CN112723500B - Environment-friendly high-efficiency nano copper ion compound and preparation method and application thereof - Google Patents
Environment-friendly high-efficiency nano copper ion compound and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an environment-friendly high-efficiency nano copper ion compound which consists of a copper ion solution with the concentration of 5-200 mu mol/L and a graphene solution with the concentration of 40-100 mg/L, wherein the volume ratio of the copper ion solution to the graphene solution is (0.5-2): 1. The invention provides an environment-friendly high-efficiency nano copper ion compound, which aims to solve the technical problem of utilizing the broad-spectrum sterilization characteristic of copper ions, and simultaneously overcoming the biotoxicity caused by the high ion concentration of the traditional copper ion bactericide, so that the copper ion bactericide becomes a high-efficiency, rapid and low-toxicity bactericide.
Description
Technical Field
The invention belongs to the technical field of bactericide preparation, and particularly relates to an environment-friendly high-efficiency nano copper ion compound and a preparation method and application thereof.
Background
Copper ions are one of the long-acting broad-spectrum antibacterial materials of inorganic type known from the past and applied very early. Studies have shown that copper ions have the effect of inhibiting the growth of various health-disturbing bacteria, viruses and microorganisms in water, such as algae, such as escherichia coli, staphylococcus aureus, salmonella, campylobacter jejuni, clostridium, mycobacterium tuberculosis, cyanobacteria, green algae and the like (curr. Med. Chem.2005,12, 2163-2175), and that microorganisms do not develop resistance thereto during their long-term use (appl. Environ. Microb.2010,76 (12): 4099-4101). Copper ion bactericides have great application potential as an antimicrobial product for daily use in health care facilities, the food industry, agriculture and other places where cleaning or disinfection is required. However, when the copper concentration exceeds a certain range, it has high toxicity, which in turn threatens environmental safety (chem. Res. Protocol. 2015,28, 1815-1822). For example, more than half of Chinese weever can die when copper ion concentration reaches 14. Mu. Mol/L (Fish physiology. Academic Press,2011, 31:417-473); the deadly threshold of copper ion concentration in the juvenile period of some fishes is 1 mu mol/L; when the copper ion concentration exceeds 16. Mu. Mol/L, toxicity to various human Cell lines such as human lung epithelial cells, human cardiac microvascular endothelial cells, kidney cells and nerve cells is generated (Cell biol. Toxicol.2011,27 (5): 333-342). In fact, a series of copper content standards are established by the health departments of various countries, the world health organization, and the like. The national health standards for domestic drinking water (GB 5749-2006) issued by the Ministry of health in 2006 require copper levels below 16. Mu. Mol/L, the World Health Organization (WHO) Water quality guidelines for drinking water require copper levels below 32. Mu. Mol/L, the European Commission for drinking water (1998) require copper levels below 32. Mu. Mol/L, the national standards for United states EPA drinking water quality (2012) require copper levels below 20. Mu. Mol/L, and the Japanese drinking water quality standards require copper levels below 16. Mu. Mol/L. In view of the toxicity of copper to aquatic organisms, the standard requirements of fresh water organisms for copper in China require that the long-term dangerous concentration of copper should be lower than 0.15umol/L when 95% of species are protected, the final acute value in the standard of fresh water organisms for copper newly revised in the United states environmental protection agency in 2007 is 0.074 mu mol/L, and the final chronic value is 0.023 mu mol/L (EPA-822-R-07-001). In the surface water environment quality standard of copper issued by the world health organization of China, the standard of the I-type water quality copper is 0.16 mu mol/L, and the standard of the II-type water quality copper is 16 mu mol/L; the standards of fishery water issued by many countries are strictly in the human health standard, and the standards of fishery water copper are 0.16 mu mol/L. In addition, when the copper ion bactericide is used for preventing and controlling agricultural product diseases, excessive copper ions are destructive to soil (Environment International 36 (2010) 138-151), and corresponding soil quality standards are established for soil pollution in various countries. In 1995, china issued the soil environmental quality Standard (GB 15618-1995) that requires the content of copper ions in agricultural soil such as farmlands, etc., the primary standard is lower than 35mg/kg, and the secondary standard is lower than 50mg/kg. Therefore, in order to more widely apply the copper ion bactericide, and meanwhile, to prevent the harm to the environment, animals, plants and human bodies in the application process, the development of the method for improving the efficiency and the sterilization speed of the copper ion bactericide and reducing the toxic side effects of the bactericide is an urgent task, and the realization of a novel environment-friendly, efficient, mass-producible and cheap bactericide or material is still a significant subject in the current sterilization application.
