Two-dimensional metal polyphenol framework material as well as preparation method and application thereof

Abstract

The invention relates to a two-dimensional metal polyphenol framework material as well as a preparation method and application thereof. The framework material is a two-dimensional sheet structure material formed by coordination of metal ions and flavonoid polyphenol molecules. Wherein the molar ratio of the metal ions to the flavonoid polyphenol is (5-20): 1; the particle size of the two-dimensional metal polyphenol framework material is 200 to 800 nm; and the thickness of the two-dimensional metal polyphenol framework material is 2 to 10 nm. Compared with the prior art, the two-dimensional metal polyphenol framework material prepared by the invention is simple, convenient and green in synthesis process, and does not need high temperature, high pressure and toxic organic solvents; the material has excellent biocompatibility and physiological stability and is suitable for biomedical application; the specific surface area is high, and drug loading and functional modification are facilitated; the structure, the size and the composition are adjustable, the flavonoid polyphenol endows the compound with various biological activities such as oxidation resistance and inflammation resistance, and the compound has wide potential in the fields of drug delivery, biological imaging, catalysis, energy environment and the like.

Description

Technical Field

[0001] This invention relates to the field of nanomaterials technology, specifically to a two-dimensional metal polyphenol framework material, its preparation method, and its application. Background Technology

[0002] In recent years, two-dimensional (2D) materials have attracted much attention due to their unique physical, chemical, and electronic properties. Traditional 2D materials such as graphene and transition metal dichalcogenides (TMDs) have shown application potential in many fields, but their preparation difficulty, functional limitations, and biocompatibility restrict further applications. Metal-organic frameworks (MOFs), as a class of porous crystalline materials, possess high specific surface area and structural tunability, but the synthesis of traditional MOFs often requires organic solvents, and their stability (especially in aqueous or physiological environments) is often insufficient, limiting their application in biomedical and other fields.

[0003] Flavonoid polyphenols are a class of natural products widely found in plants. They possess multiple phenolic hydroxyl groups and can react with various metal ions (such as Fe). 3+ Cu 2+ Zn 2+ Flavonoids (e.g., tannins) coordinate with each other. Compared to small polyphenol molecules such as tannins, flavonoids exhibit greater structural diversity and bioactivity, including antioxidant, anti-inflammatory, antitumor, and cardiovascular protective effects. Constructing metal-polyphenol frameworks (MPNs) using flavonoids as ligands not only allows for green and mild synthesis conditions but also endows MPNs with the bioactivity of flavonoids, expanding their applications in the biomedical field.

[0004] Chinese invention patent CN114099688A discloses a method for preparing micron-sized particles based on the coordination of flavonoid polyphenols and zinc ions. These micron-sized particles, formed by the coordination of zinc ions and flavonoid polyphenols, can achieve high hydrogen peroxide and free radical scavenging rates in vitro and can clear highly expressed ROS in inflammatory cells, thus treating inflammatory bowel disease. However, the product obtained by this patent is a spherical micron-sized particle. Compared to two-dimensional structures, the spherical complex of metal ions and flavonoid polyphenols only exposes the active sites on the surface of the spheres; the internal metal / polyphenol is encapsulated, making it difficult to contact the substrate and adhere flexibly to the surface of tissues or cells, resulting in poor drug loading capacity.

[0005] Two-dimensional metal-flavonoid polyphenol frameworks (2D MFPNSs) are a novel type of two-dimensional material formed by the self-assembly of metal ions and flavonoid polyphenol ligands via coordination bonds. This material combines the properties of metal ions (such as catalytic activity and magnetism) with the advantages of flavonoid polyphenols (such as biocompatibility, diverse bioactivities, and ease of modification), exhibiting characteristics such as large specific surface area, tunable structure, and abundant surface functional groups. This novel material holds great promise for applications in drug delivery, bioimaging, antibacterial applications, tissue engineering, catalysis, sensing, environmental protection, and energy storage. Particularly in the biomedical field, 2D MFPNSs are expected to overcome the limitations of traditional two-dimensional materials and MOFs, becoming a new class of biomaterials with significant application value.

