid after the solution is completely dissolved, stirring the obtained solution at a high speed of 80 ℃ for 2 hours, standing the obtained product for 2 hours, cooling the obtained product, repeatedly performing suction filtration on the obtained product by using a vacuum suction filtration device, drying the obtained product at 100 ℃ for 24 hours, and grinding the obtained product into fine powder to obtain modified montmorillonite;
step two: preparation of GQDs solution:
taking 2g of Citric Acid (CA) and putting the citric acid into a 50ml beaker, heating the citric acid to 200 ℃ and reacting for 30min to obtain orange liquid; then, adjusting the pH to be =7.0 by using a sodium hydroxide aqueous solution, dialyzing for 24h, and performing rotary evaporation to obtain a GQDs solution;
step three: the preparation of the modified MMT/ZnO/GQDs composite nano-composite antibacterial agent comprises the following steps:
adding 0.75g of sodium hydroxide into 50ml of ethanol solution, and magnetically stirring for 30min to obtain solution A; adding 1.05g of zinc nitrate into 100ml of ethanol solution, magnetically stirring for 30min, adding the GQDs obtained in the second step, carrying out ultrasonic treatment for 10min, adding 12% of modified MMT, pouring the solution into a three-neck flask, and carrying out water bath reaction at 60 ℃ for 30 min; adding the solution A to react for 20min, heating to 100 ℃ to react for 4h, cooling to room temperature after the reaction is finished, and repeatedly and alternately centrifuging for 3 times by using alcohol and water to obtain the modified MMT/ZnO/GQDs nano composite antibacterial agent; and (3) determining the minimum bacteriostatic concentration of the composite antibacterial agent by using a microplate reader, and calculating the bacteriostatic rate of the composite antibacterial agent by using an oscillation method and a flat plate counting method.
Example 3:
the method comprises the following steps: preparation of modified montmorillonite (modified MMT):
weighing 10g of sodium montmorillonite, dispersing in 200ml of deionized water, and stirring at a high speed of 80 ℃ for 30 min; dispersing 6.56g of octadecyl trimethyl ammonium chloride in 50ml of deionized water, adding the obtained solution into sodium montmorillonite dispersion liquid after the octadecyl trimethyl ammonium chloride is completely dissolved, stirring the obtained solution at a high speed of 80 ℃ for 2 hours, standing the obtained solution for 2 hours, cooling the obtained product, repeatedly performing suction filtration on the cooled product by using a vacuum suction filtration device, drying the cooled product at 100 ℃ for 24 hours, and grinding the dried product into fine powder to obtain modified montmorillonite;
step two: preparation of GQDs solution:
putting 4g of Citric Acid (CA) into a 50ml beaker, heating to 200 ℃ and reacting for 30min to obtain orange liquid; then, adjusting the pH to be =7.0 by using a sodium hydroxide aqueous solution, dialyzing for 24h, and performing rotary evaporation to obtain a GQDs solution;
step three: the preparation of the modified MMT/ZnO/GQDs composite nano-composite antibacterial agent comprises the following steps: adding 0.49 g of potassium hydroxide into 50ml of ethanol solution, and magnetically stirring for 30min to obtain solution A; adding 0.98g of zinc acetate into 100ml of ethanol solution, magnetically stirring for 30min, adding GQDs obtained in the second step, carrying out ultrasonic treatment for 10min, adding 12% of modified MMT, pouring the solution into a three-neck flask, and carrying out water bath reaction at 60 ℃ for 30 min; adding the solution A to react for 20min, heating to 95 ℃ to react for 5h, cooling to room temperature after the reaction is finished, and repeatedly and alternately centrifuging for 3 times by using alcohol and water to obtain the modified MMT/ZnO/GQDs nano composite antibacterial agent; and (3) determining the minimum bacteriostatic concentration of the composite antibacterial agent by using a microplate reader, and calculating the bacteriostatic rate of the composite antibacterial agent by using an oscillation method and a flat plate counting method.
