CN110679609B - Copper-doped zinc oxide quantum dot nano antibacterial agent and preparation method thereof - Google Patents

Copper-doped zinc oxide quantum dot nano antibacterial agent and preparation method thereof Download PDF

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CN110679609B
CN110679609B CN201910941759.2A CN201910941759A CN110679609B CN 110679609 B CN110679609 B CN 110679609B CN 201910941759 A CN201910941759 A CN 201910941759A CN 110679609 B CN110679609 B CN 110679609B
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copper
zinc
source
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antibacterial agent
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CN110679609A (en
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刘俊莉
王宇涵
刘辉
洪燕南
李军奇
蔡永华
廖辉
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Gmy Lighting Technology Co ltd
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • A01N59/20—Copper
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • 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
    • 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

Abstract

The invention relates to a copper-doped zinc oxide quantum dot nano antibacterial agent and a preparation method thereof, wherein the chemical formula of the copper-doped zinc oxide quantum dot nano antibacterial agent is Zn1‑xOCux(x is 0.003-0.01). The preparation method comprises the following steps: weighing a zinc source and a copper source, dispersing the zinc source and the copper source in an organic solvent, stirring, heating in a water bath until the solution is clear and transparent, and stirring again to obtain a zinc-copper mixed precursor solution; adding an alkali source into an organic solvent, and stirring to obtain an alkali solution; dripping an alkali solution into the mixed precursor solution of zinc and copper, and stirring to obtain a mixed solution; and adding the precipitator into the mixed solution, stirring, standing, cleaning and centrifuging to obtain the copper-doped zinc oxide quantum dot nano antibacterial agent. The sizes of the Cu-doped ZnO quantum dots are mainly distributed in the range of 4-8nm, the minimum inhibitory concentration of the nano antibacterial agent on escherichia coli can reach 2.7mg/mL, and the inhibitory rate on escherichia coli can reach 81.79%.

Description

Copper-doped zinc oxide quantum dot nano antibacterial agent and preparation method thereof
Technical Field
The invention belongs to the technical field of novel antibacterial agents, and relates to a copper (Cu) doped zinc oxide quantum dot (ZnO QDs) nano antibacterial agent and a preparation method thereof.
Background
With the development of society and the improvement of living standard of materials, people have higher and higher requirements on the living environment, but the problems that the drug resistance of microorganisms to drug treatment is increased, and the growth and reproduction of harmful bacteria are controlled and killed to ensure the health and safety of human beings are increasingly concerned by various communities. In decades of infectious diseases treated by antibiotics by human beings, a large number of multiple drug-resistant strains are generated, and in order to improve the antibiotic effect, on one hand, powerful new antibiotics or composite antibacterial agents are developed, but the functions of new drugs are inevitably influenced by the drug resistance of pathogenic bacteria to reduce; on the other hand, the decrease in the therapeutic effect of the drug is compensated for by increasing the dosage of the drug, but these are burdensome to people, and therefore, the development of novel highly effective antibacterial agents is urgently needed. Most organic antibacterial agents have the defects of poor thermal stability, short service life, environmental pollution and the like. Researchers are gradually focusing their attention on new inorganic antibacterial agents including nanoparticles. Due to the particularity of the constituent elements, quantum dots inevitably produce some heavy metal ions, which means some toxicity to bacteria. Quantum dots, a typical nanoparticle, have been studied for their antibacterial activity.
The nano ZnO used as a photocatalytic antibacterial agent has the characteristics of good antibacterial effect, low toxicity, easy dispersion, good thermal stability and the like, and has important significance for developing green and environment-friendly living goods. Compared with common ZnO, the nano ZnO has larger specific surface area, small size effect and various appearances. The results of the related research show that: by reducing the size of nano ZnO, the prepared ZnO quantum dot can obviously improve the antibacterial effect. However, ZnO itself has problems of large forbidden bandwidth, easy recombination of photo-generated electron-hole pairs, and the like, and restricts the application range thereof. Metal ion doping has become one of the effective means for inhibiting the recombination of electrons and holes on the surface of the photocatalytic material. Copper nanoparticles have for many years not only received attention as a promising antibacterial drug, but also have been used for sterilization of textiles, liquids and human tissues. In addition, the research also shows that the antibacterial activity of the quantum dots is related to the form of the quantum dots, the ZnO quantum dots in the ZnO quantum dot aqueous solution and the ZnO quantum dots suspended in the polyvinylpyrrolidone gel have obvious antibacterial efficacy on Listeria monocytogenes, Salmonella enteritidis and Escherichia coli 0157: H7, and the ZnO quantum dots connected to the polystyrene film have no antibacterial effect on the three bacteria. This may be related to the dispersion state of the quantum dots, and quantum dots that are better dispersed in the medium can more fully contact the bacteria.