Meanwhile, with the current development of nanotechnology, the application of the nanomaterial in biology and medical technology is vigorous, and the interaction of the nanomaterial with cells has attracted attention, including the transmembrane action of 0-dimensional fullerene, the cell penetration action of 1-dimensional carbon nanotubes, the cleavage of cells by 2-dimensional graphene, and the massive extraction action of phospholipid molecules of cell membranes. These studies and exploration have stimulated widespread and also continually increasing research attention in nanomaterial sterilization, even with some controversy.
Disclosure of Invention
The first object of the invention is to provide an environment-friendly and efficient nano copper ion compound.
The second object of the invention is to provide a preparation method of the environment-friendly and efficient nano copper ion compound.
The third object of the invention is to provide an application of the environment-friendly high-efficiency nano copper ion compound in preparing bactericide medicines.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the first aspect of the invention provides an environment-friendly high-efficiency nano copper ion compound, which consists of a copper ion solution with the concentration of 5-200 mu mol/L and a graphene solution with the concentration of 40-100 mg/L, wherein the volume ratio of the copper ion solution to the graphene solution is (0.5-2): 1.
The volume ratio of the copper ion solution to the graphene solution is 1:1.
The copper ion solution is Cu 2+ The ionic solution is prepared by dissolving one of copper chloride, copper fluoride, copper bromide, copper sulfate, copper nitrate, etc. in water to generate Cu 2+ A solution of ions, wherein a copper sulfate solution is optimal.
The graphene solution refers to a graphene oxide solution prepared by an oxidation stripping graphite method (namely a Hummers method) and a reduced graphene oxide solution prepared by further reduction, wherein suspended graphene sheets are monoatomic layer thickness (about 0.5-1.0 nm), and the size diameter of the sheets is 5-50 mu m.
The second aspect of the invention provides a preparation method of the environment-friendly and efficient nano copper ion compound, which comprises the following steps: and mixing copper ion solution with the concentration of 5-200 mu mol/L and graphene solution with the concentration of 40-100 mg/L according to the volume ratio of (0.5-2): 1 to obtain the environment-friendly high-efficiency nano copper ion compound.
The third aspect of the invention provides the application of the environment-friendly high-efficiency nano copper ion compound in preparing bactericide medicaments in agriculture or other fields.
Other fields refer to the fields of daily necessities, washing products and the like.
The fourth aspect of the invention provides a bactericide composition, which contains the environment-friendly efficient nano copper ion compound as an active component; wherein the weight percentage of the active components in the bactericide composition is 0.1-99%.
By adopting the technical scheme, the invention has the following advantages and beneficial effects:
the environment-friendly high-efficiency nano copper ion compound provided by the invention aims to solve the technical problem that the broad-spectrum sterilization characteristic of copper ions is utilized, and simultaneously, the biotoxicity (harm to animals, plants and human bodies) caused by the high ion concentration of the traditional copper ion bactericide is overcome, so that the environment-friendly high-efficiency nano copper ion compound is a bactericide with high efficiency, high speed and low toxicity. The invention can ensure that the traditional copper ion bactericide can keep the concentration level of copper ions in extremely low environment (less than 0.2 mu mol/L), basically meets the standard requirement of fresh water biological water quality of copper in China, ensures that the long-term dangerous concentration of copper is lower than 0.15 mu mol/L when 95% of species are protected, realizes that the sterilization effect is improved by two orders of magnitude, namely, the novel bactericidal agent which is environment-friendly, efficient, mass-producible and cheap, and has good application prospect.
The graphene does not have a sterilization effect, and the environment-friendly high-efficiency nano copper ion compound provided by the invention is based on the ion pi interaction between copper ions and graphene from the functional perspective of graphene, and utilizes the high adsorptivity of graphene oxide to copper ions, and realizes the transfer of copper ions to the bacterial surface at low concentration through the electrostatic interaction between graphene with positive ions and bacterial cell membranes with negative ions after adsorption, thereby realizing the enrichment of the bacterial surface with local high concentration of copper ions, and finally realizing the two-order enhancement of the sterilization effect of copper ions under the condition of keeping extremely low environment copper ion concentration.