[0006] Compared to previously reported metal-polyphenol networks (MPNs) based on small molecule polyphenols (such as tannic acid), two-dimensional MPNs (2D MFPNs) based on flavonoid polyphenols not only inherit the advantages of MPNs (green synthesis, biocompatibility), but also have greater potential for biomedical applications and richer functions due to the stronger biological activity (antioxidant, antitumor, etc.) and more diverse structures (different flavonoid skeletons) of flavonoid compounds themselves.

[0007] Chinese invention patent CN119139259A discloses a metal-organic coordination network (MOFN). The method involves dissolving copper acetate and polyphenols separately in deionized water or dimethyl sulfoxide to form copper acetate and polyphenol solutions, respectively. The copper acetate solution is then added dropwise to the polyphenol solution, and the mixture is heated while purging with nitrogen to obtain a reaction mixture. The reaction mixture is then centrifuged to obtain a precipitated metal-organic coordination network. This metal-organic coordination network can be used to prepare materials that target and kill hypoxic tumor cells. However, the method used in this patent for preparing the metal-polyphenol network is complex, and the resulting metal-polyphenol network consists of uniform spherical nanoparticles, not 2D MFPNS.

[0008] Therefore, developing methods for preparing novel two-dimensional metal-flavonoid polyphenol framework materials, studying the relationship between their structure and properties, and exploring their applications are of great scientific significance and practical value. Summary of the Invention

[0009] The purpose of this invention is to address the shortcomings of existing technologies by providing a two-dimensional metal-polyphenol framework material, its preparation method, and its applications. By extending a metal and flavonoid polyphenols in a two-dimensional plane, a two-dimensional metal-flavonoid polyphenol framework material with a particle size much larger than its thickness is obtained. This solves the problems of existing technologies that often use toxic organic solvents and have low specific surface areas due to spherical structures in the preparation of two-dimensional metal-flavonoid polyphenol framework materials. The preparation method of this invention is green and efficient, significantly reducing dependence on traditional high temperature, high pressure, and organic solvents. The prepared two-dimensional metal-polyphenol framework material not only has excellent biocompatibility but also exhibits good structural and functional stability under simulated physiological conditions. The introduced flavonoid natural product molecules with various bioactivities endow the material with antioxidant, anti-inflammatory, and anti-tumor bioactivities, giving it broad application prospects in the biomedical field.

[0010] To achieve the above objectives, the present invention adopts the following technical solution: The first aspect of the present invention is to provide a two-dimensional metal polyphenol framework material, wherein the framework material is a two-dimensional sheet-like structure material formed by the coordination of metal ions and flavonoid polyphenol molecules; Wherein, the molar ratio of the metal ions to the flavonoid polyphenols is 5-20:1; and the particle size of the two-dimensional metal polyphenol framework material is 200-800 nm; and the thickness of the two-dimensional metal polyphenol framework material is 2-10 nm.

[0011] Preferably, the molar ratio of the metal ion to the flavonoid polyphenol is 8.6:1.

[0012] Preferably, the particle size of the two-dimensional metal polyphenol framework material is 200-400 nm.

[0013] Preferably, the thickness of the two-dimensional metal polyphenol framework material is 2-5 nm.

[0014] Furthermore, the metal ion is selected from Fe. 2+ Cu 2+ Mn 2+ Zn 2+ Zr 4+ Al 3+ Any one of them.

[0015] The aforementioned metal ions form oxophilic Lewis acids in water, possessing multiple open orbitals and high coordination numbers. They can form thermodynamically stable two-dimensional network structures with functional active sites with flavonoid polyphenols through chelation. The specific principle is as follows: (1) The above metal ions are divided into two categories: hard acids (Mn) 2+ Zr 4+ Al 3+) and crosslinking acid (Fe 2+ Cu 2+ Zn 2+ Hard acid metal ions have high charge density and small radius, and strong bonding force with oxygen atoms. Boundary acid metal ions have extremely strong oxyphilicity. Therefore, these ions can form metal-oxygen coordination bonds with flavonoid polyphenols rich in phenolic hydroxyl and carbonyl groups with high bond energy. (2) These metal ions usually have a coordination number of 4, 6 or 8, allowing one metal ion to connect 2-3 flavonoid molecules at the same time. The metal ions act as network nodes, extending the organic ligands into a two-dimensional sheet structure. (3) The transition metals (Fe, Cu, Mn, Zn, Zr) have unfilled or empty d orbitals. Al has empty p orbitals and d orbitals. It can accept lone pairs of electrons from polyphenol oxygen atoms, resulting in ligand-metal charge transfer.

