WO2023143052A1 - Application of bismuth trioxide as bactericide - Google Patents

Application of bismuth trioxide as bactericide Download PDF

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WO2023143052A1
WO2023143052A1 PCT/CN2023/071584 CN2023071584W WO2023143052A1 WO 2023143052 A1 WO2023143052 A1 WO 2023143052A1 CN 2023071584 W CN2023071584 W CN 2023071584W WO 2023143052 A1 WO2023143052 A1 WO 2023143052A1
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bismuth trioxide
bismuth
aqueous solution
trioxide
application
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PCT/CN2023/071584
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French (fr)
Chinese (zh)
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孙占奎
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中科优品(天津)科技发展有限公司
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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G29/00—Compounds of bismuth

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  • the invention belongs to the field of fungicides, and in particular relates to the application of bismuth trioxide as a fungicide.
  • antibacterial materials are divided into inorganic antibacterial agents, organic antibacterial agents, photocatalytic antibacterial agents, etc.
  • organic antibacterial agents have the characteristics of fast sterilization speed and high antibacterial efficacy, but they have poor heat resistance, insufficient persistence, and are prone to drug resistance.
  • Photocatalytic antibacterial materials have developed rapidly in recent years, but they mainly rely on ultraviolet light, and the light utilization rate is low.
  • Inorganic antibacterial agents have the characteristics of good heat resistance, good stability, broad antibacterial spectrum, long validity period, low toxicity, and no drug resistance. They are the mainstream products in the current market.
  • the most commonly used inorganic antibacterial agents are silver series antibacterial agents, which have a good bactericidal effect, but are relatively expensive, easy to change color, and silver has cumulative toxicity, so its application is limited. Copper fungicides are not as effective as silver fungicides, and copper oxide itself is very heavy in color and has certain toxicity, which limits its application range.
  • Other commonly used inorganic antibacterial agents such as titanium dioxide and molybdenum trioxide are 2B carcinogens, and their long-term safety is doubtful.
  • the purpose of the present invention is to overcome the shortcoming in the prior art, provide a kind of application of bismuth trioxide as bactericide.
  • a kind of bismuth trioxide is used as the application of bactericide, and described bismuth trioxide adopts one of following modes to prepare:
  • Method 1 At room temperature, configure a deionized aqueous solution of sodium bismuthate in the reaction vessel. At this time, the system is taupe. Heat it to 50-80 degrees. Under ultrasonic conditions, add HCl solution until it is acidic. At this time, the color of the system becomes lighter. Continue to ultrasonically stir under heating conditions until the reaction is complete, collect the product by centrifugation, dry at 80-100 degrees for 1-3 hours, then transfer to a muffle furnace and heat at 300-500 degrees for 1-3 hours. After cooling, the product will be less than 10 microns And nano bismuth trioxide, which is light white yellowish powder solid;
  • Or method 3 Add metal bismuth with a purity greater than 99% into the conical flask, add deionized water; then irradiate with laser light with an energy density of 30-160J cm -2 ; repeatedly irradiate an area for more than 5 minutes, and the frequency is at 1kHz; after the irradiation is completed, the metal bismuth is removed to obtain nano bismuth trioxide dispersed in water.
  • the concentration of the sodium bismuthate deionized aqueous solution is 0.5-5 mol/L; the concentration of the HCl solution is 1-10 mol/L.
  • the concentration of the aqueous solution of sodium bismuthate is 0.5-5 mol/L; the concentration of the aqueous solution of nitric acid is 1-10 mol/L.
  • the energy density is 100-160 J cm -2 .
  • the ultrasonic power is 200-700 watts, and the time is 10-60 minutes.
  • the present application also includes the application of the bismuth trioxide as a fungicide, and the bismuth trioxide is used in combination with silver antibacterial agents, copper antibacterial agents, zinc antibacterial agents, titanium antibacterial agents, and molybdenum antibacterial agents;
  • the mass ratio of bismuth trioxide to silver antibacterial agent, copper antibacterial agent, zinc antibacterial agent, titanium antibacterial agent and molybdenum antibacterial agent is 0.05-1:1-0.05 respectively.
  • the inorganic metal oxide bismuth trioxide prepared by using three methods in the present application has good antibacterial activity, and can effectively kill Gram-negative bacteria, Gram positive bacteria, including drug-resistant strains.
  • the active substance will show a certain acidity when it meets water. When it contacts water vapor, it will continuously release H+, thus playing a certain bactericidal effect.
  • the metal ions of the active substance can be firmly adsorbed on the surface of the bacterial cell membrane by Coulomb force, further penetrate the cell wall, cause the cell wall to rupture, cause the cytoplasm to flow out and finally lead to the death of the bacteria.
  • the active substance can excite oxygen in water or air to generate hydroxyl radicals and active oxygen ions under light irradiation, thereby generating oxidative stress, destroying the reproductive ability of bacteria, and causing the death of bacteria.
  • the active substance is stable in nature and has a long-lasting antibacterial effect. Moreover, the price is low and the economy is good.
  • the active substance can be used alone or in combination with other types of antibacterial agents to achieve a very good bactericidal effect.
  • nano-bismuth trioxide prepared by laser irradiation method can better interact with bacteria because of its sheet structure, destroying bacterial cell membranes and causing bacterial death.
  • Fig. 1 is the electron microscope schematic diagram of normal multi-drug resistant Escherichia coli (ATCC8739);
  • Fig. 2 is the electron microscope schematic diagram of Escherichia coli after using the 1mg/ml nanometer bismuth trioxide aqueous solution process that embodiment 4 prepares;
  • Fig. 3 is the electron microscope schematic diagram of the normal multi-drug resistant Staphylococcus aureus (ATCC 6538);
  • Example 4 is a schematic electron microscope view of Staphylococcus aureus treated with the 1 mg/ml nano bismuth trioxide aqueous solution prepared in Example 4.
  • Embodiment 1 this antibacterial substance bismuth trioxide (CAS accession number 1304-76-3), when the particle of nanoscale or the particle of micron scale is used alone, all can kill the Gram-negative bacterium of multi-drug resistance and Gram-negative bacteria and Gram-negative bacteria. Lambert-positive bacteria, among them, micron-sized bismuth trioxide can be directly purchased commercially.
  • Example 2 At room temperature, weigh 14.00 g of sodium bismuthate and put it into a 250 ml Erlenmeyer flask, add 80 ml of deionized water, and use a polytetrafluoroethylene rotor. The Erlenmeyer flask was fixed in an oil bath on a heating stirrer, and the system was taupe at this time. Afterwards, 5 mmol/ml aqueous HCl solution was added dropwise under ultrasonication until the pH was adjusted to 1, at which time the color of the system became lighter. Continue ultrasonic stirring at 80°C for 2h.
  • Example 3 At room temperature, weigh 14.00 g of sodium bismuthate and put it into a 250 ml Erlenmeyer flask, add 25 ml of deionized water and a Teflon rotor. Afterwards, 100 mL of HNO 3 (5 mmol/ml) solution was added dropwise, stirred at room temperature for 2 hours, and a precipitate would slowly precipitate out. The precipitate was collected and washed with HNO 3 (5 mmol/ml) solution followed by deionized water. Dry the product in a 100 degree oven. Afterwards, the product is placed in a tube furnace and calcined at 5°C per minute to 340°C for 2 hours in an atmosphere of 4% hydrogen and 96% nitrogen. After cooling, it will be less than 10 microns and nanometer bismuth trioxide, which is light white Yellowish powder solid.
