Zinc oxide / transition metal sulfide heterojunction material and preparation method thereof

Abstract

The invention belongs to the technical field of medicines, and particularly discloses a zinc oxide / transition metal sulfide heterojunction material and a preparation method thereof, and the zinc oxide / transition metal sulfide heterojunction material comprises a zinc oxide / transition metal sulfide heterojunction or a zinc oxide / transition metal sulfide heterojunction combined with a gas donor. The invention provides an efficient antibacterial material, zinc oxide is utilized to form a heterojunction, so that the light absorption range of the material can be widened, the absorption of the material to near-infrared light is increased, and the efficient antibacterial material is a powerful means for improving the photocatalytic efficiency of the material.

Description

Technical Field

[0001] The present invention belongs to the technical field of antibacterial drugs, and in particular relates to a zinc oxide / transition metal sulfide heterojunction material and a preparation method thereof. Background Art

[0002] Since the discovery of penicillin's antibacterial activity, antibiotics have been widely used in antibacterial treatments, saving countless lives. Traditional antibiotics are generally derived from natural substances or chemical synthesis, selectively inhibiting or eliminating bacteria by inhibiting protein synthesis, DNA replication, and repair. However, with the widespread use of antibiotics, bacteria have developed resistance to almost all types of traditional antibiotics through mutation or acquisition of genes from other organisms. In addition, bacterial communities can embed themselves in autocrine extracellular matrices to form biofilms, thereby increasing their resistance to antibiotics. Therefore, there is an urgent need to develop other non-antibiotic antibacterial materials to avoid bacterial resistance and achieve high-efficiency antibacterial effects.

[0003] Zinc oxide has been widely used in many fields due to its excellent electrical, optical and catalytic properties. However, its wide band gap leads to a narrow light absorption range, which results in a very limited absorption of near-infrared light, limiting its application in this area.

[0004] Meanwhile, gases such as nitric oxide (NO), carbon monoxide (CO), hydrogen sulfide (H2S), and sulfur dioxide (SO2) not only serve as signaling molecules but also play a crucial role in many pathological processes. Numerous studies have demonstrated that these gases can not only kill bacteria and disperse biofilms, but also promote wound healing in bacterial infections while preventing the development of drug resistance. These gases exhibit excellent therapeutic efficacy without significant side effects. Combining gas therapy with common antimicrobial strategies such as photodynamic therapy (PDT) and photothermal therapy (PTT) could potentially enhance their therapeutic efficacy.

[0005] Numerous materials for repairing infected wounds have been disclosed in the prior art, but these primarily focus on enhancing their antimicrobial efficacy, with limited consideration given to cellular compatibility and skin repair. Currently, no anti-infective skin repair materials combining zinc oxide-based heterojunctions with gas donors have been disclosed. Summary of the Invention

[0006] In order to solve the problems existing in the prior art, the present invention provides a zinc oxide / transition metal sulfide heterojunction material and a preparation method. By improving the absorption effect of zinc oxide material in near-infrared light and combining it with a gas donor material, it can be combined with photodynamic therapy or photothermal therapy to achieve the effects of sterilization and tissue repair.

[0007] The technical solution adopted in the present invention is: In a first aspect, the present invention provides a zinc oxide / transition metal sulfide heterojunction material, comprising a zinc oxide / transition metal sulfide heterojunction, wherein the transition metal sulfide is molybdenum sulfide, copper sulfide or silver sulfide.

[0008] In a second aspect, the present invention provides a zinc oxide / transition metal sulfide heterojunction material, comprising a zinc oxide / transition metal sulfide heterojunction combined with a gas donor, wherein the transition metal sulfide is molybdenum sulfide, copper sulfide, or silver sulfide; and the gas donor is one or more of N,N'-di-sec-butyl-N,N'-dinitroso-1,4-phenylenediamine (BNN6), L-arginine, S-nitroso-N-acetylpenicillamine (SNAP), CORM-2, and CORM-3.

[0009] In a third aspect, the present invention further provides a preparation method for preparing the zinc oxide / transition metal sulfide heterojunction described above, the specific steps being as follows: Step S100: preparing a transition metal salt and a soluble sulfur-containing compound material, dissolving them separately to form a solution, then reacting them by solvent heating or stirring at room temperature, drying them to form a transition metal sulfide, and ultrasonically treating the obtained transition metal sulfide in a solvent to form a transition metal sulfide dispersion; Step S200. Then, a zinc salt is prepared, and after dissolving the zinc salt to obtain a zinc salt solution, an alkali solution is added dropwise to the zinc salt solution to form a zinc-containing liquid system containing a zinc oxide precursor; Step S300: adding the obtained transition metal sulfide dispersion dropwise into the zinc-containing liquid system and stirring to form a reaction solution, and transferring the reaction solution to a polytetrafluoroethylene reactor for solvothermal reaction to form a liquid system containing a zinc oxide / transition metal sulfide heterojunction; Step S400: The liquid system containing the zinc oxide / transition metal sulfide heterojunction is washed alternately by centrifugation with anhydrous ethanol and deionized water to remove impurity ions, and then dried to obtain the zinc oxide / transition metal sulfide heterojunction.

[0010] In combination with the third aspect, the present invention provides a first embodiment of the third aspect, wherein the transition metal salt includes ammonium molybdate tetrahydrate, copper chloride dihydrate or silver nitrate, and the soluble sulfur-containing compound is thiourea or sodium sulfide nonahydrate; The zinc salt includes zinc acetate dihydrate and zinc chloride dihydrate, and the base includes sodium hydroxide and ammonia monohydrate; In combination with the third aspect, the present invention provides a second embodiment of the third aspect, wherein in step S200, the amounts of the zinc salt and the base are measured such that the mass ratio of zinc oxide generated by the reaction of the zinc salt and the base to the transition metal sulfide is (0.1-10):1; In the step S300, the solvent-thermal reaction temperature of the reaction solution formed when preparing the zinc oxide / transition metal sulfide heterojunction is 100-180°C, and the reaction time is 8-18 hours.