Therefore, the invention adopts a water bath method with low cost and low energy consumption to prepare the water-soluble ZnO quantum dots, and adopts Cu in the preparation process2+By ion replacement of Zn2+Lattice defects and charge defects are generated, the recombination of photoproduction electrons and photoproduction hole pairs on the surface of the ZnO quantum dots is effectively inhibited, so that the photocatalytic activity and the antibacterial activity of the ZnO quantum dots are enhanced, the small-size Cu-doped ZnO quantum dots with good biocompatibility and water solubility are formed, the ZnO quantum dots can enter bacterial cells more easily, and Zn is further introduced into the bacterial cells2+、Cu2+The functional groups on the active protease act to destroy the structure of the bacteria and influence the physiological functions of the bacteria, so that the bacteria can not complete normal physiological activities and die.
Disclosure of Invention
The invention aims to provide a novel high-efficiency copper (Cu) doped zinc oxide quantum dot (ZnO QDs) nano antibacterial agent and a preparation method thereof, which solve the problem of threat to human health caused by various bacterial infections, particularly infection of some drug-resistant bacteria.
Based on the above problems, one technical solution adopted by the present invention to solve the technical problems is:
a copper-doped zinc oxide quantum dot nano antibacterial agent has a chemical formula of Zn1-xOCuxAnd x is 0.003-0.01.
The invention also provides a preparation method of the copper-doped zinc oxide quantum dot nano antibacterial agent, which comprises the following steps:
(1) weighing a zinc source and a copper source, dispersing the zinc source and the copper source in an organic solvent, stirring, heating in a water bath until the solution is clear and transparent, and stirring again to obtain a zinc-copper mixed precursor solution;
(2) adding an alkali source into an organic solvent, and stirring to obtain an alkali solution;
(3) dripping the obtained alkali solution into the obtained zinc and copper mixed precursor solution, and stirring to obtain a mixed solution;
(4) and adding a precipitator into the mixed solution, stirring, standing, cleaning and centrifuging to obtain the copper (Cu) doped zinc oxide quantum dot (ZnO QDs) nano antibacterial agent.
According to the invention, the zinc source and the copper source are directly dispersed in the organic solvent without dispersing the zinc source and the copper source in a surfactant system, so that the solvent environment is purer, other impurity ions which are difficult to remove are not introduced, and a template agent is not additionally added in the reaction system; the invention purposefully adds the alkali solution into the zinc-copper mixed precursor solution slowly and dropwise, and a small amount of reactant MOH in the system can provide Zn and the reactant MOH2+OH of the reaction-Thereby forming ZnO product quantum dots, and thus preventing the ZnO from forming rod-shaped, sheet-shaped, flower-shaped and other large-size ZnO due to the over-fast growth of the ZnO caused by the existence of a large amount of alkali sources; in addition, OH can be reacted by adding an alkaline solution dropwise-Ions are rapidly adsorbed on the particle surface, so that ZnO QDs initially formed are negatively charged, and M is in the reaction process+(alkali metal ions) are attracted to the negatively charged ZnO QDs surface, hindering Zn2+Further growth, M+Presence of ions, especially Li+And ions can hinder the growth of ZnO QDs, and finally the small-size ZnO quantum dots are obtained.
Preferably, the molar ratio of zinc in the zinc source to copper in the copper source is 1: 0.003-0.01. Because ZnO has large forbidden band width and easy recombination of photo-generated electron-hole pairs, Cu is added2+The ZnO crystal lattice doped with the active oxygen can effectively inhibit the recombination of photo-generated electrons and holes, improve the generation amount of active oxygen substances in a system and further improve the antibacterial performance of the nano material.