Example 4:
the method comprises the following steps: preparation of modified montmorillonite (modified MMT):
weighing 12g of sodium montmorillonite, dispersing in 200ml of deionized water, and stirring at a high speed of 80 ℃ for 30 min; dispersing 14g of octadecyl trimethyl ammonium chloride in 50ml of deionized water, adding the obtained solution into sodium montmorillonite dispersion liquid after the ammonium chloride is completely dissolved, stirring the obtained solution at a high speed of 80 ℃ for 2 hours, standing the obtained solution for 2 hours, cooling the obtained product, repeatedly performing suction filtration on the cooled product by using a vacuum suction filtration device, drying the cooled product at 100 ℃ for 24 hours, and grinding the dried product into fine powder to obtain modified montmorillonite;
step two: preparation of GQDs solution:
taking 6g of Citric Acid (CA) and putting the citric acid into a 50ml beaker, heating the beaker to 200 ℃ and reacting the beaker for 30min to obtain orange liquid; then, adjusting the pH to be =7.0 by using a sodium hydroxide aqueous solution, dialyzing for 24h, and performing rotary evaporation to obtain a GQDs solution;
step three: the preparation of the modified MMT/ZnO/GQDs composite nano-composite antibacterial agent comprises the following steps: adding 0.72g of lithium hydroxide into 50ml of ethanol solution, and magnetically stirring for 30min to obtain solution A; adding 1.2g of zinc acetate into 100ml of ethanol solution, magnetically stirring for 30min, adding GQDs obtained in the second step, carrying out ultrasonic treatment for 10min, adding 14% of modified MMT, pouring the solution into a three-neck flask, and carrying out water bath reaction at 60 ℃ for 30 min; adding the solution A to react for 20min, heating to 95 ℃ to react for 5h, cooling to room temperature after the reaction is finished, and repeatedly and alternately centrifuging for 3 times by using alcohol and water to obtain the modified MMT/ZnO/GQDs nano composite antibacterial agent; and (3) determining the minimum bacteriostatic concentration of the composite antibacterial agent by using a microplate reader, and calculating the bacteriostatic rate of the composite antibacterial agent by using an oscillation method and a flat plate counting method.
According to the invention, montmorillonite (MMT) is used as a carrier of the zinc oxide (ZnO)/graphene composite quantum dot, so that the agglomeration of nanoparticles is effectively prevented, and the recombination of photoproduction electrons and holes on the surface of the ZnO quantum dot is inhibited, thereby preparing the MMT/ZnO/GQD nano composite antibacterial agent. As can be seen from FIGS. 2 and 3, the prepared nano antibacterial agent has a minimum inhibitory concentration of 2.0mg/ml to Escherichia coli, a bacteriostatic rate of 94.36% to Escherichia coli, and excellent antibacterial performance.
The invention is not limited to the examples, and any equivalent changes to the technical solution of the invention by a person skilled in the art after reading the description of the invention are covered by the claims of the invention.
Claims (8)
1. A preparation method of a modified MMT/ZnO/GQDs nano composite antibacterial agent is characterized by comprising the following steps:
the method comprises the following steps:
the method comprises the following steps: preparation of modified montmorillonite (modified MMT):
weighing 5-20g of sodium-based montmorillonite, dispersing in 200ml of deionized water, and stirring at a high speed of 80 ℃ for 30 min; dispersing 2-14 g of modifier in 50ml of deionized water, adding into the sodium-based montmorillonite dispersion liquid after the modifier is completely dissolved, stirring at a high speed of 80 ℃ for 2h, standing for 2h, cooling, repeatedly filtering with a vacuum filtration device, drying, and grinding to obtain modified montmorillonite (modified MMT);
step two: preparation of GQDs solution:
putting 1-10g of Citric Acid (CA) into a beaker, and heating to obtain an orange liquid; then, adjusting the pH to be 7.0 by using a sodium hydroxide aqueous solution, dialyzing and carrying out rotary evaporation to obtain a GQDs solution;
step three: the preparation of the modified MMT/ZnO/GQDs nano composite antibacterial agent comprises the following steps:
adding 0.2-0.9g of alkali source into 50ml of ethanol solution, and magnetically stirring for 30min to obtain solution A; adding 0.3-2g of zinc source into 100ml of ethanol solution, magnetically stirring for 30min, adding the GQDs obtained in the second step, and carrying out ultrasonic treatment for 10 min; adding modified MMT, transferring into a three-neck flask, and performing water bath reaction at 60 ℃ for 30 min; finally, adding the solution A, reacting for 20min, heating for reaction, cooling, washing and centrifuging the product after the reaction is finished, thus obtaining the modified MMT/ZnO/GQDs nano composite antibacterial agent;
in the first step, the modifier is cetyl trimethyl ammonium bromide or octadecyl trimethyl ammonium chloride.