  • Example 4 1 gram of metal bismuth with a purity greater than 99.97% was added to a conical flask, and 7 ml of deionized water was added. Afterwards, it is irradiated with 1064nm laser (Nd:YAG laser), the irradiation power is 12.5W, and the energy density is 160J cm -2 . Irradiate an area repeatedly for 5 minutes at a frequency of 1 kHz. After the irradiation is completed, the metal bismuth is removed to obtain nano bismuth trioxide dispersed in water.
  • 1064nm laser Nd:YAG laser
  • the irradiation power is 12.5W
  • the energy density 160J cm -2
  • Example 5 1 gram of metal bismuth with a purity greater than 99.97% was added to a conical flask, and 7 ml of deionized water was added. Afterwards, it is irradiated with 1064nm laser (Nd:YAG laser), the irradiation power is 12.5W, and the energy density is 160J cm -2 . Irradiate an area repeatedly for 5 minutes at a frequency of 1 kHz. After the irradiation is completed, the ultrasonic power is 300 watts; the ultrasonic wave is used for 20 minutes to make it uniformly dispersed, and then the metal bismuth is removed to obtain nano bismuth trioxide dispersed in water.
  • 1064nm laser Nd:YAG laser
  • the irradiation power 12.5W
  • the energy density 160J cm -2 . Irradiate an area repeatedly for 5 minutes at a frequency of 1 kHz.
  • the ultrasonic power is 300 watts; the ultrasonic wave is
  • Example 6 1 gram of metal bismuth with a purity greater than 99.97% was added to a conical flask, and 7 ml of deionized water was added. After that, it was irradiated with 1064nm laser (Nd:YAG laser) with an irradiation power of 12.5W and an energy density of 30J cm -2 . Irradiate an area repeatedly for 5 minutes at a frequency of 1 kHz. After the irradiation is completed, the metal bismuth is removed to obtain nano bismuth trioxide dispersed in water.
  • 1064nm laser Nd:YAG laser
  • Example 7 1 gram of metal bismuth with a purity greater than 99.97% was added to a conical flask, and 7 ml of deionized water was added. Afterwards, it is irradiated with 1064nm laser (Nd:YAG laser), the irradiation power is 12.5W, and the energy density is 100J cm -2 . Irradiate an area repeatedly for 5 minutes at a frequency of 1 kHz. After the irradiation is completed, the metal bismuth is removed to obtain nano bismuth trioxide dispersed in water.
  • the above methods can all make nano-bismuth trioxide particles, wherein the nano-bismuth trioxide particles made in Example 2 have an MIC of 250 ⁇ g/mL to Staphylococcus aureus (ATCC6538), and the nano-bismuth trioxide particles made in Example 3
  • the MIC of bismuth particles to Staphylococcus aureus (ATCC6538) is 31.25 ⁇ g/mL
  • the MIC of the nanometer bismuth trioxide particles that embodiment 4, 5, 6, 7 makes is respectively 10 ⁇ g to Staphylococcus aureus (ATCC6538) /mL, 5 ⁇ g/mL, 25 ⁇ g/mL, 15 ⁇ g/mL,.
  • the micron-sized bismuth trioxide commercially available in Example 1 also has certain anti-Staphylococcus aureus (ATCC6538) ability, and the MIC is 2-10 mg/mL.
  • the nano-bismuth trioxide prepared by laser method has the following advantages: First, what is produced is flake, not spherical, and has a larger surface area, which is helpful for more effective contact with bacteria. Secondly, because only metal bismuth and water are used in the preparation process, and no other chemicals are used, the nano surface is very clean, so the bactericidal effect is better.
  • the nano bismuth trioxide prepared by the method has a length of about 0.9-1.4 ⁇ m and a width of about 0.8-1.1 ⁇ m. Typical Gram-positive bacteria such as Staphylococcus aureus are spherical, with a diameter of 0.8 ⁇ m.
  • the size of typical Gram-negative Escherichia coli is: 0.5-0.8 ⁇ m, 1.0-3.0 ⁇ m.
  • the prepared nano-bismuth trioxide has a size similar to that of bacteria, so it can better interact with bacteria, destroy the bacterial cell membrane and cause the bacteria to die.
  • the obtained products were mainly nanoparticles.
  • the obtained products are mainly nanosheets and supplemented by nanoparticles.
  • the obtained product is sheet-like nano-bismuth trioxide, whose size is about 0.9-1.4 ⁇ m in length, about 0.8-1.1 ⁇ m in width, and 30-60nm in thickness. In this case, the growth of bismuth trioxide in a sheet structure helps to reduce the energy of the overall structure.
  • Figures 1-4 taken by a scanning electron microscope.
  • Figure 1 shows normal multi-drug resistant Escherichia coli (ATCC8739), and
  • Figure 2 shows Escherichia coli treated with 1 mg/ml nano bismuth trioxide aqueous solution.
  • Fig. 3 is normal multi-drug resistant Staphylococcus aureus (ATCC 6538), and
  • Fig. 4 is Staphylococcus aureus after using 1mg/ml nano bismuth trioxide aqueous solution to process. It can be seen that whether it is a multidrug-resistant Gram-negative bacteria or Gram-positive bacteria, the cell wall has been damaged in many places, resulting in multiple holes and severe rupture, causing cytoplasmic efflux and eventually leading to bacterial death.
  • bismuth trioxide has an inhibitory effect on Helicobacter pylori.
  • the 24-hour medium co-incubation experiment showed that 1 mg/ml bismuth trioxide aqueous solution can effectively kill Helicobacter pylori, and the bacteriostatic rate is >95% (tested according to WST650-2019 antibacterial and bacteriostatic effect evaluation method).
  • the active substance can be used in combination with silver ion antibacterial agents.
  • bismuth trioxide combined with nano-silver nitrate and nano-silver can achieve a good antibacterial effect.
  • the antibacterial rate is calculated according to the WST650-2019 antibacterial and antibacterial effect evaluation method. The specific results are shown in the table below.
  • the 24-hour medium co-incubation experiment showed that the mixture can kill a variety of bacteria, including Gram-negative bacteria Escherichia coli (ATCC8739), Gram-positive bacteria Staphylococcus aureus (ATCC 6538, ATCC 43300), vancomycin-resistant enterococci (ATCC 29212, ATCC 51299, ATCC 51559), the effects are shown in Table 1 below.
  • Gram-negative bacteria Escherichia coli ATCC8739
  • Gram-positive bacteria Staphylococcus aureus ATCC 6538, ATCC 43300
  • vancomycin-resistant enterococci ATCC 29212, ATCC 51299, ATCC 51559
  • the active substance can be used in combination with copper antibacterial agents, and can also achieve good antibacterial effects.
  • bismuth trioxide combined with nano-copper oxide and nano-copper can achieve a good antibacterial effect.
