CN112209445A - Preparation method and application of molybdenum trioxide nanodot antibacterial material - Google Patents
Preparation method and application of molybdenum trioxide nanodot antibacterial material Download PDFInfo
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/02—Oxides; Hydroxides
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
- A61K41/0052—Thermotherapy; Hyperthermia; Magnetic induction; Induction heating therapy
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K41/00—Medicinal preparations obtained by treating materials with wave energy or particle radiation ; Therapies using these preparations
- A61K41/0057—Photodynamic therapy with a photosensitizer, i.e. agent able to produce reactive oxygen species upon exposure to light or radiation, e.g. UV or visible light; photocleavage of nucleic acids with an agent
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K49/00—Preparations for testing in vivo
- A61K49/001—Preparation for luminescence or biological staining
- A61K49/0013—Luminescence
- A61K49/0017—Fluorescence in vivo
- A61K49/0019—Fluorescence in vivo characterised by the fluorescent group, e.g. oligomeric, polymeric or dendritic molecules
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- A—HUMAN NECESSITIES
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- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
- A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
- A61P31/04—Antibacterial agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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Abstract
The invention belongs to the field of nano-material preparation and performance detection and sterilization application, and relates to a preparation method and application of a molybdenum trioxide nanodot antibacterial material, wherein the molybdenum trioxide nanodots are prepared by a hydrothermal method from bottom to top, so that the molybdenum oxide nano-material is prepared by using molybdenum trichloride powder as a precursor in a one-step method, the method is simple and convenient, and is pollution-free, and the prepared molybdenum trioxide nanodots contain oxygen vacancies and have excellent infrared absorption performance, photo-thermal conversion performance and antibacterial performance; the preparation method is simple, the preparation equipment is easy to obtain, the preparation process is simple, the antibacterial effect is good and harmless to human bodies, the whole process is green and pollution-free, the application environment is friendly, and the market prospect is wide.
Description
The technical field is as follows:
the invention belongs to the field of nano material preparation and performance detection and sterilization application, and relates to a preparation method and application of a molybdenum trioxide nanodot antibacterial material.
Background art:
in recent years, bacterial infectious diseases are spreading worldwide. Currently, one of the biggest tasks is to control the spread of infectious agents. Antibiotics are commonly used antibacterial agents, the abuse of which leads to the emergence of a large number of resistant bacteria, H2O2Is widely used as an antibacterial agent for bacterial infections, and interestingly, H2O2Can be converted into hydroxyl free radical by functional nanoparticles with peroxidase property, and has great harm to bacteria, but high concentration of H2O2Is also harmful to living organisms. In order to overcome the above-mentioned drawbacks, it is urgently required to develop an antibacterial material having high efficiency in a simple and low-cost manner. Inspired by natural enzymes, one destroys bacteria by catalyzing harmful Reactive Oxygen Species (ROS) produced by nanoenzymes, which are generally easier to prepare and stable than high-cost unstable natural enzymes. These characteristics are beneficial to the application of nano enzyme in antibiosis. Now, some inorganic nanomaterials, such as graphene quantum dots, Fe, have been reported3O4Nanoparticles and CeO2The nanoparticles can mimic the properties of natural peroxidase, such as H2O2Converting into hydroxyl free radical to kill bacteria.
Today, many challenges still remain in the development of antibacterial nanoenzymes, and among various anti-infective therapies, photoactivation therapies including photothermal therapy (PTT) have attracted extensive attention due to their non-invasiveness and low side effects. In addition, the antibacterial mechanism of photothermal is different from traditional antibiotic treatment, and photothermal therapy utilizes local light-induced high temperature to cause bacterial degenerative death. Photothermal therapy using Near Infrared (NIR) photothermal agents is almost free of working distance or micro-environment limitations, which is a viable approach. Thus, NIR photoactivated photothermal agents are considered to beA candidate drug for anti-infective therapy. At the same time, besides, photodynamic therapy (PDT) is considered as a promising alternative to antibiotic resistant biofilms and bacteria. The bacterium can be substituted by OH, and1O2，O2-and Reactive Oxygen Species (ROS) killing. In general, Photosensitizers (PS) generate ROS only in the presence of light and exhibit antimicrobial properties. Thus, photodynamic therapy is controllable compared to other antibacterial agents.
