Photocatalytic synergistic antibacterial material based on metal organic frameworks (MOFs)

Abstract

The invention discloses a photocatalytic synergistic antibacterial material based on metal organic frameworks (MOFs), which is prepared by the following steps: S1, taking trimesic acid, 2, 6-diaminopyridine, zinc acetate and titanium oxalate as raw materials, and preparing a bimetallic MOFs carrier, namely Ti / Zn-MOFs, through a hydrothermal method; s2, loading light response enhanced particles CDs on the Ti / Zn-MOFs, so as to obtain Ti / Zn-MOFs (at) Mn-CDs, namely the photocatalytic synergistic antibacterial material based on the metal organic framework MOFs. The photocatalytic synergistic antibacterial material disclosed by the invention is obtained by loading the photoresponse enhanced particles CDs on the bimetal MOFs carrier in situ, and the Ti / Zn-MOFs and the Mn-CDs are constructed to form a composite system, so that the synergistic enhancement effect of the Ti / Zn-MOFs and the Mn-CDs on improving the antibacterial performance can be realized.

Description

TECHNICAL FIELD

[0001] The application relates to the field of antibacterial materials, and in particular to a photocatalytic synergistic antibacterial material based on metal organic framework MOFs. BACKGROUND

[0002] In recent years, due to the improper use of antibiotics, the phenomenon of pathogen resistance is increasingly common in life, which continuously weakens the bactericidal effect of traditional drugs and seriously threatens the life and health of people.

[0003] MOFs material has the advantages of high specific surface area, high porosity and high surface activity, and is a promising porous material, which has been widely used in food preservation, drug delivery, biomedical and antibacterial fields in recent years (Kong W, Wei K, Zhao Y, et al. Application Research Progress of Metal Organic Framework Materials and Coatings in Biological Antibacterial Field [J]. Rare Metal Materials and Engineering, 2023, 000(7): 16.). Metal organic framework compounds (MOFs) are a new type of crystalline material formed by connecting organic ligands containing nitrogen atoms or oxygen atoms and metal ions or metal clusters through coordination bonds. MOFS has various pore shapes and high porosity. In addition to good structure, MOFs material can also be endowed with antibacterial activity through many different methods, for example, MOFs material can be endowed with sterilization performance by antibacterial active metal ions or clusters (such as silver, copper, zinc, etc.) (Kong Z, Su N, Song S. Research Progress of Metal Organic Framework Antibacterial Materials [J]. Journal of Jilin Normal University: Natural Science Edition, 2022, 43(4): 1-7. DOI: 10.16862 / j.cnki.issn1674-3873.2022.04.001.). But such antibacterial performance will gradually weaken or even lose with the release and consumption of antibacterial active metal ions or clusters, and the long-acting property is poor, and the antibacterial intensity also seriously depends on the concentration of antibacterial active metal ions or clusters, and the antibacterial performance needs to be further enhanced.

[0004] Therefore, it is necessary to improve the prior art to provide a more reliable solution. SUMMARY

[0005] The technical problem solved by the application is to provide a photocatalytic synergistic antibacterial material based on metal organic framework MOFs in view of the deficiencies in the prior art.

[0006] To solve the above technical problems, the technical scheme adopted by the application is as follows: a photocatalytic synergistic antibacterial material based on metal organic framework MOFs is prepared by the following steps: S1, using trimesic acid, 2, 6-diaminopyridine, zinc acetate, titanium oxalate as raw materials, a bimetallic MOFs carrier: Ti / Zn-MOFs is prepared by hydrothermal method; S2, loading light response enhanced particles CDs on Ti / Zn-MOFs to obtain Ti / Zn-MOFs@Mn-CDs, that is, the metal organic framework MOFs based photocatalytic synergistic antibacterial material.

[0007] Preferably, step S1 is specifically: Take trimesic acid, 2, 6-diaminopyridine, zinc acetate, titanium oxalate into the first mixed solvent, ultrasonic dispersion, the obtained mixed solution is transferred into a stainless steel reaction kettle, and hydrothermal reaction is carried out under heating, after the reaction is completed, cooling, centrifugation, washing, drying, Ti / Zn-MOFs is obtained.

[0008] Preferably, the first mixed solvent is composed of deionized water and N, N-dimethylformamide.

[0009] Step S1 is specifically: Take 0.005-0.02mol trimesic acid, 0.0075-0.03mol 2, 6-diaminopyridine, 0.005-0.02mol zinc acetate, 0.0025-0.01mol titanium oxalate into 150-600mL first mixed solvent, ultrasonic dispersion 0.5-2h, the obtained mixed solution is transferred into a stainless steel reaction kettle, 120-150℃ reaction for 12-72h, cooling to room temperature, centrifugation, the solid product is washed with deionized water, vacuum drying at 60-80℃ for 6-24h, Ti / Zn-MOFs is obtained.

[0010] Preferably, the first mixed solvent is composed of deionized water and N, N-dimethylformamide in a volume ratio of 1-4:0.5-2.

[0011] Preferably, step S1 is specifically: Take 0.01mol trimesic acid, 0.015mol 2, 6-diaminopyridine, 0.01mol zinc acetate, 0.005mol titanium oxalate into 300mL first mixed solvent composed of deionized water and N, N-dimethylformamide in a volume ratio of 2:1, ultrasonic dispersion 1h, the obtained mixed solution is transferred into a stainless steel reaction kettle, 140℃ reaction for 36h, cooling to room temperature, centrifugation, the solid product is washed with deionized water, vacuum drying at 70℃ for 12h, Ti / Zn-MOFs is obtained.

