CN114009447A - Copper nanoparticle-loaded polydopamine-modified sheet MoS2Nano antibacterial agent and preparation method and application thereof - Google Patents

Copper nanoparticle-loaded polydopamine-modified sheet MoS2Nano antibacterial agent and preparation method and application thereof Download PDF

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CN114009447A
CN114009447A CN202111313873.4A CN202111313873A CN114009447A CN 114009447 A CN114009447 A CN 114009447A CN 202111313873 A CN202111313873 A CN 202111313873A CN 114009447 A CN114009447 A CN 114009447A
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mos
nano
antibacterial agent
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modified sheet
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刘俊莉
沈佳昊
樊秀怡
刘辉
李军奇
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Shaanxi University of Science and Technology
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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
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
    • A01N25/10—Macromolecular compounds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • 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
    • A01N25/26—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 in coated particulate form
    • 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
    • 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 discloses a copper nanoparticle-loaded polydopamine-modified sheet MoS2Preparation method of nano antibacterial agent, MoS prepared by hydrothermal method2Nanosheet, PDA @ MoS prepared by self-coating method2Preparing PDA @ MoS by low-temperature water bath sodium hypophosphite reduction method2Cu; the copper nanoparticle-loaded polydopamine-modified sheet MoS prepared by the preparation method2The nanometer antibacterial agent and polydopamine are uniformly coated on MoS2On the nano-chip, Cu nano-particles are uniformly dispersed in PDA @ MoS2The size of the Cu nano particles is between 20 and 40nm, the overall size of the material is about 250 to 500nm, and the small-size Cu nano particles and MoS are realized2The light-driven effect is synergistic in antibiosis, the antibiosis performance is good, the minimum bacteriostasis concentration on staphylococcus aureus can reach 0.02mg/mL, the bacteriostasis rate of the concentration on escherichia coli can reach 99.5%, and meanwhile, the cost and the energy consumption are low.

Description

Copper nanoparticle-loaded polydopamine-modified sheet MoS2Nano antibacterial agent and preparation method and application thereof
Technical Field
The invention belongs to the technical field of antibacterial materials, relates to a novel inorganic antibacterial material, and particularly relates to a copper nanoparticle-loaded polydopamine-modified sheet MoS2A nano antibacterial agent and a preparation method and application thereof.
Background
With the development and progress of science and technology, bacterial infection is increasingly recognized as one of the important causes of infectious diseases, and the situation of antibiotic abuse is also increasingly serious, resulting in the generation of various drug-resistant "superbacteria". The world health organization's latest data shows that about 70 million people worldwide die each year from "superbacterial" infections; meanwhile, the world health organization estimates that this figure may reach over 1000 million by year 2050. Therefore, the development of an efficient, safe, non-drug resistant antibacterial agent is increasingly desired. 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.
In recent years, with the continuous development of nanotechnology, a lot of novel inorganic nano antibacterial materials with various types appear, and a new opportunity is brought to the treatment of drug-resistant bacterial infection. Transition metal sulfide, as a graphene and a new two-dimensional nanomaterial, has unique physicochemical properties and excellent cell compatibility, and has attracted much attention in recent years. Wherein, molybdenum disulfide (MoS)2) Is a transition metal bis-haloalkane (TMDs) covalently bonded to X-M-X interlayer materials by weak van der Waals forces. As a two-dimensional (2D) layered nanomaterial, MoS2Due to excellent lightThe properties of optical and electronic properties, mechanical properties, photocatalytic and photothermal properties, etc. are receiving increasing attention. Furthermore, MoS2Can inhibit the growth of microorganisms through contact induced membrane stress and oxidative stress, and has potential antibacterial effect. Previous studies have shown that by reducing MoS2The band gap of the layer(s) is changed from an indirect band gap (1.2eV) to a direct band gap (1.8eV), and the conversion of the indirect band gap to the direct band gap causes MoS2The nanomaterial produces a very efficient photocatalytic effect. At the same time, MoS2Has the advantages of large surface area, strong surface adsorption capacity and the like, Mo is an essential trace element of several enzymes in cells, S is a common biological element, and therefore, molybdenum disulfide has lower cytotoxicity and genotoxicity, which leads MoS2Becoming an ideal candidate material for biological applications. Meanwhile, the material is used as a narrow-bandgap semiconductor material, has good stability, has the performances of infrared photo-thermal, catalytic oxidation and the like, has the potential of nanometer mimic enzyme, and has certain potential in the antibacterial field. 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. According to research, the PDA has the characteristics of excellent biocompatibility, capability of being combined with metal ions and the like, can be used for toxicity reduction of materials due to the characteristics, can be used in the fields of medicine transportation and the like due to the biodegradability, and can be combined with the metal ions, so that the possibility is provided for small-size uniform growth of Cu.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide the copper nanoparticle-loaded polydopamine-modified sheet MoS2Nano antibacterial agent, preparation method and application thereof, and realization of small-size Cu nanoparticles and MoS2The light-driven effect is synergistic in antibacterial property, the antibacterial performance is good, the preparation method is simple and convenient, and the cost is low.
