Porous cerium-based metal organic framework microsphere with photo-thermal characteristic as well as preparation method and application of porous cerium-based metal organic framework microsphere

Abstract

The invention relates to a porous cerium-based metal organic framework microsphere with photo-thermal characteristics and a preparation method and application thereof, and the preparation method comprises the following steps: dispersing 1, 4, 5, 8-naphthalene tetracarboxylic dianhydride and 4-amino-4H-1, 2, 4-triazole in DMF, and carrying out a reflux reaction at 140-160 DEG C to obtain an NDI ligand; the preparation method comprises the following steps: fully dissolving an NDI ligand and cerium salt in DMF at room temperature, and then adding acetic acid to obtain a reaction solution; putting the reaction liquid into a high-pressure kettle, reacting at 120 DEG C for 72 hours, and cooling to room temperature; washing and centrifuging the product for multiple times to obtain a precipitate, and drying the precipitate to obtain Ce-MOFs MS. The method is simple and easy to operate, the obtained Ce-MOFs MS is spherically distributed, the surface layer is of a layered hole structure, and the Ce-MOFs MS has good photo-thermal performance; when the material is applied to drug loading, photo-thermal-chemotherapy space-time synergistic treatment can be realized, and drug delivery can be cooperated to be applied to the fields of tumor treatment, bacterial biofilm infection and the like.

Description

Technical Field

[0001] This invention belongs to the field of nanobiotechnology, specifically relating to a porous cerium-based metal-organic framework microsphere with photothermal properties, its preparation method, and its application. Background Technology

[0002] Photothermal therapy (PTT) is a novel treatment strategy that converts light energy into heat energy using photothermal conversion materials, thereby killing diseased tissue through localized heating. It shows great promise in areas such as tumor ablation, antibacterial therapy, and wound repair. However, PTT alone has limitations, including insufficient removal of deep lesions and low treatment efficiency. Combination therapy can improve treatment efficiency and reduce adverse reactions. Traditional photothermal materials (such as gold nanorods and black phosphorus) are difficult to synergize with other treatment modalities (such as drug delivery) due to their dense structure and limited functionality. Therefore, developing novel multifunctional synergistic materials has become an important research direction in the field of photothermal therapy.

[0003] Metal-organic frameworks (MOFs) are porous crystalline materials formed by the self-assembly of metal nodes and organic ligands. Their high specific surface area, tunable pore size, and surface functionalization capabilities offer new avenues for the development of photothermal materials. By selecting ligands (such as electron-rich conjugated molecules) and modulating metal nodes, the light absorption and heat conversion efficiency of MOFs can be significantly improved. While there is considerable research on materials with single photothermal properties, the preparation and biomedical applications of cerium-based metal-organic framework microspheres (Ce-MOFs MS) possessing both drug loading capacity and photothermal properties have not yet been reported. Summary of the Invention

[0004] The purpose of this invention is to provide a porous cerium-based metal-organic framework microsphere with photothermal properties, its preparation method and application. The preparation process is simple and easy to operate. The prepared Ce-MOFs MS are spherically distributed with a layered porous structure on the surface, which can have good photothermal properties. When applied to drug loading, it can realize photothermal-chemotherapy spatiotemporal synergistic therapy.

[0005] To achieve the above-mentioned objectives, the technical solution adopted by this invention is as follows: This invention provides a method for preparing porous Ce-MOFs MS with photothermal effect. The material uses cerium as the central ion and NDI-grafted aminotriazole groups as organic ligands, and is synthesized via a solvothermal method; the method includes the following steps: S1. 1,4,5,8-naphthalenetetracarboxylic dianhydride and 4-amino-4H-1,2,4-triazole are dispersed in DMF and refluxed at 140-160 °C for 10-14 h to obtain the NDI ligand; the structural formula of the NDI ligand is as follows: ; S2. Dissolve the NDI ligand and cerium salt obtained in step S1 in DMF at room temperature, then add acetic acid to obtain a reaction solution; then place the reaction solution in an autoclave and react at 110-120 °C for 48-72 h, and cool to room temperature. S3. The product obtained in step S2 is washed and centrifuged multiple times to obtain a precipitate. The precipitate is dried to obtain Ce-MOFsMS.

[0006] 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.

[0007] Further, in step S1, after reflux reaction at 150 °C for 12 h, 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 dried under vacuum to obtain NDI ligand.

