CN111017996A - Synthesis of MoO with double simulated enzyme activity3-XMethod for producing antimicrobial material - Google Patents
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Abstract
The invention belongs to the field of the combination of inorganic nano material preparation and mimic enzyme technology, relates to a preparation method of an antibacterial material, and particularly relates to a method for synthesizing MoO with double mimic enzyme activity3‑XA method of inhibiting bacterial material. The preparation process comprises dissolving glucose powder in water completely, and adding acid to adjust the pH to acidity; then, the product is processedSealing, heating to obtain dark blue solution, dialyzing the dark blue solution, and freeze drying to obtain nanometer MoO3‑XA material; the reduced molybdenum oxide nano material prepared by the invention is applied to dual enzyme-like catalysis synergistic drug-resistant bacteria resistance. According to the severe situation of drug-resistant bacteria and biomembrane treatment, the invention solves the problems of high preparation yield, good biocompatibility, high near-infrared photothermal conversion efficiency and high dual-enzyme-imitating activity of nano MoO by a green, environment-friendly, simple and efficient one-step hydrothermal method3‑XThe key technical problem of the antibacterial agent. The application is environment-friendly, and the market prospect is wide.
Description
The technical field is as follows:
the invention belongs to the field of the combination of inorganic nano material preparation and mimic enzyme technology, relates to a preparation method of an antibacterial material, and particularly relates to a method for synthesizing MoO with double mimic enzyme activity3-XA method of inhibiting bacterial material.
Background art:
with the development of nanotechnology, the research of nano mimic enzyme is also becoming the hot point of research. Compared with natural enzymes, the nano-enzyme has the characteristics of stability, economy, high catalytic efficiency and large-scale preparation. Since the first reports of peroxidase properties of ferroferric oxide in 2007, more and more inorganic nanoparticles are found to have enzyme-simulating properties, such as gold, silver, carbon nanotubes, quantum dots, manganese dioxide, and the like. The discovery of the simulated enzymes greatly expands the application range of the enzymes. At present, most researches are mainly carried out on oxidase, peroxidase, glucose oxidase, superoxide dismutase and the like. The oxidases and peroxidases can generate active oxygen for killing tumor cells or bacteria, and the superoxide dismutase can remove free radicals to avoid the damage of the free radicals to a matrix.
In recent years, bacterial infections have become a serious threat to human health, and the emergence of antibiotics has indeed saved many patients with bacterial infections, but with the long-term use and increasing use of antibiotics, a large number of resistant bacteria are produced. To solve this problem, researchers are constantly developing new nano antibacterial agents, mainly comprising polymers, metal nanoparticles, carbon nanomaterials, two-dimensional materials (sulfides, oxides, selenides, etc.). Based on the physicochemical properties of these antibacterial agents, new therapeutic strategies were developed, mainly including photothermal therapy, which utilizes the property of the antibacterial agent to absorb near infrared light into thermal energy to kill bacteria by thermal effect, photodynamic therapy and chemokinetic therapy, which utilize free radicals to destroy the structure and composition of bacteria. The oxidase and the peroxidase can just utilize the generated free radicals to play a role in sterilization. However, the single treatment mode of antibiosis still has some problems, such as faster bacteria reproduction, longer antibiosis time, thicker bacterial cell wall, difficult penetration of simple free radicals through the cell wall to destroy the cell membrane, and short-time photo-thermal can not effectively kill the bacteria in the biological membrane, which greatly reduces the treatment effect. Therefore, in order to improve the antibacterial effect, a rapid and efficient treatment system for resisting drug-resistant bacteria infection is constructed by combining a plurality of treatment modes, and the method becomes a hotspot of research of people. However, in order to achieve various therapeutic effects, materials with single function are fused together, but the preparation process of the multifunctional nano system is complex and the yield is not high, which greatly limits the large-scale application of the nano antibacterial agent. Therefore, the development of the nano antibacterial agent which has low price, simple preparation process and multiple functions has wider application prospect and important significance.