  • the antibacterial rate is calculated according to WST650-2019 antibacterial and antibacterial effect evaluation method for testing.
  • the 24-hour medium co-incubation experiment showed that the mixture can kill a variety of bacteria, including Gram-negative bacteria E. Vegetative Enterococcus (ATCC 29212, ATCC 51299, ATCC 51559), the effects are shown in Table 2 below.
  • the active substance can be used in combination with zinc antimicrobial agents.
  • bismuth trioxide combined with nano-zinc oxide and nano-zinc can achieve a good antibacterial effect.
  • the antibacterial rate is calculated according to the WST650-2019 antibacterial and antibacterial effect evaluation method for testing.
  • the 24-hour culture medium co-incubation experiment shows that the mixture can kill a variety of bacteria, including Gram-negative bacteria Escherichia coli (ATCC8739), Gram-positive bacteria Staphylococcus aureus (ATCC 6538, ATCC 43300), and its effects are as follows Table 3 shows.
  • the active substance can be used in combination with titanium dioxide antibacterial agent.
  • Bismuth trioxide and nano-titanium dioxide were dissolved in water in proportion to test the antibacterial activity.
  • the antibacterial rate was calculated according to the WST650-2019 antibacterial and antibacterial effect evaluation method.
  • the co-incubation experiment of 24-hour medium shows that the mixture can kill a variety of bacteria, including Gram-negative bacteria Escherichia coli (ATCC8739), Gram-positive bacteria Staphylococcus aureus (ATCC 6538, ATCC 43300), and the effects are as follows Table 4 shows.
  • the active substance can be used in combination with molybdenum trioxide antibacterial agent.
  • Bismuth trioxide and molybdenum trioxide were dissolved in water in proportion to test the antibacterial activity.
  • the antibacterial rate was calculated according to the WST650-2019 antibacterial and antibacterial effect evaluation method.
  • the 24-hour co-incubation experiment with the medium shows that the mixture can kill a variety of bacteria, including Gram-negative bacteria Escherichia coli (ATCC8739), Gram-positive bacteria Staphylococcus aureus (ATCC 6538, ATCC 43300), and the effects are as follows Table 5 shows.
  • the active substance is stable in nature and has a long-lasting antibacterial effect. Moreover, the price is low and the economy is good.
  • the active substance can be used alone or in combination with other types of antibacterial agents to achieve a very good bactericidal effect, such as in combination with silver ions, copper ions, zinc ions, or in combination with titanium dioxide and molybdenum trioxide fungicides, Can kill a variety of bacteria.

Abstract

The present invention relates to the field of bactericides, and particularly relates to an application of bismuth trioxide as a bactericide. The bismuth trioxide is prepared by using one of the following methods: method I, dropwise adding a hydrochloric acid aqueous solution into a sodium bismuthate aqueous solution at room temperature under an ultrasonic condition until the sodium bismuthate aqueous solution is acidic, drying an obtained precipitate, carrying out a heating reaction in a muffle furnace, and cooling to obtain nano bismuth trioxide of 10 microns or less; method II, dropwise adding a nitric acid aqueous solution into a sodium bismuthate aqueous solution at room temperature until the sodium bismuthate aqueous solution is acidic, drying an obtained precipitate, carrying out a staged heating reaction in a tube furnace, and cooling to obtain nano bismuth trioxide of 10 microns or less; and method III, putting metal bismuth into deionized water, and carrying out laser irradiation to remove the metal bismuth, so as to obtain aqueous-phase dispersed nano bismuth trioxide. In the present application, the inorganic metal oxide bismuth trioxide prepared by the three methods has good antibacterial activity, and can effectively kill gram-negative bacteria and gram-positive bacteria, and drug-resistant strains.

Description

三氧化二铋作为杀菌剂的应用Application of bismuth trioxide as fungicide 技术领域technical field
本发明属于杀菌剂领域，具体涉及一种三氧化二铋作为杀菌剂的应用。The invention belongs to the field of fungicides, and in particular relates to the application of bismuth trioxide as a fungicide.
背景技术Background technique
常用的抗菌材料分为无机抗菌剂、有机抗菌剂、光催化抗菌剂等。其中，有机抗菌剂具有杀菌速度快、抗菌效能高的特点，但是其耐热性差，持久性不足，易产生耐药性。光催化抗菌材料近年来发展迅速，但是其主要依赖于紫外光，光利用率低。而无机抗菌剂具有耐热性好、稳定性好，抗菌谱广、有效期长、毒性低、不产生耐药性等特点，是目前市场的主流产品。Commonly used antibacterial materials are divided into inorganic antibacterial agents, organic antibacterial agents, photocatalytic antibacterial agents, etc. Among them, organic antibacterial agents have the characteristics of fast sterilization speed and high antibacterial efficacy, but they have poor heat resistance, insufficient persistence, and are prone to drug resistance. Photocatalytic antibacterial materials have developed rapidly in recent years, but they mainly rely on ultraviolet light, and the light utilization rate is low. Inorganic antibacterial agents have the characteristics of good heat resistance, good stability, broad antibacterial spectrum, long validity period, low toxicity, and no drug resistance. They are the mainstream products in the current market.
其中，最常用的无机抗菌剂是银系列抗菌剂，其杀菌效果好，但是价格较为昂贵，易变色，而且银有蓄积毒性，其应用受到一定限制。铜杀菌剂效果不如银杀菌剂，而且氧化铜本身颜色很重，有一定毒性，限制了其应用范围。其它常用的无机抗菌剂如二氧化钛、三氧化钼都是2B类致癌物，其持久安全性存疑。Among them, the most commonly used inorganic antibacterial agents are silver series antibacterial agents, which have a good bactericidal effect, but are relatively expensive, easy to change color, and silver has cumulative toxicity, so its application is limited. Copper fungicides are not as effective as silver fungicides, and copper oxide itself is very heavy in color and has certain toxicity, which limits its application range. Other commonly used inorganic antibacterial agents such as titanium dioxide and molybdenum trioxide are 2B carcinogens, and their long-term safety is doubtful.
因此，开发新型高效、无毒、稳定性高、持续性久、经济性好的抗菌剂具有非常重要的意义和极大的经济价值。Therefore, it is of great significance and great economic value to develop new high-efficiency, non-toxic, high-stability, long-lasting, and economical antibacterial agents.
发明内容Contents of the invention
本发明的目的在于克服现有技术中的缺点，提供一种三氧化二铋作为杀菌剂的应用。The purpose of the present invention is to overcome the shortcoming in the prior art, provide a kind of application of bismuth trioxide as bactericide.
