CN114223670A - Antibacterial agent and preparation method thereof - Google Patents

Antibacterial agent and preparation method thereof Download PDF

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CN114223670A
CN114223670A CN202111393058.3A CN202111393058A CN114223670A CN 114223670 A CN114223670 A CN 114223670A CN 202111393058 A CN202111393058 A CN 202111393058A CN 114223670 A CN114223670 A CN 114223670A
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antibacterial agent
deionized water
reaction kettle
alooh
pvp
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杨福
董雪雪
成捷
涂文龙
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Jiangsu University of Science and Technology
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    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N59/00Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16Heavy metals; Compounds thereof
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION 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
    • A01N25/00Biocides, 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
    • A01N25/08Biocides, 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

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  • Engineering & Computer Science (AREA)
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  • Wood Science & Technology (AREA)
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  • Inorganic Chemistry (AREA)
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Abstract

An antibacterial agent is prepared from Al (NO)3)3Adding the mixture into deionized water, then sequentially adding PVP, ethanol and acetone, and uniformly stirring to obtain a mixed solution; adding Ni (NO) to the mixed solution3)2Transferring the solution to a hydrothermal reaction kettle containing a Polytetrafluoroethylene (PTFE) lining for hydrothermal reaction, pouring out reaction liquid, centrifugally washing, drying and grinding to obtain a carrier, wherein the carrier is named as Ni-AlOOH; dispersing Ni-AlOOH in deionized water, adding AgNO3And (3) stirring the solid at room temperature, then centrifugally washing, drying and grinding, and finally calcining the obtained product in a tubular furnace to obtain the required product. The invention enables the material to have strong assembly capability through nickel doping,the synthetic material has good biocompatibility and also has good antibacterial performance.