The inorganic nano enzyme reported at present is mainly a monofunctional mimic enzyme, and most of the inorganic nano enzymes do not have the photo-thermal conversion performance. Although the molybdenum disulfide is a nano antibacterial material which is proved to have peroxidase activity and near-infrared photothermal conversion performance, the molybdenum disulfide is still a single-function mimic enzyme (ACS nano,2016,10, 11000-11011). Therefore, in order to improve the antibacterial activity, the development of the nano material with double simulated enzyme activity and near-infrared photothermal conversion performance has more theoretical and practical significance. In addition, the reduced molybdenum oxide MoO synthesized by the existing method3-xOnly photothermal and photosensitizing properties (ACS appl. Mater. interfaces,2018,10(49), 42088-. At present MoO3-xUsually by ultrasonic MoS2The nano-sheet or high-temperature hydrothermal reduction molybdate (Small 2018,14, 1801523; Sensors and DictatatorsB: Chemical, 2019,296,126517; Applied Catalysis B: Environmental, 2018, 224,671-680), the ultrasonic method has low preparation yield, the reducing agent is easily carbonized by high-temperature hydrothermal, the water solubility is reduced, and the problems limit MoO3-xThe biological application of (1).
Accordingly, the present invention seeks to design a synthetic MoO with dual mimetic enzyme activities3-XThe preparation method of the antibacterial material is simple, green and high in yield, and the prepared antibacterial material has the activities of oxidase, peroxidase and photothermal conversion performance and can be used for research on drug-resistant bacteria resistance.
The invention content is as follows:
the invention aims to overcome the defects in the prior art, and provides a green and environment-friendly method for preparing MoO with double simulated enzyme activity and photothermal conversion performance in a large scale3-XA method of nano-antibacterial agent.
In order to achieve the aim, the invention relates to a method for synthesizing MoO with double mimic enzyme activity3-XThe method of the antibacterial material is realized by the following technical scheme:
preparation of reduced molybdenum oxide
S1, dissolving glucose powder in water, adding ammonium molybdate powder after stirring and dissolving, and adding acid to adjust the pH value to acidity after completely dissolving;
s2, pouring the solution into a hydrothermal reaction kettle, sealing and heating to obtain a dark blue solution, dialyzing the dark blue solution, and freeze-drying to obtain the nano MoO3-XA material;
the reduced molybdenum oxide nano material prepared by the invention is applied to dual enzyme-like catalysis synergistic drug-resistant bacteria resistance.
The invention provides an antibacterial system combining double enzyme-mimetic catalysis with near-infrared photothermal synergistic drug-resistant bacteria, which comprises MoO3-XAntibacterial materials, hydrogen peroxide solutions and near infrared lasers.
According to the severe situation of drug-resistant bacteria and biomembrane treatment, the invention solves the problems of high preparation yield, good biocompatibility, high near-infrared photothermal conversion efficiency and high dual-enzyme-imitating activity of nano MoO by a green, environment-friendly, simple and efficient one-step hydrothermal method3-XThe key technical problem of the antibacterial agent.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention takes glucose with no toxicity and high biocompatibility as a reducing agent, prepares the reduced molybdenum oxide nano material in a large scale by a simple, high-efficiency, green and environment-friendly hydrothermal synthesis method in one step, improves the yield and biocompatibility of molybdenum oxide, and the prepared molybdenum oxide is basically 1-2 layers, has large specific surface area and larger contact area with bacteria and is easier to sterilize.
(2)MoO3-XThe nano material has higher near-infrared photo-thermal conversion efficiency, and the near-infrared photo-thermal treatment can effectively destroy the structure of bacteria by utilizing the characteristic that near-infrared light is beneficial to penetrating tissues.