Preferably, the zinc source is one or more of zinc acetate, zinc nitrate, zinc sulfate and zinc chloride. More preferably, the zinc source is one or more of zinc acetate dihydrate, anhydrous zinc acetate, zinc nitrate hexahydrate, zinc sulfate heptahydrate and anhydrous zinc chloride.
Preferably, the copper source is one or more of copper acetate, copper nitrate, copper sulfate and copper chloride. More preferably, the copper source is one or more of copper acetate monohydrate, anhydrous copper acetate, copper nitrate trihydrate, copper sulfate pentahydrate and copper chloride dihydrate.
Preferably, a zinc source and a copper source are weighed and dispersed in an organic solvent, and the mass volume ratio of the zinc source to the organic solvent is 0.5-2 g: 80-120 mL.
Preferably, the reaction temperature of the water bath heating is 60-90 ℃, and the heat preservation time is 0.5-2 h.
Preferably, the alkali source is one or more of potassium hydroxide, sodium hydroxide and lithium hydroxide.
Preferably, the organic solvent is ethanol. The Cu-doped ZnO quantum dots prepared in an ethanol system are water-soluble and can be stably dispersed in an aqueous solution; in addition, the method does not need to use other organic solvents, is safe, non-toxic and environment-friendly, does not need the steps of solvent replacement, PTFE filter membrane filtration, coordination reaction and the like, is simple to operate, and is convenient for industrial production.
Preferably, an alkali source is added into the organic solvent, and the mass volume ratio of the alkali source to the organic solvent is 0.15-1 g: 80-120 mL.
Preferably, the alkali source is added into the organic solvent, and the mixture is magnetically stirred for 20-40min to obtain the alkali solution.
Preferably, the obtained alkali solution is dropwise added into the obtained zinc and copper mixed precursor solution, and the volume ratio of the alkali solution to the zinc and copper mixed precursor solution is 1-2: 1-2.
Preferably, the obtained alkali solution is dripped into the obtained zinc-copper mixed precursor solution, and Zn in the zinc-copper mixed precursor solution2+OH with the alkali solution-The molar ratio is 1: 0.5-4.5.
Preferably, when the obtained alkali solution is dropwise added into the obtained zinc and copper mixed precursor solution, the temperature of the alkali solution and the zinc and copper mixed precursor solution is 20-30 ℃.
Preferably, the obtained alkali solution is dropwise added into the obtained zinc and copper mixed precursor solution, and the mixture is stirred at the temperature of 20-30 ℃ to obtain a mixed solution. More preferably, the obtained alkali solution is dripped into the obtained zinc and copper mixed precursor solution, and the mixed solution is obtained by magnetic stirring for 20-40min at the temperature of 20-30 ℃. The earlier research basis of the applicant shows that the smaller the ZnO size is, the better the antibacterial performance is, so that the copper-doped zinc oxide quantum dots are prepared by adopting low-temperature water bath heating (20-30 ℃, 20-40min), and the growth direction of ZnO is regulated and controlled by controlling mild reaction conditions, so that the small-size copper-doped zinc oxide quantum dots are obtained.
Preferably, the precipitating agent is deionized water.
Preferably, a precipitating agent is added into the obtained mixed solution, and the volume ratio of the precipitating agent to the mixed solution is 1-2: 2-4.
Preferably, the precipitator is added into the mixed solution until the mixed solution becomes milk white, the mixed solution is magnetically stirred for 5 to 20min at the temperature of between 20 and 30 ℃, and the nano antibacterial agent with the copper doped zinc oxide quantum dots is obtained after standing, cleaning and centrifugation.
Preferably, the centrifugation speed is 6000-10000rpm, and the centrifugation time is 15-30 min.