Drawings
FIG. 1 is a graph showing the comparison of the sterilizing effect of the environment-friendly high-efficiency nano copper ion complex and the conventional copper ion sterilizing agent on Escherichia coli in example 1.
Fig. 2 is a graph showing the comparison of the sterilizing effect of the environment-friendly and efficient nano-copper ion complex and the conventional copper ion sterilizing agent on staphylococcus aureus in example 2.
FIG. 3 is a graph showing the comparison of the killing effect of the environment-friendly and efficient nano-copper ion complex and the conventional copper ion bactericide on Chlamydomonas reinhardtii in example 3.
Fig. 4 is a graph showing the comparison of the killing effect of the environment-friendly high-efficiency nano copper ion complex and the conventional copper ion bactericide on blue algae in example 4.
FIG. 5 is a schematic illustration of a process flow of an environmentally friendly high efficiency nano copper ion complex.
Detailed Description
In order to more clearly illustrate the present invention, the present invention will be further described with reference to preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and that this invention is not limited to the details given herein.
The reagents used in the present invention are shown in Table 1:
table 1 preparation of graphene oxide materials as main raw materials
| Raw material name | Specification of specification | Manufacturer' s |
| Natural graphite (C) | Analytical grade (A.R.) 325 mesh | Shanghai colloid chemical plant |
| Hydrochloric acid (HCl) | Analytically pure (A.R.) | Sinopharm Group Chemical Reagent Co., Ltd. |
| Phosphorus pentoxide (P) 2 O 5 ) | Analytically pure (A.R.) | Sinopharm Group Chemical Reagent Co., Ltd. |
| Potassium persulfate (K) 2 S 2 O 8 ) | Analytically pure (A.R.) | Sinopharm Group Chemical Reagent Co., Ltd. |
| Potassium permanganate (KMnO) 4 ) | Analytically pure (A.R.) | SHANGHAI HAOSHEN CHEMICAL REAGENT Co.,Ltd. |
| Hydrogen peroxide (H) 2 O 2 ) | Analytically pure (A.R.) | SHANGHAI HAOSHEN CHEMICAL REAGENT Co.,Ltd. |
| Concentrated sulfuric acid (H) 2 SO 4 ) | Analytically pure (A.R.) | Sinopharm Group Chemical Reagent Co., Ltd. |
| Copper sulfate (CuSO) 4 ·5H 2 O) | Analytically pure (A.R.) | Sinopharm Group Chemical Reagent Co., Ltd. |
| Cupric chloride (CuCl) 2 ·2H 2 O) | Analytically pure (A.R.) | Sinopharm Group Chemical Reagent Co., Ltd. |
| Copper fluoride (CuF) 2 ·2H 2 O) | Analytically pure (A.R.) | Sinopharm Group Chemical Reagent Co., Ltd. |
| Copper nitrate (Cu (NO) 3 ) 2 ·2.5H 2 O) | Analytically pure (A.R.) | Sinopharm Group Chemical Reagent Co., Ltd. |
| Deionized water | Sartorius Arium611 ultrapure water machine in germany |
Example 1
As shown in fig. 5, fig. 5 is a schematic process flow diagram of the environment-friendly and efficient nano copper ion complex.
The preparation method of the environment-friendly high-efficiency nano copper ion compound comprises the following steps: and mixing a copper ion solution with the concentration of 100 mu mol/L and a graphene solution with the concentration of 80mg/L according to the volume ratio of 1:1 to obtain the environment-friendly high-efficiency nano copper ion compound.
The copper ion solution: with copper sulphate (CuSO) 4 ·5H 2 O) the crystals were prepared as an aqueous solution at a concentration of 100. Mu. Mol/L, and then filtered through a 0.22 μm filter, and the mother liquor was allowed to stand at room temperature.
The graphene solution is prepared by an oxidation exfoliation graphite method (i.e., hummers method), wherein suspended graphene sheets are monoatomic layer thickness (about 0.5 nm) and have a sheet size diameter of 5-50 μm.