(3)MoO3-XThe nano material also has the characteristics of double mimic enzymes of oxidase and peroxidase. Oxidases are capable of generating three free radicals: (1O2，O2 ∙-∙ OH), whereas the peroxidase catalytic function can reduce H2O2Catalyzes the production of ∙ OH from low-dose hydrogen peroxide. When near-infrared photothermal therapy is carried out, the generation of free radicals is further enhanced by illumination, the cell wall of bacteria is damaged by using the photothermal effect, the sensitivity of the bacteria to active oxygen free radicals is improved, and on the basis, low-dose hydrogen peroxide and MoO are added3-XCatalysis H2O2∙ OH is generated, the photo-thermal and chemical dynamics cooperative treatment strategy is utilized to effectively destroy the bacterial structure, the dosage of the antibacterial agent is reduced, the illumination time is shortened, and the antibacterial aging is improved.
Description of the drawings:
FIG. 1 shows a MoO synthesized by a one-step hydrothermal method according to the present invention3-XHigh resolution transmission electron microscopy images.
FIG. 2 shows the MoO prepared according to the present invention3-XXRD pattern of (a).
FIG. 3a is an embodiment of the invention in MoO3-XTemperature rising curve of the aqueous solution in the process of 808nm near-infrared laser irradiation.
FIG. 3b is a MoO according to the present invention3-XThe temperature change diagram of the water solution is heated under near infrared illumination and cooled naturally.
FIG. 4a is a scheme for providing 1, 3-diphenyl isobenzoylDetecting ROS (Di Rif) (DPBF) by taking furan (DPBF) as probe1O2、O2 ·-) The generated ultraviolet spectrogram.
FIG. 4b is a fluorescence spectrum of the probe Terephthalic Acid (TA) according to the present invention when OH is generated.
FIG. 4c is a schematic representation of the present invention involving providing H2O2And Tetramethylbenzidine (TMB) as a double substrate ultraviolet spectrum when OH was detected.
Figure 5a is a graph showing the relationship between the present invention and a light source provided in dark and near infrared light conditions,1O2electron spin resonance spectrum of (a).
FIG. 5b is a graph of O provided under dark and near infrared light conditions in accordance with the present invention2 ·-Electron spin resonance spectrum of (a).
FIG. 5c is the electron spin resonance spectrum of OH under dark and near infrared illumination conditions provided by the present invention.
FIG. 5d is the electron spin resonance spectrum of OH under the hydrogen peroxide addition condition provided by the present invention.
FIG. 6a is a graphical representation of the presence or absence of near infrared illumination and hydrogen peroxide of methicillin-resistant Staphylococcus aureus provided in accordance with the present invention.
FIG. 6b is a diagram showing the presence or absence of near infrared illumination and hydrogen peroxide of E.coli producing extended spectrum β -lactamase according to the present invention.
FIG. 7 is a graph of MoO provided at various concentrations in accordance with the present invention3-XEffects on normal fibroblast activity in mice.
The specific implementation mode is as follows:
in order to make the technical solutions and advantages of the present invention more clear, the following detailed descriptions of the technical solutions of the present invention with specific embodiments and accompanying drawings will help those skilled in the art to more fully understand the present invention, but the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. Other embodiments, which can be derived by those skilled in the art from the embodiments of the present invention without inventive step, are within the scope of the present invention.
Example 1:
the method for synthesizing the molybdenum oxide antibacterial material with double simulated enzyme activity provided by the embodiment comprises the following steps:
s1, dissolving glucose in water, adding molybdate after stirring and dissolving, and continuing stirring until the molybdate is completely dissolved to obtain a mixed solution;
s2, adding hydrochloric acid into the mixed solution prepared in the S1, and adjusting the pH of the mixed solution to be acidic;
s3, pouring the uniformly stirred mixed solution in the step S2 into a reaction kettle with a tetrafluoroethylene inner container, sealing and heating to obtain a blue solution;
s4, dialyzing the blue solution by using a dialysis bag, and freeze-drying the rest substances after dialysis to obtain the nano MoO3-XAnd (5) the antibacterial agent material is sealed and stored in dark.
Preferably, the mass-to-volume ratio of glucose to water in this embodiment S1 is 0.3-2.0 g: 30 mL.
Preferably, the mass ratio of glucose to molybdate in this embodiment S1 is 1-10: 1.