Specifically, the preparation method of the copper-doped zinc oxide quantum dot nano antibacterial agent comprises the following steps:
respectively weighing 0.5-2.0g of zinc source and mixing the zinc source and the copper source according to the molar ratio of zinc in the zinc source to copper in the copper source of 1: dispersing 0.003-0.01 copper source in 80-120mL of organic solvent, uniformly stirring, pouring into a three-neck flask, heating in water bath at 60-90 ℃, keeping the temperature for reaction for 0.5-2h until the solution is clear and transparent, and continuously stirring at 20-30 ℃ for later use to obtain a zinc-copper mixed precursor solution; adding 0.15-1g of alkali source into 80-120mL of organic solvent, magnetically stirring for 20-40min at 20-30 ℃, dropwise adding the obtained alkali solution into the zinc-copper mixed precursor solution prepared in the previous stage, uniformly mixing, magnetically stirring for 20-40min at 20-30 ℃, adding 50-100mL of precipitator after the reaction is finished until the solution becomes milky white, magnetically stirring for 5-20min at 20-30 ℃, standing, cleaning, and centrifuging for 15-30min at 6000-10000rpm to obtain the copper (Cu) doped zinc oxide quantum dot (QZnO Ds) nano antibacterial agent.
More specifically, the preparation method of the copper-doped zinc oxide quantum dot nano antibacterial agent comprises the following steps:
respectively weighing 1.396g of zinc acetate dihydrate and 8.89mg of copper acetate monohydrate, dispersing in 100mL of absolute ethanol, uniformly stirring, pouring into a three-neck flask, heating in a water bath at 80 ℃, carrying out heat preservation reaction for 1h until the solution is clear and transparent, and continuously stirring at 25 ℃ for later use to obtain a zinc-copper mixed precursor solution; adding 0.45g of sodium hydroxide into 100mL of ethanol solution, magnetically stirring for 30min at 25 ℃, dropwise adding the obtained alkali solution into the zinc-copper mixed precursor solution prepared in the earlier stage, uniformly mixing, magnetically stirring for 30min at 25 ℃, adding 100mL of deionized water until the solution becomes milky white after the reaction is finished, magnetically stirring for 10min at 25 ℃, standing, cleaning, and centrifuging for 20min at 7500rpm/min to obtain the copper (Cu) doped zinc oxide quantum dots (ZnO QDs) nano antibacterial agent.
The invention also provides application of the copper-doped zinc oxide quantum dot nano antibacterial agent, and the copper-doped zinc oxide quantum dot nano antibacterial agent prepared by the preparation method is a novel antibacterial agent which is safe, environment-friendly and strong in drug resistance. Preferably, the paint can be added to materials such as paint, fiber, plastic, ceramic, glass, metal and the like. More preferably, the copper-doped zinc oxide quantum dot nano antibacterial agent can be added into food appliances, electronic communication products, household appliances, building materials, office supplies, toys, medical and health supplies and other daily supplies.
The invention has the following beneficial effects:
the invention takes one or more of copper acetate, copper nitrate, copper sulfate and copper chloride as doping agents, takes a novel photoelectric functional material ZnO quantum dot as a main antibacterial component, and utilizes Cu2+The novel nano antibacterial agent occupies a conventional Zn site of a ZnO lattice, and finishes the doping of metal ions to zinc oxide quantum dots along with the replacement of Cu ions at the Zn site to form small-size Cu-doped ZnO quantum dots with good biocompatibility and water solubility, kills bacteria by utilizing a large amount of Reactive Oxygen Species (ROS) generated on the surface of the Cu-doped ZnO quantum dots and the release of the zinc ions caused by the Cu doping, and finally designs and prepares the novel nano antibacterial agent with good biocompatibility and high antibacterial activity. Compared with the traditional antibacterial agent, the nano antibacterial agent prepared by the invention has the advantages of safety, environmental protection, strong drug resistance and the like, and the Cu-doped ZnO quantum dots prepared by the invention have smaller size, and the particle size is mainly distributed in 4-8nm and accounts for more than 95%. The minimum inhibitory concentration of the nano antibacterial agent on escherichia coli can reach 2.7mg/mL, and the inhibitory rate on escherichia coli can reach 81.79%.
Drawings
The invention is further described below with reference to the accompanying drawings.