[0011] In a fourth aspect, the present invention further provides a preparation method for preparing the zinc oxide / transition metal sulfide heterojunction combined with a gas donor, the specific steps being as follows: Step H100: Prepare a transition metal salt and a soluble sulfur-containing compound material, dissolve them separately to form a solution, react them in a solvent-heated or room-temperature stirring manner, dry them to form a transition metal sulfide, and ultrasonically treat the resulting transition metal sulfide in a solvent to form a transition metal sulfide dispersion; Step H200. Then, a zinc salt is prepared, and after dissolving the zinc salt to obtain a zinc salt solution, an alkali solution is added dropwise to the zinc salt solution to form a zinc-containing liquid system containing a zinc oxide precursor; Step H300. The obtained transition metal sulfide dispersion is then dropped into the zinc-containing liquid system and stirred to form a reaction solution. The reaction solution is transferred to a polytetrafluoroethylene reactor for a solvent thermal reaction to form a liquid system containing a zinc oxide / transition metal sulfide heterojunction; Step H400. The liquid system containing the zinc oxide / transition metal sulfide heterojunction is alternately centrifuged and washed with anhydrous ethanol and deionized water to remove impurity ions, and then dried to obtain a zinc oxide / transition metal sulfide heterojunction; Step H500. Add the obtained zinc oxide / transition metal sulfide heterojunction and gas donor to deionized water, ultrasonically mix and then stir to obtain a mixed dispersion, centrifuge the mixed dispersion to remove excess deionized water and then dry to obtain a zinc oxide / transition metal sulfide heterojunction combined with a gas donor.

[0012] In combination with the fourth aspect, the present invention provides a first embodiment of the fourth aspect, wherein the transition metal salt includes ammonium molybdate tetrahydrate, copper chloride dihydrate, or silver nitrate; the soluble sulfur-containing compound is thiourea or sodium sulfide nonahydrate; the zinc salt includes zinc acetate dihydrate or zinc chloride dihydrate; and the base is sodium hydroxide or ammonia monohydrate; In the step H200, the amounts of the zinc salt and the base are measured so that the mass ratio of zinc oxide generated by the reaction of the zinc salt and the base to transition metal sulfide is (0.1-10):1. In the step H300, the solvent-thermal reaction temperature of the reaction solution formed when preparing the zinc oxide / transition metal sulfide heterojunction is 100-180° C., and the reaction time is 8-18 hours.

[0013] In combination with the fourth aspect, the present invention provides a second implementation method of the fourth aspect, wherein in step H500, when the zinc oxide / transition metal sulfide heterojunction and the gas donor are added to deionized water to form a mixed solution, the mass ratio of the added zinc oxide / silver sulfide heterojunction and the gas donor is 1-10:1.

[0014] The beneficial effects of the present invention are: 1. The present invention provides a highly effective antibacterial material. Using zinc oxide to form a heterojunction can significantly reduce the material's band gap, broadening the material's light absorption range, thereby increasing the material's absorption of near-infrared light. This is a powerful means of improving the material's photocatalytic efficiency. 2. The zinc oxide / transition metal sulfide heterojunction material combined with a gas donor, prepared by the method of the present invention, not only achieves photocatalytic antibacterial properties like conventional heterojunction materials, but also allows for the balance between its antibacterial and repair capabilities to be adjusted by controlling the amount of the combined gas donor. Furthermore, gases released by some gas donors, such as nitric oxide, not only promote angiogenesis and skin repair but also react with free radicals generated by photocatalysis to form a more potent antibacterial agent, achieving both skin repair and highly effective antibacterial properties. 3. The zinc oxide / transition metal sulfide heterojunction material combined with a gas donor of the present invention can control the antibacterial and skin healing effects by adjusting the power of near-infrared light (NIR) and the amount of gas donor combined, thus facilitating adjustment according to clinical needs; 4. The method of the present invention has simple process, mild reaction conditions, low energy consumption, and is easy for mass production, thus being conducive to popularization and application; 5. The zinc oxide / transition metal sulfide heterojunction material combined with a gas donor described in the present invention can inhibit the expression of inflammation-related pathways and promote cell circulation in the absence of external stimulation, thereby synergistically promoting cell proliferation. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 is an XRD spectrum of the zinc oxide / molybdenum sulfide heterojunction prepared in an embodiment of the present invention; Figure 2 is a UV-visible diffuse reflectance spectrum of zinc oxide and zinc oxide / molybdenum sulfide heterojunction prepared in an embodiment of the present invention; Figure 3 The photoluminescence spectra of zinc oxide and zinc oxide / molybdenum sulfide heterojunction prepared in the embodiment of the present invention are shown in FIG. Figure 4 Surface photovoltage diagrams of zinc oxide, molybdenum sulfide, and zinc oxide / molybdenum sulfide heterojunctions prepared in the embodiments of the present invention; Figure 5This is a graph showing the peroxynitrite anion yield of a 0.4 mg / mL dispersion of the zinc oxide / molybdenum sulfide heterojunction prepared in an embodiment of the present invention and the zinc oxide / molybdenum sulfide heterojunction combined with BNN6 under 808 nm near-infrared light excitation at a power of 1.5 W / cm2 for 8 minutes; Figure 6 This is a comparison chart of the bactericidal effects of the zinc oxide / molybdenum sulfide heterojunction prepared in the examples of the present invention, BNN6, a dispersion of the zinc oxide / molybdenum sulfide heterojunction combined with BNN6, and a PBS solution on Escherichia coli; Figure 7 Comparison of the bactericidal effects of the zinc oxide / molybdenum sulfide heterojunction prepared in the examples of the present invention, BNN6, a dispersion of the zinc oxide / molybdenum sulfide heterojunction combined with BNN6, and a PBS solution on Staphylococcus aureus; Figure 8 Illustration of the reactive oxygen species generated by the dispersions of zinc oxide, molybdenum sulfide, and zinc oxide / molybdenum sulfide heterojunction prepared in the examples of the present invention and PBS solution under the excitation of near-infrared light; Figure 9 3. It is a graphical representation of the experimental results of the compatibility of the dispersion prepared by the zinc oxide / molybdenum sulfide heterojunction combined with BNN6 prepared in the embodiment of the present invention and the PBS solution with L929 cells. DETAILED DESCRIPTION

[0016] The present invention will be further explained below with reference to the accompanying drawings and specific embodiments.