Preferably, in this embodiment S1, the molybdate is one or more of ammonium molybdate tetrahydrate, sodium molybdate dihydrate and ammonium heptamolybdate.
Preferably, the pH of the mixed solution in the embodiment S2 is 1-6;
preferably, the heating temperature of the hydrothermal reaction in this embodiment S3 is 50-100 degrees, and the reaction time is 6-24 hours.
Preferably, the molecular weight of the dialysis bag in this embodiment S4 is 500-10000 Da.
The nano MoO prepared by the invention3-XHigh yield, good biocompatibility, high photo-thermal conversion efficiency and high dual-enzyme-like catalytic activity.
Example 2:
s1, 1.5g of glucose and 0.5g of ammonium molybdate are dissolved in 30mL of water and stirred for 20 minutes until all the components are dissolved;
s2, dropwise adding hydrochloric acid into the mixed solution, adjusting the pH value of the solution to 4, and stirring for 5 minutes;
s3, pouring the mixed solution into a tetrafluoroethylene reaction kettle, sealing, and heating at 80 ℃ for 12 hours;
s4, pouring the crude product into a dialysis bag (10Kda dialysis membrane), dialyzing for 48 hours, then freeze-drying, sealing and storing in dark place.
Example 3:
essentially the same as in example 2, except that:
in step S1, the mass-to-volume ratio of glucose to water is 1.2 g: 30 mL;
the mass ratio of the glucose to the sodium molybdate is 3: 1;
in the step S2, the mixed solution has a pH of 1 and is stirred for 15 minutes;
in step S3, the hydrothermal reaction temperature was 80 degrees, and the reaction was carried out for 6 hours.
Example 4:
essentially the same as in example 2, except that:
in the step S1, the molybdate is heptamolybdic acid;
in the step S2, the mixed solution has a pH of 6 and is stirred for 20 minutes;
in step S3, the hydrothermal reaction temperature was 60 degrees, and the reaction was carried out for 24 hours.
Example 5:
FIG. 1 shows a nano-MoO prepared by the synthesis method of the present invention3-XThe crystal structure of molybdenum oxide can be clearly observed by a high-resolution transmission electron microscope. FIG. 2 shows MoO prepared according to the present invention3-XThe XRD pattern of the compound is analyzed by the XRD spectrogram, and the product is identical with the molybdenum oxide standard cards 21-0569 and 13-0142, thereby proving that the nano MoO with the catalytic activities of the oxidase and the peroxidase is synthesized for the first time in example 13-XAnd use of MoO3-XThe novel technology for constructing the synergistic drug-resistant bacteria by combining the dual enzyme-imitating catalytic function with the NIR photothermal property overcomes the defects of single photothermal bacteria resistance, combines the oxidase and peroxidase to catalyze and generate active oxygen free Radicals (ROS), and can enhance the strategy of killing the drug-resistant bacteria by photothermal, thereby shortening the NIR light irradiation time, reducing the side effect caused by long-time irradiation, and further realizing the next stepThe antibacterial rate is increased, and a new opportunity is provided for developing a novel antibacterial agent which is green, environment-friendly, simple to prepare and high-efficiency in bacteriostasis.
Example 6:
the following experiments prove the nano MoO3-XThe antibacterial agent has the application effect in the combination of double enzyme-like catalysis function and near-infrared photo-thermal synergistic antibacterial.
Nano MoO3-XThe near infrared thermal effect and the double enzyme simulating catalytic activity research:
(1) research on near-infrared thermal effect
Synthetic nano MoO3-XHas absorption in the near infrared region and can convert near infrared light energy into heat energy, which is the basis for photo-thermal antibacterial, and FIG. 3a shows 400 μ g/mL nano MoO of 100-3-XTemperature rise curve of the aqueous solution irradiated by 808nm near-infrared laser for 5 minutes, and FIG. 3b shows nano MoO3-XTemperature change graphs of the temperature rise and the temperature drop of the aqueous solution (the concentration is 300 mu g/mL) under near infrared illumination.