Description

Antibacterial agent and preparation method thereof
Technical Field
The invention relates to the technical field of new materials, in particular to a nano Ag-loaded nickel modified nano flower-shaped AlOOH antibacterial agent and a preparation method thereof.
Background
Pathogenic contamination in the environment has raised serious public concern. Due to the complexity of the hospital environment, various infectious microorganisms have strong resistance to disinfectants and drugs. The united states centers for disease control and prevention (CDC) estimates that, despite hospital disinfection being valued, approximately 170 million patients in the united states infect hospital-related infections each year, with an additional medical cost of $ 45-65 billion per year. Therefore, broad-spectrum and highly effective bactericides have been the focus of research.
Chlorination is the most common method of reducing the risk of nosocomial infections due to the pungent odor and the limitation of harmful by-products of the sterilization product. At present, many methods related to the resistance of microorganisms and antibacterial agents, particularly the application of inorganic nanoparticles such as Cu, ZnO, Ti, Ag, have been studied. The silver nanoparticles have broad-spectrum antibacterial activity and can be used for targeted treatment of some stubborn microorganisms. It is noted, however, that controlling the state of the silver nano-species, including size and shape, is critical to enhance antimicrobial activity, since silver ions are reasonably released from the final nanomaterial. In addition, the interaction between the constructed nano-species and the support also affects the release of Ag ions to attack these bacteria. For example, Cheng et al (New Chemical Materials,2020,48(7):265-270) attempted to load Ag nanoparticles onto mesoporous silica using a designed strategy, but these results tended to encapsulate the Ag nanoparticles into their limited mesopores, which may prevent efficient release of silver ions due to the long diffusion distance of silver ions through the mesoporous channels to the bacteria. In addition, silica lacks abundant surface groups and fails to build strong interactions between silver nano-species and bacteria to trigger controlled attack pathways. Patent CN109221249A discloses a method for preparing a ZnO nanorod-supported nano-Ag composite antibacterial agent, but the synthesized antibacterial agent must have antibacterial activity under the condition of ultraviolet irradiation. Therefore, designing powerful two-dimensional materials that assemble and modify functional silver species to trigger better antimicrobial performance can be a challenge.
Disclosure of Invention
The technical problem to be solved is as follows: the present invention provides an antimicrobial agent and a method for preparing the same, which produces a powerful two-dimensional material for assembling and modifying functional silver species to trigger better antimicrobial properties.
The technical scheme is as follows: a method for preparing an antibacterial agent comprises the following steps: step 1, adding Al (NO)3)3Adding into deionized water, sequentially adding PVP, ethanol and acetone, and stirring to obtain mixed solution, wherein Al (NO) is3)3The mass ratio of the PVP to the PVP, water, ethanol to acetone is 1 (0.2-2.5) to (40-60) to (9.6-111) to (10-60); step 2, adding 0.5-1 wt.% of Ni (NO) into the mixed solution obtained in the step 13)2Solution, Ni (NO)3)2The concentration of the carrier is 0.5-1 mol/L, then the carrier is transferred to a hydrothermal reaction kettle containing Polytetrafluoroethylene (PTFE) lining, hydrothermal reaction is carried out for 12-32 h at the temperature of 150-200 ℃, then reaction liquid is poured out, and the carrier is obtained by centrifugal washing, drying and grinding, and is named as Ni-AlOOH; step 3, dispersing Ni-AlOOH in deionized water, and adding AgNO3Stirring the solid at room temperature, then centrifugally washing, drying and grinding, and finally calcining the obtained product in a tubular furnace to obtain the required product, wherein the calcining heating rate is 1-5 ℃/min, the calcining temperature is 200-500 ℃, and the time is 1-5 h.
Preferably, Al (NO) in step 13)3The mass ratio of the PVP to the water to the ethanol to the acetone is 1:1.2:60:60:10
Preferably, Ni (NO) in step 23)2The concentration of (2) is 0.6 mol/L.
The set rotating speed and the set time of the centrifuge in the step 2 and the step 3 are 5000-10000 r/min and 2-6 min respectively.
Preferably, the volume of the deionized water in the step 3 is 50mL, and the volume is Ni-AlOOH or AgNO3The amount of the raw materials is 0.1g and 0.7084 g respectively, and the stirring time is 3-12 h.
Preferably, in the step 3, the temperature rise rate in the tubular furnace is 2 ℃/min, the calcination temperature is 450 ℃, and the time is 1-5 h.
The antibacterial agent prepared by the above preparation method
Has the advantages that: the nickel doping enables the material to have strong assembly capability (as can be embodied in fig. 2). The synthetic material has good biocompatibility. The material has good antibacterial performance (table 1, as shown in figure 2).
Drawings
FIG. 1 is a schematic diagram of the synthesis procedure;
the left picture of fig. 2 is an electron microscope photo of the composite material of the nickel modified nanometer flower-shaped AlOOH loaded with the nanometer Ag, and the right picture is an electron microscope photo of the composite material of the nanometer flower-shaped AlOOH loaded with the nanometer Ag.