[0017] In order to make the purpose, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below in combination with the drawings in the embodiments of the present application. Obviously, the described embodiments are only part of the embodiments of the present application, not all of the embodiments.

[0018] Therefore, the following detailed description of the embodiments of the present application provided in the accompanying drawings is not intended to limit the scope of the present application for protection, but merely represents selected embodiments of the present application. All other embodiments obtained by persons of ordinary skill in the art based on the embodiments in the present application without making any creative efforts shall fall within the scope of protection of the present application.

[0019] Example 1: This embodiment discloses an antibacterial material, which improves the existing zinc oxide photosensitive material so that it can also achieve good antibacterial effects under the irradiation of near-infrared light.

[0020] The antibacterial material contains a zinc oxide / transition metal sulfide heterojunction. This material itself can release zinc ions when used, which can bind to functional proteins on the cell membrane, change the permeability of the cell membrane, and thus affect the survival of bacteria. It can also bind to enzymes in the cell, affect enzymatic reactions, weaken the glycolysis process, and induce cell death.

[0021] Transition metal sulfides (such as copper sulfide, silver sulfide, etc.) can also release metal ions (such as Cu² + 、Ag + ), these metal ions also have antibacterial activity, especially silver ions (Ag + ).

[0022] At the same time, under light, zinc oxide can activate electron-hole pairs, generating reactive oxygen species (ROS). ROS are highly oxidizing and can oxidize biomacromolecules such as lipids, proteins, and nucleic acids within bacterial cells, leading to cell death. Transition metal sulfides (such as silver sulfide) can also generate ROS under light. After forming a heterojunction with zinc oxide, the material system's photocatalytic efficiency and absorption of near-infrared light increase, further enhancing the efficiency of ROS generation and thus improving antibacterial properties. (The heterojunction between zinc oxide and transition metal sulfides is not a simple synergistic effect, but rather a "1+1>2" effect.) Furthermore, the antibacterial material includes a nano zinc oxide / transition metal sulfide heterojunction, and the irregular shape of the nanomaterial can directly destroy the bacterial cell wall.

[0023] Furthermore, with respect to transition metal sulfides, this embodiment provides several preferred materials, wherein the transition metal sulfides are molybdenum sulfide, copper sulfide or silver sulfide.

[0024] Furthermore, this embodiment also provides a photosensitive antibacterial and tissue repair material based on the above materials, which is characterized by comprising a zinc oxide / transition metal sulfide heterojunction combined with a gas donor.

[0025] Among them, the combined gas donor is an independent material. When subjected to near-infrared light irradiation, this gas donor can release the corresponding gas and form a gaseous atmosphere on the affected area or the surface of skin tissue, regulating the expression of related genes such as angiogenesis and inflammation, thereby having physiological effects such as anti-inflammatory, cell protection, and anti-apoptosis.

[0026] Furthermore, the gas donor is one or more of N,N'-di-sec-butyl-N,N'-dinitroso-1,4-phenylenediamine (BNN6), L-arginine, S-nitroso-N-acetylpenicillamine (SNAP), CORM-2, and CORM-3.

[0027] Among them, N,N'-di-sec-butyl-N,N'-dinitroso-1,4-phenylenediamine (BNN6), L-arginine and S-nitroso-N-acetylpenicillamine (SNAP) can release nitric oxide under the action of light, and CORM-2 and CORM-3 can release carbon monoxide in water or under light.

[0028] Some experiments have shown that these two gases can significantly improve the inflammatory response of mice with cecal ligation and perforation and mice stimulated with LPS, effectively protect their important organs from damage, and improve their survival rate.

[0029] For the above two materials, this embodiment also provides a preparation method, which is as follows: First, a transition metal salt and a soluble sulfur-containing compound material are prepared, dissolved separately to form a solution, and then reacted by solvent heating or stirring at room temperature. After drying, a transition metal sulfide is formed. The obtained transition metal sulfide is ultrasonically treated in a solvent to form a transition metal sulfide dispersion.

[0030] Then, a zinc salt is prepared, and after dissolving the zinc salt to obtain a zinc salt solution, an alkaline solution is added dropwise to the zinc salt solution to form a zinc-containing liquid system containing a zinc oxide precursor, the obtained transition metal sulfide dispersion is added dropwise to the zinc-containing liquid system and stirred to form a reaction liquid, and the reaction liquid is transferred to a polytetrafluoroethylene reactor for solvent thermal reaction to form a liquid system containing a zinc oxide / transition metal sulfide heterojunction; the liquid system containing the zinc oxide / transition metal sulfide heterojunction is alternately centrifuged and washed with anhydrous ethanol and deionized water to remove impurity ions, and the zinc oxide / transition metal sulfide heterojunction is obtained after drying.

[0031] The obtained zinc oxide / transition metal sulfide heterojunction and gas donor are added to deionized water, ultrasonically mixed and then stirred to obtain a mixed dispersion, the mixed dispersion is centrifuged to remove excess deionized water and then dried to obtain a zinc oxide / transition metal sulfide heterojunction combined with a gas donor.

[0032] The zinc salt includes zinc acetate dihydrate and zinc chloride dihydrate, and the base includes sodium hydroxide and ammonia monohydrate. The amounts of the zinc salt and the base are measured based on a mass ratio of zinc oxide generated by the reaction of the zinc salt and the base to transition metal sulfide of (0.1-10):1. The solvent-thermal reaction temperature of the reaction solution formed when preparing the zinc oxide / transition metal sulfide heterojunction is 100-180°C, and the reaction time is 8-18 hours.