(2) Study of catalytic Activity of oxidase mimic
The key point of synergistically improving the antibacterial effect is that the catalytic activity of the pseudoenzyme is high, and the MoO prepared by one-step hydrothermal preparation in the embodiment 1-43-XStudy of MoO in an aqueous System as the subject of the study3-XOxidase activity, oxidases are capable of producing three active oxygen radicals, including1O2，O2 ∙-∙ OH, all had a killing effect on bacteria, and MoO was studied in this example3-XWhether three free radicals and the influence of near-infrared illumination on the intensities of the three free radicals are generated or not is respectively selected for DPBF detection1O2HE detection of O2 ∙-Detecting ∙ OH by Terephthalic Acid (TA), and testing the spectral changes of DPBF, HE and TA by an ultraviolet spectrophotometer or a fluorescence spectrophotometer;
DPBF detection1O2The steps of (1): the experimental system is divided into four groups, DPBF solution is used as an experimental group 1, DPBF + NIR illumination is used as an experimental group 2, and DPBF + MoO3-XDPBF + MoO for Experimental group 33-X+ NIR illumination for test group 4, after 5 minutes of reaction, the measurement of the solventUltraviolet absorption spectrum of the liquid, and the test result is shown in figure 4 a;
HE detection of O2 ∙-The steps of (1): the experimental system is divided into four groups, HE solution is an experimental group 1, HE + NIR illumination is an experimental group 2, HE + MoO3-XFor experimental group 3, HE + MoO3-X+ NIR illumination for experiment 4, after 5 minutes of reaction, the fluorescence spectrum of the solution was measured and the test results are shown in FIG. 4 b;
step of TA detection ∙ OH: the experimental system is divided into four groups, TA solution is an experimental group 1, TA + NIR illumination is an experimental group 2, TA + MoO3-XFor experimental group 3, TA + MoO3-X+ NIR illumination for test group 4, after 5 minutes of reaction, the UV absorption spectrum of the solution is determined and the test results are shown in FIG. 4 c;
as can be seen from the three figures, the MoO synthesized in examples 1-43-XThree active oxygen free radicals can be generated, the generation of ROS can be greatly enhanced by near-infrared illumination, more free radicals can be generated under the illumination condition, and the killing capacity of photo-thermal to drug-resistant bacteria can be effectively enhanced;
(3) peroxidase mimic enzyme catalytic activity study
Except for detecting the nano MoO3-XOxidase catalytic activity, MoO3-XThe peroxidase catalytic activity of (2) was also investigated in acetic acid buffer solution with Tetramethylbenzidine (TMB) and H2O2Study of MoO as a peroxidase substrate3-XCatalysis H2O2The color reaction of the oxidized TMB comprises the following specific steps: pure H is added2O2Solution as test group 1, H2O2+ TMB as Experimental group 2, H2O2+TMB+MoO3-XAs an experimental group 3, the material is verified to have peroxidase catalytic activity through TMB color development and change of ultraviolet absorption value;
(4) embodiments of synergistic antimicrobial systems
Selecting two typical drug-resistant bacteria as research objects, namely methicillin-resistant staphylococcus aureus (gram-positive bacteria) and escherichia coli (gram-negative bacteria) capable of producing extended-spectrum β -lactamase, and diluting a strain culture solution to a concentration of 1 × 106CFU/mL, thinningAdding 50 mu L of the strain culture solution into a 96-well plate, then adding different materials, shaking and uniformly mixing, and dividing experimental components into 8 groups: group 1 is the bacterial group, group 2 is bacteria + H2O2Group 3 is bacteria + nano MoO3-XGroup 4 is bacterium + H2O2+ nano MoO3-XGroup 5 bacteria + NIR illumination, group 6 bacteria + H2O2+ NIR illumination, group 7 bacteria + Nano MoO3-X+ NIR illumination, group 8 bacteria + H2O2+ nano MoO3-XAnd the near infrared illumination condition is that the laser with the wavelength of 808nm is used for irradiating for 5 minutes. For synergistic groups 4 and 8, the nano-MoO was added first3-XThe solution concentration was 100. mu.g/mL, incubated in the dark or irradiated with NIR for 5 minutes, followed by addition of H2O2，H2O2The final concentration was 100. mu.M. And uniformly smearing the treated bacterial liquid in an LB culture medium for 12 hours at 37 ℃, and recording the colony number of the bacteria. From the results of FIGS. 6a and 6b, it is clear that H is a little more than H alone2O2And nano MoO3-XIn the treatment group, under the non-illumination condition, the antibacterial effect of the double-enzyme synergistic catalysis is better than that of the single-enzyme catalysis, and more importantly, the antibacterial effect of the double-enzyme catalysis and NIR illumination (group 8) is the best.