[0016] Furthermore, the flavonoid polyphenol molecules are selected from any one of catechin, quercetin, flavonoid, trihydroxyflavone, luteolin, and succinate.

[0017] The above-mentioned flavonoid polyphenols share the following common characteristics: (1) Sharing the “C6-C3-C6” benzo-γ-pyranone skeleton: a carbon skeleton with two benzene rings (A ring and B ring) connected by an oxygen-containing heterocycle (C ring). Due to the presence of the C2=C3 double bond, the whole molecule forms a large planar conjugated system. This “planar rigid structure” is the geometric basis for forming “two-dimensional” sheets. (2) Possessing a specific "bitent chelating pocket": The positions of oxygen atoms in the above-mentioned flavonoid polyphenol molecules are conducive to the chelation of metal ions, mainly including three types of oxygen atom sites: α-hydroxy ketone sites (quercetin, rosin, trihydroxyflavone), β-hydroxy ketone sites (quercetin, luteolin, apigenin), and catechol sites (quercetin, catechin, rosin, luteolin); (3) Multi-site binding ability: The above-mentioned flavonoid polyphenols can chelate two or more metal ions simultaneously as metal ligands; (4) π-π stacking: The above-mentioned flavonoid polyphenols are rich in aromatic rings and conjugated double bonds. In addition to the metal-ligand coordination bonds providing lateral connections, flavonoid polyphenol molecules can also achieve longitudinal stability through the π-π stacking of benzene rings. (5) Functionality: All of the above-mentioned flavonoid polyphenols have reducing and antioxidant properties.

[0018] Therefore, the above-mentioned metal ion Fe 2+ Cu 2+ Mn 2+ Zn 2+ Zr 4+ Al3+ It can be arbitrarily coordinated with the above-mentioned flavonoid polyphenol molecules, such as catechin, quercetin, rosin, trihydroxyflavone, luteolin, and succinin, to synthesize two-dimensional metal polyphenol framework materials with antioxidant properties.

[0019] A second aspect of the present invention is to provide a method for preparing a two-dimensional metal polyphenol framework material as described in any of the first aspects of the present invention, comprising the following steps: 1) Dissolve the metal salt in water to obtain a metal ion solution; 2) Dissolve flavonoid polyphenol molecules in an alcohol solvent to obtain a flavonoid polyphenol alcohol solution; 3) Add the metal ion solution dropwise to the phosphate buffer solution and stir until homogeneous to form a stable dispersion; 4) The flavonoid polyphenol alcohol solution was added dropwise to the dispersion system, and the reaction was stirred at room temperature. After post-treatment, the two-dimensional metal polyphenol framework material was obtained.

[0020] Furthermore, the metal salt is a hydrated metal salt, including any one of ferrous chloride tetrahydrate, copper chloride dihydrate, manganese chloride tetrahydrate, zinc nitrate hexahydrate, zirconium oxychloride octahydrate, and aluminum chloride hexahydrate.

[0021] Furthermore, in the metal ion solution, the concentration of the metal ion is 10-200 mmol / L.

[0022] Furthermore, the alcohol solvent includes either methanol or ethanol. Taking lacquer xanthophyll as an example, lacquer xanthophyll is a highly hydrophobic molecule. Methanol dissolves lacquer xanthophyll, achieving molecular-level dissolution of the ligands. At the same time, methanol, as an organic solvent, regulates the polarity and surface tension of the mixed solvent, slowing down the metal-ligand complexation rate and allowing time for the molecules to arrange themselves in an orderly manner, thereby growing into two-dimensional crystals.