[0033] In order to verify the effectiveness of the above preparation method and the prepared materials, the following content is verified and explained through specific implementation methods.

[0034] 1. Preparation of transition metal sulfides Ammonium molybdate tetrahydrate and thiourea were selected as raw materials, 7.21 g of ammonium molybdate tetrahydrate and 11.98 g of thiourea were weighed and dissolved in 50 mL and 100 mL of deionized water, respectively, to prepare ammonium molybdate solution and thiourea solution, the ammonium molybdate solution was dropped into the thiourea solution and stirred for reaction for 2 h to form a reaction liquid, the reaction liquid was placed in a 200 mL polytetrafluoroethylene reactor, and hydroheated at 210 ° C for 18 h to form a liquid system containing molybdenum sulfide, the liquid system containing molybdenum sulfide was alternately centrifuged and washed with anhydrous ethanol and deionized water to remove impurity ions, and then placed in a freeze dryer and freeze-dried for 12 h to obtain powdered molybdenum sulfide.

[0035] 2. Preparation of zinc oxide / transition metal sulfide heterojunction 0.12 g of synthesized molybdenum sulfide was weighed, and then 66 mL of anhydrous ethanol was added to the molybdenum sulfide and ultrasonically mixed for 20 minutes to form a molybdenum sulfide dispersion; 0.324 g of zinc acetate dihydrate and 0.6 g of sodium hydroxide were weighed and dissolved in 3 mL of deionized water to prepare zinc acetate solution and sodium hydroxide solution, respectively, and then the sodium hydroxide solution was dropped into the zinc acetate solution and stirred for 20 minutes to generate a liquid system containing a zinc oxide precursor, and then the molybdenum sulfide dispersion was dropped into the liquid system containing the zinc oxide precursor and stirred for 30 minutes to form a reaction solution.

[0036] The reaction solution was transferred to a 100 mL polytetrafluoroethylene reactor and reacted at 100°C for 13 h to form a liquid system containing a zinc oxide / molybdenum sulfide heterojunction. The liquid system containing the zinc oxide / molybdenum sulfide heterojunction was alternately centrifuged and washed with anhydrous ethanol and deionized water to remove impurity ions, and then dried in a vacuum dryer at 60°C for 12 h to obtain a zinc oxide / molybdenum sulfide heterojunction. The amounts of zinc acetate dihydrate and sodium hydroxide were calculated based on a mass ratio of zinc oxide to molybdenum sulfide formed by the reaction of zinc acetate and sodium hydroxide of 1:1. 3. Preparation of ZnO / transition metal sulfide heterojunctions with gas donors 100 mg of zinc oxide / molybdenum sulfide heterojunction and 100 mg of N,N'-di-sec-butyl-N,N'-dinitroso-1,4-phenylenediamine (BNN6) were weighed and placed in 250 mL of deionized water. The mixture was ultrasonically mixed for 10 minutes and then stirred for 18 hours to obtain a mixed dispersion. The mixed dispersion was centrifuged to remove excess deionized water and then placed in a freeze dryer for freeze drying for 12 hours to obtain a zinc oxide / molybdenum sulfide heterojunction combined with BNN6.

[0037] Reference Figure 1 The zinc oxide / molybdenum sulfide heterojunction (ZM) prepared in this embodiment was subjected to XRD analysis. It can be seen from the figure that the biological heterojunction prepared in this embodiment is composed of ZnO and MoS2, and the preparation method is effective.

[0038] UV-visible diffuse reflectance spectroscopy was then performed on the zinc oxide / molybdenum sulfide heterojunction (ZM) prepared in this example and the ZnO prepared using the method described in this example. The ZnO was prepared by dissolving 0.324 g of zinc acetate dihydrate and 0.6 g of sodium hydroxide in 3 mL of deionized water to prepare a zinc acetate solution and a sodium hydroxide solution, respectively. The zinc acetate solution and the sodium hydroxide solution were then reacted, and 66 mL of anhydrous ethanol was added. The ZnO was then hydrothermaled at 100°C for 13 hours.

[0039] Reference Figure 2 The UV-visible diffuse reflectance spectra of ZnO and zinc oxide / molybdenum sulfide heterojunction (ZM) were tested at room temperature. It can be seen from the figure that compared with pure zinc oxide, the light absorption of zinc oxide / molybdenum sulfide heterojunction (ZM) in the near-infrared region is enhanced after the formation of heterojunction, indicating that the formation of heterojunction is beneficial for the material to absorb near-infrared light and thus improve the photocatalytic efficiency, which means that zinc oxide can be effectively applied in near-infrared light therapy to produce and release active ingredients through modification.

[0040] Then the zinc oxide / molybdenum sulfide heterojunction (ZM) prepared in this example and the ZnO prepared by the method described in this example were subjected to photoluminescence spectroscopy (PL spectroscopy) testing. The photoluminescence spectroscopy testing steps were to detect the PL spectra of ZnO and zinc oxide / molybdenum sulfide heterojunction (ZnO-MoS2) at room temperature using 371nm excitation light. The test results were compared with those of Figure 3 .

[0041] As can be seen from the figure, compared with zinc oxide, the PL spectrum intensity of the zinc oxide / molybdenum sulfide heterojunction (ZM) is significantly reduced, indicating that the electron-hole recombination in ZM is significantly hindered, that is, the zinc oxide / molybdenum sulfide heterojunction is conducive to promoting electron-hole separation and thus promoting photoexcitation to produce ROS, and has stronger photodynamic performance than ZnO.

[0042] Photovoltage tests were conducted on the zinc oxide / molybdenum sulfide heterojunction (ZM) prepared in this example, as well as MoS2 and ZnO prepared using the method described in this example. MoS2 was prepared by dissolving 7.21 g of ammonium molybdate tetrahydrate and 11.98 g of thiourea in 50 mL and 100 mL of deionized water, respectively, to prepare an ammonium molybdate solution and a thiourea solution. The ammonium molybdate solution and the thiourea solution were then mixed and hydrothermaled at 210°C for 18 hours.