In addition, this example also investigated nano-MoO3-XEffect on activity of normal L929 cells. As can be seen from FIG. 7, the material has little toxicity to cells within the concentration range of 200. mu.g/mL, and the cell survival rate reaches more than 80%, which shows that the MoO synthesized by the invention3-XHas good biocompatibility.
The research shows that the invention utilizes one-step hydrothermal synthesis of novel antibacterial agent nano MoO which integrates multiple functions and is green, environment-friendly, simple and efficient3-xThe antibacterial agent has the unique advantages of good water solubility, good biocompatibility, high dual-enzyme-mimetic catalytic activity, high NIR photothermal conversion efficiency and the like, provides a new idea for developing a high-efficiency synergistic antibacterial system, overcomes a plurality of problems of a single treatment system, and greatly simplifies the complicated steps of synthesizing a common multifunctional treatment system. This example utilizes MoO synthesized in a simple one-step hydrothermal process3-xHas the properties of oxidase, peroxidase and NIR photothermal conversionIn combination with MoO3-xThe excellent properties of the composite material construct a synergistic drug-resistant bacteria resisting system of NIR photothermal and double-enzyme catalysis chemodynamics treatment. MoO3-xThe oxidase catalytic activity of the compound can generate active oxygen free radicals, the active oxygen free radicals have the bactericidal effect, and the NIR light can enhance MoO while the NIR light is used for performing photothermal therapy3-xThe oxidase activity of the antibacterial agent can generate more free radicals to destroy the cell structure and enhance the antibacterial efficiency. In addition, H2O2Is an excellent antibacterial agent, however, in the case of general antibacterial, H2O2The effective antibacterial concentration of (1) is 170mM, the normal tissue is damaged when the concentration is higher, and the bacteria are easy to generate drug resistance. Using MoO3-xPeroxidase activity of (2) catalytic H2O2The rapid and efficient decomposition generates a large amount of ∙ OH, effectively destroys cell walls and cell membranes, and can make up for the defect of poor effect of pure photothermal antibacterial thermotherapy.
Finally, it should be noted that: although the invention has been described in detail in the foregoing specification by way of general description, specific embodiments and experiments. It will be apparent to those skilled in the art that modifications and improvements may be made thereto without departing from the spirit and scope of the invention as defined in the appended claims. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (9)
1. Nano MoO3-xThe synthesis method of the antibacterial material is characterized by comprising the following steps:
s1, dissolving glucose in water, adding molybdate after stirring and dissolving, and continuing stirring until the molybdate is completely dissolved to obtain a mixed solution;
s2, adding hydrochloric acid into the mixed solution prepared in the S1, and adjusting the pH of the mixed solution to be acidic;
s3, pouring the uniformly stirred mixed solution in the step S2 into a reaction kettle with a tetrafluoroethylene inner container, sealing and heating to obtain a blue solution;
s4, dialyzing the blue solution by using a dialysis bag, and freeze-drying the rest substances after dialysis to obtain the nano MoO3-XAnd (5) the antibacterial agent material is sealed and stored in dark.
2. The synthesis method according to claim 1, wherein the mass-to-volume ratio of glucose to water in step S1 is 0.3-2.0 g: 30mL, and the mass ratio of glucose to molybdate is 1-10: 1.