In order to achieve the purpose, the invention adopts the following technical scheme:
copper nanoparticle-loaded polydopamine-modified sheet MoS2Nano-antibacterialThe preparation method of the agent comprises the following steps:
step one, weighing a molybdenum source and a sulfur source according to the mass ratio of atomic substances of 3:7, dispersing the molybdenum source and the sulfur source into deionized water, stirring until the molybdenum source and the sulfur source are dissolved, and performing ultrasonic dispersion to obtain a transparent solution, wherein the mass volume ratio of solids to deionized water is (1-1.2) g: (220-240) ml;
step two, transferring the transparent solution prepared in the step one into a polytetrafluoroethylene lining, putting the polytetrafluoroethylene lining into a hydrothermal kettle, reacting for 20-24 hours in an oven at the temperature of 180-220 ℃, separating precipitates after the reaction is finished, washing and centrifuging to obtain MoS2Drying the nanosheets for later use;
step three, taking the obtained MoS according to the mass ratio of 1: 0.5-1.02Dispersing the nanosheets and dopamine hydrochloride into a trihydroxymethyl aminomethane hydrochloride buffer solution, wherein the mass-to-volume ratio of the solid to the buffer solution is (1-1.2) g: (300-500) ml, and carrying out ultrasonic treatment to obtain a mixed solution A;
step four: reacting the mixed solution A for 6-8 h under the condition of keeping out of the sun, separating precipitates after the reaction is finished, washing and centrifuging to obtain PDA @ MoS2Drying the composite material for later use;
step five, taking PDA @ MoS according to the mass ratio of 1:102Mixing the copper source and the anhydrous ethanol in a mass-volume ratio of (1-1.25) g to (200-250) ml, stirring until the copper source and the anhydrous ethanol are dissolved, performing ultrasonic dispersion to obtain a mixed solution B, stirring and reacting the mixed solution B for 1.5-2.5 h, and standing for 11-13 h to obtain a reaction precursor solution;
sixthly, dispersing a reducing agent sodium hypophosphite monohydrate into absolute ethyl alcohol according to the mass volume ratio of 1g (220-250) ml, and stirring until the reducing agent solution is obtained;
step seven, discarding the supernatant in the reaction precursor solution, adding a reducing agent solution with the same volume as the reaction precursor solution before discarding the supernatant, transferring the mixture into a round-bottom flask, carrying out condensation reflux reaction at 75-85 ℃ for 25-35 min, naturally cooling after the reaction is finished, standing, collecting solid precipitate, washing and centrifuging to obtain the copper nanoparticle-loaded polydopamine modified sheet MoS2Nanometer antibacterial agent, oven drying, and storing。
The invention also has the following technical characteristics:
preferably, the molybdenum source is one or more of ammonium molybdate and sodium molybdate;
the sulfur source is one or more of sodium sulfide, thiourea and L-cysteine;
the copper source is one or more of copper acetate, copper sulfate and copper chloride.
Preferably, the filling ratio of the polytetrafluoroethylene lining in the second step is 50-65%.
Preferably, the washing and centrifuging in the second step, the fourth step and the seventh step are repeated and washed for 5 times by using alcohol and water alternately at 6000-8000 rpm.
Preferably, the drying in the second step, the fourth step and the seventh step is to place the sample in an oven at 50 ℃.
Preferably, in the step one, the step three and the step five, the ultrasonic dispersion is to place the mixed solution in an ultrasonic cleaner for ultrasonic treatment for 25-40 min.
Preferably, the stirring in the first step, the fifth step and the sixth step is performed by a magnetic stirrer.