[0043] The photovoltage test is as follows: the surface photovoltage of ZnO, MoS2 and zinc oxide / molybdenum sulfide heterojunction (ZM) is tested at room temperature. Figure 4 The results show that after the formation of heterojunction, the surface photovoltage of zinc oxide / molybdenum sulfide heterojunction (ZM) increases compared with ZnO and MoS2, indicating the improvement of the photocatalytic performance of the material.

[0044] The zinc oxide / molybdenum sulfide heterojunction (ZM) combined with BNN6 prepared in this example and ZnO prepared using the method described in this example were subjected to peroxynitrite anion testing.

[0045] Peroxynitrite anion production test: zinc oxide / molybdenum sulfide heterojunction (ZMB) dispersion and zinc oxide / molybdenum sulfide heterojunction (ZM) dispersion with a concentration of 400µg / mL were prepared with deionized water, and 1µL of the commercially available peroxynitrite anion fluorescent probe stock solution was added to 1mL of the zinc oxide / molybdenum sulfide heterojunction (ZMB) dispersion and 1mL of the zinc oxide / molybdenum sulfide heterojunction (ZM) dispersion. The peroxynitrite anion fluorescence probe was detected by 808nm near-infrared laser at a power of 1.5W / cm 2 After being treated with light excitation for 8 minutes, the cells were incubated in the dark for 15 minutes. Finally, the peak intensity at 516 nm under 488 nm excitation was measured using a fluorescence spectrometer. The test results were referred to Figure 5 .

[0046] from Figure 5 It can be seen that under near-infrared light excitation energy, the zinc oxide / molybdenum sulfide heterojunction (ZM) dispersion without BNN6 cannot produce peroxynitrite anions, while the zinc oxide / molybdenum sulfide heterojunction (ZMB) dispersion after combining BNN6 can produce peroxynitrite anions, indicating that the superoxide and nitric oxide produced by the material can combine to generate more toxic peroxynitrite anions, which is beneficial to further improve the antibacterial ability of the material for subsequent antibacterial experiments.

[0047] The principle of generating peroxynitrite anions is explained as follows: In the zinc oxide / molybdenum sulfide heterojunction group combined with BNN6 in this embodiment, the main role of NO provided by BNN6 in the system is to cooperate with the heterojunction system to produce more superoxide (a type of reactive oxygen), thereby combining with NO to generate peroxynitrite anions. Peroxynitrite anions have stronger antibacterial ability than reactive oxygen, so the heterojunction combined with the gas donor can achieve faster and more efficient sterilization, and the excess NO release can promote anti-inflammatory effects and thus assist in skin repair. Cell sequencing results show that the role of NO is to produce anti-inflammatory effects by inhibiting the expression of inflammation-related genes, thereby promoting subsequent skin repair.

[0048] The monomer BNN6 is a nitroso compound, and its molecular structure contains a nitroso (-NO) functional group. Existing technology shows that BNN6 will first generate intermediates such as nitroso free radicals through processes such as single electron transfer. These intermediates have been verified in this embodiment and found that they only react further with superoxide in the system (NO reacts with superoxide) to eventually generate peroxynitrite anions. At the same time, because it is a material formed by combining BNN6, it can interact with the heterojunction more stably and at a closer distance in the system. After NO is released from BNN6, it can more efficiently combine with the superoxide generated by the heterojunction to generate peroxynitrite anions, and the whole process has better synergy and higher reaction efficiency.

[0049] If monomer BNN6 is used together with a zinc oxide / molybdenum sulfide heterojunction or conventional zinc oxide or molybdenum sulfide monomer materials, the contact and interaction between BNN6 and the heterojunction or monomer material will be relatively weak and unstable. The amount of superoxide generated by the monomer material itself will be reduced, and the probability and efficiency of NO combining with superoxide after release may be affected. NO can easily diffuse to other locations in the system before combining with superoxide, resulting in a decrease in the efficiency of generating peroxynitrite anions. Experimental verification found that the amount of peroxynitrite anions generated by the dispersion of BNN6 alone and zinc oxide / molybdenum sulfide heterojunction (ZM) was significantly less than that of the zinc oxide / molybdenum sulfide heterojunction (ZMB) group after combining with BNN6.

[0050] The zinc oxide / molybdenum sulfide heterojunction prepared in this example was subjected to antibacterial experiments on Escherichia coli and Staphylococcus aureus: the Escherichia coli (ATCC25922) used in the experiment was purchased from Shanghai Yaji Biotechnology Co., Ltd., and Staphylococcus aureus (ATCC25923) was purchased from Shenzhen Zike Biotechnology Co., Ltd.

[0051] Escherichia coli and Staphylococcus aureus at appropriate concentrations after gradient dilution were inoculated into two 48-well plates, and then 0.5 mL of 0.2 mg / mL zinc oxide / molybdenum sulfide heterojunction, BNN6, zinc oxide / molybdenum sulfide heterojunction dispersion combined with BNN6 and PBS solution were added to different wells to form zinc oxide / molybdenum sulfide heterojunction group, BNN6 group, zinc oxide / molybdenum sulfide heterojunction group combined with BNN6 and PBS group. Each group of each bacteria had three wells, among which the zinc oxide / molybdenum sulfide heterojunction group, BNN6 group and zinc oxide / molybdenum sulfide heterojunction group combined with BNN6 must be heated at 1.5 W / cm 2 Irradiate with 808nm near-infrared light for 5 minutes. After that, mix the bacterial solutions in each well plate and evenly spread 0.1mL of bacterial solution on a solid LB agar plate. Transfer to a 37℃ constant temperature oven and incubate for a period of time before taking photos and recording.