2. The preparation method of the modified MMT/ZnO/GQDs nano composite antibacterial agent according to claim 1, characterized in that:
in the first step, the drying temperature and time are respectively 100 ℃ and 24 hours.
3. The preparation method of the modified MMT/ZnO/GQDs nano composite antibacterial agent according to claim 1, characterized in that:
in the second step, the heating reaction temperature and time are respectively 200 ℃ and 30 min.
4. The preparation method of the modified MMT/ZnO/GQDs nano composite antibacterial agent according to claim 1, characterized in that:
in the second step, the dialysis time is 24 h.
5. The preparation method of the modified MMT/ZnO/GQDs nano composite antibacterial agent according to claim 1, characterized in that:
in the third step, the alkali source is potassium hydroxide, sodium hydroxide or lithium hydroxide.
6. The preparation method of the modified MMT/ZnO/GQDs nano composite antibacterial agent according to claim 1, characterized in that:
in the third step, the zinc source is zinc acetate dihydrate or zinc nitrate hexahydrate.
7. The preparation method of the modified MMT/ZnO/GQDs nano composite antibacterial agent according to claim 1, characterized in that:
in the third step, the heating reaction is carried out at the temperature of 80-100 ℃ for 3-7 h.
8. The preparation method of the modified MMT/ZnO/GQDs nano composite antibacterial agent according to claim 1, characterized in that:
in the third step, the dosage of the modified MMT is 2-20 wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810900240.5A CN109077062B (en) | 2018-08-09 | 2018-08-09 | Preparation method of modified MMT/ZnO/GQDs nano composite antibacterial agent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810900240.5A CN109077062B (en) | 2018-08-09 | 2018-08-09 | Preparation method of modified MMT/ZnO/GQDs nano composite antibacterial agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109077062A CN109077062A (en) | 2018-12-25 |
| CN109077062B true CN109077062B (en) | 2021-05-18 |
Family
ID=64833904
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810900240.5A Active CN109077062B (en) | 2018-08-09 | 2018-08-09 | Preparation method of modified MMT/ZnO/GQDs nano composite antibacterial agent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109077062B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109806857A (en) * | 2019-02-21 | 2019-05-28 | 重庆大学 | A kind of nano zinc oxide photocatalysis composite material and preparation method |
| CN110352982A (en) * | 2019-07-16 | 2019-10-22 | 陕西科技大学 | A kind of quaternary alkylphosphonium salt modified montmorillonoid load Co-doped ZnO quantum dot nano complex antimicrobials and preparation method thereof |
| WO2021084825A1 (en) * | 2019-10-29 | 2021-05-06 | 株式会社クレハ | Carbon quantum dot-containing composition, and method for producing the same |
| CN111436459B (en) * | 2019-12-27 | 2021-12-28 | 福建格瑞诗化工科技有限公司 | Inorganic mildew-proof antibacterial material, preparation method and application thereof, and inorganic mildew-proof antibacterial liquid |
| CN112472806B (en) * | 2020-11-16 | 2021-08-24 | 安徽农业大学 | Sph-Ru-MMT @ PZ nano antibacterial agent and preparation method and application thereof |
| CN112400869A (en) * | 2020-12-04 | 2021-02-26 | 陕西科技大学 | Cl-modified GQD/ZnO/acidified attapulgite nano composite antibacterial agent and preparation method thereof |
| CN113826616B (en) * | 2021-06-28 | 2022-08-30 | 温州新意特种纸业有限公司 | Preparation method of composite antibacterial material and application of composite antibacterial material in special paper |