Mixing the environment-friendly high-efficiency nano copper ion compound with a solution containing bacteria or algae to be treated according to an equal volume ratio, and reacting for 2 hours at room temperature, wherein the concentration of graphene oxide in the system is 40mg/L, the concentration of copper ions after mixing is 50 mu mol/L, and the concentration level of environmental copper ions (free copper ions) is less than 0.2 mu mol/L. (the mixed solution was passed through a microfiltration filter having a pore size of 0.22 μm, vacuum-filtered to remove graphene oxide, and then experimental measurement was performed using an ion-emitter spectrometer (ICP-OES))
The bactericidal activity was detected by a clone counting method: e.coli concentration of 10 8 mL -1 The sterilization activity experiment is carried out by deionized water solution, 3 mu mol/L pure copper ion solution and environment-friendly high-efficiency nano copper ion compound. Wherein, the water solution is used as a control experiment, and 3 mu mol/L pure copper ion solution is used as a reference control experiment of the sterilizing effect of the traditional copper ion bactericide. The test samples were continuously shaken at 200rpm for 2 hours at room temperature to perform an antibacterial test. Each sample was diluted 10 with a standard serial dilution 4 Multiple and 500 μl of suspension from each sample was spread evenly on LB agar plates and after incubation at 37 ℃ for 24 hours, the number of viable bacterial colonies was counted. The ratio of the colony number in the aqueous solution control experiment to the colony number in the environment-friendly and efficient nano copper ion complex sterilization experiment is used as the antibacterial activity of the environment-friendly and efficient nano copper ion complex.
As shown in FIG. 1, FIG. 1 is a graph comparing the sterilizing effect of the environment-friendly and efficient nano copper ion compound in example 1 with that of the traditional copper ion sterilizing agent on escherichia coli, and the sterilizing effect of the environment-friendly and efficient nano copper ion compound is improved by two orders of magnitude (225 times) compared with that of the traditional copper ion sterilizing agent under the condition that the concentration level of the environment-friendly and efficient nano copper ion compound is kept to be lower than 0.2 mu mol/L, which basically meets the standard requirement of fresh water biological water quality of copper in China, and the long-term dangerous concentration of copper is lower than 0.15 mu mol/L when 95% of species is protected.
Example 2
The preparation method of the environment-friendly high-efficiency nano copper ion compound comprises the following steps: and mixing a copper ion solution with the concentration of 100 mu mol/L and a graphene solution with the concentration of 80mg/L according to the volume ratio of 1:1 to obtain the environment-friendly high-efficiency nano copper ion compound.
The copper ion solution: with cupric chloride (CuCl) 2 ·2H 2 O) the crystals were prepared as an aqueous solution at a concentration of 100. Mu. Mol/L, and then filtered through a 0.22 μm filter, and the mother liquor was allowed to stand at room temperature.
The graphene solution is prepared by an oxidation exfoliation graphite method (i.e., hummers method), wherein suspended graphene sheets are monoatomic layer thickness (about 0.5 nm) and have a sheet size diameter of 5-50 μm.
Mixing the environment-friendly high-efficiency nano copper ion compound with a solution containing bacteria or algae to be treated according to an equal volume ratio, and reacting for 2 hours at room temperature, wherein the concentration of graphene oxide in the system is 40mg/L, the concentration of copper ions after mixing is 50 mu mol/L, and the concentration level of environmental copper ions (free copper ions) is less than 0.2 mu mol/L.
The bactericidal activity was detected by a clone counting method. Staphylococcus aureus concentration of 10 10 mL -1 The sterilization activity experiment is carried out by deionized water solution, 3 mu mol/L pure copper ion solution and environment-friendly high-efficiency nano copper ion compound. Wherein, the water solution is used as a control experiment, and 3 mu mol/L pure copper ion solution is used as a reference control experiment of the sterilizing effect of the traditional copper ion bactericide. The test samples were continuously shaken at 200rpm for 2 hours at room temperature to perform an antibacterial test. Each sample was diluted 10 with a standard serial dilution 4 Doubling and spreading the 500. Mu.L of suspension from each sample evenly on LB agar plates at 37 ℃After 24 hours of incubation, the number of viable bacterial colonies was counted. The ratio of the colony number in the aqueous solution control experiment to the colony number in the environment-friendly and efficient nano copper ion complex sterilization experiment is used as the antibacterial activity of the environment-friendly and efficient nano copper ion complex.