Currently, molybdenum oxide material has attracted much attention worldwide as a new transition metal oxide due to its wide use. Molybdenum oxide has many excellent properties due to its unique crystal structure, and is widely used in reagents for spectroscopic analysis. Molybdenum is an essential trace element in mammals and humans, and is a cofactor for various enzymes such as xanthine oxidase, aldehyde oxidase and sulfite oxidase. Dietary molybdenum deficiency leads to an increased incidence of esophageal cancer. Molybdenum (VI) complexes are effective antidiabetics. Recently, some new functions of nano molybdenum oxide have been gradually explored, especially in the field of biomedical applications. As a multifunctional material, the molybdenum oxide nano material has high photo-thermal conversion efficiency in a Near Infrared (NIR) region. And then used as a degradable photothermal agent and drug carrier. In addition, due to different valence states and forms of the molybdenum oxide nano material, the molybdenum trioxide nanodots (MoO)3-xNDs) belong to a class of zero-dimensional nanodots (0D-NDs) with smaller size and abundant surface defects, making them more catalytically active than their bulk form.
Molybdenum oxide nanodots are generally prepared in the existing preparation mode by taking molybdenum disulfide or molybdenum powder as a molybdenum precursor and synthesizing the molybdenum disulfide or molybdenum powder in the presence of hydrogen peroxide or ethanol. The synthesis process has many safety hazards and the removal of strong oxidants complicates the preparation process. Compared with the method, the solvothermal method has the advantages that the preparation process is extremely simple and is most widely applied, the prior top-down solvothermal stripping technology generally needs pre-treatment steps such as ultrasonic crushing of a large molybdenum oxide raw material, the steps are complicated and time-consuming, and the material conversion rate and the yield are relatively low. Therefore, in order to further research the application and development of the molybdenum oxide nano material, a simple, easy and efficient preparation method of the molybdenum oxide nano structure is needed, and if the molybdenum oxide nano material with multiple valence states can be prepared by a one-step method, the preparation and research efficiency of the molybdenum oxide nano material can be greatly improved, but no research report is found at present. Therefore, the invention seeks to design and provide a simple, green and pollution-free one-step method for preparing the molybdenum oxide nanodots.
The invention content is as follows:
the invention aims to overcome the defects in the prior art and provides a preparation method and application of a molybdenum trioxide nanodot antibacterial material.
In order to achieve the purpose, the preparation method of the molybdenum trioxide nanodot antibacterial material comprises the following specific process steps:
(1) preparing a molybdenum trichloride aqueous solution with the mass concentration of 0.005g/mL-0.006g/mL, fully stirring to uniformly disperse the molybdenum trichloride aqueous solution, and putting the molybdenum trichloride aqueous solution into a reaction kettle;
(2) putting the reaction kettle into a blast drier, and heating and reacting for 10 hours at 200 ℃;
(3) taking out the reacted sample, centrifuging at 12000rpm/min for 9-11 minutes, removing the precipitate, collecting the supernatant, centrifuging the supernatant at 12000rpm/min for 9-11 minutes, removing the precipitate, collecting the supernatant again, repeating the steps of centrifuging, removing the precipitate and collecting the supernatant for several times until no precipitate appears in the centrifuged solution, obtaining the colorless dispersed molybdenum trioxide nanodot solution, and completing the preparation of the molybdenum trioxide nanodot antibacterial material.
The molybdenum trioxide nanodots related by the invention have uniform particle size of less than 10nm, average particle size of 3.07 +/-0.45 nm and thickness of 1.43 +/-0.08 nm, and good dispersibility.
The molybdenum trioxide nanodots provided by the invention contain oxygen vacancies, have more surface oxygen defects, have more active sites, and can better utilize the property of the nanoenzyme to inhibit and kill drug-resistant bacteria in wounds.
The molybdenum trioxide nanodots related by the invention have wide absorption range from visible light to near infrared wavelength of 300-1000nm, and have excellent infrared absorption performance.
The molybdenum trioxide nanodots can well convert light energy into heat energy under near-infrared irradiation, and just reach the optimal temperature of enzyme-like (peroxidase) activity, so that the enzyme activity state is optimal, a proper amount of active oxygen is generated, and the growth of thalli is inhibited; the light-heat conversion efficiency reaches 21.26 percent.
The invention also provides application of the molybdenum trioxide nanodots in a photothermal imaging material, and particularly relates to application of the molybdenum trioxide nanodots as the photothermal imaging material for photo-thermal imaging of a photo-thermal imaging instrument.