[0008] Preferably, in step S2, the cerium salt is (NH4)2Ce(NO3)6; the concentration of (NH4)2Ce(NO3)6 is 0.0875 mol / L, the molar ratio of (NH4)2Ce(NO3)6 to NDI ligand is 1:1, and the volume ratio of DMF to acetic acid is 6.7:1.

[0009] Preferably, in step S2, the reaction is carried out at 120°C for 72 h, and the reaction solution is sonicated for 10-20 min until the NDI ligand and cerium salt are fully dissolved.

[0010] Preferably, in step S3, the product obtained in step S2 is washed three times with DMF, then washed three times with methanol, and then vacuum dried at 85 °C for 12 h.

[0011] To achieve the above-mentioned objectives, the present invention also provides porous cerium-based metal-organic framework microspheres with photothermal properties prepared by the above-mentioned preparation method.

[0012] To achieve the above-mentioned objectives, the present invention also provides the application of the above-mentioned porous cerium-based metal-organic framework microspheres with photothermal properties in drug loading.

[0013] Compared with the prior art, the beneficial effects of the present invention are as follows: This invention utilizes NDI as an organic ligand to construct a method for preparing cerium-based metal-organic framework microspheres (Ce-MOFs MS) with photothermal properties by binding with Ce ions. Naphthalimide (NDI) possesses a low LUMO energy level and an electron-deficient conjugated framework, making it a highly efficient electron acceptor that significantly enhances the capture ability of photogenerated electrons, resulting in excellent photocatalytic properties. The prepared Ce-MOFs MS exhibits photothermal properties under 808 nm near-infrared (NIR) excitation. Its lamellar porous structure allows for drug loading, and the thermal effect expands the intervascular space of tissues, promoting deep drug penetration. This enables spatiotemporal synergistic photothermal-chemotherapy therapy, showing potential applications in tumor treatment, antibacterial therapy, and wound repair. Attached Figure Description

[0014] Figure 1 Scanning electron microscope (SEM) images of Ce-MOFs prepared in Example 1; (A) 100 μm, (B) 50 μm; Figure 2 The image shows a scanning electron microscope (10 μm) image of Ce-MOFs prepared in Example 2. Figure 3 The image shows a scanning electron microscope (10 μm) of the Ce-MOFs prepared in Example 3. Figure 4 The image shows a scanning electron microscope (40 μm) image of Ce-MOFs prepared in Example 4. Figure 5 Temperature curves and thermal images of Ce-MOFs MS aqueous solutions prepared in Example 1 under 808 nm laser irradiation; (A) Ce-MOFs MS aqueous solutions of different concentrations (2 mg / mL, 1 mg / mL, 0.5 mg / mL) and ddH2O at 1 W / cm 2 Temperature curves at (B) 1 mg / mL Ce-MOFs MS and ddH2O at 1 W / cm 2 Thermal imaging at power densities, (C) 1 mg / mL Ce-MOFs MS at different power densities (2 W / cm²) 2 1 W / cm 2 0.5 W / cm 2 Temperature curves of 1 mg / mL Ce-MOFs at 1 W / cm², and MS of 1 mg / mL Ce-MOFs at 1 W / cm². 2 Temperature cycling curves below. Detailed Implementation

[0015] The present invention will be further described in detail below with reference to the accompanying drawings and specific examples.

[0016] The 1,4,5,8-naphthocarboxylic anhydride, 4-amino-1,2,4-triazole, and cerium ammonium nitrate used in the following examples are all commercially available.

[0017] Example 1 A method for preparing porous cerium-based metal-organic framework microspheres with photothermal properties, using cerium as the central ion and NDI-grafted aminotriazole groups as organic ligands, is synthesized via a solvothermal method; specifically, the method includes the following steps: S1. 353 mg of 4-amino-1,2,4-triazole and 536 mg of 1,4,5,8-naphthalenetetracarboxylic anhydride were dispersed in 30 mL of DMF and refluxed at 150 °C for 12 h. After cooling to room temperature, deionized water and methanol were added to precipitate the product, and the precipitate was obtained by filtration. The precipitate was washed three times by alternating centrifugation with ethanol and deionized water at 8000 rpm, and then dried under vacuum to obtain the NDI ligand. The reaction formula is shown below: S2. Dissolve 140 mg NDI ligand and 192 mg (NH4)2Ce(NO3)6 in 4 mL DMF, then add 602 μL acetic acid, and sonicate for 10-20 min until completely dissolved to obtain a reaction solution; place the reaction solution in an autoclave and react at 120 ℃ for 72 h, then cool to room temperature; S3. The product obtained in step S2 was washed three times with DMF, then three times with methanol, and then vacuum dried at 85 °C for 12 h to obtain Ce-MOFs MS. Its morphology is shown in [Figure 1]. Figure 1 The scanning electron microscope image shows that the synthesized Ce-MOFs MS are spherically distributed with a layered porous structure on the surface.