[0012] Preferably, step S2 is specifically: S2-1, take Ti / Zn-MOFs into the second mixed solvent, ultrasonic dispersion, to obtain carrier dispersion liquid; S2-2, add dithiosalicylic acid, phthalic acid, reduced glutathione to the carrier dispersion liquid, stir; S2-3, add manganese (III) citrate to the mixture obtained in step S2-1, stir, and transfer the obtained mixture into a stainless steel reaction kettle for reaction under heating, cool after reaction, centrifuge, wash, and dry to obtain Ti / Zn-MOFs@Mn-CDs, i.e. the metal organic framework MOFs-based photocatalytic synergistic antibacterial material.

[0013] Preferably, the second mixed solvent is composed of deionized water and ethanol at a volume ratio of 0.5-2:1.

[0014] Preferably, step S2 is specifically as follows: S2-1, take 1-4g Ti / Zn-MOFs and add into 100-400mL of a second mixed solvent composed of deionized water and ethanol at a volume ratio of 1:1, and ultrasonic dispersion for 0.5-2h to obtain a carrier dispersion liquid; S2-2, add 0.306-1.224g dithiosalicylic acid, 0.332-1.328g phthalic acid, and 0.1535-0.614g reduced glutathione to the carrier dispersion liquid, and stir for 0.5-2h; S2-3, add 0.494-1.976g manganese (III) citrate to the mixture obtained in step S2-1, stir for 0.5-2h, transfer the obtained mixture into a stainless steel reaction kettle, and react at 130-160℃ for 12-48h, cool to room temperature, centrifuge, wash the solid product with deionized water, and vacuum dry at 70-90℃ for 6-24h to obtain Ti / Zn-MOFs@Mn-CDs, i.e. the metal organic framework MOFs-based photocatalytic synergistic antibacterial material.

[0015] Preferably, step S2 is specifically as follows: S2-1, take 2g Ti / Zn-MOFs and add into 200mL of a second mixed solvent composed of deionized water and ethanol at a volume ratio of 1:1, and ultrasonic dispersion for 1h to obtain a carrier dispersion liquid; S2-2, add 0.612g dithiosalicylic acid, 0.664g phthalic acid, and 0.307g reduced glutathione to the carrier dispersion liquid, and stir for 1h; S2-3, add 0.988g manganese (III) citrate to the mixture obtained in step S2-1, stir for 1h, transfer the obtained mixture into a stainless steel reaction kettle, and react at 150℃ for 24h, cool to room temperature, centrifuge, wash the solid product with deionized water, and vacuum dry at 80℃ for 12h to obtain Ti / Zn-MOFs@Mn-CDs, i.e. the metal organic framework MOFs-based photocatalytic synergistic antibacterial material.

[0016] The beneficial effects of the present application are: The present application provides a kind of photocatalysis synergistic antibacterial material (Ti / Zn-MOFs@Mn-CDs) based on metal organic framework MOFs, which is obtained by in situ loading light response enhanced particles CDs on double metal MOFs carrier:Ti / Zn-MOFs, in the Ti / Zn-MOFs@Mn-CDs system: (1) Ti / Zn-MOFs provides certain all-scene (light or non-light) antibacterial activity, and the Mn-CDs loaded thereon can provide enhanced antibacterial activity under light, so that the antibacterial performance of the system under light is significantly enhanced, and the antibacterial activity under light has long-term effect, which can provide longer antibacterial activity, thereby making up for the deficiency of Ti / Zn-MOFs in this respect, and realizing synergistic enhancement of antibacterial effect.

[0017] (2) Ti / Zn-MOFs as a carrier realizes the loading of a large number of carbon dots (Mn-CDs) and can realize the uniform dispersion of nanoscale carbon dots, effectively avoiding the agglomeration of carbon dots, and the three-dimensional porous structure of Ti / Zn-MOFs can also provide more reactive sites for carbon dot photocatalysis, capture and store reaction raw materials oxygen or water, promote the reaction of photoexcited electrons and holes with oxygen or water in the carbon dot photocatalysis process to generate ROS, thereby helping to improve the ROS generation efficiency; At the same time, the central ion Ti of Ti / Zn-MOFs can dope the carbon dots to enhance: enhance the separation and transmission efficiency of photoexcited electron-hole pairs, enhance the light absorption capacity and promote electron transmission, thereby significantly improving the photocatalytic efficiency. The Mn doping in Mn-CDs itself can increase the electron cloud density, regulate the electronic structure and energy band structure of carbon quantum dots, inhibit the recombination of photoexcited electrons and holes, broaden the light absorption range, and improve the ROS generation capacity.

[0018] In the present application, by constructing a composite system of Ti / Zn-MOFs and Mn-CDs, the synergistic enhancement effect of both in improving antibacterial performance can be achieved. BRIEF DESCRIPTION OF DRAWINGS

[0019] Figure 1 Infrared absorption spectrum of Ti / Zn-MOFs@Mn-CDs prepared in Example 1; Figure 2 Singlet oxygen generation performance of the antibacterial materials prepared in Example 1, Comparative Example 2 and Comparative Example 4; Figure 3 Antibacterial performance test results of the examples and comparative examples. DETAILED DESCRIPTION

[0020] The application will be further described in detail below with reference to the embodiments so that those skilled in the art can implement the application according to the description.