| CN113693063A (en) * | 2021-08-09 | 2021-11-26 | 广州市拓瑞科技有限公司 | Efficient antibacterial cream and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103205049A (en) * | 2013-04-27 | 2013-07-17 | 安徽国泰印务有限公司 | High-resistance antibacterial PE (polyethylene) film and preparation method thereof |
| CN103891775A (en) * | 2013-11-28 | 2014-07-02 | 龙岩学院 | Zinc-carrying nano organic montmorillonite antimicrobial agent and preparation method thereof |
| CN105268423A (en) * | 2015-09-08 | 2016-01-27 | 陕西科技大学 | ZnO quantum dot-MMT composite photocatalytic material and preparation method |
| WO2016045045A1 (en) * | 2014-09-25 | 2016-03-31 | 深圳粤网节能技术服务有限公司 | Method for preparing graphene quantum dots |
| CN106359373A (en) * | 2016-08-29 | 2017-02-01 | 佛山市高明区尚润盈科技有限公司 | Porous graphene zinc-oxide-loaded antibacterial composite material and preparation method thereof |
| CN107372600A (en) * | 2017-08-10 | 2017-11-24 | 陕西科技大学 | Optical driving type nano antibacterial agent and preparation method thereof |
| KR20170142601A (en) * | 2016-06-20 | 2017-12-28 | 한국과학기술연구원 | Matter for detecting virus using ZnO-carbon based quantom dot and method for fabricating the same |
-
2018
- 2018-08-09 CN CN201810900240.5A patent/CN109077062B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103205049A (en) * | 2013-04-27 | 2013-07-17 | 安徽国泰印务有限公司 | High-resistance antibacterial PE (polyethylene) film and preparation method thereof |
| CN103891775A (en) * | 2013-11-28 | 2014-07-02 | 龙岩学院 | Zinc-carrying nano organic montmorillonite antimicrobial agent and preparation method thereof |
| WO2016045045A1 (en) * | 2014-09-25 | 2016-03-31 | 深圳粤网节能技术服务有限公司 | Method for preparing graphene quantum dots |
| CN105268423A (en) * | 2015-09-08 | 2016-01-27 | 陕西科技大学 | ZnO quantum dot-MMT composite photocatalytic material and preparation method |
| KR20170142601A (en) * | 2016-06-20 | 2017-12-28 | 한국과학기술연구원 | Matter for detecting virus using ZnO-carbon based quantom dot and method for fabricating the same |
| CN106359373A (en) * | 2016-08-29 | 2017-02-01 | 佛山市高明区尚润盈科技有限公司 | Porous graphene zinc-oxide-loaded antibacterial composite material and preparation method thereof |
| CN107372600A (en) * | 2017-08-10 | 2017-11-24 | 陕西科技大学 | Optical driving type nano antibacterial agent and preparation method thereof |
Non-Patent Citations (5)
| Title |
|---|
| Cu2+/ZnO-蒙脱石抗菌材料的制备及抑菌活性研究;麻晓霞等;《硅酸盐通报》;20171215;第36卷(第12期);第4117-4121、4128页；第1节，第2.2.1节，第3.1-3.2节 * |
| Formation of zinc oxide particles in cetyltrimethylammonium-smectites;Nuttaporn Khumchoo等;《Applied Clay Science》;20150331;第105卷;第236-242页 * |
| Photo-enhanced antibacterial activity of ZnO/graphene quantum dot nanocomposites;Junli Liu等;《Nanoscale》;20180107;第10卷(第1期);第158-166页；第1节第4段，第2.2节，第3.2-3.3节 * |
| Preparation of zinc oxide-montmorillonite hybrids;Nithima Khaorapapong等;《Materials Letters》;20110228;第65卷(第4期);第657-660页；摘要，第2节，第3节 * |
| 改性MMT/ZnO/GQDs纳米复合材料的制备及其抗菌性能;刘俊莉等;《陕西科技大学学报》;20190109;第37卷(第1期);第113-117页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109077062A (en) | 2018-12-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109077062B (en) | Preparation method of modified MMT/ZnO/GQDs nano composite antibacterial agent | |
| CN108969537B (en) | Preparation method of ZnO/GQD-PEI composite quantum dot antibacterial agent | |
| CN107951902B (en) | Graphene antibacterial composition and sanitary material using same | |