3. The method of claim 1, wherein the molybdate in step S1 is selected from the group consisting of ammonium molybdate tetrahydrate, sodium molybdate dihydrate and ammonium heptamolybdate.
4. The method of claim 1, wherein the pH of the mixed solution in step S2 is 1-6.
5. The synthesis method according to claim 1, wherein the hydrothermal reaction heating temperature in step S3 is 50-100 degrees, and the reaction time is 6-24 hours.
6. The method as set forth in claim 1, wherein the molecular weight of the dialysis bag in step S3 is 500-10000 Da.
7. The synthesis method according to claims 1 to 6, characterized in that the prepared nano-MoO3-xHas oxidase and peroxidase catalytic activity and NIR photothermal conversion performance.
8. The nano-MoO of claim 73-xThe antibacterial material is applied to the combination of double-enzyme catalysis chemical kinetics therapy and NIR photothermal synergistic antibacterial.
9. The synergistic drug-resistant bacteria combination system of claim 7, wherein the near-infrared laser is a 808nm wavelength laser for adding nano-MoO3-xThe aqueous solution was irradiated for 5 minutes and the hydrogen peroxide solution was added after the NIR laser irradiation.
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| CN112915204A (en) * | 2021-02-03 | 2021-06-08 | 青岛大学 | Anti-pseudomonas aeruginosa targeted bactericide and preparation method thereof |
| CN113769768A (en) * | 2021-09-08 | 2021-12-10 | 中国科学院海洋研究所 | Double-function composite nano material and preparation method and application thereof |
| CN113896242A (en) * | 2021-11-08 | 2022-01-07 | 苏州大学附属第一医院 | Preparation method and application of oxygen vacancy molybdenum trioxide nanoparticles |
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| CN113952984A (en) * | 2020-07-17 | 2022-01-21 | 中国科学院高能物理研究所 | High-catalytic-activity molybdenum-based nanoenzyme and preparation method and application thereof |
| CN113952984B (en) * | 2020-07-17 | 2022-07-22 | 中国科学院高能物理研究所 | High-catalytic-activity molybdenum-based nanoenzyme and preparation method and application thereof |
| CN112891535A (en) * | 2021-02-03 | 2021-06-04 | 青岛大学 | Nanocomposite with quadruple antibacterial effect and preparation method thereof |
| CN112915204A (en) * | 2021-02-03 | 2021-06-08 | 青岛大学 | Anti-pseudomonas aeruginosa targeted bactericide and preparation method thereof |
| CN114904011A (en) * | 2021-07-06 | 2022-08-16 | 中国科学院上海硅酸盐研究所 | Non-iron-based glutathione consumption synergistic active oxygen species reinforced composite material and preparation method and application thereof |
| CN114904011B (en) * | 2021-07-06 | 2023-10-13 | 中国科学院上海硅酸盐研究所 | Non-iron-based glutathione consumption synergistic active oxygen species reinforced composite material, and preparation method and application thereof |
| CN113769768A (en) * | 2021-09-08 | 2021-12-10 | 中国科学院海洋研究所 | Double-function composite nano material and preparation method and application thereof |
| CN113769768B (en) * | 2021-09-08 | 2023-05-26 | 中国科学院海洋研究所 | Double-function composite nano material and preparation method and application thereof |
| CN113896242A (en) * | 2021-11-08 | 2022-01-07 | 苏州大学附属第一医院 | Preparation method and application of oxygen vacancy molybdenum trioxide nanoparticles |
| CN115246656A (en) * | 2022-01-12 | 2022-10-28 | 青岛大学 | Preparation method and application of molybdenum oxide/iron nano material |
| CN115246656B (en) * | 2022-01-12 | 2023-07-25 | 青岛大学 | Preparation method and application of molybdenum oxide/iron nano material |
| CN114452386A (en) * | 2022-01-14 | 2022-05-10 | 江苏大学 | Preparation method and application of gold-copper bimetallic nano-enzyme composite material |
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