FIG. 3 shows the inhibition zones of the nanocomposite (a) AlNiO, (B) AlO, (C) Ag-AlNiO and (D) Ag-AlO on (A) gram-negative E.coli, (B) Pseudomonas aeruginosa, (C) Staphylococcus aureus, and (D) Candida albicans.
Detailed Description
The foregoing and/or other advantages of the invention will become further apparent from the following detailed description of the invention when taken in conjunction with the accompanying drawings.
Example 1
Mixing Al (NO)3)3·9H2O in 30mL deionized water, followed by 0.6g PVP in 30mL ethanol and 5mL acetone with a pipette in a fume hood, and finally 400. mu.L of 0.6mol/L Ni (NO) with a pipette gun3)2And transferring the solution into a Polytetrafluoroethylene (PTFE) hydrothermal reaction kettle, keeping the reaction kettle at a set temperature (160 ℃) for 20 hours, taking out the reaction kettle, cooling the reaction kettle to room temperature, then obtaining a white precipitate, transferring the reaction kettle into a centrifuge tube in a fume hood, washing the reaction kettle once at a rotating speed of 6000r/min for 6 minutes, washing the reaction kettle twice with ethanol, drying the reaction kettle in an oven at 70 ℃, grinding the reaction kettle with an agate mortar, and collecting the product, namely AlNiO.
Example 2
Mixing Al (NO)3)3·9H2Dissolving O in 30mL of deionized water, adding 0.6g of PVP dissolved in 30mL of ethanol, adding 5mL of Acetone (AR) in a fume hood by using a pipette, transferring the mixture to a Polytetrafluoroethylene (PTFE) hydrothermal reaction kettle, keeping the reaction kettle at a set temperature (160 ℃) for 20 hours, taking out the reaction kettle, cooling the reaction kettle to room temperature to obtain a white precipitate, transferring the reaction kettle to a centrifuge tube in the fume hood at the rotating speed of 6000r/min for 6min, washing the reaction kettle once with waterWashing with ethanol twice, drying in an oven at 70 deg.C, grinding with agate mortar, and collecting and named AlO.
Example 3
Mixing Al (NO)3)3·9H2O in 30mL deionized water, followed by 0.6g PVP in 30mL ethanol and 5mL acetone with a pipette in a fume hood, and finally 400. mu.L of 0.6mol/L Ni (NO) with a pipette gun3)2Transferring the solution into a Polytetrafluoroethylene (PTFE) hydrothermal reaction kettle, keeping the reaction kettle at a set temperature (160 ℃) for 20 hours, taking out the reaction kettle, cooling the reaction kettle to room temperature, taking out the reaction kettle, transferring the reaction kettle into a centrifuge tube in a fume hood, washing the reaction kettle once at a rotating speed of 6000r/min for 6 minutes, washing the reaction kettle twice with ethanol, drying the reaction kettle in an oven at 70 ℃, grinding the reaction kettle with agate, collecting the solution, dissolving 0.10g of Ni-AlOOH in 50mL of deionized water, and weighing 1wt.% of AgNO3Dissolving the solution in the solution, stirring the solution for 8 hours on a magnetic stirrer, washing the solution by water and ethanol once respectively, drying the solution at 70 ℃, grinding the solution, and then carrying out heat treatment on the ground solution in a tubular furnace for 2 hours to obtain a product named as Ag-AlNiO, wherein the heating rate in the tubular furnace is 2 ℃/min, and the calcining temperature is 450 ℃.
Example 4
Mixing Al (NO)3)3·9H2Dissolving O in 30mL of deionized water, adding 0.6g of PVP dissolved in 30mL of ethanol, adding 5mL of Acetone (AR) in a fume hood by using a pipette, transferring the mixture to a Polytetrafluoroethylene (PTFE) hydrothermal reaction kettle, keeping the reaction kettle at a set temperature (160 ℃) for 20 hours, taking out the reaction kettle, cooling the reaction kettle to room temperature to obtain a white precipitate, transferring the reaction kettle to a centrifuge tube in the fume hood at the rotating speed of 6000r/min for 6 minutes, washing the reaction kettle once, washing the reaction kettle twice with ethanol, drying the reaction kettle in an oven at the temperature of 70 ℃, grinding the reaction kettle with agate, collecting the product, dissolving 0.10g of nano flower-shaped AlOOH in 50mL of deionized water, weighing 1wt.% of AgNO, dissolving the product in 50mL of deionized water, and grinding the product with an agate mortar to obtain a fine powder3Dissolving the solution in the solvent, adding a rotor, stirring the solution for 8 hours on a magnetic stirrer, washing the solution by water and ethanol once respectively, drying the solution at the temperature of 70 ℃, grinding the solution, and then carrying out heat treatment on the solution for 2 hours in a tubular furnace to obtain a product named as Ag-AlO, wherein the heating rate in the tubular furnace is 2 ℃/min, and the calcining temperature is 450 ℃.
The above examples 1-4 were evaluated for the antifungal properties of Ag-AlNiO, Ag-AlO and AlO using the Microplate Alamar Blue method. The Minimum Inhibitory Concentration (MIC) values are shown in Table 1. Wherein BCG and MDR are BCG vaccine and multidrug resistant respectively. (MIC (minimum inhibition concentration): minimum inhibitory concentration) of the lowest drug concentration that completely inhibits the growth of bacteria in a test tube or a small hole in the dilution method for microorganism identification)
TABLE 1 MIC values (μ g/mL) of the synthesized nanocomposites for Mycobacterium tuberculosis
Figure RE-GDA0003511639390000041