| CN102548901B (en) | There is the colloidal dispersion killed livestock of the silica dioxide granule being adsorbed on silver ion thereon | |
| Riduan et al. | Recent advances of zinc‐based antimicrobial materials | |
| CN103461382B (en) | Silver-loading modified montmorillonite antibacterial agent, preparation method and application thereof | |
| Wang et al. | Modified magnetic chitosan materials for heavy metal adsorption: a review | |
| CN107570191B (en) | Preparation method and application of visible light catalyst | |
| CN110115272B (en) | Cu nanoparticle coupled graphene hydrogel composite material and preparation method and application thereof | |
| CN108715556A (en) | Multifunctional ceramic material and its preparation method and application | |
| CN110352982A (en) | A kind of quaternary alkylphosphonium salt modified montmorillonoid load Co-doped ZnO quantum dot nano complex antimicrobials and preparation method thereof | |
| CN105536877A (en) | Preparation of superparamagnetic Fe3O4-PAMAM-ZnO / TiO2 nanoparticles with core-shell composite structure | |
| CN103877985B (en) | A kind of visible light-responded magnetic photocatalytic material and preparation method | |
| CN102499261B (en) | Preparation method for antibacterial agent | |
| CN103011276A (en) | Method for preparing silver-loaded titanium oxide-zirconium phosphate composite nanometer material | |
| CN113456671B (en) | Friendly type durable antibacterial disinfection gel and preparation method thereof | |
| CN112795098A (en) | Antibacterial plastic and preparation method thereof | |
| CN103623779A (en) | Hydrophilic functional carbon sphere and application thereof for removing heavy metal ions in waste water | |
| CN105457663A (en) | Bi2WO6 / Ag3PO4 composite photocatalytic fungicide and preparation method thereof | |
| CN106857656A (en) | A kind of compound hydrotalcite type nano material of ruthenium complex joint Nano Silver and its production and use | |
| Li et al. | MMT and ZrO2 jointly regulate the pore size of graphene oxide-based composite aerogel materials to improve the selective removal ability of Cu (II) | |
| CN101856726B (en) | Method for preparing multifunctional nano silver solution | |
| CN102284291A (en) | Titanium dioxide load-type nanometer cold catalyst for air purifier inside car | |
| Imam et al. | Influence of various operational parameters on the photocatalytic degradation of ciprofloxacin in aqueous media: a short review | |
| JP2016082963A (en) | Production process of pet urinal pad having deammoniation function and high saline water absorption ability |
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 |
Effective date of registration: 20230103 Address after: 201801 B-12, No. 1255, Huyi Road, Jiading District, Shanghai Patentee after: Shanghai Pengtu Antibacterial New Material Co.,Ltd. Patentee after: Wang Jin Address before: 518000 room 321, building 2, Nanke Chuangyuan Valley, Taoyuan community, Dalang street, Longhua District, Shenzhen City, Guangdong Province Patentee before: Shenzhen lizhuan Technology Transfer Center Co.,Ltd. Effective date of registration: 20230103 Address after: 518000 room 321, building 2, Nanke Chuangyuan Valley, Taoyuan community, Dalang street, Longhua District, Shenzhen City, Guangdong Province Patentee after: Shenzhen lizhuan Technology Transfer Center Co.,Ltd. Address before: 710021 Shaanxi city of Xi'an province Weiyang University City Patentee before: SHAANXI University OF SCIENCE & TECHNOLOGY |
|
| TR01 | Transfer of patent right |