为实现上述目的，本发明用的技术方案为：For realizing the above object, the technical scheme used in the present invention is:
一种三氧化二铋作为杀菌剂的应用，所述的三氧化二铋采用下述之一的方式进行制备:A kind of bismuth trioxide is used as the application of bactericide, and described bismuth trioxide adopts one of following modes to prepare:
方法一、室温下，配置铋酸钠去离子水溶液至于反应容器中，此时体系为灰褐色，加热至50-80度，超声条件下滴入HCl溶液直至酸性，此时，体系颜色变浅，继续在加热条件下超声搅拌至反应完全，离心分离收集产物，80-100度烘干1-3小时，之后转入马弗炉中300-500度加热1-3小时冷却后就得10微米以下及纳米三氧化二铋，为浅白偏黄粉固体； Method 1. At room temperature, configure a deionized aqueous solution of sodium bismuthate in the reaction vessel. At this time, the system is taupe. Heat it to 50-80 degrees. Under ultrasonic conditions, add HCl solution until it is acidic. At this time, the color of the system becomes lighter. Continue to ultrasonically stir under heating conditions until the reaction is complete, collect the product by centrifugation, dry at 80-100 degrees for 1-3 hours, then transfer to a muffle furnace and heat at 300-500 degrees for 1-3 hours. After cooling, the product will be less than 10 microns And nano bismuth trioxide, which is light white yellowish powder solid;
或者方法二、室温下，称量铋酸钠放入锥形瓶中，加入去离子水和聚四氟乙烯转子；之后滴入HNO 3溶液，室温搅拌，会慢慢有沉淀析出；将沉淀收集，之后用HNO 3溶液洗涤，接着用去离子水洗涤；将产物置于烘箱中烘干；之后将产物放置管式炉中，在4％氢气和96％氮气氛围下，以每分钟5度升温至300-500度煅烧1-3小时，冷却后就得10微米以下及纳米三氧化二铋，为浅白偏黄粉固体； Or method 2. At room temperature, weigh sodium bismuthate and put it into an Erlenmeyer flask, add deionized water and a Teflon rotor; then drop in HNO 3 solution, stir at room temperature, and a precipitate will slowly precipitate out; collect the precipitate , and then washed with HNO 3 solution, followed by deionized water; the product was placed in an oven to dry; then the product was placed in a tube furnace, and the temperature was raised at 5 degrees per minute under an atmosphere of 4% hydrogen and 96% nitrogen Calcined at 300-500 degrees for 1-3 hours, and after cooling, the nano bismuth trioxide below 10 microns is obtained, which is a light white yellowish powder solid;
或者方法三、将纯度大于99％的金属铋加入到锥形瓶中，加入去离子水；之后用激光照射，能量密度为30-160J cm -2；重复照射一个区域持续大于5分钟，频率在1kHz；照射完成之后，金属铋被移去，得到水相分散的纳米三氧化二铋。 Or method 3: Add metal bismuth with a purity greater than 99% into the conical flask, add deionized water; then irradiate with laser light with an energy density of 30-160J cm -2 ; repeatedly irradiate an area for more than 5 minutes, and the frequency is at 1kHz; after the irradiation is completed, the metal bismuth is removed to obtain nano bismuth trioxide dispersed in water.
具体地，方法一中，铋酸钠去离子水溶液的浓度为0.5-5mol/L；HCl溶液的浓度为1-10mol/L。Specifically, in method one, the concentration of the sodium bismuthate deionized aqueous solution is 0.5-5 mol/L; the concentration of the HCl solution is 1-10 mol/L.
具体地，方法二中，铋酸钠水溶液的浓度为0.5-5mol/L；硝酸水溶液为1-10mol/L。Specifically, in the second method, the concentration of the aqueous solution of sodium bismuthate is 0.5-5 mol/L; the concentration of the aqueous solution of nitric acid is 1-10 mol/L.
具体地，方法三中，能量密度为100-160J cm -2。 Specifically, in the third method, the energy density is 100-160 J cm -2 .
具体地，方法三中，移去金属铋前对水相分散的纳米三氧化二铋进行超声分散，超声功率200-700瓦，时间10-60分钟。Specifically, in the third method, before removing the metal bismuth, ultrasonically disperse the nano bismuth trioxide dispersed in the water phase, the ultrasonic power is 200-700 watts, and the time is 10-60 minutes.
本申请还包括一种所述的三氧化二铋作为杀菌剂的应用，所述的三氧化二铋与银抗菌剂、铜抗菌剂、锌抗菌剂、钛抗菌剂、钼抗菌剂联合使用；The present application also includes the application of the bismuth trioxide as a fungicide, and the bismuth trioxide is used in combination with silver antibacterial agents, copper antibacterial agents, zinc antibacterial agents, titanium antibacterial agents, and molybdenum antibacterial agents;
三氧化二铋与银抗菌剂、铜抗菌剂、锌抗菌剂、钛抗菌剂、钼抗菌剂的质量比为分别为0.05-1:1-0.05。The mass ratio of bismuth trioxide to silver antibacterial agent, copper antibacterial agent, zinc antibacterial agent, titanium antibacterial agent and molybdenum antibacterial agent is 0.05-1:1-0.05 respectively.
与现有技术相比，本发明的有益效果是：Compared with prior art, the beneficial effect of the present invention is:
本申请使用三种方法制备得到的无机金属氧化物三氧化二铋相较于市售的微米级的三氧化二铋均具有很好的抗菌活性，可以有效杀死革兰氏阴性菌、革兰氏阳性菌，包括耐药菌株。Compared with commercially available micron-sized bismuth trioxide, the inorganic metal oxide bismuth trioxide prepared by using three methods in the present application has good antibacterial activity, and can effectively kill Gram-negative bacteria, Gram positive bacteria, including drug-resistant strains.
该活性物质遇水会显示一定的酸性。当其接触水气时，会持续不断释放H+，从而起到一定杀菌作用。同时，该活性物质的金属离子能依靠库仑力牢固地吸附于细菌细胞膜表面， 进一步穿透细胞壁，导致细胞壁破裂，引起细胞质外流最终导致细菌死亡。另外，该活性物质在光照射下能够激发水或空气中的氧产生羟自由基及活性氧离子，从而产生氧化应激反应，破坏细菌的繁殖能力，致使细菌死亡。The active substance will show a certain acidity when it meets water. When it contacts water vapor, it will continuously release H+, thus playing a certain bactericidal effect. At the same time, the metal ions of the active substance can be firmly adsorbed on the surface of the bacterial cell membrane by Coulomb force, further penetrate the cell wall, cause the cell wall to rupture, cause the cytoplasm to flow out and finally lead to the death of the bacteria. In addition, the active substance can excite oxygen in water or air to generate hydroxyl radicals and active oxygen ions under light irradiation, thereby generating oxidative stress, destroying the reproductive ability of bacteria, and causing the death of bacteria.
该活性物质性质稳定，抗菌效果持久。而且价格低廉，经济性好。将该活性物质单独使用，或者联合其它类型的抗菌剂使用都能起到非常好的杀菌效果。The active substance is stable in nature and has a long-lasting antibacterial effect. Moreover, the price is low and the economy is good. The active substance can be used alone or in combination with other types of antibacterial agents to achieve a very good bactericidal effect.
其中，作为优选的形式，采用激光照射法制备的纳米三氧化二铋，因为其为片状结构，能更好的跟细菌作用，破坏细菌细胞膜导致细菌死亡。Among them, as a preferred form, nano-bismuth trioxide prepared by laser irradiation method can better interact with bacteria because of its sheet structure, destroying bacterial cell membranes and causing bacterial death.