Preferably, the buffer solution of tris hydrochloride has a pH of 8.5.
The invention also discloses the copper nanoparticle-loaded polydopamine-modified sheet MoS prepared by the preparation method2The nanometer antibacterial agent and polydopamine are uniformly coated on MoS2On the nano-chip, Cu nano-particles are uniformly dispersed in PDA @ MoS2The above step (1);
the Cu nano-particles have the size of 20-40 nm, and the total size of the material is about 250-500 nm.
The invention also protects the copper nanoparticle-loaded polydopamine-modified sheet MoS2The application of the nano antibacterial agent can ensure that the minimum inhibitory concentration to staphylococcus aureus can reach 0.02mg/mL and the inhibitory rate to escherichia coli can reach 99.5%.
Compared with the prior art, the invention has the following technical effects:
the invention relates to a PDA @ MoS2The excellent antibacterial effect of the-Cu composite is mainly due to MoS2And the synergistic antibacterial action of Cu nano particles: first, MoS2Photo-generated electron hole pairs are generated under the excitation of light, and the electron hole pairs react with water and oxygen on the surface of the material to generate ROS, so that the antibacterial property is exerted; the Cu nanoparticles can produce Cu2+The dissolution effect destroys the protein of the bacteria, thereby inactivating the bacteria and achieving the effect of killing the bacteria; mixing MoS2After the Cu nanoparticles are compounded with the Cu nanoparticles, the SPR effect can be generated after the Cu nanoparticles are illuminated, so that the Cu nanoparticles become electron donors which are MoS2Electrons are transported, so that more ROS can be generated to improve the antibacterial performance of the material;
furthermore, when the size of the Cu nano particles is small, the antibacterial performance of the Cu nano particles is optimal, and Cu is directly loaded on MoS2The size of the nano sheet is about 50 nanometers after being arranged on the nano sheet, the nano sheet is easy to aggregate and grow, and the method is not favorable for improving the antibacterial performance of the composite material2And a linking bridge of the Cu nanoparticles, so that the small-size Cu nanoparticles can be uniformly distributed in MoS2Surface growth to develop its optimal antibacterial properties; meanwhile, MoS is coated by a self-coating method2The nano-sheet is modified by PDA, the PDA has certain conductivity under the condition of full hydration, and the Cu nano-particle is used as an electron donor to inject electrons into MoS2The channel condition is provided, so that the antibacterial performance of the antibacterial material is improved;
the minimum inhibitory concentration of the nano antibacterial agent on staphylococcus aureus can reach 0.02mg/mL, and the inhibitory rate on escherichia coli can reach 99.5%;
MoS prepared by hydrothermal method2Nanosheet, PDA @ MoS prepared by self-coating method2Preparing PDA @ MoS by low-temperature water bath sodium hypophosphite reduction method2Cu, low cost and low energy consumption.
Drawings
FIG. 1 is the MoS prepared in example 12、PDA@MoS2、PDA@MoS2XRD pattern of Cu nano antibacterial agent;
FIG. 2 isPDA @ MoS prepared in example 12SEM photograph of/Cu nano antibacterial agent;
FIG. 3 is the PDA @ MoS prepared in example 12-TEM photograph of Cu ternary composite material 500 nm;
FIG. 4 is the PDA @ MoS prepared in example 12-TEM photograph of Cu ternary composite material at 100 nm;
FIG. 5 is the PDA @ MoS prepared in example 12-TEM images of Cu ternary composites, wherein (c1) is the diffraction lattice pattern of selected areas in (c);
FIG. 6 is the PDA @ MoS prepared in example 12-TEM photograph of Cu ternary composite, wherein (d1) is high resolution TEM photograph of selected area in (d);
FIG. 7 is a blank control group of Staphylococcus aureus;
FIG. 8 is a photograph showing the growth of Staphylococcus aureus after PDA treatment;
FIG. 9 shows MoS in example 12A picture of the growth of the treated staphylococcus aureus;
FIG. 10 is the PDA @ MoS of example 12A picture of the growth of the treated staphylococcus aureus;
FIG. 11 is the PDA @ MoS of example 12-photographs of staphylococcus aureus growth after Cu treatment;
FIG. 12 shows the PDA, MoS in example 1, from left to right2PDA @ MoS of example 12PDA @ MoS of example 12A bacteriostatic rate comparison graph of Cu to staphylococcus aureus;
FIG. 13 is PDA @ MoS2The antibacterial mechanism diagram of the/Cu nano composite material.
