Bimetal MOFs with photo-thermal and anti-oxidation effects and preparation method and application thereof
By preparing Fe/Cu-MOFs materials and combining photothermal conversion and antioxidant properties, the problems of limited deep tissue penetration and insufficient ROS removal of existing MOFs materials in photothermal therapy have been solved, achieving a synergistic therapeutic effect of highly efficient sterilization and antioxidation.
Patent Information
- Application Number
- CN202511199530.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-08-26
- Publication Date
- 2025-12-02
AI Technical Summary
Existing MOF materials have limitations in photothermal therapy, resulting in limited penetration into deep tissues and insufficient treatment efficiency. They also cannot effectively remove excess reactive oxygen species (ROS), leading to oxidative stress damage and making it difficult to achieve synergistic treatment with efficient sterilization and antioxidation.
Using Fe and Cu as central ions and NDI-grafted aminotriazole groups as DBPT organic ligands, bimetallic MOFs were synthesized via a solvothermal method, resulting in Fe/Cu-MOFs with a needle-like structure that combine photothermal conversion performance and antioxidant properties.
It achieves the killing of bacteria under photothermal conditions and the removal of excess ROS under non-photothermal conditions, thereby regulating the inflammatory microenvironment and improving the treatment effect of bacterial infection and related inflammation.
Smart Images
Figure CN121045569A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of biomedicine, specifically to a bimetallic MOF with photothermal and antioxidant effects, its preparation method, and its application. Background Technology
[0002] Metal-organic frameworks (MOFs) are an emerging type of crystalline porous functional material that has shown great potential in the biomedical field, especially in disease treatment, due to their designable structures and diverse functions. The long-term presence of bacterial infection foci easily induces inflammatory responses; therefore, effective treatment strategies not only require the effective elimination of pathogens but also the simultaneous regulation of the inflammatory microenvironment to promote tissue healing and reduce damage.
[0003] Photothermal therapy (PTT) is a technique that converts light energy into heat energy using photothermal conversion materials, achieving physical sterilization through localized heating, and shows great promise in antibacterial treatment. However, PTT alone has limitations in penetrating deep tissues and has insufficient treatment efficiency. Furthermore, the high temperatures generated during PTT and the immune response in the infection microenvironment can induce a burst of reactive oxygen species (ROS).
[0004] While moderate amounts of ROS can aid in sterilization, excessive accumulation can cause oxidative damage to the DNA, proteins, and lipids of normal cells, exacerbating inflammatory responses and even leading to apoptosis and secondary tissue damage. Therefore, precisely regulating ROS levels to alleviate oxidative stress while achieving efficient sterilization is crucial for synergistic therapy. Although some MOF materials have been reported to possess photothermal conversion properties and can be used for PTT sterilization, they typically lack effective ROS scavenging capabilities and cannot address the oxidative stress damage caused by PTT and the infection itself. On the other hand, while some studies have reported MOF materials with antioxidant capabilities that can mimic the activity of natural antioxidant enzymes to scavenge excess ROS, these materials only possess single antioxidant properties and are insufficient to meet the demands of highly efficient antibacterial treatment.
[0005] In summary, existing single-function MOF materials cannot simultaneously achieve efficient sterilization while removing excess ROS to protect normal tissues and alleviate inflammation. Therefore, developing a novel multifunctional MOF material that possesses both highly efficient photothermal conversion properties for bacterial killing and strong antioxidant activity for removing excess ROS and regulating the inflammatory microenvironment is urgently needed and of great significance for improving the comprehensive therapeutic effect of bacterial infections and related inflammations. Summary of the Invention
[0006] This invention addresses the problems of traditional MOFs having limited functionality, insufficient ROS regulation capabilities, and difficulty in achieving synergistic photothermal and antioxidant therapy. It proposes a bimetallic MOF with photothermal and antioxidant effects, along with its preparation method and applications. The preparation process is simple and easy to operate, and the prepared Fe / Cu-MOFs exhibit a needle-like distribution with excellent photothermal and antioxidant properties. When applied to antibacterial and anti-inflammatory fields, it can achieve synergistic photothermal and antioxidant therapy.