附图说明Description of drawings
图1是正常的多重耐药大肠杆菌(ATCC8739)的电镜示意图；Fig. 1 is the electron microscope schematic diagram of normal multi-drug resistant Escherichia coli (ATCC8739);
图2是使用了实施例4制备的1mg/ml纳米三氧化二铋水溶液处理之后的大肠杆菌的电镜示意图；Fig. 2 is the electron microscope schematic diagram of Escherichia coli after using the 1mg/ml nanometer bismuth trioxide aqueous solution process that embodiment 4 prepares;
图3是正常的多重耐药的金黄色葡萄球菌(ATCC 6538)的电镜示意图；Fig. 3 is the electron microscope schematic diagram of the normal multi-drug resistant Staphylococcus aureus (ATCC 6538);
图4是使用了实施例4制备的1mg/ml纳米三氧化二铋水溶液处理之后的金黄色葡萄球菌的电镜示意图。4 is a schematic electron microscope view of Staphylococcus aureus treated with the 1 mg/ml nano bismuth trioxide aqueous solution prepared in Example 4.
具体实施方式Detailed ways
为了使本技术领域的技术人员更好地理解本发明的技术方案，下面结合实施例对本发明作进一步的详细说明。In order to enable those skilled in the art to better understand the technical solutions of the present invention, the present invention will be further described in detail below in conjunction with examples.
实施例1：该抗菌物质三氧化二铋(CAS登录号1304-76-3)，纳米级别的颗粒或者微米级别的颗粒单独使用时，都能够杀死多重耐药的革兰氏阴性菌和革兰氏阳性菌，其中，微米级的三氧化二铋可以直接购买市售的。Embodiment 1: this antibacterial substance bismuth trioxide (CAS accession number 1304-76-3), when the particle of nanoscale or the particle of micron scale is used alone, all can kill the Gram-negative bacterium of multi-drug resistance and Gram-negative bacteria and Gram-negative bacteria. Lambert-positive bacteria, among them, micron-sized bismuth trioxide can be directly purchased commercially.
而纳米三氧化二铋的制备方法如下：And the preparation method of nano bismuth trioxide is as follows:
实施例2：室温下，称量14.00g铋酸钠放入250ml锥形瓶中，加入80ml去离子水，聚四氟乙烯转子。将锥形瓶固定于加热搅拌器上油浴中，此时体系为灰褐色。之后在超声下滴入5mmol/ml的HCl水溶液直至pH调节至1，此时体系颜色变浅。继续在80度下超声搅拌2h。 之后，待反应体系温度降至室温，将反应体系在4200rpm条件下离心8分钟，测上清液pH，若上清液为酸性，则加入去离子水，将体系搅拌均匀，以同样条件继续离心。若上清液为中性，则收集沉淀，用去离子水洗一次，收集产物。将产物置于100度烘箱中烘干，此时会浅色结块，将结块碾碎。将上述产物加入坩埚中，放置马弗炉中加热至500度反应2小时，冷却后就得10微米以下及纳米三氧化二铋，为浅白偏黄粉固体。Example 2: At room temperature, weigh 14.00 g of sodium bismuthate and put it into a 250 ml Erlenmeyer flask, add 80 ml of deionized water, and use a polytetrafluoroethylene rotor. The Erlenmeyer flask was fixed in an oil bath on a heating stirrer, and the system was taupe at this time. Afterwards, 5 mmol/ml aqueous HCl solution was added dropwise under ultrasonication until the pH was adjusted to 1, at which time the color of the system became lighter. Continue ultrasonic stirring at 80°C for 2h. After that, when the temperature of the reaction system drops to room temperature, centrifuge the reaction system at 4200rpm for 8 minutes, measure the pH of the supernatant, if the supernatant is acidic, add deionized water, stir the system evenly, and continue centrifugation under the same conditions . If the supernatant is neutral, collect the precipitate, wash once with deionized water, and collect the product. Put the product in a 100-degree oven to dry, and at this time there will be light-colored agglomerates, and the agglomerates should be crushed. Add the above product into a crucible, place it in a muffle furnace and heat it to 500°C for 2 hours to react. After cooling, you can get nano bismuth trioxide below 10 microns, which is a light white yellowish powder solid.
实施例3：室温下，称量14.00g铋酸钠放入250ml锥形瓶中，加入25ml去离子水和聚四氟乙烯转子。之后滴入100mL的HNO 3(5mmol/ml)溶液，室温搅拌2h，会慢慢有沉淀析出。将沉淀收集，之后用HNO 3(5mmol/ml)溶液洗涤，接着用去离子水洗涤。将产物置于100度烘箱中烘干。之后将产物放置管式炉中，在4％氢气和96％氮气氛围下，以每分钟5度升温至340度煅烧2小时，冷却后就得10微米以下及纳米三氧化二铋，为浅白偏黄粉固体。 Example 3: At room temperature, weigh 14.00 g of sodium bismuthate and put it into a 250 ml Erlenmeyer flask, add 25 ml of deionized water and a Teflon rotor. Afterwards, 100 mL of HNO 3 (5 mmol/ml) solution was added dropwise, stirred at room temperature for 2 hours, and a precipitate would slowly precipitate out. The precipitate was collected and washed with HNO 3 (5 mmol/ml) solution followed by deionized water. Dry the product in a 100 degree oven. Afterwards, the product is placed in a tube furnace and calcined at 5°C per minute to 340°C for 2 hours in an atmosphere of 4% hydrogen and 96% nitrogen. After cooling, it will be less than 10 microns and nanometer bismuth trioxide, which is light white Yellowish powder solid.
实施例4：将1克纯度大于99.97％纯度的金属铋加入到锥形瓶中，加入7ml去离子水。之后用1064nm激光(Nd:YAG激光器)照射，照射功率为12.5W，能量密度为160J cm -2。重复照射一个区域持续5分钟，频率在1kHz。照射完成之后，金属铋被移去，得到水相分散的纳米三氧化二铋。 Example 4: 1 gram of metal bismuth with a purity greater than 99.97% was added to a conical flask, and 7 ml of deionized water was added. Afterwards, it is irradiated with 1064nm laser (Nd:YAG laser), the irradiation power is 12.5W, and the energy density is 160J cm -2 . Irradiate an area repeatedly for 5 minutes at a frequency of 1 kHz. After the irradiation is completed, the metal bismuth is removed to obtain nano bismuth trioxide dispersed in water.
实施例5：将1克纯度大于99.97％纯度的金属铋加入到锥形瓶中，加入7ml去离子水。之后用1064nm激光(Nd:YAG激光器)照射，照射功率为12.5W，能量密度为160J cm -2。重复照射一个区域持续5分钟，频率在1kHz。照射完成之后，超声功率300瓦；用超声波超声20分钟，使其均匀分散，之后金属铋被移去，得到水相分散的纳米三氧化二铋。 Example 5: 1 gram of metal bismuth with a purity greater than 99.97% was added to a conical flask, and 7 ml of deionized water was added. Afterwards, it is irradiated with 1064nm laser (Nd:YAG laser), the irradiation power is 12.5W, and the energy density is 160J cm -2 . Irradiate an area repeatedly for 5 minutes at a frequency of 1 kHz. After the irradiation is completed, the ultrasonic power is 300 watts; the ultrasonic wave is used for 20 minutes to make it uniformly dispersed, and then the metal bismuth is removed to obtain nano bismuth trioxide dispersed in water.