Detailed Description
The present invention will be explained in further detail with reference to examples.
Example 1
Step one, weighing 1g of ammonium molybdate and thiourea according to the mass ratio of atomic substances of 3:7, dispersing the ammonium molybdate and the thiourea into 220ml of deionized water, stirring the mixture on a magnetic stirrer until the ammonium molybdate and the thiourea are dissolved, and placing the mixed solution in an ultrasonic cleaner for ultrasonic dispersion for 30min to obtain a transparent solution;
step (ii) ofSecondly, transferring the transparent solution prepared in the first step into a polytetrafluoroethylene lining with a filling ratio of 60%, placing the transparent solution into a hydrothermal kettle to react for 24 hours in an oven at the temperature of 220 ℃, separating precipitates after the reaction is finished, alternately and repeatedly centrifuging and washing the precipitates for 5 times by using alcohol water at 6000rpm to obtain MoS2Nanosheets, namely drying the obtained sample in a 50 ℃ oven, and then filling the dried sample into a sample bag for storage for later use;
step three, dispersing 0.605g of tris (hydroxymethyl) aminomethane into 50ml of deionized water to prepare Tirs buffer solution, and adjusting the pH value to 8.5 by using concentrated hydrochloric acid; taking the obtained MoS according to the mass ratio of 1:0.82Dispersing 0.12g of the nano-sheets and dopamine hydrochloride into 50ml of tris (hydroxymethyl) aminomethane hydrochloride buffer solution, and performing ultrasonic treatment for 30min to obtain a mixed solution A;
step four: reacting the mixed solution A for 6h under the condition of keeping out of the sun, alternately and repeatedly washing and centrifuging 5 times by using alcohol water at the rotating speed of 6000rpm to obtain the PDA @ MoS2The composite material is prepared by drying the obtained sample in a 50 ℃ oven, and then filling the sample into a sample bag for storage;
step five, taking PDA @ MoS according to the mass ratio of 1:102Mixing and dispersing 1.25g of copper acetate and 250ml of absolute ethyl alcohol, stirring until the copper acetate and the absolute ethyl alcohol are dissolved, ultrasonically dispersing the mixed solution for 30min to obtain a mixed solution B, stirring and reacting the ultrasonically-treated mixed solution B on a magnetic stirrer for 2h, and standing for 12h to obtain a reaction precursor solution;
step six, dispersing 1g of reducing agent sodium hypophosphite monohydrate into 250ml of absolute ethyl alcohol to obtain reducing agent dispersion liquid;
seventhly, discarding supernatant in the reaction precursor solution, adding reducing agent solution with the same volume as the reaction precursor solution before discarding the supernatant, transferring the mixture into a round-bottom flask, placing the round-bottom flask into a water bath kettle, carrying out condensation reflux reaction at 80 ℃ for 30min, naturally cooling to room temperature after the reaction is finished, collecting solid precipitate, alternately and repeatedly centrifuging and washing the solid precipitate for 5 times by using alcohol water at the rotating speed of 6000rpm, and thus obtaining the copper nanoparticle-loaded polydopamine-modified sheet MoS2And (3) a nano antibacterial agent, drying the obtained sample in an oven at 50 ℃, and then filling the sample into a sample bag for storage.