[0052] Reference Figure 6and Figure 7 In both figures, from left to right, there are PBS, zinc oxide / molybdenum sulfide heterojunction, BNN6, zinc oxide / molybdenum sulfide heterojunction group combined with BNN6, Figure 6 、 Figure 7 It can be seen that compared with the PBS group, the ZnO / MoS heterojunction group, the BNN6 group and the ZnO / MoS heterojunction group combined with BNN6 have a higher thermal conductivity than the PBS group at 1.5W / cm 2 Under 808nm near-infrared light excitation, the zinc oxide / molybdenum sulfide heterojunction group exhibited a certain degree of bactericidal activity against Escherichia coli and Staphylococcus aureus. Among them, the zinc oxide / molybdenum sulfide heterojunction group combined with BNN6 produced the fewest colonies on the culture plate, indicating that it had enhanced antibacterial activity (especially against Staphylococcus aureus) compared to the zinc oxide / molybdenum sulfide heterojunction group and the BNN6 group. This is likely due to the increased superoxide generated by the zinc oxide / molybdenum sulfide heterojunction and the nitric oxide released by BNN6, which combined to form the more toxic peroxynitrite anion.

[0053] The appropriate concentrations of Staphylococcus aureus after gradient dilution were inoculated into 48-well plates, and then 0.5 mL of 0.2 mg / mL zinc oxide, molybdenum sulfide, zinc oxide / molybdenum sulfide heterojunction dispersion and PBS solution were added to different wells to form zinc oxide / molybdenum sulfide heterojunction group, molybdenum sulfide group, zinc oxide / molybdenum sulfide heterojunction group and PBS group. Except for the PBS group, the other three groups were required to be heated at 1.5 W / cm 2 The samples were irradiated with 808nm near-infrared light for 5 minutes. After standing for five minutes, the material was carefully washed with PBS. 2,7-dichlorodihydrofluorescein diacetate (DCFH-DA) was then used as a fluorescent probe for reactive oxygen species to stain each group in the dark for 30 minutes. After staining, the samples were washed with PBS and then observed and photographed under an inverted fluorescence microscope.

[0054] Reference Figure 8 , where from left to right are PBS group, zinc oxide group, molybdenum sulfide group and zinc oxide / molybdenum sulfide heterojunction group. It can be seen from the figure that compared with pure zinc oxide and molybdenum sulfide, the zinc oxide / molybdenum sulfide heterojunction significantly produces more reactive oxygen species in Staphylococcus aureus under the excitation of near-infrared light, which indicates that the material has stronger photocatalytic properties and can be used to enhance antibacterial properties under light excitation.

[0055] Furthermore, the BNN6-bound zinc oxide / molybdenum sulfide heterojunction prepared in this example was tested for compatibility with L929 mouse fibroblasts. The L929 mouse fibroblasts used in this experiment were purchased from Shanghai Meiyan Biotechnology Co., Ltd. L929 mouse fibroblasts were cultured in DMEM medium supplemented with 10% fetal bovine serum (FBS) and 1% penicillin / streptomycin at 37°C and 5% CO2. All samples and equipment used were sterilized by autoclaving and irradiated with ultraviolet light for at least 0.5 hours.

[0056] L929 mouse fibroblasts were placed in a 48-well plate, and cell slides were placed in the well plate in advance. The cell density was 2×10 3 After incubation for 24 hours, 0.5 mL of 0.2 mg / mL BNN6-bound zinc oxide / molybdenum sulfide heterojunction dispersion and PBS were added to form BNN6-bound zinc oxide / molybdenum sulfide heterojunction group and PBS group, each group had three wells, and the zinc oxide / molybdenum sulfide heterojunction group must be heated at 1.5 W / cm 2 Irradiate with 808nm near-infrared light for 5 minutes.

[0057] After the end, the material was aspirated and washed three times with PBS to remove the material, then fixed with 4% paraformaldehyde fixative for 5 minutes, aspirated the fixative, and washed three times with PBS; stained with rhodamine phalloidin kit for 60 minutes, aspirated the dye solution, washed three times with PBS, then stained with 4,6-diamino-2-phenylindole (DAPI) for 3 minutes, aspirated, and washed three times with PBS, and finally observed and photographed under an inverted fluorescence microscope. The photos taken refer to Figure 9 , from left to right are the PBS group and the zinc oxide / molybdenum sulfide heterojunction group combined with BNN6. Figure 9 It can be seen that the cells in both groups have clear morphology, are well stretched and have pseudopodia, indicating that the zinc oxide / molybdenum sulfide heterojunction combined with BNN6 has good compatibility with L929 cells.

[0058] The experiments above are mainly to verify the biocompatibility of zinc oxide / molybdenum sulfide heterojunction materials combined with BNN6 to L929 mouse fibroblasts.

[0059] Biocompatibility refers to the ability of a material to maintain good interactions within or in contact with an organism, without causing significant biological toxicity or adverse reactions. For materials used in biomedical applications, biocompatibility is a key factor in their safe and effective use in humans or animals.

[0060] In this experiment, L929 mouse fibroblasts were used as model cells to evaluate the effects of ZnO / MoS heterojunctions on cell growth and morphology. The experiment was performed using the following steps: Cell culture: L929 mouse fibroblasts were cultured in DMEM medium supplemented with fetal bovine serum and penicillin / streptomycin to provide a standard cell growth environment.

[0061] Sample treatment: Cells were plated in 48-well plates and treated with a dispersion of BNN6-bound zinc oxide / molybdenum sulfide heterojunctions and PBS as experimental and control groups, respectively. The experimental groups were also irradiated with near-infrared light.

[0062] Cell fixation and staining: Cells were fixed with paraformaldehyde and then stained with rhodamine phalloidin kit and DAPI for observation under an inverted fluorescence microscope.

[0063] Observation and photography: Observe and photograph the morphology and distribution of cells under an inverted fluorescence microscope.

[0064] The experimental results showed that the cells in both groups had clear morphology, were well stretched, and had pseudopodia formed.