实施例6：将1克纯度大于99.97％纯度的金属铋加入到锥形瓶中，加入7ml去离子水。之后用1064nm激光(Nd:YAG激光器)照射，照射功率为12.5W，能量密度为30J cm -2。重复照射一个区域持续5分钟，频率在1kHz。照射完成之后，金属铋被移去，得到水相分散的纳米三氧化二铋。 Example 6: 1 gram of metal bismuth with a purity greater than 99.97% was added to a conical flask, and 7 ml of deionized water was added. After that, it was irradiated with 1064nm laser (Nd:YAG laser) with an irradiation power of 12.5W and an energy density of 30J cm -2 . Irradiate an area repeatedly for 5 minutes at a frequency of 1 kHz. After the irradiation is completed, the metal bismuth is removed to obtain nano bismuth trioxide dispersed in water.
实施例7：将1克纯度大于99.97％纯度的金属铋加入到锥形瓶中，加入7ml去离子水。 之后用1064nm激光(Nd:YAG激光器)照射，照射功率为12.5W，能量密度为100J cm -2。重复照射一个区域持续5分钟，频率在1kHz。照射完成之后，金属铋被移去，得到水相分散的纳米三氧化二铋。 Example 7: 1 gram of metal bismuth with a purity greater than 99.97% was added to a conical flask, and 7 ml of deionized water was added. Afterwards, it is irradiated with 1064nm laser (Nd:YAG laser), the irradiation power is 12.5W, and the energy density is 100J cm -2 . Irradiate an area repeatedly for 5 minutes at a frequency of 1 kHz. After the irradiation is completed, the metal bismuth is removed to obtain nano bismuth trioxide dispersed in water.
以上方法都可制得纳米三氧化二铋颗粒，其中实施例2制得的纳米三氧化二铋颗粒对金黄色葡萄球菌(ATCC6538)的MIC为250μg/mL，实施例3制得的纳米三氧化二铋颗粒对金黄色葡萄球菌(ATCC6538)的MIC为31.25μg/mL，实施例4、5、6、7制得的纳米三氧化二铋颗粒对金黄色葡萄球菌(ATCC6538)的MIC分别为10μg/mL、5μg/mL、25μg/mL、15μg/mL、。另外，实施例1市售的微米级别的三氧化二铋也具有一定的抗金黄色葡萄球菌(ATCC6538)的能力，MIC为2-10mg/mL。The above methods can all make nano-bismuth trioxide particles, wherein the nano-bismuth trioxide particles made in Example 2 have an MIC of 250 μg/mL to Staphylococcus aureus (ATCC6538), and the nano-bismuth trioxide particles made in Example 3 The MIC of bismuth particles to Staphylococcus aureus (ATCC6538) is 31.25 μ g/mL, and the MIC of the nanometer bismuth trioxide particles that embodiment 4, 5, 6, 7 makes is respectively 10 μ g to Staphylococcus aureus (ATCC6538) /mL, 5μg/mL, 25μg/mL, 15μg/mL,. In addition, the micron-sized bismuth trioxide commercially available in Example 1 also has certain anti-Staphylococcus aureus (ATCC6538) ability, and the MIC is 2-10 mg/mL.
利用激光方法制得的纳米三氧化二铋有如下优点：首先，制得的是片状的，不是球状的，具有更大的表面积，有助于更有效的跟细菌接触。其次，因为制备过程中只使用金属铋和水，不使用其它化学物质，所以纳米表面非常干净，因此杀菌效果更好。该方法制得的纳米三氧化二铋其长度约为0.9-1.4μm，宽度约为0.8-1.1μm。而典型的***比如金黄色葡萄球菌为球型，直径0.8μm。典型的革兰氏阴性大肠杆菌其大小为：0.5～0.8μm，1.0～3.0μm。制得的纳米三氧化二铋尺寸跟细菌相仿，因此能更好的跟细菌作用，破坏细菌细胞膜导致细菌死亡。The nano-bismuth trioxide prepared by laser method has the following advantages: First, what is produced is flake, not spherical, and has a larger surface area, which is helpful for more effective contact with bacteria. Secondly, because only metal bismuth and water are used in the preparation process, and no other chemicals are used, the nano surface is very clean, so the bactericidal effect is better. The nano bismuth trioxide prepared by the method has a length of about 0.9-1.4 μm and a width of about 0.8-1.1 μm. Typical Gram-positive bacteria such as Staphylococcus aureus are spherical, with a diameter of 0.8 μm. The size of typical Gram-negative Escherichia coli is: 0.5-0.8 μm, 1.0-3.0 μm. The prepared nano-bismuth trioxide has a size similar to that of bacteria, so it can better interact with bacteria, destroy the bacterial cell membrane and cause the bacteria to die.
最后，激光照射完成之后，用超声波超声2小时，有助于得到均匀度更好的纳米三氧化二铋，从而产生更好的杀菌效果。Finally, after the laser irradiation is completed, use ultrasonic waves for 2 hours, which will help to obtain nano-bismuth trioxide with better uniformity, thereby producing better bactericidal effect.
此外，当我们使用的激光照射能量密度为30J cm -2时，获得的产物以纳米颗粒为主。而激光照射能量密度为100J cm -2时，得到的产物以纳米片为主，纳米颗粒为辅。而激光照射能量密度为160J cm -2时，得到的产物是片状的纳米三氧化二铋，其尺寸为长度约为0.9-1.4μm，宽度约为0.8-1.1μm，厚度为30-60nm。此种情况下，三氧化二铋采取片状结构生长有助于降低整体结构的能量。 In addition, when the energy density of the laser irradiation we used was 30J cm -2 , the obtained products were mainly nanoparticles. When the energy density of laser irradiation is 100J cm -2 , the obtained products are mainly nanosheets and supplemented by nanoparticles. When the energy density of laser irradiation is 160J cm -2 , the obtained product is sheet-like nano-bismuth trioxide, whose size is about 0.9-1.4μm in length, about 0.8-1.1μm in width, and 30-60nm in thickness. In this case, the growth of bismuth trioxide in a sheet structure helps to reduce the energy of the overall structure.
纳米三氧化二铋颗粒的杀菌效果如扫描电子显微镜拍摄的图1-图4所示。其中图1是正常的多重耐药大肠杆菌(ATCC8739)，图2是使用了1mg/ml纳米三氧化二铋水溶液处理之后的大肠杆菌。图3是正常的多重耐药的金黄色葡萄球菌(ATCC 6538)，图4是使用了1mg/ml纳米三氧化二铋水溶液处理之后的金黄色葡萄球菌。可以看到无论是多重耐药的革兰氏阴性菌或是革兰氏阳性菌，细胞壁都遭到多处破坏，产生多个孔洞，破裂严重，引起细胞质外流最终导致细菌死亡。The bactericidal effect of nano-bismuth trioxide particles is shown in Figures 1-4 taken by a scanning electron microscope. Figure 1 shows normal multi-drug resistant Escherichia coli (ATCC8739), and Figure 2 shows Escherichia coli treated with 1 mg/ml nano bismuth trioxide aqueous solution. Fig. 3 is normal multi-drug resistant Staphylococcus aureus (ATCC 6538), and Fig. 4 is Staphylococcus aureus after using 1mg/ml nano bismuth trioxide aqueous solution to process. It can be seen that whether it is a multidrug-resistant Gram-negative bacteria or Gram-positive bacteria, the cell wall has been damaged in many places, resulting in multiple holes and severe rupture, causing cytoplasmic efflux and eventually leading to bacterial death.