Example 2
Step one, weighing 1.2g of sodium molybdate and L-cysteine according to the atomic substance weight ratio of 3:7, dispersing into 240ml of deionized water, stirring on a magnetic stirrer until the sodium molybdate and the L-cysteine are dissolved, and placing the mixed solution in an ultrasonic cleaner for ultrasonic treatment for 25min to obtain a transparent solution;
step two, transferring the transparent solution prepared in the step one into a polytetrafluoroethylene lining with the filling ratio of 50%, placing the transparent solution into a hydrothermal kettle to react for 22 hours in an oven at the temperature of 180 ℃, separating precipitates after the reaction is finished, alternately and repeatedly centrifuging and washing the precipitates for 5 times by using 7000rpm alcohol water to obtain MoS2Nanosheets, namely drying the obtained sample in a 50 ℃ oven, and then filling the dried sample into a sample bag for storage for later use;
step three, dispersing 0.605g of tris (hydroxymethyl) aminomethane into 50ml of deionized water to prepare Tirs buffer solution, and adjusting the pH value to 8.5 by using concentrated hydrochloric acid; taking the obtained MoS according to the mass ratio of 1:12Dispersing 0.1g of the nano-sheets and dopamine hydrochloride into 30ml of trihydroxymethyl aminomethane hydrochloride buffer solution, and carrying out ultrasonic treatment for 25min to obtain a mixed solution A;
step four: reacting the mixed solution A for 8 hours under the condition of keeping out of the sun, alternately and repeatedly washing and centrifuging 5 times by using alcohol water at the rotating speed of 6000rpm to obtain the PDA @ MoS2The composite material is prepared by drying the obtained sample in a 50 ℃ oven, and then filling the sample into a sample bag for storage;
step five, taking PDA @ MoS according to the mass ratio of 1:102Mixing and dispersing 1g of the mixed solution and copper sulfate into 200ml of absolute ethyl alcohol, stirring until the mixed solution is dissolved, ultrasonically dispersing the mixed solution for 25min to obtain a mixed solution B, stirring and reacting the ultrasonically-dispersed mixed solution B on a magnetic stirrer for 1.5h, and standing for 13h to obtain a reaction precursor solution;
step six, dispersing 1g of reducing agent sodium hypophosphite monohydrate into 220ml of absolute ethyl alcohol to obtain reducing agent dispersion liquid;
seventhly, discarding the supernatant in the reaction precursor solution, adding a reducing agent solution with the same volume as the reaction precursor solution before discarding the supernatant, transferring the reducing agent solution into a round-bottom flask together, placing the round-bottom flask into a water bath kettle, carrying out condensation reflux reaction at 75 ℃ for 35min, naturally cooling to room temperature after the reaction is finished, and collecting the solid precipitateThe precipitate is alternately and repeatedly centrifuged and washed for 5 times by using alcohol water at the rotating speed of 6000rpm to obtain the sheet MoS modified by the copper nano particle loaded with polydopamine2And (3) a nano antibacterial agent, drying the obtained sample in an oven at 50 ℃, and then filling the sample into a sample bag for storage.
Example 3
Step one, weighing 1.1g of sodium molybdate and sodium sulfide according to the mass ratio of atomic substances of 3:7, dispersing into 230ml of deionized water, stirring on a magnetic stirrer until the sodium molybdate and the sodium sulfide are dissolved, and placing the mixed solution in an ultrasonic cleaner for ultrasonic 40min to disperse to obtain a transparent solution;
step two, transferring the transparent solution prepared in the step one into a polytetrafluoroethylene lining with a filling ratio of 65%, placing the transparent solution into a hydrothermal kettle to react for 20 hours in an oven at the temperature of 200 ℃, separating precipitates after the reaction is finished, alternately and repeatedly centrifuging and washing the precipitates for 5 times by using alcohol water at 8000rpm to obtain MoS2Nanosheets, namely drying the obtained sample in a 50 ℃ oven, and then filling the dried sample into a sample bag for storage for later use;
step three, dispersing 0.605g of tris (hydroxymethyl) aminomethane into 50ml of deionized water to prepare Tirs buffer solution, and adjusting the pH value to 8.5 by using concentrated hydrochloric acid; taking the obtained MoS according to the mass ratio of 1:0.52Dispersing 0.11g of the nano-sheets and dopamine hydrochloride into 40ml of tris (hydroxymethyl) aminomethane hydrochloride buffer solution, and performing ultrasonic treatment for 40min to obtain a mixed solution A;
step four: reacting the mixed solution A for 7 hours under the condition of keeping out of the sun, alternately and repeatedly washing and centrifuging 5 times by using alcohol water at the rotating speed of 6000rpm to obtain the PDA @ MoS2The composite material is prepared by drying the obtained sample in a 50 ℃ oven, and then filling the sample into a sample bag for storage;
step five, taking PDA @ MoS according to the mass ratio of 1:102Mixing and dispersing 1.1g of copper chloride and 220ml of absolute ethyl alcohol, stirring until the copper chloride and the absolute ethyl alcohol are dissolved, ultrasonically dispersing the mixed solution for 40min to obtain a mixed solution B, stirring and reacting the ultrasonically-treated mixed solution B on a magnetic stirrer for 2.5h, and standing for 11h to obtain a reaction precursor solution;
step six, dispersing 1g of reducing agent sodium hypophosphite monohydrate into 230ml of absolute ethyl alcohol to obtain reducing agent dispersion liquid;
step sevenDiscarding supernatant in the reaction precursor solution, adding reducing agent solution with the same volume as the reaction precursor solution before discarding the supernatant, transferring the reducing agent solution into a round-bottom flask together, placing the round-bottom flask into a water bath kettle, carrying out condensation reflux reaction at 85 ℃ for 25min, naturally cooling to room temperature after the reaction is finished, collecting solid precipitate, alternately and repeatedly centrifuging and washing the solid precipitate for 5 times by using alcohol water at a rotating speed of 6000rpm, and thus obtaining the copper nanoparticle-loaded polydopamine-modified sheet MoS2And (3) a nano antibacterial agent, drying the obtained sample in an oven at 50 ℃, and then filling the sample into a sample bag for storage.