[0021] It should be understood that the terms such as "have", "contain" and "include" used herein do not exclude the presence or addition of one or more other elements or combinations thereof.

[0022] The test methods used in the following examples are conventional methods unless otherwise specified. The materials and reagents used in the following examples are commercially available unless otherwise specified. The specific conditions are not specified in the following examples, and are carried out according to conventional conditions or the conditions recommended by the manufacturer. The reagents or instruments used are not specified by the manufacturer, and are conventional products that can be purchased on the market.

[0023] The application provides a metal-organic framework MOFs-based photocatalytic synergistic antibacterial material, which is prepared by the following steps: S1, using trimesic acid, 2, 6-diaminopyridine, zinc acetate, titanium oxalate as raw materials, a bimetallic MOFs carrier Ti / Zn-MOFs is prepared by a hydrothermal method: 0.005-0.02 mol of trimesic acid, 0.0075-0.03 mol of 2, 6-diaminopyridine, 0.005-0.02 mol of zinc acetate, and 0.0025-0.01 mol of titanium oxalate are added to 150-600 mL of a first mixed solvent, ultrasonic dispersion is carried out for 0.5-2 h, the obtained mixed solution is transferred into a stainless steel reaction kettle, reaction is carried out at 120-150 °C for 12-72 h, cooling to room temperature, centrifugation, the solid product is washed with deionized water, vacuum drying at 60-80 °C for 6-24 h, and Ti / Zn-MOFs is obtained.

[0024] S2, loading light response enhanced particles CDs on the Ti / Zn-MOFs to obtain Ti / Zn-MOFs@Mn-CDs, i.e. a metal-organic framework MOFs-based photocatalytic synergistic antibacterial material: S2-1, 1-4 g of Ti / Zn-MOFs is added to 100-400 mL of a second mixed solvent composed of deionized water and ethanol at a volume ratio of 1:1, ultrasonic dispersion is carried out for 0.5-2 h, and a carrier dispersion liquid is obtained; S2-2, 0.306-1.224 g of dithiosalicylic acid, 0.332-1.328 g of phthalic acid, and 0.1535-0.614 g of reduced glutathione (chemical formula: C 10 H 17 N3O6S) are added to the carrier dispersion liquid, and stirring is carried out for 0.5-2 h; S2-3, 0.494-1.976 g of manganese (III) citrate (chemical formula: C6H8MnO7, CAS number: 5968-88-7) is added to the mixture obtained in step S2-1, stirred for 0.5-2 h, the obtained mixture is transferred into a stainless steel reaction kettle, reacted at 130-160 ℃ for 12-48 h, cooled to room temperature, centrifuged, the solid product is washed with deionized water, vacuum dried at 70-90 ℃ for 6-24 h, to obtain Ti / Zn-MOFs@Mn-CDs, namely metal organic framework MOFs-based photocatalytic synergistic antibacterial material.

[0025] Inventive mechanism 1, The application first uses trimesic acid and 2,6-diaminopyridine as ligands, zinc and titanium as central ions, and prepares metal organic framework MOFs: Ti / Zn-MOFs through a hydrothermal reaction. Then, Ti / Zn-MOFs is used as a carrier, dithiosalicylic acid, 0.664 g of phthalic acid, 0.307 g of reduced glutathione are used as carbon sources, manganese (III) citrate is used as a doping component, and manganese-doped carbon dots are in-situ synthesized on the carrier through one-pot hydrothermal method to obtain metal organic framework MOFs-based photocatalytic synergistic antibacterial material: Ti / Zn-MOFs@Mn-CDs.

[0026] 2, In the application, Ti / Zn-MOFs is a kind of metal organic framework material, which forms a three-dimensional porous structure through self-assembly, has high porosity and specific surface area, and can also provide good antibacterial performance, and the antibacterial mechanism is to release metal ions Zn 2+ to realize antibacterial effect (Kong Z, Su H, Song S. Research progress of metal organic framework antibacterial materials [J]. Journal of Jilin Normal University: Natural Science Edition, 2022, 43(4): 1-7. DOI: 10.16862 / j.cnki.issn1674-3873.2022.04.001.). 2+ has cytotoxicity, can cause microorganisms to be destroyed due to lipid layer, and cell contents to flow out, thereby promoting bacterial death and realizing antibacterial effect (Kong Z, Su H, Song S. Research progress of metal organic framework antibacterial materials [J]. Journal of Jilin Normal University: Natural Science Edition, 2022, 43(4): 1-7. DOI: 10.16862 / j.cnki.issn1674-3873.2022.04.001.). 2+ The antibacterial performance will gradually weaken or even be lost with the consumption of Zn 2+ release, and the antibacterial intensity also seriously depends on the release amount of Zn 2+ Therefore, in the application, the metal organic framework material is modified by loading the light-responsive particles CDs to improve the antibacterial performance and antibacterial time effect.