另外，三氧化二铋对幽门螺旋杆菌有抑制效果。24小时培养基共孵育实验表明1mg/ml三氧化二铋水溶液能够有效杀死幽门螺旋杆菌，抑菌率＞95％(按照WST650-2019抗菌和抑菌效果评价方法来进行测试)。In addition, bismuth trioxide has an inhibitory effect on Helicobacter pylori. The 24-hour medium co-incubation experiment showed that 1 mg/ml bismuth trioxide aqueous solution can effectively kill Helicobacter pylori, and the bacteriostatic rate is >95% (tested according to WST650-2019 antibacterial and bacteriostatic effect evaluation method).
该活性物质可联合银离子抗菌剂使用。比如三氧化二铋联合纳米硝酸银、纳米银，能取得很好的抗菌效果。将纳米三氧化二铋与纳米硝酸银按比例溶于水中，进行抗菌活性测试，抑菌率计算按照WST650-2019抗菌和抑菌效果评价方法来进行测试。具体结果如下表所示，24小时培养基共孵育实验表明，其混合物能够杀死多种细菌，包括革兰氏阴性菌大肠杆菌(ATCC8739)、革兰氏阳性菌金黄色葡萄球菌(ATCC 6538,ATCC 43300)、耐万古霉素肠球菌(ATCC 29212、ATCC 51299、ATCC 51559)，其效果如下表1所示。The active substance can be used in combination with silver ion antibacterial agents. For example, bismuth trioxide combined with nano-silver nitrate and nano-silver can achieve a good antibacterial effect. Dissolve nano-bismuth trioxide and nano-silver nitrate in water in proportion to test the antibacterial activity. The antibacterial rate is calculated according to the WST650-2019 antibacterial and antibacterial effect evaluation method. The specific results are shown in the table below. The 24-hour medium co-incubation experiment showed that the mixture can kill a variety of bacteria, including Gram-negative bacteria Escherichia coli (ATCC8739), Gram-positive bacteria Staphylococcus aureus (ATCC 6538, ATCC 43300), vancomycin-resistant enterococci (ATCC 29212, ATCC 51299, ATCC 51559), the effects are shown in Table 1 below.
表1Table 1
Figure PCTCN2023071584-appb-000001
Figure PCTCN2023071584-appb-000001
该活性物质可联合铜抗菌剂使用，也能取得很好的抗菌效果。比如三氧化二铋联合纳米氧化 铜、纳米铜，能取得很好的抗菌效果。将纳米三氧化二铋与纳米氧化铜按比例溶于水中，进行抗菌活性测试，抑菌率计算按照WST650-2019抗菌和抑菌效果评价方法来进行测试。24小时培养基共孵育实验表明，其混合物能够杀死多种细菌，包括革兰氏阴性菌大肠杆菌(ATCC8739)、革兰氏阳性菌金黄色葡萄球菌(ATCC 6538,ATCC 43300)、耐万古霉素肠球菌(ATCC 29212、ATCC 51299、ATCC 51559)，其效果如下表2所示。The active substance can be used in combination with copper antibacterial agents, and can also achieve good antibacterial effects. For example, bismuth trioxide combined with nano-copper oxide and nano-copper can achieve a good antibacterial effect. Dissolve nano-bismuth trioxide and nano-copper oxide in water in proportion to conduct antibacterial activity test. The antibacterial rate is calculated according to WST650-2019 antibacterial and antibacterial effect evaluation method for testing. The 24-hour medium co-incubation experiment showed that the mixture can kill a variety of bacteria, including Gram-negative bacteria E. Vegetative Enterococcus (ATCC 29212, ATCC 51299, ATCC 51559), the effects are shown in Table 2 below.
表2Table 2
Figure PCTCN2023071584-appb-000002
Figure PCTCN2023071584-appb-000002
该活性物质可联合锌抗菌剂使用。比如三氧化二铋联合纳米氧化锌、纳米锌，能取得很好的抗菌效果。将纳米三氧化二铋与纳米氧化锌按比例溶于水中，进行抗菌活性测试，抑菌率计算按照WST650-2019抗菌和抑菌效果评价方法来进行测试。24小时培养基共孵育实验表明，其混合物能够杀死多种细菌，包括革兰氏阴性菌大肠杆菌(ATCC8739)、革兰氏阳性菌金黄色葡萄球菌(ATCC 6538,ATCC 43300)，其效果如下表3所示。The active substance can be used in combination with zinc antimicrobial agents. For example, bismuth trioxide combined with nano-zinc oxide and nano-zinc can achieve a good antibacterial effect. Dissolve nano-bismuth trioxide and nano-zinc oxide in water in proportion to test the antibacterial activity. The antibacterial rate is calculated according to the WST650-2019 antibacterial and antibacterial effect evaluation method for testing. The 24-hour culture medium co-incubation experiment shows that the mixture can kill a variety of bacteria, including Gram-negative bacteria Escherichia coli (ATCC8739), Gram-positive bacteria Staphylococcus aureus (ATCC 6538, ATCC 43300), and its effects are as follows Table 3 shows.
表3table 3
Figure PCTCN2023071584-appb-000003
Figure PCTCN2023071584-appb-000003
该活性物质可联合二氧化钛抗菌剂使用。将三氧化二铋与纳米二氧化钛按比例溶于水中，进行抗菌活性测试，抑菌率计算按照WST650-2019抗菌和抑菌效果评价方法来进行测试。24 小时培养基共孵育实验表明，其混合物能够杀死多种细菌，包括革兰氏阴性菌大肠杆菌(ATCC8739)、革兰氏阳性菌金黄色葡萄球菌(ATCC 6538,ATCC 43300)，其效果如下表4所示。The active substance can be used in combination with titanium dioxide antibacterial agent. Bismuth trioxide and nano-titanium dioxide were dissolved in water in proportion to test the antibacterial activity. The antibacterial rate was calculated according to the WST650-2019 antibacterial and antibacterial effect evaluation method. The co-incubation experiment of 24-hour medium shows that the mixture can kill a variety of bacteria, including Gram-negative bacteria Escherichia coli (ATCC8739), Gram-positive bacteria Staphylococcus aureus (ATCC 6538, ATCC 43300), and the effects are as follows Table 4 shows.