[0065] Finally, KEGG enrichment analysis categorized the differentially expressed genes in RAW 264.7 cells after the different treatments compared to the control group based on their involvement in different pathways and functions. NOD-like receptors are important pattern recognition receptors, involved in innate immune recognition of pathogen-associated molecular patterns and damage-associated molecular patterns, regulating inflammatory responses and host defense. The NF-κB and TNF signaling pathways also play a crucial role in regulating inflammation and immune responses. Figure 10 shows that compared with the PBS group, the ZMB- group primarily downregulated the NOD-like receptor, NF-κB, and TNF signaling pathways, indicating that the material itself can inhibit the expression of inflammatory pathways in the absence of external stimulation. Furthermore, the material promotes cell cycle. Upon application of external stimulation, the material further inhibited these pathways, but the more significant change was the upregulation of the TCA cycle and cell cycle-related pathways. This upregulation of the TCA cycle increases the cell's energy and biomass, synergistically promoting cell proliferation.

[0066] Furthermore, this embodiment also provides two additional materials and corresponding preparation methods.

[0067] As an embodiment, the photosensitive antibacterial repair material includes a zinc oxide / copper sulfide heterojunction combined with SNAP, and the preparation method thereof is as follows: 1 g of copper chloride dihydrate and 0.72 g of sodium sulfide nonahydrate were weighed and dissolved in 30 mL of deionized water to prepare a copper chloride solution and a sodium sulfide solution, respectively. The copper chloride solution was dropped into the sodium sulfide solution to form a reaction solution. The reaction solution was stirred and reacted at room temperature for 4 hours to form a liquid system containing copper sulfide. The liquid system containing copper sulfide was alternately centrifuged and washed with anhydrous ethanol and deionized water to remove impurity ions, and then placed in a freeze dryer and freeze-dried for 12 hours to obtain powdered copper sulfide.

[0068] 0.1 g of synthesized copper sulfide was weighed, and then 90 mL of anhydrous ethanol was added to the copper sulfide and ultrasonically mixed for 20 minutes to form a copper sulfide dispersion; 0.424 g of zinc chloride dihydrate and 0.5 g of sodium hydroxide were weighed and dissolved in 6 mL of deionized water to prepare zinc chloride solution and sodium hydroxide solution respectively, and then the sodium hydroxide solution was dropped into the zinc chloride solution and stirred for 20 minutes to generate a liquid system containing a zinc oxide precursor, and then the copper sulfide dispersion was dropped into the liquid system containing the zinc oxide precursor and stirred for 30 minutes to form a reaction liquid; the reaction liquid was transferred to a 150 mL polytetrafluoroethylene reactor and reacted at 120° C. for 15 hours to form a liquid system containing a zinc oxide / copper sulfide heterojunction, and the liquid system containing the zinc oxide / copper sulfide heterojunction was alternately centrifuged and washed with anhydrous ethanol and deionized water to remove impurity ions, and then placed in a vacuum dryer and dried at 60° C. for 12 hours to obtain a zinc oxide / copper sulfide heterojunction. The amounts of zinc chloride dihydrate and sodium hydroxide are measured based on a mass ratio of zinc oxide to copper sulfide generated by the reaction of zinc chloride and sodium hydroxide of 2:1. 100 mg of copper oxide / copper sulfide heterojunction and 150 mg of S-nitroso-N-acetylpenicillamine (SNAP) were weighed and placed in 300 mL of deionized water. The mixture was ultrasonically mixed for 10 minutes and then stirred for 24 hours to obtain a mixed dispersion. The mixed dispersion was centrifuged to remove excess deionized water and then placed in a freeze dryer for freeze drying for 12 hours to obtain a zinc oxide / copper sulfide heterojunction combined with SNAP.

[0069] As an embodiment, the photosensitive antibacterial repair material includes a zinc oxide / silver sulfide heterojunction combined with L-arginine, and the preparation method thereof is as follows: 1.167 g of silver nitrate and 0.825 g of sodium sulfide nonahydrate were weighed and dissolved in 50 mL of deionized water to prepare a silver nitrate solution and a sodium sulfide solution, respectively. The sodium sulfide solution was then dropped into the silver nitrate solution to form a reaction solution. The reaction solution was stirred at room temperature for 3 hours to form a liquid system containing silver sulfide. The liquid system containing silver sulfide was alternately centrifuged and washed with anhydrous ethanol and deionized water to remove impurity ions, and then placed in a freeze dryer and freeze-dried for 12 hours to obtain powdered silver sulfide. 0.16 g of synthesized silver sulfide was weighed, and then 100 mL of deionized water was added to the silver sulfide and ultrasonically mixed for 20 minutes to form a silver sulfide dispersion; 0.216 g of zinc chloride dihydrate was weighed and dissolved in 5 mL of deionized water to prepare a zinc chloride solution, and then 4 mL of ammonia monohydrate was taken, and the ammonia monohydrate was dropped into the zinc chloride solution and stirred for 20 minutes to generate a liquid system containing a zinc oxide precursor, and then the silver sulfide dispersion was dropped into the liquid system containing the zinc oxide precursor and stirred for 30 minutes to form a reaction liquid; the reaction liquid was transferred to a 150 mL polytetrafluoroethylene reactor, and reacted at 130° C. for 18 hours to form a liquid system containing a zinc oxide / silver sulfide heterojunction, and the liquid system containing the zinc oxide / silver sulfide heterojunction was alternately centrifuged and washed with anhydrous ethanol and deionized water to remove impurity ions, and then placed in a freeze dryer for freeze drying for 12 hours to obtain a zinc oxide / silver sulfide heterojunction. The amounts of the zinc chloride dihydrate and sodium hydroxide are measured based on a mass ratio of zinc oxide to silver sulfide generated by the reaction of zinc chloride and sodium hydroxide of 1:2; 100 mg of zinc oxide / silver sulfide heterojunction and 50 mg of L-arginine were weighed and placed in 250 mL of deionized water. After ultrasonic mixing for 10 minutes, the mixture was stirred for 24 hours to obtain a mixed dispersion. The mixed dispersion was centrifuged to remove excess deionized water and then placed in a freeze dryer for freeze drying for 12 hours to obtain a zinc oxide / silver sulfide heterojunction combined with L-arginine.