FIG. 1 is an XRD (X-ray diffraction) spectrum of a ZnO quantum dot prepared in comparative example 1 and a Cu-doped ZnO quantum dot nano antibacterial agent prepared in example 2.
FIG. 2a is a TEM photograph of the ZnO quantum dot nanomaterial prepared in comparative example 1.
FIG. 2b is a TEM photograph of the Cu-doped ZnO quantum dot nanomaterial prepared in example 2.
Fig. 3 is a particle size distribution diagram of the Cu-doped ZnO quantum dot nanomaterial prepared in example 2.
FIG. 4a is a blank E.coli control.
FIG. 4b shows the antibacterial effect of the ZnO quantum dot nanomaterial prepared in comparative example 1 on Escherichia coli.
FIG. 4c shows the antibacterial effect of the Cu-doped ZnO quantum dot nanomaterial prepared in example 2 on Escherichia coli.
FIG. 5a is a result of the concentration test of the ZnO quantum dot nanomaterial prepared in comparative example 1 on Escherichia coli.
Fig. 5b is a result of a test of the inhibitory concentration of the Cu-doped ZnO quantum dot nanomaterial prepared in example 2 on escherichia coli.
Detailed Description
The invention will now be described in detail with reference to specific examples, which are intended to illustrate the invention but not to limit it further.
A preparation method of a Cu-doped ZnO quantum dot nano antibacterial agent comprises the following steps:
respectively weighing 0.5-2.0g of zinc source and mixing the zinc source and the copper source according to the molar ratio of zinc in the zinc source to copper in the copper source of 1: dispersing 0.003-0.01 copper source in 80-120mL of organic solvent, uniformly stirring, pouring into a three-neck flask, heating in water bath at 60-90 ℃, keeping the temperature for reaction for 0.5-2h until the solution is clear and transparent, and continuously stirring at 20-30 ℃ for later use to obtain a zinc-copper mixed precursor solution; adding 0.15-1g of alkali source into 80-120mL of organic solvent, magnetically stirring for 20-40min at 20-30 ℃, dropwise adding the obtained alkali solution into the zinc-copper mixed precursor solution prepared in the previous stage, uniformly mixing, magnetically stirring for 20-40min at 20-30 ℃, adding 50-100mL of precipitator after the reaction is finished until the solution becomes milky white, magnetically stirring for 5-20min at 20-30 ℃, standing, cleaning, and centrifuging for 15-30min at 6000-10000rpm to obtain the copper (Cu) doped zinc oxide quantum dot (ZnO QDs) nano antibacterial agent. And (3) determining the minimum inhibitory concentration of the nano antibacterial agent by using an enzyme-labeling instrument, and calculating the inhibitory rate of the nano antibacterial agent by using an oscillation method and a flat plate counting method.
The zinc source is one or more of zinc acetate dihydrate, anhydrous zinc acetate, zinc nitrate hexahydrate, zinc sulfate heptahydrate and anhydrous zinc chloride.
The copper source is one or more of copper acetate monohydrate, anhydrous copper acetate, copper nitrate trihydrate, copper sulfate pentahydrate and copper chloride dihydrate.
The alkali source is one or more of potassium hydroxide, sodium hydroxide and lithium hydroxide.
The precipitator is deionized water.
Example 1
A preparation method of a copper-doped zinc oxide quantum dot nano antibacterial agent comprises the following steps:
respectively weighing 0.768g of zinc acetate dihydrate and 4.89mg of copper acetate monohydrate, dispersing in 100mL of absolute ethyl alcohol, uniformly stirring, pouring into a three-neck flask, heating in a water bath at 80 ℃ for reaction for 0.5h until the solution is clear and transparent, and continuously stirring at 20 ℃ for later use to obtain a zinc-copper mixed precursor solution; adding 0.15g of lithium hydroxide into 100mL of ethanol solution, magnetically stirring at 20 ℃ for 30min, dropwise adding the obtained alkali solution into the zinc-copper mixed precursor solution prepared in the earlier stage, uniformly mixing, magnetically stirring at 20 ℃ for 30min, adding 80mL of deionized water after the reaction is finished until the solution becomes milky white, magnetically stirring at 20 ℃ for 10min, standing, cleaning, and centrifuging at 6000rpm for 30min to obtain the copper (Cu) doped zinc oxide quantum dots (ZnO QDs) nano antibacterial agent; and (3) determining the minimum inhibitory concentration of the nano antibacterial agent by using an enzyme-labeling instrument, and calculating the inhibitory rate of the nano antibacterial agent by using an oscillation method and a flat plate counting method.