表4Table 4
Figure PCTCN2023071584-appb-000004
Figure PCTCN2023071584-appb-000004
该活性物质可联合三氧化钼抗菌剂使用。将三氧化二铋与三氧化钼按比例溶于水中，进行抗菌活性测试，抑菌率计算按照WST650-2019抗菌和抑菌效果评价方法来进行测试。24小时培养基共孵育实验表明，其混合物能够杀死多种细菌，包括革兰氏阴性菌大肠杆菌(ATCC8739)、革兰氏阳性菌金黄色葡萄球菌(ATCC 6538,ATCC 43300)，其效果如下表5所示。The active substance can be used in combination with molybdenum trioxide antibacterial agent. Bismuth trioxide and molybdenum trioxide were dissolved in water in proportion to test the antibacterial activity. The antibacterial rate was calculated according to the WST650-2019 antibacterial and antibacterial effect evaluation method. The 24-hour co-incubation experiment with the medium shows that the mixture can kill a variety of bacteria, including Gram-negative bacteria Escherichia coli (ATCC8739), Gram-positive bacteria Staphylococcus aureus (ATCC 6538, ATCC 43300), and the effects are as follows Table 5 shows.
表5table 5
Figure PCTCN2023071584-appb-000005
Figure PCTCN2023071584-appb-000005
综上可以看出，该活性物质性质稳定，抗菌效果持久。而且价格低廉，经济性好。将该活性物质单独使用，或者联合其它类型的抗菌剂使用都能起到非常好的杀菌效果，例如联合银离子、铜离子、锌离子抗菌剂，或者联合二氧化钛、三氧化钼类杀菌剂使用，可杀死多种细菌。In summary, it can be seen that the active substance is stable in nature and has a long-lasting antibacterial effect. Moreover, the price is low and the economy is good. The active substance can be used alone or in combination with other types of antibacterial agents to achieve a very good bactericidal effect, such as in combination with silver ions, copper ions, zinc ions, or in combination with titanium dioxide and molybdenum trioxide fungicides, Can kill a variety of bacteria.
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为 本发明的保护范围。The above is only a preferred embodiment of the present invention, it should be pointed out that, for those of ordinary skill in the art, without departing from the principle of the present invention, some improvements and modifications can also be made, and these improvements and modifications can also be made. It should be regarded as the protection scope of the present invention.

Claims (6)

  1. 一种三氧化二铋作为杀菌剂的应用，其特征在于，所述的三氧化二铋采用下述之一的方式进行制备:A kind of application of bismuth trioxide as bactericide, it is characterized in that, described bismuth trioxide adopts one of following modes to prepare:
    方法一、室温下，配置铋酸钠去离子水溶液至于反应容器中，此时体系为灰褐色，加热至50-80度，超声条件下滴入HCl溶液直至酸性，此时，体系颜色变浅，继续在加热条件下超声搅拌至反应完全，离心分离收集产物，80-100度烘干1-3小时，之后转入马弗炉中300-500度加热1-3小时冷却后就得到10微米以下及纳米三氧化二铋，为浅白偏黄粉固体；Method 1. At room temperature, configure a deionized aqueous solution of sodium bismuthate in the reaction vessel. At this time, the system is taupe. Heat it to 50-80 degrees. Under ultrasonic conditions, add HCl solution until it is acidic. At this time, the color of the system becomes lighter. Continue to stir ultrasonically under heating conditions until the reaction is complete, collect the product by centrifugation, dry at 80-100 degrees for 1-3 hours, then transfer to a muffle furnace and heat at 300-500 degrees for 1-3 hours. After cooling, the product is less than 10 microns And nano bismuth trioxide, which is light white yellowish powder solid;
    或者方法二、室温下，称量铋酸钠放入锥形瓶中，加入去离子水和聚四氟乙烯转子；之后滴入HNO 3溶液，室温搅拌，会慢慢有沉淀析出；将沉淀收集，之后用HNO 3溶液洗涤，接着用去离子水洗涤；将产物置于烘箱中烘干；之后将产物放置管式炉中，在4％氢气和96％氮气氛围下，以每分钟5度升温至300-500度煅烧1-3小时，冷却后就得到10微米以下及纳米三氧化二铋，为浅白偏黄粉固体； Or method 2. At room temperature, weigh sodium bismuthate and put it into an Erlenmeyer flask, add deionized water and a Teflon rotor; then drop in HNO 3 solution, stir at room temperature, and a precipitate will slowly precipitate out; collect the precipitate , and then washed with HNO 3 solution, followed by deionized water; the product was placed in an oven to dry; then the product was placed in a tube furnace, and the temperature was raised at 5 degrees per minute under an atmosphere of 4% hydrogen and 96% nitrogen Calcined at 300-500 degrees for 1-3 hours, and after cooling, nano bismuth trioxide below 10 microns is obtained, which is a light white yellowish powder solid;
    或者方法三、将纯度大于99％的金属铋加入到锥形瓶中，加入去离子水；之后用激光照射，能量密度为30-160J cm -2；重复照射一个区域持续大于5分钟，频率在1kHz；照射完成之后，金属铋被移去，得到水相分散的纳米三氧化二铋。 Or method 3: Add metal bismuth with a purity greater than 99% into the conical flask, add deionized water; then irradiate with laser light with an energy density of 30-160J cm -2 ; repeatedly irradiate an area for more than 5 minutes, and the frequency is at 1kHz; after the irradiation is completed, the metal bismuth is removed to obtain nano bismuth trioxide dispersed in water.
  2. 根据权利要求1所述的三氧化二铋作为杀菌剂的应用，其特征在于，方法一中，铋酸钠去离子水溶液的浓度为0.5-5mol/L；HCl溶液的浓度为1-10mol/L。The application of bismuth trioxide according to claim 1 as a fungicide is characterized in that, in method one, the concentration of sodium bismuthate deionized aqueous solution is 0.5-5mol/L; the concentration of HCl solution is 1-10mol/L .
  3. 根据权利要求1所述的三氧化二铋作为杀菌剂的应用，其特征在于，方法二中，铋酸钠水溶液的浓度为0.5-5mol/L；硝酸水溶液为1-10mol/L。The application of bismuth trioxide according to claim 1 as a fungicide is characterized in that, in method two, the concentration of the sodium bismuthate aqueous solution is 0.5-5mol/L; the nitric acid aqueous solution is 1-10mol/L.
  4. 根据权利要求1所述的三氧化二铋作为杀菌剂的应用，其特征在于，方法三中，能量密度为100-160J cm -2。 The application of bismuth trioxide as a fungicide according to claim 1, characterized in that in the third method, the energy density is 100-160J cm -2 .
  5. 根据权利要求4所述的三氧化二铋作为杀菌剂的应用，其特征在于，方法三中，移去金属铋前对水相分散的纳米三氧化二铋进行超声分散，超声功率200-700瓦，时间10-60分钟。The application of bismuth trioxide according to claim 4 as a fungicide is characterized in that, in the method three, before removing the metal bismuth, the nanometer bismuth trioxide dispersed in the aqueous phase is ultrasonically dispersed, and the ultrasonic power is 200-700 watts , time 10-60 minutes.
  6. 根据权利要求1-5任一项所述的三氧化二铋作为杀菌剂的应用，其特征在于，所述的三氧 化二铋与银抗菌剂、铜抗菌剂、锌抗菌剂、钛抗菌剂、钼抗菌剂联合使用。According to the application of bismuth trioxide described in any one of claims 1-5 as a bactericide, it is characterized in that, described bismuth trioxide and silver antibacterial agent, copper antibacterial agent, zinc antibacterial agent, titanium antibacterial agent, Molybdenum antibacterial agent used in combination.
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