The invention also provides application of the molybdenum trioxide nanodots as a bacteriostatic material, in particular application of the molybdenum trioxide nanodots as the bacteriostatic material in treating wounds.
The molybdenum trioxide nanodot-based material is used as a multifunctional material, has peroxidase activity, high photothermal conversion efficiency and good photodynamic property in Near Infrared (NIR), and the photothermal effect after NIR irradiation just reaches the optimal temperature of the enzyme-like property, so that the enzyme-like activity reaches the optimal state. Therefore, the method for inhibiting bacteria by utilizing the near infrared absorption and the enzyme-like property of the molybdenum trioxide nanodots has very important significance and application prospect.
Compared with the prior art, the molybdenum trioxide nanodots have the advantages of high catalytic activity, long-term storage, high tolerance to severe environment, high stability, adjustable catalytic activity and the like; the molybdenum trioxide nanodots prepared by the hydrothermal method realize that the molybdenum oxide nanomaterial is prepared by using molybdenum trichloride powder as a precursor through one-step method, the method is simple and convenient, and is pollution-free, and the prepared molybdenum trioxide nanodots contain oxygen vacancies and have excellent infrared absorption performance, photo-thermal conversion performance and antibacterial performance; the preparation method is simple, the preparation equipment is easy to obtain, the preparation process is simple, the antibacterial effect is good and harmless to human bodies, the whole process is green and pollution-free, the application environment is friendly, and the market prospect is wide.
Description of the drawings:
fig. 1 is a schematic diagram of a bacteriostatic principle of the molybdenum trioxide nanodots.
Fig. 2 is a transmission electron microscope image and a size distribution diagram of the molybdenum trioxide nanodots prepared in example 1, where fig. 2A is the transmission electron microscope image and the high-resolution transmission electron microscope image, fig. 2B is the size distribution diagram, and fig. 2C is an atomic force transmission microscope image.
FIG. 3 is a schematic diagram of the detection of oxygen vacancy (A), near infrared absorption property (B) and peroxidase property (C) of the molybdenum trioxide nanodot of the present invention.
FIG. 4 is a medium diagram of in vitro bacteriostasis experiment of the molybdenum trioxide nanodot solution.
FIG. 5 is a photograph showing the results of in vivo bacteriostatic experiments on the molybdenum trioxide nanodots of example 5 according to the present invention.
FIG. 6 is a comparison graph of the results of the application experiment of the molybdenum trioxide nanodots of example 3 in the aspect of photothermal imaging.
Fig. 7 is a comparative image of a wound section of a mouse treated with molybdenum trioxide nanodots according to example 4 of the present invention.
Fig. 8 is a graph showing the cytotoxicity test results of the molybdenum trioxide nanodots according to example 4 of the present invention.
The specific implementation mode is as follows:
the present invention will be described in detail below with reference to specific embodiments and accompanying drawings.
Example 1:
the preparation method of the molybdenum trioxide nanodot antibacterial material comprises the following specific process steps:
(1) accurately weighing 0.2 g of molybdenum trichloride powder by using an electronic balance, putting the molybdenum trichloride powder into a 50ml reaction kettle, adding 35 ml of ultrapure water, and fully stirring to uniformly disperse the molybdenum trichloride powder;
(2) putting the reaction kettle into a blast drier, and heating and reacting for 10 hours at 200 ℃;
(3) and taking out the reacted sample, centrifuging at 12000rpm/min for 10min, removing the precipitate, collecting the supernatant, centrifuging the supernatant at 12000rpm/min for 10min, removing the precipitate, collecting the supernatant, repeating the steps of centrifuging, removing the precipitate and collecting the supernatant for several times until no precipitate appears in the solution after centrifuging, thus obtaining the colorless dispersion liquid of the molybdenum trioxide nanodots and finishing the preparation of the molybdenum trioxide nanodot antibacterial material.
The molybdenum trioxide nanodots prepared by the embodiment have uniform particle size of less than 10nm, average particle size of 3.07 +/-0.45 nm and thickness of 1.43 +/-0.08 nm, and good dispersibility.