[0027] 3、In the application, the light response enhanced particle CDs loaded on the Ti / Zn-MOFs is a kind of metal manganese doped carbon dots, which can efficiently produce reactive oxygen species (ROS) under light irradiation, and the killing effect of ROS on bacteria can significantly enhance the antibacterial performance of Ti / Zn-MOFs. The main antibacterial mechanism of ROS is that ROS reacts with the cell membrane or enters the inside of the bacteria, destroys the bacterial cell membrane, causes internal material leakage, further inactivates bacterial DNA and protein, ROS can cause oxidative stress in bacteria, extracellular ROS entering the bacteria can cause a sharp increase in intracellular ROS level, reacts with antioxidant enzymes, destroys the balance of oxidation and antioxidant in the bacteria, thereby killing the bacteria (JIA Q, SONG Q, LI P, et al. Rejuvenated Photodynamic Therapy for Bacterial Infections [J]. Adv Healthc Mater.. 2019, 8(14): e1900608.). Unlike Ti / Zn-MOFs, the antibacterial activity of the light response enhanced particle CDs does not consume metal ions, and can provide longer antibacterial performance.

[0028] In the Ti / Zn-MOFs@Mn-CDs system constructed by the application: (1) Ti / Zn-MOFs provides certain all-scene (light or non-light) antibacterial activity, and the Mn-CDs loaded thereon can provide enhanced antibacterial activity under light, so that the antibacterial performance of the system under light is significantly enhanced, and the antibacterial activity under light has long-term effect, which can provide longer antibacterial activity, thereby making up for the deficiency of Ti / Zn-MOFs in this respect, and realizing synergistic enhancement of antibacterial effect.

[0029] (2) Ti / Zn-MOFs as a carrier realizes large loading of carbon dots (Mn-CDs), and can realize uniform dispersion of nanoscale carbon dots, effectively avoiding agglomeration of carbon dots, and the three-dimensional porous structure of Ti / Zn-MOFs can also provide more reactive sites for photocatalysis of carbon dots, capture and store reaction raw materials oxygen or water, promote the reaction of photoexcited electrons and holes with oxygen or water to produce ROS in the photocatalytic reaction process of carbon dots, thereby helping to improve the ROS production efficiency; at the same time, the central ion Ti of Ti / Zn-MOFs can produce doping enhancement of carbon dots: enhance the separation and transmission efficiency of photoinduced electron-hole pairs, enhance the light absorption capacity and promote electron transmission, thereby significantly improving the photocatalytic efficiency.

[0030] The doping of Mn in the Mn-CDs itself can improve the electron cloud density, regulate the electronic structure and energy band structure of the carbon quantum dots, inhibit the recombination of photo-generated electrons and holes, broaden the light absorption range, and improve the ROS generation capacity.

[0031] Therefore, in the present application, by constructing a composite system of Ti / Zn-MOFs and Mn-CDs, a synergistic enhancement effect of both in improving the antibacterial performance can be achieved.

[0032] The above is the general idea of the present application, and the following provides detailed examples and comparative examples based thereon to further illustrate the present application.

[0033] Example 1 A metal organic framework MOFs-based photocatalytic synergistic antibacterial material is prepared by the following steps: S1, a bimetallic MOFs carrier Ti / Zn-MOFs is prepared by a hydrothermal method using trimesic acid, 2, 6-diaminopyridine, zinc acetate, and titanium oxalate as raw materials: Take 0.01 mol of trimesic acid, 0.015 mol of 2, 6-diaminopyridine, 0.01 mol of zinc acetate, and 0.005 mol of titanium oxalate and add them into 300 mL of a first mixed solvent composed of deionized water and N, N-dimethylformamide in a volume ratio of 2:1, ultrasonic dispersion for 1 h, the obtained mixture is transferred into a stainless steel reaction kettle, reaction at 140℃ for 36 h, cooling to room temperature, centrifugation, the solid product is washed with deionized water, vacuum drying at 70℃ for 12 h, to obtain Ti / Zn-MOFs.

[0034] S2, load light response enhanced particles CDs on Ti / Zn-MOFs to obtain Ti / Zn-MOFs@Mn-CDs, i.e. a metal organic framework MOFs-based photocatalytic synergistic antibacterial material: S2-1, take 2g of Ti / Zn-MOFs and add them into 200 mL of a second mixed solvent composed of deionized water and ethanol in a volume ratio of 1:1, ultrasonic dispersion for 1 h to obtain a carrier dispersion liquid; S2-2, add 0.612g of dithiosalicylic acid, 0.664g of phthalic acid, and 0.307g of reduced glutathione to the carrier dispersion liquid and stir for 1 h; S2-3, add 0.988g of manganese(III) citrate to the mixture obtained in step S2-1 and stir for 1 h, the obtained mixture is transferred into a stainless steel reaction kettle, reaction at 150℃ for 24 h, cooling to room temperature, centrifugation, the solid product is washed with deionized water, vacuum drying at 80℃ for 12 h, to obtain Ti / Zn-MOFs@Mn-CDs, i.e. a metal organic framework MOFs-based photocatalytic synergistic antibacterial material.