Data analysis
FIG. 1 shows MoS2、PDA@MoS2And PDA @ MoS2XRD pattern of/Cu nanocomposite, MoS is shown in FIG. 12All peaks in the XRD pattern of (1) are in contact with MoS2The standard data card (PDF96-101-1287) of (1) is not formed with any impurities correspondingly. Wherein the diffraction peak of the (002) crystal face is strong, which shows that the MoS is prepared by taking sodium molybdate as a molybdenum source and L-cysteine as a sulfur source through a hydrothermal method2The flakes have a good layered structure. By observing PDA @ MoS2XRD pattern of the nanocomposite is known, and MoS2In contrast, PDA @ MoS2The diffraction peak of the nano composite material shows obvious peak broadening, which can indicate that the PDA succeeds with MoS to a certain extent2The composite is successful, and the organic material is introduced, so that the crystallinity of the composite material is reduced. At PDA @ MoS2MoS can be found in XRD pattern of/Cu2The diffraction peak of the material is still obvious, and the diffraction peaks of Cu (111) and Cu (002) crystal planes appear, which corresponds to the standard data card (PDF96-151-2505), which shows that Cu is successfully synthesized in the material.
FIG. 2 is PDA @ MoS2Scanning electron microscope image of/Cu. It can be seen that Cu is in PDA @ MoS2The dispersion is uniform and the size is stable at about 20 nm.
FIG. 3, 4, 5, 6 are PDA @ MoS2Transmission electron micrograph of/Cu. As can be seen from FIG. 3, PDA @ MoS2The size of the/Cu nano composite material is about 300 nm. FIG. 4 is a partial enlarged view of FIG. 3, showing that the PDA can be coated on the MoS more uniformly2In the above-mentioned manner,meanwhile, Cu nanoparticles with the particle size of about 10nm are found on the surface of the nano-particles, and the nano-particles are uniformly dispersed in PDA @ MoS2The surface shows that the metal ion loading site of the PDA plays a great role in the dispersed growth of the Cu nanoparticles. FIGS. 5 and 6 PDA @ MoS, respectively2Cu nano particles and MoS in/Cu nano composite material2HRTEM of nanosheets, and fourier transform of the image of Cu nanoparticles to obtain its diffraction pattern, as shown in fig. 5(c1), were performed in this study. The diffraction pattern shows that the Cu nanoparticles have good crystallinity, two groups of crystal faces (111) and (002) can be clearly seen, and meanwhile, the three groups of crystal lattice stripes in the image are measured, and the spacing between the two groups of crystal faces is about 0.181nm, and the spacing between the other group of crystal faces is about 0.209nm, which is consistent with the data of the two groups of crystal faces of Cu. The result shows that the PDA @ MoS can be successfully prepared by the sodium hypophosphite reduction copper acetate method in the experiment2Cu nano composite material and Cu nano particle homodisperse PDA @ MoS2A surface.