The prepared molybdenum trioxide nanodots were then subjected to Electron Paramagnetic Resonance (EPR) to further verify oxygen vacancies as it provided evidence for surface defects and electrons trapped in the sample being tested. As shown in fig. 3A, the molybdenum trioxide nanodot sample showed an EPR signal at g 2.001, which is due to electrons captured by oxygen vacancies, indicating that the molybdenum trioxide nanodots have better oxygen vacancies. Meanwhile, the nanodots have good near infrared absorption performance under near infrared light irradiation, the temperature reached during irradiation is the optimal temperature of the nanoenzyme (peroxidase), and the more oxygen vacancies, the better the enzyme activity, and the peroxidase can exert the best activity (fig. 3C).
Example 2:
this example relates to an experiment of applying molybdenum trioxide nanodots to in vitro bacteriostasis, in which the molybdenum trioxide nanodot solution prepared in example 1 was applied to an in vitro antibacterial experiment, a single colony of non-drug resistant and drug resistant bacteria on a solid LB medium was inoculated into 50mL of sterile liquid LB medium containing tryptone (0.5g), yeast extract (0.25g) and NaCl (0.5g), and then the suspension of the drug resistant bacteria was cultured overnight at 37 ℃ at 180rpm/min on a rotary shaker. The bacteria were then diluted to 10 with sterile PBS6CFU/mL, mixing the obtained bacterial solution (100 microliter) with 300 microliter of 9 mass concentration0μg·mL -150 microliter of H with a molar concentration of 100 micromoles per liter2O2And 550. mu.l of PBS buffer at 37 ℃ for 30 minutes, then sucking 50. mu.l of the solution and spreading it on a solid medium uniformly, incubating the solid medium in an incubator at 37 ℃ for 12 hours, counting bacterial colonies by the CFU method, using PBS as a blank, and incubating the bacteria alone with H2O2Or molybdenum trioxide nanodots. The measurement results are shown in FIG. 4, and H is added simultaneously under the irradiation of infrared light2O2And molybdenum trioxide nanodots, the plate has only a few bacterial colonies, the antibacterial rates to drug-resistant escherichia coli and staphylococcus aureus are 98.4% and 98%, respectively, which indicates that the molybdenum trioxide nanodots are under near infrared light and H light2O2Under the existing condition, the antibacterial agent has extremely strong antibacterial performance.
Example 3:
this example is an experiment of applying the molybdenum trioxide nanodots in photothermographic imaging, wherein the molybdenum trioxide nanodots prepared in example 1 are applied in effective photothermographic imaging with a mass concentration of 300 microliters of 90 μ g/mL-1The molybdenum trioxide nanodot solution is injected to the wound part of a mouse, the experimental result is shown in figure 6, and the imaging temperature of the mouse is 35 ℃ when the near infrared irradiation is not added; 2W/cm at a wavelength of 808nm2After the near infrared light is irradiated for 20 minutes, the imaging temperature of the mouse is 55 ℃, which shows that the molybdenum trioxide nanodots can effectively convert light energy into heat energy, and then a photothermal imager can clearly and accurately shoot the wound of the mouse.
This example illustrates that the molybdenum trioxide nanodots have good photo-thermal conversion efficiency, and the photo-thermal conversion efficiency is calculated by the photo-thermal conversion formula to be 21.26%.
Example 4:
this example is an experiment of applying molybdenum trioxide nanodots in biotoxicity test, the cells used in the experiment are mouse L929 cells, and the cells are respectively treated with 100 microliter solutions of molybdenum trioxide nanodots with different concentrations (0. mu.g/mL, 2.5. mu.g/mL, 5. mu.g/mL, 10. mu.g/mL, 25. mu.g/mL, 50. mu.g/mL, 100. mu.g/mL) and 150 microliter solutions of molybdenum trioxide nanodotsThe 7 mixed solutions of the DMEM solution were incubated for 24 hours, 10mL of MTT solution containing 5mg/mL was added, and the reaction was continued with 5% CO2And incubation for 4 hours at 37 ℃, finally, fully dissolving the crystals by 100 mu L of dimethyl sulfoxide, measuring the absorbance of each well at 490nm of an enzyme-linked immunosorbent assay (ELISA) detector, wherein the measurement result is shown in FIG. 8, the activity of the cells which are not incubated by the molybdenum trioxide nanodot solution is set to be 100%, and the results show that the activity of the cells can be maintained to be more than 99% after the cells are incubated by the molybdenum trioxide nanodot solutions with different concentrations (0 mu g/mL, 2.5 mu g/mL, 5 mu g/mL, 10 mu g/mL, 25 mu g/mL, 50 mu g/mL and 100 mu g/mL).