[0035] Example 2 A metal-organic framework MOFs-based photocatalytic synergistic antibacterial material is prepared by the following steps: S1, using trimesic acid, 2, 6-diaminopyridine, zinc acetate, titanium oxalate as raw materials, a bimetallic MOFs carrier: Ti / Zn-MOFs is prepared by hydrothermal method: Take 0.01 mol trimesic acid, 0.015 mol 2, 6-diaminopyridine, 0.01 mol zinc acetate, 0.004 mol titanium oxalate into 300 mL of the first mixed solvent composed of deionized water and N, N-dimethylformamide in a volume ratio of 2:1, ultrasonic dispersion for 1 h, the obtained mixture is transferred into a stainless steel reaction kettle, and reacted at 140℃ for 36 h, cooled to room temperature, centrifuged, the solid product is washed with deionized water, and vacuum dried at 70℃ for 12 h to obtain Ti / Zn-MOFs.

[0036] S2, load light response enhanced particles CDs on Ti / Zn-MOFs to obtain Ti / Zn-MOFs@Mn-CDs, i.e. metal-organic framework MOFs-based photocatalytic synergistic antibacterial material: S2-1, take 1.65g Ti / Zn-MOFs into 200mL of the second mixed solvent composed of deionized water and ethanol in a volume ratio of 1:1, ultrasonic dispersion for 1h to obtain a carrier dispersion liquid; S2-2, add 0.612g dithiosalicylic acid, 0.664g phthalic acid, 0.307g reduced glutathione to the carrier dispersion liquid, and stir for 1h; S2-3, add 0.988g manganese (III) citrate to the mixture obtained in step S2-1, stir for 1h, the obtained mixture is transferred into a stainless steel reaction kettle, and reacted at 140℃ for 24h, cooled to room temperature, centrifuged, the solid product is washed with deionized water, and vacuum dried at 80℃ for 12h to obtain Ti / Zn-MOFs@Mn-CDs, i.e. metal-organic framework MOFs-based photocatalytic synergistic antibacterial material.

[0037] Example 3 A metal-organic framework MOFs-based photocatalytic synergistic antibacterial material is prepared by the following steps: S1, using trimesic acid, 2, 6-diaminopyridine, zinc acetate, titanium oxalate as raw materials, a bimetallic MOFs carrier: Ti / Zn-MOFs is prepared by hydrothermal method: Take 0.01 mol of trimesic acid, 0.015 mol of 2,6-diaminopyridine, 0.01 mol of zinc acetate, 0.004 mol of titanium oxalate into 300 mL of the first mixed solvent composed of deionized water and N, N-dimethylformamide in a volume ratio of 2:1, ultrasonic dispersion for 1 h, the obtained mixture is transferred into a stainless steel reaction kettle, reaction at 130℃ for 36 h, cooling to room temperature, centrifugation, the solid product is washed with deionized water, vacuum drying at 70℃ for 12 h, to obtain Ti / Zn-MOFs.

[0038] S2, load light response enhanced particles CDs on Ti / Zn-MOFs to obtain Ti / Zn-MOFs@Mn-CDs, i.e. photocatalytic synergistic antibacterial material based on metal organic framework MOFs: S2-1, take 2.2 g of Ti / Zn-MOFs into 200 mL of the second mixed solvent composed of deionized water and ethanol in a volume ratio of 1:1, ultrasonic dispersion for 1 h to obtain a carrier dispersion liquid; S2-2, add 0.612 g of dithiosalicylic acid, 0.664 g of phthalic acid, 0.307 g of reduced glutathione to the carrier dispersion liquid, stir for 1 h; S2-3, add 0.988 g of manganese (III) citrate to the mixture obtained in step S2-1, stir for 1 h, the obtained mixture is transferred into a stainless steel reaction kettle, reaction at 160℃ for 24 h, cooling to room temperature, centrifugation, the solid product is washed with deionized water, vacuum drying at 80℃ for 12 h, to obtain Ti / Zn-MOFs@Mn-CDs, i.e. photocatalytic synergistic antibacterial material based on metal organic framework MOFs.

[0039] Example 4 A photocatalytic synergistic antibacterial material based on metal organic framework MOFs is prepared by the following steps: S1, using trimesic acid, 2,6-diaminopyridine, zinc acetate, titanium oxalate as raw materials, a double metal MOFs carrier: Ti / Zn-MOFs is prepared by hydrothermal method: Take 0.01 mol of trimesic acid, 0.015 mol of 2,6-diaminopyridine, 0.008 mol of zinc acetate, 0.006 mol of titanium oxalate into 300 mL of the first mixed solvent composed of deionized water and N, N-dimethylformamide in a volume ratio of 2:1, ultrasonic dispersion for 1 h, the obtained mixture is transferred into a stainless steel reaction kettle, reaction at 135℃ for 36 h, cooling to room temperature, centrifugation, the solid product is washed with deionized water, vacuum drying at 70℃ for 12 h, to obtain Ti / Zn-MOFs.

[0040] S2, loading light response enhanced particles CDs on Ti / Zn-MOFs to obtain Ti / Zn-MOFs@Mn-CDs, i.e., a metal organic framework MOFs-based photocatalytic synergistic antibacterial material: S2-1, 1.8 g of Ti / Zn-MOFs was added into 200 mL of a second mixed solvent composed of deionized water and ethanol at a volume ratio of 1:1, and ultrasonic dispersion was performed for 1 h to obtain a carrier dispersion liquid; S2-2, 0.612 g of dithiosalicylic acid, 0.664 g of phthalic acid, and 0.307 g of reduced glutathione were added into the carrier dispersion liquid, and stirring was performed for 1 h; S2-3, 0.988 g of manganese (III) citrate was added into the mixture obtained in step S2-1, stirring was performed for 1 h, the obtained mixture was transferred into a stainless steel reaction kettle, reaction was performed at 140 ℃ for 24 h, cooling was performed to room temperature, centrifugation was performed, the solid product was washed with deionized water, and vacuum drying was performed at 80 ℃ for 12 h to obtain Ti / Zn-MOFs@Mn-CDs, i.e., a metal organic framework MOFs-based photocatalytic synergistic antibacterial material.