[0007] To achieve the above-mentioned objectives, the technical solution adopted by this invention is as follows:
[0008] This invention provides a method for preparing bimetallic MOFs with photothermal and antioxidant effects, using Fe and Cu as central ions, and NDI grafted with an aminotriazole group as a DBPT organic ligand, synthesized via a solvothermal method; specifically including the following steps:
[0009] S1. 1,4,5,8-Naphthalenetetracarboxylic dianhydride and 4-amino-4H-1,2,4-triazole are dispersed in DMF and refluxed at 140-160℃ for 10-14 h to obtain the DBPT organic ligand; the structural formula of the DBPT organic ligand is as follows:
[0010] S2. Add the DBPT organic ligand, anhydrous ferric chloride, anhydrous copper nitrate and fluoroboric acid obtained in step S1 to DMF to obtain a reaction solution. Sonicate and stir the reaction solution until completely dissolved. Place the resulting solution in a high-pressure reactor for heating reaction. After the reaction is completed, cool to room temperature.
[0011] S3. After centrifuging the product obtained in step S2, wash and dry it to obtain Fe / Cu-MOFs.
[0012] Preferably, in step S1, the concentrations of 1,4,5,8-naphthotetracarboxylic dianhydride and 4-amino-4H-1,2,4-triazole in DMF are 11.8 g / L and 17.9 g / L, respectively.
[0013] Preferably, in step S1, after reflux reaction at 150°C for 12 hours, the mixture is cooled to room temperature, deionized water and methanol are added to precipitate the product, and the precipitate is obtained by filtration. The precipitate is washed three times by alternating centrifugation with ethanol and deionized water at 8000 rpm, and then vacuum dried to obtain the DBPT organic ligand.
[0014] Preferably, in step S2, the reaction solution is sonicated for 10-20 minutes until the DBPT ligand, anhydrous ferric chloride, and anhydrous copper nitrate are fully dissolved, the mass ratio between anhydrous ferric chloride and anhydrous copper nitrate is 1:(0.5-2), and the volume ratio between DMF and fluoroboric acid is 150:1.
[0015] Preferably, in step S2, the heating reaction temperature is 120°C and the reaction time is 24-72 h.
[0016] Preferably, in step S3, the product obtained after centrifugation is washed three times alternately with DMF and ethanol, and then vacuum dried at 85°C for 24 hours.
[0017] To achieve the above-mentioned objectives, the present invention also provides a bimetallic MOF with photothermal and antioxidant effects prepared by the above-mentioned preparation method, wherein the bimetallic MOF has a needle-like structure.
[0018] To achieve the above-mentioned objectives, the present invention also provides the application of the above-mentioned bimetallic MOFs with photothermal and antioxidant effects in the fields of antibacterial and anti-inflammatory.
[0019] Compared with the prior art, the beneficial effects of the present invention are as follows:
[0020] This invention uses DBPT as an organic ligand to combine with Fe and Cu to prepare bimetallic Fe / Cu-MOFs. The prepared Fe / Cu-MOFs exhibit photothermal conversion properties to kill bacteria under near-infrared light excitation, and exhibit antioxidant activity to remove excess ROS and regulate the inflammatory microenvironment under non-light conditions. This is of urgent need and great significance for improving the treatment effect of bacterial infection and related inflammation. Attached Figure Description
[0021] Figure 1 Scanning electron microscope (SEM) images of Fe / Cu-MOFs (1:0.5)-24 prepared in Example 1; (A) 30 μm, (B) 50 μm;
[0022] Figure 2 Scanning electron microscope (SEM) images of Fe / Cu-MOFs (1:0.5)-48 prepared in Example 2; (A) 40 μm, (B) 50 μm;
[0023] Figure 3 Scanning electron microscope (SEM) images of Fe / Cu-MOFs (1:0.5)-72 prepared in Example 3; (A) 40 μm, (B) 40 μm;
[0024] Figure 4 Scanning electron microscope (SEM) images of Fe / Cu-MOFs(1:1)-24 prepared in Example 4; (A) 30 μm, (B) 50 μm;