As shown in fig. 2, fig. 2 is a graph showing the comparison of the sterilizing effect of the environment-friendly and efficient nano copper ion complex in example 2 and the conventional copper ion sterilizing agent on staphylococcus aureus. The method can realize the environment-friendly high-efficiency nano copper ion compound sterilization capability which is improved by an order of magnitude (23 times) compared with the sterilization effect of the traditional copper ion bactericide under the condition of keeping the concentration level of copper ions in extremely low environment (less than 0.2 mu mol/L) and basically meeting the fresh water biological water quality standard requirement of copper in China and protecting 95% of species and the long-term dangerous concentration of copper to be lower than 0.15 mu mol/L).
Example 3
The preparation method of the environment-friendly high-efficiency nano copper ion compound comprises the following steps: and mixing a copper ion solution with the concentration of 100 mu mol/L and a graphene solution with the concentration of 80mg/L according to the volume ratio of 1:1 to obtain the environment-friendly high-efficiency nano copper ion compound.
The copper ion solution: with copper fluoride (CuF) 2 ·2H 2 O) the crystals were prepared as an aqueous solution at a concentration of 100. Mu. Mol/L, and then filtered through a 0.22 μm filter, and the mother liquor was allowed to stand at room temperature.
The graphene solution is prepared by an oxidation stripping graphite method (namely a Hummers method), wherein suspended graphene sheets are monoatomic layer thickness (about 0.5 nm), and the sheet size diameter is 5-50 mu m:
mixing the environment-friendly high-efficiency nano copper ion compound with a solution containing bacteria or algae to be treated according to an equal volume ratio, and reacting for 2 hours at room temperature, wherein the concentration of graphene oxide in the system is 40mg/L, the concentration of copper ions after mixing is 50 mu mol/L, and the concentration level of environmental copper ions (free copper ions) is less than 0.2 mu mol/L.
The activity of Chlamydomonas reinhardtii was determined by Fluorescein Diacetate (FDA) staining imaging. Chlamydomonas reinhardtii concentration of 10 6 mL -1 Deionized water solution, 3 mu mol/L pure copper ion solution and environment-friendly high-efficiency nanometerCopper ion complexes were used for algicidal activity experiments. Wherein, the water solution is used as a control experiment, and 3 mu mol/L pure copper ion solution is used as a reference control experiment of the algicidal effect of the traditional copper ion algicide. The experimental samples were incubated at room temperature for 30 minutes for the Chlamydomonas reinhardtii test, then incubated with FDA staining of the cells for 5 minutes, and live cells were identified by green fluorescence of fluorescein. mu.L of cell suspension from each sample was spread evenly on a siliconized glass cover slip. The number of living cells was calculated by taking a fluorescent picture using an inverted confocal microscope system. The ratio of the cell number in the aqueous solution control experiment to the cell number in the environment-friendly and efficient nano copper ion complex algicidal experiment is used as the algicidal activity of the environment-friendly and efficient nano copper ion complex.
As shown in fig. 3, fig. 3 is a graph showing the comparison of the killing effect of the environment-friendly and efficient nano-copper ion complex and the conventional copper ion bactericide on chlamydomonas reinhardtii in example 3. Realizing the environment-friendly high-efficiency nano copper ion compound algae killing capability which is improved by an order of magnitude (27 times) compared with the algae killing effect of the traditional copper ion algae killing agent under the condition of keeping the concentration level of copper ions in extremely low environment (less than 0.2 mu mol/L) and basically meeting the standard requirement of fresh water biological water quality of copper in China and protecting 95 percent of species and the long-term dangerous concentration of copper to be lower than 0.15 mu mol/L).
Example 4
The preparation method of the environment-friendly high-efficiency nano copper ion compound comprises the following steps: and mixing a copper ion solution with the concentration of 100 mu mol/L and a graphene solution with the concentration of 80mg/L according to the volume ratio of 1:1 to obtain the environment-friendly high-efficiency nano copper ion compound.