[0023] Furthermore, in the flavonoid polyphenol alcohol solution, the concentration of flavonoid polyphenols is 5-100 mmol / L.

[0024] Furthermore, the phosphate buffer solution has a concentration of 10-20 mM and a pH of 4-8. The phenolic hydroxyl groups of flavonoid polyphenols require deprotonation to coordinate with metal ions. At too low a pH, the phenolic hydroxyl groups exist primarily in a protonated form, resulting in weak coordination ability. At too high a pH, metal ions readily form hydroxide precipitates directly, or grow disorderly due to excessively rapid reactions. Therefore, precise pH control is necessary to ensure the pH is within the controllable range of the coordination reaction, allowing for ordered molecular assembly.

[0025] Furthermore, the volume ratio of the metal salt ion solution to the phosphate buffer solution is (1-2):20.

[0026] Furthermore, in the dispersion system, the molar ratio of metal salt ions to flavonoid polyphenols is (5-20):1.

[0027] Furthermore, the stirring is performed at 800-1200 rpm for 10-60 minutes.

[0028] Furthermore, the post-processing includes centrifugation, washing, and drying.

[0029] Preferably, the centrifugation speed is 8000-12000 g.

[0030] Preferably, the washing includes washing with deionized water and methanol.

[0031] Through the above steps, using the aforementioned metal ions Fe 2+ Cu 2+ Mn 2+ Zn 2+ Zr 4+ Al 3+ Two-dimensional metal polyphenol frameworks with antioxidant properties can be synthesized by arbitrarily coordinating with the aforementioned flavonoid polyphenol molecules, including catechin, quercetin, rosin, trihydroxyflavone, luteolin, and salicumin. The prepared two-dimensional metal polyphenol frameworks exhibit excellent antioxidant properties, biocompatibility, and stability. The specific principle is as follows: (1) Antioxidant properties: Flavonoid ligands contain abundant phenolic hydroxyl groups, which can capture reactive oxygen species in the environment and quench them. The metal ions involved in this invention are mostly active cofactors of SOD and CAT enzymes. When these metal ions are fixed on the surface of a 2D network by flavonoid ligands, the coordination environment regulates the redox potential of the metals, giving the nanomaterials the activity of mimicking superoxide dismutase (SOD) and catalase (CAT). (2) Biocompatibility: Fe, Cu, Mn, and Zn are all essential trace elements for the human body and participate in normal metabolic cycles, while Zr and Al have low toxicity in their complex states. Flavonoid polyphenols, which act as ligands, are widely found in fruits, vegetables, and tea and are recognized as safe dietary nutrients. Meanwhile, the metal-polyphenol coordination bond is pH sensitive. In a weakly acidic environment, it will competitively bind to phenolic anions, leading to the breakage of the coordination bond. Therefore, 2D MFPNs will not accumulate non-specifically in the body for a long time, but can be gradually decomposed and excreted from the body through metabolic processes, thus having good biosafety. (3) Stability: On the one hand, the specific structure of flavonoid molecules can form five-membered or six-membered ring structures with metal ions of high valence / high charge density. According to thermodynamic principles, the formation of cyclic chelates has higher entropy increase and bond energy than monodentate coordination. At the same time, there is charge transfer between the empty orbitals of the metal and the oxygen atoms of the ligand, which further enhances the bond strength and makes it able to resist the interference of physiological salt ion strength. On the other hand, the "bident / multidentate bridging" property of flavonoid ligands connects metal nodes into an infinitely extended 2D coordination polymer network. At the same time, the rigid planar benzene ring skeleton of flavonoid molecules promotes tight π-π stacking between layers. This structure of "lateral coordination lock" plus "longitudinal van der Waals force lock" endows 2D MFPs with excellent colloidal stability.

[0032] A third aspect of the present invention is to provide a product containing a two-dimensional metal polyphenol framework material, the product comprising a two-dimensional metal polyphenol framework material as described in any of the first aspects of the present invention or a two-dimensional metal polyphenol framework material prepared by any of the preparation methods described in any of the second aspects of the present invention.