FIGS. 7, 8, 9, 10 and 11 are photographs of a Staphylococcus aureus blank control group using PDA and MoS, respectively2、PDA@MoS2、PDA@MoS2Photograph of growth of Staphylococcus aureus after Cu treatment. Fig. 12 shows the bacteriostatic ratios obtained by calculation and analysis of the photographs of fig. 7, 8, 9, 10, and 11. As can be seen from FIG. 8, there was no reduction but an increase in the number of Staphylococcus aureus treated with PDA, which was due to the biodegradability of PDA, which, while acting with bacteria, was decomposed by the bacteria, but instead provided nutrients for the growth of the bacteria. As can be seen from FIGS. 9 and 10, MoS2After the surface modification of PDA, the bacteriostasis rate is reduced to 40 percent (MoS)2) Down to 18% (PDA @ MoS)2) This may also be a result of the biodegradability of PDA. However, as can be seen from FIG. 11, PDA @ MoS2the/Cu nano composite material has obvious inhibiting effect on staphylococcus aureus, and the bacteriostasis rate reaches about 99.5 percent, which is probably because the Cu nano particles can release Cu when reacting with bacteria2+And Cu2+Is a good antibacterial agent per se. Meanwhile, after photoexcitation, the Cu nanoparticles exist on the surfacePlasma resonance effect (SPR) to MoS2Provides a prerequisite for the composite material to generate more ROS, and PDA acts as MoS2The intermediate link with Cu nanoparticles has a certain conductivity for passing electrons from Cu nanoparticles to MoS2Channel conditions are provided. A schematic diagram of which is shown in fig. 13.

Claims (10)

1. Copper nanoparticle-loaded polydopamine-modified sheet MoS2The preparation method of the nano antibacterial agent is characterized by comprising the following steps:
step one, weighing a molybdenum source and a sulfur source according to the mass ratio of atomic substances of 3:7, dispersing the molybdenum source and the sulfur source into deionized water, stirring until the molybdenum source and the sulfur source are dissolved, and performing ultrasonic dispersion to obtain a transparent solution, wherein the mass volume ratio of solids to deionized water is (1-1.2) g: (220-240) ml;
step two, transferring the transparent solution prepared in the step one into a polytetrafluoroethylene lining, putting the polytetrafluoroethylene lining into a hydrothermal kettle, reacting for 20-24 hours in an oven at the temperature of 180-220 ℃, separating precipitates after the reaction is finished, washing and centrifuging to obtain MoS2Drying the nanosheets for later use;
step three, taking the obtained MoS according to the mass ratio of 1: 0.5-1.02Dispersing the nanosheets and dopamine hydrochloride into a trihydroxymethyl aminomethane hydrochloride buffer solution, wherein the mass-to-volume ratio of the solid to the buffer solution is (1-1.2) g: (300-500) ml, and carrying out ultrasonic treatment to obtain a mixed solution A;
step four: reacting the mixed solution A for 6-8 h under the condition of keeping out of the sun, separating precipitates after the reaction is finished, washing and centrifuging to obtain PDA @ MoS2Drying the composite material for later use;
step five, taking PDA @ MoS according to the mass ratio of 1:102Mixing the copper source and the anhydrous ethanol in a mass-volume ratio of (1-1.25) g to (200-250) ml, stirring until the copper source and the anhydrous ethanol are dissolved, performing ultrasonic dispersion to obtain a mixed solution B, stirring and reacting the mixed solution B for 1.5-2.5 h, and standing for 11-13 h to obtain a reaction precursor solution;
sixthly, dispersing a reducing agent sodium hypophosphite monohydrate into absolute ethyl alcohol according to the mass volume ratio of 1g (220-250) ml, and stirring until the reducing agent solution is obtained;
step seven, discarding the supernatant in the reaction precursor solution, adding a reducing agent solution with the same volume as the reaction precursor solution before discarding the supernatant, transferring the mixture into a round-bottom flask, carrying out condensation reflux reaction at 75-85 ℃ for 25-35 min, naturally cooling after the reaction is finished, standing, collecting solid precipitate, washing and centrifuging to obtain the copper nanoparticle-loaded polydopamine modified sheet MoS2And (5) drying and storing the nano antibacterial agent.
2. The copper nanoparticle-loaded polydopamine-modified sheet MoS of claim 12The preparation method of the nano antibacterial agent is characterized in that the molybdenum source is one or more of ammonium molybdate and sodium molybdate;
the sulfur source is one or more of sodium sulfide, thiourea and L-cysteine;
the copper source is one or more of copper acetate, copper sulfate and copper chloride.
3. The copper nanoparticle-loaded polydopamine-modified sheet MoS of claim 12The preparation method of the nano antibacterial agent is characterized in that the filling ratio of the polytetrafluoroethylene lining in the second step is 50-65%.
