A magnesium-cerium-gallic acid metal organic framework and preparation and application thereof

Abstract

The application relates to a magnesium-cerium-gallic acid metal organic framework and preparation and application thereof, and the metal organic framework material is prepared by the following method: (1) dissolving a soluble cerium salt and a soluble magnesium salt in water, then adding gallic acid, and stirring to form a milky white colloidal solution; (2) adjusting the pH of the milky white colloidal solution obtained in step (1) to make it change from a milky white suspension to a dark brown solution; (3) transferring the obtained dark brown solution into a reaction kettle, heating and reacting, and then separating, washing and drying the obtained reaction product to obtain the target product, a magnesium-cerium-gallic acid metal organic framework. 2+ Adjusting an immune microenvironment and accelerating tissue regeneration.

Description

Technical Field

[0001] This invention belongs to the field of metal-organic framework technology, and relates to a magnesium-cerium-gallic acid metal-organic framework and its preparation and application. Background Technology

[0002] Metal-organic frameworks (MOFs) possess high specific surface area, well-developed porosity, abundant catalytic sites, and favorable biodegradability, thus attracting widespread research in materials science, catalysis, energy, and biomedicine. MOFs with diverse properties and functions can be synthesized through screening metal ions and organic ligands. In recent years, the field of biorepair materials in pathological environments has garnered significant attention. The pathological microenvironment can adversely affect tissue regeneration through various pathways, including ROS overexpression and inflammatory responses. Therefore, designing a novel, multifunctional MOF material capable of scavenging ROS and releasing functional ions or active factors to regulate the immune microenvironment and promote tissue regeneration is of great research importance.

[0003] Due to the variability of valence states of cerium (Ce), 3+ Ce 4+ Cerium oxide (CeO) possesses strong redox properties. Therefore, cerium oxide and cerium-containing materials exhibit unique ROS scavenging capabilities in the biological microenvironment. Gallic acid, a polyphenolic organic compound, possesses various biological activities such as free radical scavenging, antioxidant, and anti-inflammatory effects. Magnesium (Mg) is the fourth most abundant element in the human body and a key cofactor for ATP and many enzymes, playing a crucial role in many basic biochemical reactions. Studies have shown that Mg ion deficiency can induce oxidative stress, inhibit cell division, and accelerate telomere wear, thereby accelerating the aging of endothelial cells and fibroblasts. Appropriate supplementation of a certain amount of Mg ions can induce macrophage polarization from the M1 pro-inflammatory phenotype to the M2 anti-inflammatory phenotype, regulating the immune microenvironment and thus accelerating tissue regeneration. However, currently, there is no technology that cleverly combines magnesium ions, cerium ions, and gallic acid to simultaneously exert antioxidant effects and regulate the pathological microenvironment. Furthermore, most current methods for preparing Ce-MOFs are cumbersome, employing solvent-based preparation processes that use toxic and harmful organic solvents. Therefore, it is of great significance to find a simpler and greener method to obtain more functional biological Ce-Mg-MOF. Summary of the Invention

[0004] The purpose of this invention is to provide a magnesium-cerium-gallic acid metal-organic framework, its preparation and application, which can achieve efficient removal of hydrogen peroxide, dynamically adjust the acidic microenvironment to a weakly alkaline pH, and simultaneously release Mg. 2+ .

[0005] The objective of this invention can be achieved through the following technical solutions:

[0006] One of the technical solutions of the present invention provides a method for preparing a magnesium-cerium-gallic acid metal-organic framework, comprising the following steps:

[0007] (1) Dissolve soluble cerium salt and soluble magnesium salt in water, then add gallic acid and stir to form a milky white colloidal solution;

[0008] (2) Adjust the pH of the milky white colloidal solution obtained in step (1) to change it from a milky white suspension to a dark brown solution;

[0009] (3) The resulting dark brown solution was transferred to a reaction vessel and heated to react. The resulting reaction product was separated, washed, and dried to obtain the target product, magnesium-cerium-gallic acid metal-organic framework.

[0010] Furthermore, in step (1), the soluble cerium salt is cerium chloride.

[0011] Furthermore, in step (1), the soluble magnesium salt is magnesium chloride.

[0012] Furthermore, in step (1), the mass ratio of soluble cerium salt, soluble magnesium salt and gallic acid is (0.05~0.2):(0.8~0.95):3.8.

[0013] Furthermore, in step (1), the reagent used to adjust the pH is a KOH solution with a concentration of 8-12 mol / L.