[0025] Figure 5 Scanning electron microscope (SEM) images of Fe / Cu-MOFs(1:1)-48 prepared in Example 5; (A) 40 μm, (B) 50 μm;
[0026] Figure 6Scanning electron microscope (SEM) images of Fe / Cu-MOFs(1:1)-72 prepared in Example 6; (A) 30 μm, (B) 50 μm;
[0027] Figure 7 Scanning electron microscope (SEM) images of Fe / Cu-MOFs(1:2)-24 prepared in Example 7; (A) 40 μm, (B) 50 μm;
[0028] Figure 8 Scanning electron microscope (SEM) images of Fe / Cu-MOFs(1:2)-48 prepared in Example 8; (A) 40 μm, (B) 50 μm;
[0029] Figure 9 Scanning electron microscope (SEM) images of Fe / Cu-MOFs(1:2)-72 prepared in Example 9; (A) 30 μm, (B) 50 μm;
[0030] Figure 10 XPS spectra of Fe / Cu-MOFs(1:2)-72 prepared in Example 9; (A) Total XPS spectrum, (B) Oxygen peak spectrum, (C) Nitrogen peak spectrum, (D) Iron peak spectrum, (E) Copper peak spectrum, (F) Carbon peak spectrum;
[0031] Figure 11 Temperature curves and thermal images of the Fe / Cu-MOFs(1:2)-72 aqueous solution prepared in Example 9 under 808 nm laser irradiation; (A) Temperature curves and thermal images of Fe / Cu-MOFs(1:2)-72 aqueous solutions of different concentrations (1 mg / mL, 0.5 mg / mL, 0.2 mg / mL, 0.1 mg / mL) and ddH2O under 1.5 W / cm² laser irradiation. 2 (A) Temperature curves of 0.5 mg / mL Fe / Cu-MOFs and ddH2O at a power density of 1.5 W / cm2; (B) Thermal imaging of 0.5 mg / mL Fe / Cu-MOFs (1:2)-72 at different power densities (2.5 W / cm2). 2 1.5W / cm 2 0.5W / cm 2 Temperature curves of (D)0.5 mg / mL Fe / Cu-MOFs (1:2)-72 at 2.5 W / cm 2 Temperature cycling curves below;
[0032] Figure 12 The graph shows the total antioxidant capacity of Fe / Cu-MOFs(1:2)-72 aqueous solutions of different concentrations (0.5 mg / ml, 0.25 mg / ml, 0.125 mg / ml and 0.0625 mg / ml) prepared in Example 9. Detailed Implementation
[0033] The present invention will be further described below with reference to the embodiments, but the present invention is not limited to the following embodiments.
[0034] Example 1
[0035] A method for preparing bimetallic MOFs with photothermal and antioxidant effects, using Fe and Cu as central ions and naphthalimide (NDI) grafted with an aminotriazole group as a DBPT organic ligand, is synthesized via a solvothermal method; specifically, the following steps are included:
[0036] S1. Dissolve 536 mg of 1,4,5,8-naphthalenetetracarboxylic acid dianhydride (NTCDA) and 353 mg of 4-amino-1,2,4-triazole (4-AT) in 30 ml of N,N-dimethylamide (DMF) to obtain a mixed solution. Sonicate and stir until homogeneous. React at 400 rpm and 150 °C in an oil bath for 8-12 h. After the reaction is terminated, add deionized water until the precipitate is completely formed. Filter and wash to obtain the DBPT ligand. The reaction formula is shown below:
[0037]
[0038] S2. Weigh 150 mg DBPT ligand, 100 mg anhydrous FeCl3, and 50 mg anhydrous Cu(NO3)2 (the mass ratio of FeCl3 to Cu(NO3)2 is 1:0.5). Measure 200 μl of fluoroboric acid (HBF4) and add it to 30 ml of DMF to obtain a reaction solution. Sonicate and stir the reaction solution until completely dissolved. Then transfer it to a glass vial and place it in a stainless steel high-pressure reactor. React at 120 °C for 24 h. Cool to room temperature. The obtained product is denoted as Fe / Cu-MOFs(1:0.5)-24.
[0039] S3. The obtained reaction product was centrifuged at 2000 rpm and washed three times with DMF and anhydrous ethanol, respectively. It was then vacuum dried at 85 °C for 24 h to obtain Fe / Cu-MOFs; its morphology is as follows. Figure 1 As shown, it has a needle-like structure; its photothermal effect is similar to that of Example 9.
[0040] Example 2
[0041] The only difference between this embodiment and Example 1 is that the reaction time in step S2 is 48 hours; all other steps are the same as in Example 1. The product obtained in this embodiment is denoted as Fe / Cu-MOFs(1:0.5)-48, and its morphology is as follows: Figure 2 As shown, it exhibits a needle-like structure similar to Fe / Cu-MOFs(1:0.5)-24; its photothermal effect is similar to that of Example 9.