[0041] Comparative Example 1 An antibacterial material was prepared by the following steps: S1, 0.01 mol of trimesic acid, 0.015 mol of 2,6-diaminopyridine, 0.01 mol of zinc acetate, and 0.005 mol of titanium oxalate were added into 300 mL of a first mixed solvent composed of deionized water and N,N-dimethylformamide at a volume ratio of 2:1, ultrasonic dispersion was performed for 1 h, the obtained mixture was transferred into a stainless steel reaction kettle, reaction was performed at 140 ℃ for 36 h, cooling was performed to room temperature, centrifugation was performed, the solid product was washed with deionized water, and vacuum drying was performed at 70 ℃ for 12 h to obtain Ti / Zn-MOFs, i.e., an antibacterial material.

[0042] Comparative Example 2 A metal organic framework MOFs-based photocatalytic synergistic antibacterial material was prepared by the following steps: S1, 0.01 mol of trimesic acid, 0.015 mol of 2,6-diaminopyridine, and 0.01 mol of zinc acetate were added into 300 mL of a first mixed solvent composed of deionized water and N,N-dimethylformamide at a volume ratio of 2:1, ultrasonic dispersion was performed for 1 h, the obtained mixture was transferred into a stainless steel reaction kettle, reaction was performed at 140 ℃ for 36 h, cooling was performed to room temperature, centrifugation was performed, the solid product was washed with deionized water, and vacuum drying was performed at 70 ℃ for 12 h to obtain Zn-MOFs.

[0043] S2, loading light response enhanced particles CDs on Zn-MOFs to obtain Zn-MOFs@Mn-CDs, i.e., a metal organic framework MOFs-based photocatalytic synergistic antibacterial material: S2-1, 2 g of Zn-MOFs was taken and added to 200 mL of a second mixed solvent composed of deionized water and ethanol in a volume ratio of 1:1, ultrasonic dispersion for 1 h to obtain a carrier dispersion liquid; S2-2, 0.612 g of dithiosalicylic acid, 0.664 g of phthalic acid, and 0.307 g of reduced glutathione were added to the carrier dispersion liquid and stirred for 1 h; S2-3, 0.988 g of manganese (III) citrate was added to the mixture obtained in step S2-1 and stirred for 1 h, the obtained mixture was transferred into a stainless steel reaction kettle, reacted at 150°C for 24 h, cooled to room temperature, centrifuged, the solid product was washed with deionized water, and vacuum dried at 80°C for 12 h to obtain Zn-MOFs@Mn-CDs, i.e. a metal organic framework MOFs-based photocatalytic synergistic antibacterial material.

[0044] Comparative Example 3 An antibacterial material was prepared by the following steps: S1, 0.612 g of dithiosalicylic acid, 0.664 g of phthalic acid, and 0.307 g of reduced glutathione were added to 200 mL of a mixed solvent composed of deionized water and ethanol in a volume ratio of 1:1, and stirred for 1 h S2-3, 0.988 g of manganese (III) citrate was added to the mixture obtained in step S1 and stirred for 1 h, the obtained mixture was transferred into a stainless steel reaction kettle, reacted at 150°C for 24 h, cooled to room temperature, centrifuged, the solid product was washed with deionized water, and vacuum dried at 80°C for 12 h to obtain Mn-CDs, i.e. an antibacterial material.

[0045] Comparative Example 4 A metal organic framework MOFs-based photocatalytic synergistic antibacterial material was prepared by the following steps: S1, using trimesic acid, 2,6-diaminopyridine, zinc acetate, and titanium oxalate as raw materials, a bimetallic MOFs carrier Ti / Zn-MOFs was prepared by a hydrothermal method, and the specific method was the same as that of Example 1; S2, loading light response enhanced particles CDs on the Ti / Zn-MOFs to obtain Ti / Zn-MOFs@CDs, i.e. a metal organic framework MOFs-based photocatalytic synergistic antibacterial material: S2-1, 2 g of Ti / Zn-MOFs was taken and added to 200 mL of a second mixed solvent composed of deionized water and ethanol in a volume ratio of 1:1, ultrasonic dispersion for 1 h to obtain a carrier dispersion liquid; S2-2, 0.612 g of dithiosalicylic acid, 0.664 g of phthalic acid, and 0.307 g of reduced glutathione were added to the carrier dispersion liquid and stirred for 1 h; S2-3. Add 0.768 g of citric acid to the mixture obtained in step S2-1, stir for 1 h, transfer the resulting mixture into a stainless-steel autoclave, react at 150 °C for 24 h, cool to room temperature, centrifuge, wash the solid product with deionized water, and dry it under vacuum at 80 °C for 12 h to obtain Ti / Zn-MOFs@CDs, that is, a photocatalytic synergistic antibacterial material based on metal-organic framework MOFs.