[0018] Figure 5 The temperature curve and thermal image of the Ce-MOFs MS aqueous solution prepared in Example 1 under 808 nm laser irradiation are shown. Figure 5 As can be seen, Ce-MOFs MS exhibits excellent photothermal properties under 808 nm laser irradiation and good photothermal cycling stability.

[0019] Example 2 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 morphology of the product obtained in this embodiment is shown in [reference needed]. Figure 2 The scanning electron microscope image shows that the synthesized Ce-MOFs MS has a porous structure; its photothermal effect is similar to that of Example 1.

[0020] Example 3 The only difference between this embodiment and Example 1 is that the reaction temperature in step S2 is 110℃ and the reaction time is 72h; all other steps are the same as in Example 1. The morphology of the product obtained in this embodiment is shown in [reference needed]. Figure 3 The scanning electron microscope image shows that the synthesized Ce-MOFs MS has a porous structure; its photothermal effect is similar to that of Example 1.

[0021] Example 4 The only difference between this embodiment and Example 1 is that the reaction temperature in step S2 is 110°C and the reaction time is 48 hours; all other steps are the same as in Example 1. The morphology of the product obtained in this embodiment is shown in [reference needed]. Figure 4 The scanning electron microscope image shows that the synthesized Ce-MOFs MS has a porous structure; its photothermal effect is similar to that of Example 1.

[0022] In summary, the Ce-MOFs prepared by this invention have a simple and easy-to-operate MS synthesis process, the particles are spherically distributed, the surface has a layered porous structure, and they have good photothermal properties. When applied to drug loading, they can achieve photothermal-chemotherapy spatiotemporal synergistic treatment.

[0023] 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 porous cerium-based metal-organic framework microspheres with photothermal properties, characterized in that, Using cerium as the central ion and NDI grafted with an aminotriazole group as the organic ligand, the synthesis was carried out via a solvothermal method; specifically, the following steps were included: S1. 1,4,5,8-naphthalenetetracarboxylic dianhydride and 4-amino-4H-1,2,4-triazole were dispersed in DMF and refluxed at 140-160℃ for 10-14 h to obtain the NDI ligand; the structural formula of the NDI ligand is as follows: ; S2. Dissolve the NDI ligand and cerium salt obtained in step S1 in DMF at room temperature, then add acetic acid to obtain a reaction solution; then place the reaction solution in an autoclave and react at 110-120℃ for 48-72 h, and cool to room temperature. S3. The product obtained in step S2 is washed and centrifuged multiple times to obtain a precipitate. The precipitate is dried to obtain Ce-MOFs MS.

2. The method for preparing porous cerium-based metal-organic framework microspheres with photothermal properties 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 porous cerium-based metal-organic framework microspheres with photothermal properties according to claim 1, characterized in that, In step S1, the product was refluxed at 150 °C for 12 h and then 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 three times by alternating centrifugation with ethanol and deionized water at 8000 rpm, and then dried under vacuum to obtain the NDI ligand.

4. The method for preparing porous cerium-based metal-organic framework microspheres with photothermal properties according to claim 1, characterized in that, In step S2, the cerium salt is (NH4)2Ce(NO3)6; the molar ratio of (NH4)2Ce(NO3)6 to NDI ligand is 1:1, the concentration of (NH4)2Ce(NO3)6 is 0.0875 mol / L; and the volume ratio of DMF to acetic acid is 6.7:

1.

5. The method for preparing porous cerium-based metal-organic framework microspheres with photothermal properties according to claim 1, characterized in that, In step S2, the reaction is carried out at 120°C for 72 h, and the reaction solution is sonicated for 10-20 min until the NDI ligand and cerium salt are fully dissolved.

6. The method for preparing porous cerium-based metal-organic framework microspheres with photothermal properties according to claim 1, characterized in that, In step S3, the product obtained in step S2 is washed three times with DMF, then three times with methanol, and then vacuum dried at 85 °C for 12 h.

7. A porous cerium-based metal-organic framework microsphere with photothermal properties prepared by the preparation method according to any one of claims 1-6.

8. The application of porous cerium-based metal-organic framework microspheres with photothermal properties as described in claim 7 in drug loading.

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