The copper ion solution: with copper nitrate (Cu (NO) 3 ) 2 ·2.5H 2 O) the crystals were prepared as an aqueous solution at a concentration of 100. Mu. Mol/L, and then filtered through a 0.22 μm filter, and the mother liquor was allowed to stand at room temperature.
The graphene solution is prepared by an oxidation stripping graphite method (namely a Hummers method), wherein suspended graphene sheets are monoatomic layer thickness (about 0.5 nm), and the sheet size diameter is 5-50 mu m:
mixing the environment-friendly high-efficiency nano copper ion compound with a solution containing bacteria or algae to be treated according to an equal volume ratio, and reacting for 2 hours at room temperature, wherein the concentration of graphene oxide in the system is 40mg/L, the concentration of copper ions after mixing is 50 mu mol/L, and the concentration level of environmental copper ions (free copper ions) is less than 0.2 mu mol/L.
Blue algae killing activity was determined by Fluorescein Diacetate (FDA) staining imaging. Blue algae concentration of 10 6 mL -1 And carrying out blue algae killing activity experiments by using deionized water solution, 3 mu mol/L pure copper ion solution and environment-friendly high-efficiency nano copper ion compound. Wherein, the water solution is used as a control experiment, and 3 mu mol/L pure copper ion solution is used as a reference control experiment of the algicidal effect of the traditional copper ion algicide. The test samples were incubated at room temperature for 30 minutes for blue algae killing, then the cells were stained with FDA for 5 minutes for incubation, and living cells were identified by green fluorescence of fluorescein. mu.L of cell suspension from each sample was spread evenly on a siliconized glass cover slip. The fluorescence intensity of fluorescein at 512nm was measured with a fluorescence spectrophotometer, and the number of living cells was calculated from the fluorescence intensity in direct proportion to the number of living cells. The ratio of the cell number in the aqueous solution control experiment to the cell number in the blue algae killing experiment of the nano copper ion complex is used as the blue algae killing activity of the environment-friendly high-efficiency nano copper ion complex.
As shown in fig. 4, fig. 4 is a graph showing the comparison of the killing effect of the environment-friendly and efficient nano copper ion complex and the conventional copper ion bactericide on blue algae in example 4. The blue algae killing capability of the environment-friendly high-efficiency nano copper ion compound is improved by 6 times compared with that of the traditional copper ion algicide under the condition that the copper ion concentration level is kept to be extremely low (less than 0.2 mu mol/L), the standard requirement of fresh water living things water quality of copper in China is basically met, and the long-term dangerous concentration of copper in the process of protecting 95% of species is required to be lower than 0.15 mu mol/L).
The foregoing description is only illustrative of the preferred embodiment of the present invention, and is not to be construed as limiting the invention, but is to be construed as limiting the invention to any and all simple modifications, equivalent variations and adaptations of the embodiments described above, which are within the scope of the invention, may be made by those skilled in the art without departing from the scope of the invention.
Claims (4)
1. An application of environment-friendly high-efficiency nano copper ion compound in removing bacteria or algae in solution;
wherein the environment-friendly high-efficiency nano copper ion compound consists of copper ion solution with the concentration of 5-200 mu mol/L and graphene solution with the concentration of 40-100 mg/L according to the volume ratio of (0.5-2): 1;
the bacteria are escherichia coli or staphylococcus aureus, and the algae are chlamydomonas reinhardtii;
the graphene solution refers to a graphene oxide solution prepared by oxidation stripping graphite and a reduced graphene oxide solution prepared by further reduction, wherein suspended graphene sheets are monoatomic layers, the thickness is 0.5-1.0 nm, and the size diameter of each sheet is 5-50 mu m.
2. The use according to claim 1, wherein the volume ratio of copper ion solution to graphene solution is 1:1.
3. The use according to claim 1 or 2, wherein the copper ion solution is Cu 2+ An ionic solution.
4. The use according to claim 3, wherein the copper ion solution is a solution of one of copper chloride, copper fluoride, copper bromide, copper sulfate, copper nitrate in water to produce Cu 2+ A solution of ions.
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| RU2698713C1 (en) * | 2018-11-28 | 2019-08-29 | федеральное государственное бюджетное образовательное учреждение высшего образования "Тамбовский государственный университет имени Г.Р. Державина" | Method of producing composite material with antimicrobial properties based on graphene oxide and copper oxide nanoparticles |
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