[0046] Performance Test 1. Infrared Spectrum Ref. Figure 1 , is the infrared absorption spectrum of Ti / Zn-MOFs@Mn-CDs (a photocatalytic synergistic antibacterial material based on metal-organic framework MOFs) prepared in Example 1, indicating the successful synthesis of Ti / Zn-MOFs@Mn-CDs.

[0047] 2. Singlet Oxygen Generation Performance Test the singlet oxygen generation performance of the antibacterial materials prepared in Example 1, Comparative Example 2, and Comparative Example 4 according to the following method: Add the antibacterial material to deionized water and disperse it by ultrasonic wave for 45 min to prepare an antibacterial material solution with a concentration of 0.5 mg / mL. Perform fluorescence test (excitation peak 504 nm, emission peak 525 nm) with SOSG singlet oxygen fluorescence probe (Vander Beijing Biotechnology). The fluorescence intensity at 525 nm is positively correlated with the singlet oxygen concentration: the greater the fluorescence intensity, the stronger the singlet oxygen generation ability.

[0048] From the test results ( Figure 1 ), it can be seen that the antibacterial materials prepared in Example 1, Comparative Example 2, and Comparative Example 4 can continuously generate singlet oxygen under light, and the singlet oxygen generation performance of Example 1 is significantly stronger than that of Comparative Example 2 and Comparative Example 4.

[0049] 3. Antibacterial Performance Test The Oxford cup method is used to measure the inhibition zone, and the antibacterial performance is evaluated by the size of the inhibition zone: Take the antibacterial materials prepared in the examples and comparative examples, grind them into powder, pass through a 300-mesh sieve, add them to deionized water, and disperse them by ultrasonic wave for 30 min to prepare an antibacterial dispersion with a concentration of 1 mg / mL; Add 0.2 mL of Staphylococcus aureus bacterial solution (1×10 8CFU / mL) were uniformly spread on agar plates containing sufficient medium (satisfying the culture requirements in this experiment), and an Oxford cup was placed on the agar plates. 10 μL of the antibacterial dispersion was added to the Oxford cup, and the agar plates were cultured under xenon lamp irradiation (100 W, located 50 cm above the agar plates). The xenon lamp was intermittently operated in an on 1 h, off 1 h manner. The diameters of the bacterial growth inhibition zones around the Oxford cups were measured at different culture times to evaluate the antibacterial performance. The greater the diameter of the inhibition zone, the stronger the antibacterial ability.

[0050] In the blank control example, 10 μL of deionized water was used instead of the antibacterial dispersion, and the rest was the same as above.

[0051] In the dark control example, the antibacterial material of Example 1 was used, and the culture process was carried out in a dark environment, and the rest was the same as above.

[0052] The test results are shown in Table 1 and Figure 3 Table 1 As can be seen from the test results, Examples 1-4 can achieve long-acting antibacterial effect under light; The comparison between the dark control example and Example 1 shows that the antibacterial ability is significantly enhanced under light relative to the dark environment, proving that the ability of the antibacterial material prepared in Example 1 to produce reactive oxygen under light is an important factor for the enhancement of antibacterial performance. Moreover, the antibacterial performance decreases rapidly with the extension of the culture time, indicating that the long-acting nature of the antibacterial performance provided by Ti / Zn-MOFs is insufficient, while the light-responsive enhancing particles CDs loaded thereon can provide long-acting antibacterial performance through photocatalytic production of ROS. The results of Comparative Example 1 show that when the light-responsive enhancing particles CDs are not loaded on Ti / Zn-MOFs, the antibacterial performance decreases significantly, and decreases rapidly with the extension of the culture time, due to the insufficient long-acting nature of the antibacterial performance provided by Ti / Zn-MOFs; The decrease in the antibacterial performance of Comparative Example 2 is due to the absence of Ti doping in MOFs. The decrease in the antibacterial performance of Comparative Example 3 is due to the use of light-responsive enhancing particles CDs as the antibacterial material, which loses the antibacterial activity provided by Ti / Zn-MOFs. Moreover, the antibacterial performance decreases rapidly with the extension of the culture time, due to the significant decrease in the dispersion stability of the light-responsive enhancing particles CDs without being loaded by Ti / Zn-MOFs, which gradually agglomerate over time, resulting in a significant decrease in the ROS production performance under light. The decrease in the antibacterial performance of Comparative Example 2 is due to the absence of Mn doping in the light-responsive enhancing particles CDs.

[0053] ​While embodiments of the application have been disclosed in connection with the preferred embodiments of the application, it should be understood that there can be other embodiments which fall within the broad concept of the application as defined in the claims and their equivalents.