Example 2
A preparation method of a copper-doped zinc oxide quantum dot nano antibacterial agent comprises the following steps:
respectively weighing 1.1g of zinc nitrate hexahydrate and 6.98mg of copper nitrate trihydrate, dispersing in 100mL of absolute ethanol, uniformly stirring, pouring into a three-neck flask, heating in a water bath at 80 ℃ for reaction for 1h until the solution is clear and transparent, and continuously stirring at 23 ℃ for later use to obtain a zinc-copper mixed precursor solution; adding 0.3g of lithium hydroxide into 100mL of ethanol solution, magnetically stirring for 30min at 23 ℃, dropwise adding the obtained alkali solution into the zinc-copper mixed precursor solution prepared in the earlier stage, uniformly mixing, magnetically stirring for 30min at 23 ℃, adding 100mL of deionized water until the solution becomes milky white after the reaction is finished, magnetically stirring for 10min at 23 ℃, standing, cleaning, and centrifuging at 8000rpm for 18min to obtain the copper (Cu) doped zinc oxide quantum dots (ZnO QDs) nano antibacterial agent; and (3) determining the minimum inhibitory concentration of the nano antibacterial agent by using an enzyme-labeling instrument, and calculating the inhibitory rate of the nano antibacterial agent by using an oscillation method and a flat plate counting method.
Example 3
A preparation method of a copper-doped zinc oxide quantum dot nano antibacterial agent comprises the following steps:
respectively weighing 1.396g of zinc acetate dihydrate and 8.89mg of copper acetate monohydrate, dispersing in 100mL of absolute ethanol, uniformly stirring, pouring into a three-neck flask, heating in a water bath at 80 ℃ for reaction for 1h until the solution is clear and transparent, and continuously stirring at 25 ℃ for later use to obtain a zinc-copper mixed precursor solution; adding 0.45g of sodium hydroxide into 100mL of ethanol solution, magnetically stirring for 30min at 25 ℃, dropwise adding the obtained alkali solution into the zinc-copper mixed precursor solution prepared in the earlier stage, uniformly mixing, magnetically stirring for 30min at 25 ℃, adding 100mL of deionized water after the reaction is finished until the solution becomes milky white, magnetically stirring for 10min at 25 ℃, standing, cleaning, and centrifuging at 7500rpm for 20min to obtain the cobalt (Co) doped zinc oxide quantum dot (ZnO QDs) nano antibacterial agent; and (3) determining the minimum inhibitory concentration of the nano antibacterial agent by using an enzyme-labeling instrument, and calculating the inhibitory rate of the nano antibacterial agent by using an oscillation method and a flat plate counting method.
Example 4
A preparation method of a copper-doped zinc oxide quantum dot nano antibacterial agent comprises the following steps:
respectively weighing 1.5g of zinc nitrate hexahydrate and 9.55mg of copper nitrate trihydrate, dispersing in 100mL of absolute ethanol, uniformly stirring, pouring into a three-neck flask, heating in a water bath at 80 ℃ for reaction for 1h until the solution is clear and transparent, and continuously stirring at 30 ℃ for later use to obtain a zinc-copper mixed precursor solution; adding 0.46g of potassium hydroxide into 100mL of ethanol solution, magnetically stirring at 30 ℃ for 30min, dropwise adding the obtained alkali solution into the zinc-copper mixed precursor solution prepared in the earlier stage, uniformly mixing, magnetically stirring at 30 ℃ for 30min, adding 100mL of deionized water after the reaction is finished until the solution becomes milky white, magnetically stirring at 30 ℃ for 10min, standing, cleaning, and centrifuging at 10000rpm for 15min to obtain the copper (Cu) doped zinc oxide quantum dots (ZnO QDs) nano antibacterial agent; and (3) determining the minimum inhibitory concentration of the nano antibacterial agent by using an enzyme-labeling instrument, and calculating the inhibitory rate of the nano antibacterial agent by using an oscillation method and a flat plate counting method.