[0014] Furthermore, the pH was adjusted to 7-9.

[0015] Furthermore, in step (3), the heating reaction is carried out at a temperature of 110–130°C for 18–30 h.

[0016] Furthermore, in step (3), the drying temperature is 50-70℃.

[0017] The second technical solution of the present invention provides a magnesium-cerium-gallic acid metal-organic framework, which is prepared by any of the preparation methods described above.

[0018] The third technical solution of the present invention provides an application of magnesium-cerium-gallic acid metal-organic framework in the preparation of tissue engineering materials and regenerative medicine materials under pathological conditions.

[0019] Compared with the prior art, the present invention has the following advantages:

[0020] (1) The obtained Ce-Mg-MOF material can achieve efficient removal of ROS in the microenvironment, while simultaneously releasing Mg.2+ This suggests the potential to regulate the immune microenvironment and accelerate tissue regeneration.

[0021] (2) Ce-Mg-MOF materials are synthesized through a simple metal-organic self-assembly process, which is easy to operate and implement. Attached Figure Description

[0022] Figure 1 SEM morphology and elemental distribution maps of different MOFs.

[0023] Figure 2 SEM images and elemental distribution diagrams of the MOF materials prepared in Example 2 and Comparative Example 1.

[0024] Figure 3 XRD patterns of different MOF materials.

[0025] Figure 4 The graph shows the efficiency of the MOF material prepared in Example 2 in removing H2O2 from the solution.

[0026] Figure 5 The image shows the XPS results of the MOF material in Example 2.

[0027] Figure 6 This is a graph showing the effect of adjusting the pH of the solution using the MOF material prepared in Example 2.

[0028] Figure 7 The image shows the effect of sustained magnesium ion release from the MOF material prepared in Example 2.

[0029] Figure 8 The biocompatibility of the MOF material prepared in Example 2 is shown. Detailed Implementation

[0030] The present invention will now be described in detail with reference to the accompanying drawings and specific embodiments. These embodiments are based on the technical solution of the present invention and provide detailed implementation methods and specific operating procedures. However, the scope of protection of the present invention is not limited to the following embodiments.

[0031] In the following embodiments, unless otherwise specified, the raw materials or processing techniques are conventional commercially available raw materials or conventional processing techniques in the art.

[0032] Example 1:

[0033] 0.05 g of cerium chloride and 0.95 g of magnesium chloride were dissolved in 50 mL of deionized water. After complete dissolution, 3.8 g of gallic acid was added, and the mixture was stirred for 10 min. Then, 10 M KOH solution was added to adjust the pH to 8, and the mixture was transferred to a reaction vessel. The reaction was carried out at 120 °C for 24 h. After naturally cooling to room temperature, the mixture was centrifuged, washed, and dried to obtain the final product Mg-Ce0.05-MOF. Figure 1 SEM characterization results showed that the Mg-Ce0.05-MOF prepared by this method was a stacked nanosheet, and the elemental distribution results showed that Mg and a small amount of Ce were uniformly distributed in the MOF. Figure 3 The XRD results showed its specific MOF crystal structure.

[0034] Example 2:

[0035] 0.1 g of cerium chloride and 0.9 g of magnesium chloride were dissolved in 50 mL of deionized water. After complete dissolution, 3.8 g of gallic acid was added, and the mixture was stirred for 10 min. Then, 10 M KOH solution was added to adjust the pH to 8, and the mixture was transferred to a reaction vessel. The reaction was carried out at 120 °C for 24 h. After naturally cooling to room temperature, the product was centrifuged, washed, and dried to obtain the final product Mg-Ce0.1-MOF. Figure 1 , Figure 2 SEM characterization results revealed that the prepared MOF exhibited a flower-like structure with a diameter of approximately 10 μm. Mg and Ce ions were uniformly distributed within the MOF, and... Figure 3 The XRD results of this MOF show that its crystal structure is consistent with that of the MOF obtained in Example 1. Figure 4 This demonstrates that the MOF possesses excellent H2O2 removal capabilities, with a removal rate exceeding 60% after 12 hours. Figure 5 XPS results confirmed the coexistence of Ce in MOF. 3+ Ce 4+ In addition, by Figure 6 It was found that this MOF also exhibited the ability to dynamically regulate pH. Under initial pH conditions of 3-7, it could adjust the pH to a slightly alkaline level of 7-8 within 3 hours. This is of great significance for regulating the tissue acid-base microenvironment under pathological conditions, enabling the rapid construction of a slightly alkaline microenvironment conducive to osteogenic growth. 0.1 wt% of the MOF in deionized water at 37°C achieved complete release of Mg ions in approximately 14 days. Figure 7 This means that the MOF material prepared by this invention can gradually release Mg ions during the tissue regeneration period in vivo, regulate the Mg ion level in the microenvironment, and thus promote tissue regeneration.