Claims

1. A metal-organic framework (MOF) -based photocatalytic synergistic antibacterial material, characterized in that, It is prepared by the following steps: S1, using trimesic acid, 2, 6-diaminopyridine, zinc acetate, titanium oxalate as raw materials, a bimetallic MOFs carrier: Ti / Zn-MOFs is prepared by hydrothermal method; S2, loading light response enhanced particles CDs on Ti / Zn-MOFs to obtain Ti / Zn-MOFs@Mn-CDs, namely the metal organic framework MOFs based photocatalytic synergistic antibacterial material. 2.The metal-organic framework (MOF) -based photocatalytic synergistic antibacterial material according to claim 1, characterized in that, Step S1 is specifically: Take trimesic acid, 2, 6-diaminopyridine, zinc acetate, titanium oxalate and add them to the first mixed solvent, ultrasonic dispersion, the obtained mixed solution is transferred into a stainless steel reaction kettle, hydrothermal reaction is carried out under heating, after the reaction is completed, cooling, centrifugation, washing, drying, Ti / Zn-MOFs is obtained. 3.The metal-organic framework (MOF) -based photocatalytic synergistic antibacterial material according to claim 2, characterized in that, The first mixed solvent is composed of deionized water and N, N-dimethylformamide. 4.The metal-organic framework (MOF) -based photocatalytic synergistic antibacterial material according to claim 3, characterized in that, Step S1 is specifically: Take 0.005-0.02mol trimesic acid, 0.0075-0.03mol 2, 6-diaminopyridine, 0.005-0.02mol zinc acetate, 0.0025-0.01mol titanium oxalate, add them to 150-600mL first mixed solvent, ultrasonic dispersion for 0.5-2h, the obtained mixed solution is transferred into a stainless steel reaction kettle, reaction is carried out at 120-150℃ for 12-72h, cooling to room temperature, centrifugation, the solid product is washed with deionized water, vacuum drying at 60-80℃ for 6-24h, Ti / Zn-MOFs is obtained. 5.The metal-organic framework (MOF) -based photocatalytic synergistic antibacterial material according to claim 4, characterized in that, The first mixed solvent is composed of deionized water and N, N-dimethylformamide in a volume ratio of 1-4:0.5-2. 6.The metal-organic framework (MOF) -based photocatalytic and synergistic antibacterial material according to claim 5, characterized in that, Step S1 is specifically: Take 0.01mol trimesic acid, 0.015mol 2, 6-diaminopyridine, 0.01mol zinc acetate, 0.005mol titanium oxalate, add them to 300mL first mixed solvent composed of deionized water and N, N-dimethylformamide in a volume ratio of 2:1, ultrasonic dispersion for 1h, the obtained mixed solution is transferred into a stainless steel reaction kettle, reaction is carried out at 140℃ for 36h, cooling to room temperature, centrifugation, the solid product is washed with deionized water, vacuum drying at 70℃ for 12h, Ti / Zn-MOFs is obtained. 7.The metal-organic framework (MOF) -based photocatalytic and synergistic antibacterial material according to claim 1, wherein, Step S2 is specifically: S2-1, take Ti / Zn-MOFs and add it to the second mixed solvent, ultrasonic dispersion, to obtain a carrier dispersion liquid; S2-2, add dithiosalicylic acid, phthalic acid, reduced glutathione to the carrier dispersion liquid and stir; S2-3, add manganese (III) citrate to the mixture obtained in step S2-1 and stir, the obtained mixture is transferred into a stainless steel reaction kettle, reaction is carried out under heating, after the reaction is completed, cooling, centrifugation, washing, drying, Ti / Zn-MOFs@Mn-CDs, namely the metal organic framework MOFs based photocatalytic synergistic antibacterial material is obtained. 8.The metal-organic framework (MOF) -based photocatalytic and synergistic antibacterial material according to claim 7, characterized in that, The second mixed solvent is composed of deionized water and ethanol in a volume ratio of 0.5-2:

1. 9.The metal-organic framework (MOF) -based photocatalytic and synergistic antibacterial material of claim 8, wherein, Step S2 is specifically: S2-1, take 1-4 g Ti / Zn-MOFs and add to 100-400 mL of a second mixed solvent composed of deionized water and ethanol at a volume ratio of 1:1, ultrasonic dispersion for 0.5-2 h to obtain a carrier dispersion liquid; S2-2, add 0.306-1.224 g of dithiosalicylic acid, 0.332-1.328 g of phthalic acid, and 0.1535-0.614 g of reduced glutathione to the carrier dispersion liquid, and stir for 0.5-2 h; S2-3, add 0.494-1.976 g of manganese (III) citrate to the mixture obtained in step S2-1, stir for 0.5-2 h, transfer the obtained mixture into a stainless steel reaction kettle, react at 130-160 °C for 12-48 h, cool to room temperature, centrifuge, wash the solid product with deionized water, and vacuum dry at 70-90 °C for 6-24 h to obtain Ti / Zn-MOFs@Mn-CDs, i.e., the metal-organic framework MOFs-based photocatalytic synergistic antibacterial material. 10.The metal-organic framework (MOF) -based photocatalytic and synergistic antibacterial material according to claim 9, characterized in that, Step S2 is specifically: S2-1, take 2 g Ti / Zn-MOFs and add to 200 mL of a second mixed solvent composed of deionized water and ethanol at a volume ratio of 1:1, ultrasonic dispersion for 1 h to obtain a carrier dispersion liquid; S2-2, add 0.612 g of dithiosalicylic acid, 0.664 g of phthalic acid, and 0.307 g of reduced glutathione to the carrier dispersion liquid, and stir for 1 h; S2-3, add 0.988 g of manganese (III) citrate to the mixture obtained in step S2-1, stir for 1 h, transfer the obtained mixture into a stainless steel reaction kettle, react at 150 °C for 24 h, cool to room temperature, centrifuge, wash the solid product with deionized water, and vacuum dry at 80 °C for 12 h to obtain Ti / Zn-MOFs@Mn-CDs, i.e., the metal-organic framework MOFs-based photocatalytic synergistic antibacterial material.

Images