Claims (7)

1. The preparation method of the antibacterial agent is characterized by comprising the following steps: step 1, adding Al (NO)3)3Adding into deionized water, sequentially adding PVP, ethanol and acetone, and stirring to obtain mixed solution, wherein Al (NO) is3)3The mass ratio of the PVP to the PVP, water, ethanol to acetone is 1 (0.2-2.5) to (40-60) to (9.6-111) to (10-60); step 2, adding 0.5-1 wt.% of Ni (NO) into the mixed solution obtained in the step 13)2Solution, Ni (NO)3)2The concentration of the carrier is 0.5-1 mol/L, then the carrier is transferred to a hydrothermal reaction kettle containing Polytetrafluoroethylene (PTFE) lining, hydrothermal reaction is carried out for 12-32 h at the temperature of 150-200 ℃, then reaction liquid is poured out, and the carrier is obtained by centrifugal washing, drying and grinding, and is named as Ni-AlOOH; step 3, dispersing Ni-AlOOH in deionized water, and adding AgNO3Stirring the solid at room temperature, then centrifugally washing, drying and grinding, and finally calcining the obtained product in a tubular furnace to obtain the required product, wherein the calcining heating rate is 1-5 ℃/min, the calcining temperature is 200-500 ℃, and the time is 1-5 h.
2. The method for producing the antibacterial agent according to claim 1, wherein Al (NO) in step 13)3The mass ratio of the PVP to the water to the ethanol to the acetone is 1:1.2:60:60: 10.
3. The method for producing the antibacterial agent according to claim 1, wherein Ni (NO) in step 23)2The concentration of (2) is 0.6 mol/L.
4. The method for producing an antibacterial agent according to claim 1, characterized in that: in the step 2 and the step 3, the set rotating speed and the set time of the centrifuge are 5000-10000 r/min and 2-6 min respectively.
5. The method for producing an antibacterial agent according to claim 1, characterized in that: step 3, the volume of the deionized water is 50mL, and the deionized water is Ni-AlOOH and AgNO3The amount of the raw materials is 0.1g and 0.7084 g respectively, and the stirring time is 3-12 h.
6. The method for producing an antibacterial agent according to claim 1, characterized in that: and 3, heating in the tubular furnace at a rate of 2 ℃/min, calcining at a temperature of 450 ℃ for 1-5 h.
7. An antibacterial agent obtained by the process according to any one of claims 1 to 6.
CN202111393058.3A 2021-11-23 2021-11-23 Antibacterial agent and preparation method thereof Pending CN114223670A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105948087A (en) * 2016-03-25 2016-09-21 南开大学 Preparation method of gamma-AlOOH and gamma-Al2O3 nanotube and nanostructure
CN107897203A (en) * 2017-10-11 2018-04-13 河南师范大学 A kind of nickel cobalt layered double-hydroxide composite material of silver ion and its preparation method and application
CN108991016A (en) * 2018-08-02 2018-12-14 张家港市汇鼎新材料科技有限公司 A kind of preparation method of alumina load copper zinc antibacterial agent
CN110015676A (en) * 2018-01-09 2019-07-16 中国石油天然气股份有限公司 Alumina material and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105948087A (en) * 2016-03-25 2016-09-21 南开大学 Preparation method of gamma-AlOOH and gamma-Al2O3 nanotube and nanostructure
CN107897203A (en) * 2017-10-11 2018-04-13 河南师范大学 A kind of nickel cobalt layered double-hydroxide composite material of silver ion and its preparation method and application
CN110015676A (en) * 2018-01-09 2019-07-16 中国石油天然气股份有限公司 Alumina material and preparation method thereof
CN108991016A (en) * 2018-08-02 2018-12-14 张家港市汇鼎新材料科技有限公司 A kind of preparation method of alumina load copper zinc antibacterial agent

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
YAO ZHOU ET AL.: "Adsorption and On-Site Transformation of Transition Metal Cations on Ni-Doped AlOOH Nanoflowers for OER Electrocatalysis", 《ACS SUSTAINABLE CHEM. ENG.》 *
王春华 等: "纳米银和抗结核药物对耐药结核分枝杆菌联合作用初探", 《中国卫生检验杂质》 *
许孟飞 等: "Al2O3/ZnO纳米复合材料的制备及其应用研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 *

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