[0036] Furthermore, to demonstrate the application potential of the novel Mg-Ce-MOF in tissue regeneration, the biocompatibility of Mg-Ce0.1-MOF was investigated using rat bone mesenchymal stem cells (BMSCs). Cell numbers at 0.1% concentrations for 1, 4, and 7 days were measured using a CCK-8 assay. Figure 8 The results showed that there was no statistically significant difference between the MOF and the control group, indicating good biocompatibility.

[0037] Example 3:

[0038] Dissolve 0.2 g of cerium chloride and 0.8 g of magnesium chloride in 50 mL of deionized water. After complete dissolution, add 3.8 g of gallic acid, stir for 10 min, add 10 M KOH solution, adjust the pH to 8, and transfer to a reaction vessel. React at 120 °C for 24 h. After naturally cooling to room temperature, centrifuge, wash and dry to obtain the final product Mg-Ce0.2-MOF. Figure 1 SEM characterization results showed that the assembly morphology of the MOF changed with increasing Ce ion content, becoming an irregular sheet-like structure. Meanwhile, Figure 3 The XRD results showed that its MOF characteristic peaks were weakened.

[0039] Comparative Example 1:

[0040] Compared with Example 2, most of the results are the same, except that the addition of magnesium chloride is omitted and the resulting product is denoted as Ce-MOF. Figure 1 SEM images in the middle section characterized the rod-like structure of Ce-MOF. Furthermore, EDX mapping results showed that the Ce-MOF had a higher Ce content compared to the Mg-Ce0.1-MOF in Example 2. Additionally, according to... Figure 3 The XRD characterization results of Examples 1-3 and Comparative Example 1 show that the addition of Mg ions is beneficial to the crystal structure construction of Ce-Mg-MOF. Among them, the Mg-Ce0.05-MOF with the highest Mg ion content has the best crystallinity, while the Ce-MOF prepared in Comparative Example 1 has poor crystallinity.

[0041] The above description of the embodiments is provided to enable those skilled in the art to understand and use the invention. It will be apparent to those skilled in the art that various modifications can be made to these embodiments, and the general principles described herein can be applied to other embodiments without inventive effort. Therefore, the present invention is not limited to the above embodiments, and any improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the invention should be within the protection scope of the present invention.

Claims

1. A method for preparing a magnesium-cerium-gallic acid metal-organic framework, characterized in that, Includes the following steps: (1) Dissolve soluble cerium salt and soluble magnesium salt in water, then add gallic acid and stir to form a milky white colloidal solution; (2) Adjust the pH of the milky white colloidal solution obtained in step (1) to change it from a milky white colloidal solution to a dark brown solution; (3) The resulting dark brown solution was transferred to a reaction vessel and heated to react. The resulting reaction product was separated, washed, and dried to obtain the target product, magnesium-cerium-gallic acid metal-organic framework. In step (1), the soluble cerium salt is cerium chloride; In step (1), the soluble magnesium salt is magnesium chloride; In step (1), the mass ratio of soluble cerium salt, soluble magnesium salt and gallic acid is (0.05~0.2):(0.8~0.95):3.8; In step (2), the pH is adjusted to 7-9.

2. The method for preparing a magnesium-cerium-gallic acid metal-organic framework according to claim 1, characterized in that, In step (2), the reagent used to adjust the pH is KOH solution with a concentration of 8-12 mol / L.

3. The method for preparing a magnesium-cerium-gallic acid metal-organic framework according to claim 1, characterized in that, In step (3), the temperature of the heating reaction is 100~150℃ and the time is 12~36h.

4. The method for preparing a magnesium-cerium-gallic acid metal-organic framework according to claim 1, characterized in that, In step (3), the drying temperature is 50-70℃.

5. A magnesium-cerium-gallic acid metal-organic framework, which is prepared by the preparation method according to any one of claims 1-4.

6. The application of the magnesium-cerium-gallic acid metal-organic framework as described in claim 5 in the preparation of tissue engineering materials and regenerative medicine materials under pathological conditions.

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