In addition, the major organs (liver, heart, lung, spleen and kidney) of the mice were treated with PBS and molybdenum trioxide nanodots at mass concentrations of 100 μ g/mL and 200 μ g/mL, respectively, and as a result, as shown in fig. 7, no significant damage or tissue abnormality was observed in any of the liver, heart, lung, spleen and kidney, demonstrating that the prepared molybdenum trioxide nanodots have good biocompatibility and low cytotoxicity.
Example 5:
in this example, the application of the molybdenum trioxide nanodots in vivo bacteriostasis is realized, the molybdenum trioxide nanodot solution prepared in example 1 is applied to in vivo antibacterial experiments, and a mouse wound infection model is established by using male and female mixed mice (six weeks, 180-200g, 32 SD mice in total). Circular skin lesions of about 1cm diameter were made on the backs of all mice, which, after infection with MRSA (methicillin-resistant staphylococcus aureus), were divided into 8 groups of 4 mice each. Each group received different therapeutic agents, PBS, H2O2Molybdenum trioxide nanodots, H2O2+ molybdenum trioxide nanodots, PBS + NIR, H2O2+ NIR, molybdenum trioxide nanodots + NIR, H2O2+ molybdenum trioxide nanodots + NIR. Photographs of the wounds were collected every other day and the entire course of treatment was designated as 6 days. As can be seen from FIG. 5, H2O2The minimum wound treated by the molybdenum trioxide nanodots and the NIR group shows that the molybdenum trioxide nanodots have obvious antibacterial performance on various drug-resistant bacteria, so that the wound of the mouse can be quickly healed。
Claims (8)
1. A preparation method of a molybdenum trioxide nanodot antibacterial material is characterized by comprising the following specific process steps:
(1) preparing a molybdenum trichloride aqueous solution with the mass concentration of 0.005g/mL-0.006g/mL, fully stirring to uniformly disperse the molybdenum trichloride aqueous solution, and putting the molybdenum trichloride aqueous solution into a reaction kettle;
(2) putting the reaction kettle into a blast drier, and heating and reacting for 10 hours at 200 ℃;
(3) and taking out the reacted sample, centrifuging at 12000rpm/min for 9-11 minutes, removing the precipitate, collecting the supernatant, centrifuging the supernatant at 12000rpm/min for 9-11 minutes, removing the precipitate, collecting the supernatant again, repeating the steps of centrifuging, removing the precipitate and collecting the supernatant for several times until no precipitate appears in the solution after centrifuging, thus obtaining the colorless dispersion liquid of the molybdenum trioxide nanodots and finishing the preparation of the molybdenum trioxide nanodot antibacterial material.
2. The method for preparing the molybdenum trioxide nanodot antibacterial material as in claim 1, wherein the molybdenum trioxide nanodots have uniform particle size of less than 10nm, average particle size of 3.07 ± 0.45nm, thickness of 1.43 ± 0.08nm, and good dispersibility.
3. The preparation method of the molybdenum trioxide nanodot antibacterial material as in claim 1, wherein the molybdenum trioxide nanodots contain oxygen vacancies and have more surface oxygen defects, so that the molybdenum trioxide nanodots have more active sites and can better utilize the property of the nanoenzyme to inhibit and kill thalli in wounds.
4. The method for preparing the molybdenum trioxide nanodot bacteriostatic material as claimed in claim 1, wherein the molybdenum trioxide nanodots have wide absorption from visible light to near infrared wavelength of 300-1000nm and excellent infrared absorption performance.
5. The method for preparing the molybdenum trioxide nanodot antibacterial material as claimed in claim 1, wherein the molybdenum trioxide nanodots can convert light energy into heat energy well under near infrared irradiation, and just reach the optimal temperature of enzyme-like activity, so that the enzyme activity state is optimal, and a proper amount of active oxygen is generated to inhibit the growth of thalli. The light-heat conversion efficiency reaches 21.26 percent.
6. A molybdenum trioxide nanodot prepared by the method of claim 1.
7. The use of the molybdenum trioxide nanodots as claimed in claim 6 in photothermographic materials, wherein the molybdenum trioxide nanodots are used as photothermographic materials for photo-thermal imaging.
8. Use of the molybdenum trioxide nanodots as defined in claim 6 as a bacteriostatic material.
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