[0070] The present invention is not limited to the above optional embodiments. Anyone can derive various other forms of products based on the teachings of the present invention. The above specific embodiments should not be construed as limiting the scope of protection of the present invention. The scope of protection of the present invention shall be based on the scope defined in the claims, and the description can be used to interpret the claims.

Claims

1. Zinc oxide / transition metal sulfide heterojunction material, characterized by: The invention comprises a zinc oxide / transition metal sulfide heterojunction, wherein the transition metal sulfide is molybdenum sulfide, copper sulfide or silver sulfide.

2. Zinc oxide / transition metal sulfide heterojunction material, characterized by: The invention relates to a zinc oxide / transition metal sulfide heterojunction with a combined gas donor, wherein the transition metal sulfide is molybdenum sulfide, copper sulfide or silver sulfide; and the gas donor is one or more of N,N'-di-sec-butyl-N,N'-dinitroso-1,4-phenylenediamine, L-arginine, S-nitroso-N-acetylpenicillamine, CORM-2 and CORM-3.

3. A preparation method, characterized in that: The specific steps for preparing the zinc oxide / transition metal sulfide heterojunction in claim 1 are as follows: Step S100: preparing a transition metal salt and a soluble sulfur-containing compound material, dissolving them separately to form a solution, then reacting them by solvent heating or stirring at room temperature, drying them to form a transition metal sulfide, and ultrasonically treating the obtained transition metal sulfide in a solvent to form a transition metal sulfide dispersion; Step S200. Then, a zinc salt is prepared, and after dissolving the zinc salt to obtain a zinc salt solution, an alkali solution is added dropwise to the zinc salt solution to form a zinc-containing liquid system containing a zinc oxide precursor; Step S300: adding the obtained transition metal sulfide dispersion dropwise into the zinc-containing liquid system and stirring to form a reaction solution, and transferring the reaction solution to a polytetrafluoroethylene reactor for solvothermal reaction to form a liquid system containing a zinc oxide / transition metal sulfide heterojunction; Step S400: The liquid system containing the zinc oxide / transition metal sulfide heterojunction is washed alternately by centrifugation with anhydrous ethanol and deionized water to remove impurity ions, and then dried to obtain the zinc oxide / transition metal sulfide heterojunction.

4. A preparation method according to claim 3, characterized in that: The transition metal salt includes ammonium molybdate tetrahydrate, copper chloride dihydrate or silver nitrate, and the soluble sulfur-containing compound is thiourea or sodium sulfide nonahydrate; The zinc salt includes zinc acetate dihydrate and zinc chloride dihydrate, and the base includes sodium hydroxide and ammonia monohydrate; The preparation method according to claim 3, characterized in that: in step S200, the amounts of zinc salt and alkali are measured so that the mass ratio of zinc oxide generated by the reaction of zinc salt and alkali to transition metal sulfide is (0.1-10):1; In the step S300, the solvent-thermal reaction temperature of the reaction solution formed when preparing the zinc oxide / transition metal sulfide heterojunction is 100-180°C, and the reaction time is 8-18 hours.

5. A preparation method, characterized in that: The specific steps for preparing the zinc oxide / transition metal sulfide heterojunction combined with a gas donor in claim 2 are as follows: Step H100: Prepare a transition metal salt and a soluble sulfur-containing compound material, dissolve them separately to form a solution, react them in a solvent-heated or room-temperature stirring manner, dry them to form a transition metal sulfide, and ultrasonically treat the resulting transition metal sulfide in a solvent to form a transition metal sulfide dispersion; Step H200. Then, a zinc salt is prepared, and after dissolving the zinc salt to obtain a zinc salt solution, an alkali solution is added dropwise to the zinc salt solution to form a zinc-containing liquid system containing a zinc oxide precursor; Step H300. The obtained transition metal sulfide dispersion is then dropped into the zinc-containing liquid system and stirred to form a reaction solution. The reaction solution is transferred to a polytetrafluoroethylene reactor for a solvent thermal reaction to form a liquid system containing a zinc oxide / transition metal sulfide heterojunction; Step H400. The liquid system containing the zinc oxide / transition metal sulfide heterojunction is alternately centrifuged and washed with anhydrous ethanol and deionized water to remove impurity ions, and then dried to obtain a zinc oxide / transition metal sulfide heterojunction; Step H500. Add the obtained zinc oxide / transition metal sulfide heterojunction and gas donor to deionized water, ultrasonically mix and then stir to obtain a mixed dispersion, centrifuge the mixed dispersion to remove excess deionized water and then dry to obtain a zinc oxide / transition metal sulfide heterojunction combined with a gas donor.

6. A preparation method according to claim 6, characterized in that: The transition metal salt includes ammonium molybdate tetrahydrate, copper chloride dihydrate or silver nitrate, the soluble sulfur-containing compound is thiourea or sodium sulfide nonahydrate; the zinc salt includes zinc acetate dihydrate and zinc chloride dihydrate, and the base is sodium hydroxide or ammonia monohydrate; In the step H200, the amounts of the zinc salt and the base are measured so that the mass ratio of zinc oxide generated by the reaction of the zinc salt and the base to transition metal sulfide is (0.1-10):

1. In the step H300, the solvent-thermal reaction temperature of the reaction solution formed when preparing the zinc oxide / transition metal sulfide heterojunction is 100-180° C., and the reaction time is 8-18 hours.

7. A preparation method according to claim 6, characterized in that: In step H500, when the zinc oxide / transition metal sulfide heterojunction and the gas donor are added to deionized water to form a mixed solution, the mass ratio of the added zinc oxide / transition metal sulfide heterojunction and the gas donor is 1-10:1.

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