Comparative example 1
A preparation method of a copper-undoped zinc oxide quantum dot nano antibacterial agent comprises the following steps:
weighing 1.1g of zinc nitrate hexahydrate, dispersing the zinc nitrate hexahydrate in 100mL of absolute ethyl alcohol, uniformly stirring, pouring the mixture into a three-neck flask, heating the mixture in a water bath at the temperature of 80 ℃ for reaction for 1 hour until the solution is clear and transparent, and continuously stirring the mixture at the temperature of 23 ℃ for later use to obtain a zinc precursor solution; adding 0.3g of lithium hydroxide into 100mL of ethanol solution, magnetically stirring at 23 ℃ for 30min, dropwise adding the obtained alkali solution into the zinc precursor solution prepared in the earlier stage, uniformly mixing, magnetically stirring at 23 ℃ for 30min, adding 100mL of deionized water after the reaction is finished until the solution becomes milky white, magnetically stirring at 23 ℃ for 10min, standing, cleaning, and centrifuging at 8000rpm for 18min to obtain the copper-undoped zinc oxide quantum dot (ZnO QDs) nano antibacterial agent; and (3) determining the minimum bacteriostatic concentration of the antibacterial agent by using an enzyme-labeling instrument, and calculating the bacteriostatic rate of the antibacterial agent by using a vibration method and a flat plate counting method.
The invention takes copper sources such as copper acetate, copper nitrate and the like as doping agents, takes a novel photoelectric functional material ZnO quantum dot as a main antibacterial component, and utilizes Cu2+Occupies the conventional Zn site of the ZnO crystal lattice, completes the substitution of Cu ions at the Zn site, reduces the forbidden bandwidth of a ZnO semiconductor, and improves the visible light region of a doped sampleThe response range of (2) is wide, and the small-size Cu-doped ZnO quantum dots with good biocompatibility and water solubility are formed. Referring to the attached figure 1, which shows XRD patterns of the ZnO quantum dots prepared according to the comparative example 1 and the Cu-doped ZnO quantum dot nano antibacterial agent prepared according to the example 2, it can be seen from the figures that the diffraction peaks of the ZnO quantum dots not doped with Cu and the Cu-doped ZnO quantum dot nano material are substantially matched with the diffraction peak of the XRD standard diffraction card, which indicates that the ZnO quantum dot nano material is synthesized, and the XRD diffraction peak intensity of the Cu-doped ZnO quantum dot nano material is enhanced compared with that of the ZnO quantum dots not doped with Cu, indicating that the Cu metal ions are successfully doped.
Referring to the attached drawings 2a-2b, which are TEM photographs of the Cu-undoped ZnO quantum dots prepared according to the technical scheme of the comparative example 1 and the Cu-doped ZnO quantum dot nanomaterials prepared according to the technical scheme of the example 2, respectively, it can be seen from the photographs that the Cu-doped ZnO quantum dots prepared in the example 2 are still in a circular dot shape, the morphology is not changed, and the size is smaller, compared with the ZnO quantum dots prepared in the comparative example 1. In addition, in order to compare the particle size distribution of the Cu-doped ZnO quantum dot nanomaterial, based on statistical analysis of 100 nanoparticles, referring to fig. 3, a particle size distribution diagram of the Cu-doped ZnO quantum dot nanomaterial prepared according to the technical scheme of example 2 is shown, and it can be seen from the diagram that the particle size of the Cu-doped ZnO quantum dot prepared in example 2 is mainly distributed between 4 nm and 8nm, accounting for 95% or more, and the particle size distribution is the largest between 6 nm and 7 nm.