4. The copper nanoparticle-loaded polydopamine-modified sheet MoS of claim 12The preparation method of the nano antibacterial agent is characterized in that the step two, the step four and the step seven are washing agents and centrifugation, wherein alcohol and water are used for repeatedly centrifuging and washing for 5 times alternately at 6000-8000 rpm.
5. The copper nanoparticle-loaded polydopamine-modified sheet MoS of claim 12The preparation method of the nano antibacterial agent is characterized in that the drying in the second step, the fourth step and the seventh step is to place the sample in a 50 ℃ drying oven for drying.
6. The copper nanoparticle-loaded polydopamine-modified sheet MoS of claim 12The preparation method of the nano antibacterial agent is characterized in that in the first step, the third step and the fifth step, ultrasonic dispersion is carried out, namely, the mixed solution is placed in an ultrasonic cleaner for ultrasonic treatment for 25-40 min.
7. The copper nanoparticle-loaded polydopamine-modified sheet MoS of claim 12The preparation method of the nano antibacterial agent is characterized in that the stirring in the first step, the fifth step and the sixth step is performed by adopting a magnetic stirrer.
8. The copper nanoparticle-loaded polydopamine-modified sheet MoS of claim 12The preparation method of the nano antibacterial agent is characterized in that the pH value of the tris hydrochloride buffer solution is 8.5.
9. Copper nanoparticle-loaded polydopamine-modified sheet MoS prepared by the preparation method according to any one of claims 1-82The nano antibacterial agent is characterized in that polydopamine is uniformly wrapped on MoS2On the nano-chip, Cu nano-particles are uniformly dispersed in PDA @ MoS2The above step (1);
the Cu nano-particles have the size of 20-40 nm, and the total size of the material is about 250-500 nm.
10. The copper nanoparticle-loaded polydopamine-modified sheet MoS of claim 92The application of the nano antibacterial agent is characterized in that the minimum inhibitory concentration to staphylococcus aureus can reach 0.02mg/mL, and the inhibitory rate of the concentration to escherichia coli can reach 99.5%.
CN202111313873.4A 2021-11-08 2021-11-08 Copper nanoparticle-loaded polydopamine-modified sheet MoS2Nano antibacterial agent and preparation method and application thereof Withdrawn CN114009447A (en)

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CN114984309A (en) * 2022-05-30 2022-09-02 四川大学 Preparation method and application of amphoteric ion polymer modified nanosheet
CN114989577A (en) * 2022-06-02 2022-09-02 浙江理工大学 Preparation method and application of antibacterial and antiviral master batch
CN115252905A (en) * 2022-07-14 2022-11-01 山东第一医科大学(山东省医学科学院) Bionic material with physical sterilization and immune cell regulation functions and construction method
CN115300482A (en) * 2022-08-17 2022-11-08 山东大学 Bovine serum albumin coated chlorhexidine loaded nickel phosphide nano-capsule, preparation method and antibacterial application thereof
CN115779965A (en) * 2022-11-15 2023-03-14 陕西科技大学 MoS with antibacterial property and potential tumor inhibition property 2 Preparation method and application of nano enzyme

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114984309A (en) * 2022-05-30 2022-09-02 四川大学 Preparation method and application of amphoteric ion polymer modified nanosheet
CN114989577A (en) * 2022-06-02 2022-09-02 浙江理工大学 Preparation method and application of antibacterial and antiviral master batch
CN114989577B (en) * 2022-06-02 2024-03-12 浙江理工大学 Preparation method and application of antibacterial and antiviral master batch
CN115252905A (en) * 2022-07-14 2022-11-01 山东第一医科大学(山东省医学科学院) Bionic material with physical sterilization and immune cell regulation functions and construction method
CN115300482A (en) * 2022-08-17 2022-11-08 山东大学 Bovine serum albumin coated chlorhexidine loaded nickel phosphide nano-capsule, preparation method and antibacterial application thereof
CN115300482B (en) * 2022-08-17 2023-11-28 山东大学 Bovine serum albumin coated chlorhexidine loaded nickel phosphide nanocapsule, preparation method and antibacterial application thereof
CN115779965A (en) * 2022-11-15 2023-03-14 陕西科技大学 MoS with antibacterial property and potential tumor inhibition property 2 Preparation method and application of nano enzyme

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