[0042] Example 3
[0043] The only difference between this embodiment and Example 1 is that the reaction time in step S2 is 72 hours; all other steps are the same as in Example 1. The product obtained in this embodiment is denoted as Fe / Cu-MOFs(1:0.5)-72, and its morphology is as follows: Figure 3 As shown, it exhibits a needle-like structure similar to Fe / Cu-MOFs(1:0.5)-24; its photothermal effect is similar to that of Example 9.
[0044] Example 4
[0045] The difference between this embodiment and Example 1 is that in step S2, 100 mg of anhydrous FeCl3 and 100 mg of anhydrous Cu(NO3)2 are used (the mass ratio of FeCl3 to Cu(NO3)2 is 1:1). All other steps are consistent with Example 1. The product obtained in this embodiment is denoted as Fe / Cu-MOFs(1:1)-24, and its morphology is as follows... Figure 4 As shown in the figure, the synthesized Fe / Cu-MOFs exhibit a fine needle-like cluster structure, with a more pronounced bouquet-like structure. Its photothermal effect is similar to that of Example 9.
[0046] Example 5
[0047] The difference between this embodiment and Example 4 is that in step S2, 100 mg of anhydrous FeCl3 and 100 mg of anhydrous Cu(NO3)2 (the mass ratio of FeCl3 to Cu(NO3)2 is 1:1), and the reaction time is 48 h. All other steps are consistent with Example 1. The product obtained in this embodiment is denoted as Fe / Cu-MOFs(1:1)-48, and its morphology is as follows... Figure 5 As shown, it exhibits a fine needle-like cluster and bouquet-like structure similar to Fe / Cu-MOFs(1:1)-24. Its photothermal effect is similar to that of Example 9.
[0048] Example 6
[0049] The difference between this embodiment and Example 4 is that in step S2, 100 mg of anhydrous FeCl3 and 100 mg of anhydrous Cu(NO3)2 (the mass ratio of FeCl3 to Cu(NO3)2 is 1:1) are used, and the reaction time is 72 h. All other steps are consistent with Example 1. The product obtained in this embodiment is denoted as Fe / Cu-MOFs(1:1)-72, and its morphology is as follows... Figure 6 As shown, it exhibits a fine needle-like cluster and bouquet-like structure similar to Fe / Cu-MOFs(1:1)-24. Its photothermal effect is similar to that of Example 9.
[0050] Example 7
[0051] The only difference between this embodiment and Example 1 is the addition of 100 mg anhydrous FeCl3 and 200 mg anhydrous Cu(NO3)2 in step S2 (the mass ratio of FeCl3 to Cu(NO3)2 is 1:2). All other steps are identical to those in Example 1. The product obtained in this embodiment is denoted as Fe / Cu-MOFs(1:2)-24, and its morphology is as follows: Figure 7 As shown, the synthesized Fe / Cu-MOFs exhibit needle-like clusters and a relatively obvious banded structure. Their photothermal effect is similar to that of Example 9.
[0052] Example 8
[0053] The difference between this embodiment and Example 1 is that in step S2, 100 mg of anhydrous FeCl3 and 200 mg of anhydrous Cu(NO3)2 (the mass ratio of FeCl3 to Cu(NO3)2 is 1:2), and the reaction time is 48 h. All other steps are consistent with Example 1. The product obtained in this embodiment is denoted as Fe / Cu-MOFs(1:2)-48, and its morphology is as follows... Figure 8 As shown, it exhibits a needle-like and banded structure similar to Fe / Cu-MOFs(1:2)-24. Its photothermal effect is similar to that of Example 9.