A large amount of Reactive Oxygen Species (ROS) generated on the surface of the Cu-doped ZnO quantum dot and zinc ion release caused by Cu doping are utilized to kill bacteria, and finally, a novel nano antibacterial agent with good biocompatibility and high antibacterial activity is designed and prepared. Referring to fig. 4, the antibacterial effect of the ZnO quantum dots prepared according to comparative example 1 and the Cu-doped ZnO quantum dot nanomaterial prepared according to example 2 on escherichia coli is shown; fig. 5 shows the results of Minimum Inhibitory Concentration (MIC) test of the ZnO quantum dots prepared according to comparative example 1 and the Cu-doped ZnO quantum dot nanomaterial prepared according to example 2 on escherichia coli. As can be seen from FIG. 4, the nano antibacterial agent prepared by the invention has excellent antibacterial performance, and compared with a blank group without the sample, the number of Escherichia coli colonies is obviously reduced after the sample of example 2 is added, which indicates that the sample has good inhibition effect on Escherichia coli; as can be seen from fig. 5, compared with a blank control (control), both the ZnO quantum dot and the Cu-doped ZnO quantum dot nanomaterial have an obvious inhibition effect on the growth of escherichia coli colonies. In FIG. 5a, 4.5mg/mL of ZnO quantum dots can significantly inhibit bacterial growth, and the OD value of the bacteria is kept constant, i.e. the MIC of the ZnO quantum dots is 4.5 mg/mL; as shown in fig. 5b, the Cu-doped ZnO quantum dot nanomaterial can significantly inhibit the growth of escherichia coli. Wherein, the minimum inhibitory concentration to the escherichia coli can reach 2.7mg/mL, and the inhibitory rate to the escherichia coli can reach 81.79% through calculation.
"copper", "copper ion", "Cu", and "Cu2+"and" Cu ion "are used interchangeably herein and mean the 2-valent copper ion (Cu)2+) (ii) a "Zn", "zinc ion", "Zn2+"and" Zn ion "are used interchangeably herein and mean the 2-valent zinc ion (Zn)2 +)。
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 copper-doped zinc oxide quantum dot nano antibacterial agent is characterized by comprising the following steps:
weighing a zinc source and a copper source, dispersing the zinc source and the copper source in an organic solvent, stirring, heating in a water bath until the solution is clear and transparent, and stirring again to obtain a zinc-copper mixed precursor solution; wherein the molar ratio of zinc in the zinc source to copper in the copper source is 1: 0.003-0.01;
adding an alkali source into an organic solvent, and stirring to obtain an alkali solution;
dripping the obtained alkali solution into the obtained zinc-copper mixed precursor solution, and stirring at 20-30 ℃ to obtain a mixed solution;
adding a precipitator into the mixed solution, stirring, standing, cleaning and centrifuging to obtain the copper-doped zinc oxide quantum dot nano antibacterial agent;
the chemical formula of the obtained copper-doped zinc oxide quantum dot nano antibacterial agent is Zn1-xOCuxThe value of x is 0.003-0.01; the copper-doped zinc oxide quantum dot nano antibacterial agent is in a round dot shape with the particle size distribution of 4-8 nm.
2. The method of claim 1, wherein the zinc source is one or more of zinc acetate, zinc nitrate, zinc sulfate, and zinc chloride.
3. The method according to claim 1, wherein the copper source is one or more selected from the group consisting of copper acetate, copper nitrate, copper sulfate, and copper chloride.
4. The preparation method according to claim 1, wherein the zinc source and the copper source are weighed and dispersed in the organic solvent, and the mass ratio of the zinc source to the organic solvent is 0.5-2 g: 80-120 mL.
5. The preparation method according to claim 1, wherein the alkali source is one or more of potassium hydroxide, sodium hydroxide and lithium hydroxide; the organic solvent is ethanol.
6. The method according to claim 1, wherein an alkali source is added to the organic solvent, and the ratio of the mass of the alkali source to the volume of the organic solvent is 0.15 to 1 g: 80-120 mL.
7. The production method according to claim 1, wherein the obtained alkali solution is dropwise added to the obtained zinc-copper mixed precursor solution, and the volume ratio of the alkali solution to the zinc-copper mixed precursor solution is 1-2: 1-2.
8. The method of claim 1, wherein the precipitating agent is deionized water; adding a precipitating agent into the obtained mixed solution, wherein the volume ratio of the precipitating agent to the mixed solution is 1-2: 2-4.
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