[0054] Example 9
[0055] The difference between this embodiment and Example 1 is that in step S2, 100 mg of anhydrous FeCl3 and 200 mg of anhydrous Cu(NO3)2 (the mass ratio of FeCl3 to Cu(NO3)2 is 1:2), and the reaction time is 72 h. All other steps are the same as in Example 1. The product obtained in this embodiment is denoted as Fe / Cu-MOFs(1:2)-72, and its morphology is as follows... Figure 9 As shown, it exhibits needle-like and banded structures similar to Fe / Cu-MOFs(1:2)-24; Figure 10 The image shows the XPS spectrum of Fe / Cu-MOFs(1:2)-72. It can be seen from the image that Fe and Cu coexist in the MOFs framework and are connected by nitrogen / oxygen ligands to form a bimetallic center. Figure 11 The temperature curve and thermal imaging of the Fe / Cu-MOFs(1:2)-72 aqueous solution prepared in Example 9 under 808nm laser irradiation are shown. As can be seen from the figure, Fe / Cu-MOFs(1:2)-72 exhibits excellent photothermal properties under 808nm laser irradiation and good photothermal cycle stability. The photothermal effect of Fe / Cu-MOFs prepared in Examples 1-9 is similar. Figure 12 The figure shows the total antioxidant capacity of Fe / Cu-MOFs with different concentrations prepared in Example 9. As can be seen from the figure, Fe / Cu-MOFs have significant antioxidant properties.
[0056] In summary, the Fe / Cu-MOFs prepared by this invention have a simple and easy synthesis process, the particles are distributed in clusters, and they have good photothermal properties and antioxidant capacity. They can be applied to various medical scenarios such as bacterial therapy and inflammatory microenvironment control.
[0057] The above description is merely a preferred embodiment of the present invention, and the scope of protection of the present invention is not limited thereto. Any simple changes or equivalent substitutions of the technical solutions that can be obviously obtained by those skilled in the art within the scope of the technology disclosed in the present invention shall fall within the scope of protection of the present invention.
Claims
1. A method for preparing bimetallic MOFs with photothermal and antioxidant effects, characterized in that, Using Fe and Cu as central ions, and NDI grafted with aminotriazole groups as organic ligands for DBPT, the method was synthesized via a solvothermal approach; specifically, the following steps were included: S1. 1,4,5,8-Naphthalenetetracarboxylic dianhydride and 4-amino-4H-1,2,4-triazole are dispersed in DMF and refluxed at 140-160℃ for 10-14 h to obtain the DBPT organic ligand; the structural formula of the DBPT organic ligand is as follows: S2. Add the DBPT organic ligand, anhydrous ferric chloride, anhydrous copper nitrate and fluoroboric acid obtained in step S1 to DMF to obtain a reaction solution. Sonicate and stir the reaction solution until completely dissolved. Place the resulting solution in a high-pressure reactor for heating reaction. After the reaction is completed, cool to room temperature. S3. After centrifuging the product obtained in step S2, wash and dry it to obtain Fe / Cu-MOFs.
2. The method for preparing bimetallic MOFs with photothermal and antioxidant effects according to claim 1, characterized in that, In step S1, the concentrations of 1,4,5,8-naphthotetracarboxylic dianhydride and 4-amino-4H-1,2,4-triazole in DMF are 11.8 g / L and 17.9 g / L, respectively.
3. The method for preparing bimetallic MOFs with photothermal and antioxidant effects according to claim 1, characterized in that, In step S1, after reflux reaction at 150℃ for 12h, the mixture was cooled to room temperature, deionized water and methanol were added to precipitate the product, and the precipitate was obtained by filtration. The precipitate was washed by alternating centrifugation three times with ethanol and deionized water at 8000 rpm, and then vacuum dried to obtain the DBPT organic ligand.
4. The method for preparing bimetallic MOFs with photothermal and antioxidant effects according to claim 1, characterized in that, In step S2, the reaction solution is sonicated for 10-20 minutes until the DBPT ligand, anhydrous ferric chloride, and anhydrous copper nitrate are fully dissolved. The mass ratio between anhydrous ferric chloride and anhydrous copper nitrate is 1:(0.5-2), and the volume ratio between DMF and fluoroboric acid is 150:
1.
5. The method for preparing bimetallic MOFs with photothermal and antioxidant effects according to claim 1, characterized in that, In step S2, the heating reaction temperature is 120℃ and the reaction time is 24-72h.
6. The method for preparing bimetallic MOFs with photothermal and antioxidant effects according to claim 1, characterized in that, In step S3, the product obtained after centrifugation is washed three times alternately with DMF and ethanol, and then vacuum dried at 85°C for 24 hours.
7. A bimetallic MOF with photothermal and antioxidant effects prepared by the preparation method according to any one of claims 1-6, wherein the bimetallic MOF has a needle-like structure.
8. The application of bimetallic MOFs with photothermal and antioxidant effects as described in claim 7 in the fields of antibacterial and anti-inflammatory applications.