[0033] Furthermore, the product is a therapeutic agent prepared by dispersing the two-dimensional metal polyphenol framework material in a solvent.

[0034] Furthermore, the solvent is a biocompatible solvent, including any one of phosphate buffer solution, physiological saline, and culture medium.

[0035] Furthermore, the concentration of the two-dimensional metal polyphenol framework material in the solvent is 1-2000 µg / mL.

[0036] Preferably, the concentration of the two-dimensional metal polyphenol framework material in physiological saline is 2 µg / mL.

[0037] Preferably, the concentration of the two-dimensional metal polyphenol framework material in the culture medium is 100 µg / mL.

[0038] A fourth aspect of the present invention is to provide an application of a two-dimensional metal polyphenol framework material, wherein the two-dimensional metal polyphenol framework material is any of the two-dimensional metal polyphenol framework materials described in any of the first aspects of the present invention, or a two-dimensional metal polyphenol framework material prepared by any of the preparation methods described in any of the second aspects of the present invention, or a product described in any of the third aspects of the present invention.

[0039] Furthermore, the application is selected from at least one of the following applications: applications for preparing drug-loaded materials, applications for preparing antioxidant biomaterials, and applications for preparing biocompatible materials.

[0040] Furthermore, applications for the preparation of biocompatible materials include applications of biocompatible materials targeting mouse ovarian granulosa cells.

[0041] The present invention adopts the above technical solution and has the following technical effects compared with the prior art: (1) The two-dimensional metal polyphenol framework material prepared by this invention has a particle size much larger than its thickness, exhibiting a typical two-dimensional ultrathin sheet structure. This morphology brings multiple advantages: high specific surface area enhances drug loading capacity; ultrathin thickness allows the reaction sites to be fully exposed, enabling efficient reactions without substrate diffusion; it achieves "surface contact" when interacting with biological interfaces, resulting in better compatibility; and the long-range ordered structure of the crystalline framework endows it with excellent physiological stability. Therefore, the two-dimensional metal polyphenol framework material shows significant potential in drug loading, catalysis, and biological applications.

[0042] (2) The two-dimensional metal polyphenol framework structure material prepared by the present invention has good biomedical application adaptability, specifically reflected in excellent biocompatibility, physiological stability and antioxidant activity: The two-dimensional metal polyphenol framework material of the present invention has good biocompatibility and a thickness of only about 2 nm. Its ultrathin flexibility can achieve "surface adhesion" with cells, avoiding physical damage and rapid kidney clearance; the large lateral size forms a long-range ordered coordination network, the lattice structure is stable, it can resist ion interference, maintain structural integrity for a long time, and has good physiological stability; the antioxidant effect is due to the extremely high specific surface area brought by the ultrathin structure, the active sites are almost completely exposed, and they are in full contact with free radicals, resulting in significant clearance efficiency.

[0043] (3) The two-dimensional metal polyphenol framework material of the present invention is prepared by a simple, green and efficient aqueous synthesis method, avoiding the use of high temperature, high pressure and toxic organic solutions in the traditional material preparation process. Attached Figure Description

[0044] Figure 1 This is a TEM image of a two-dimensional metal polyphenol framework material in one embodiment of the present invention.

[0045] Figure 2 This is an HRTEM image of a two-dimensional metal polyphenol framework material in one embodiment of the present invention.

[0046] Figure 3 This is a selected area electron diffraction image of a two-dimensional metal polyphenol framework material in one embodiment of the present invention.

[0047] Figure 4 This is an AFM image (left) of a two-dimensional metal multi-frame material and the sample thickness (right) at the corresponding position in one embodiment of the present invention.

[0048] Figure 5 This is an EDS elemental surface scan image of a two-dimensional metal polyphenol framework material in one embodiment of the present invention.

[0049] Figure 6 This is the XPS full spectrum of a two-dimensional metal polyphenol framework material in one embodiment of the present invention.

[0050] Figure 7 This is a high-resolution spectrum of Zn element in a two-dimensional metal polyphenol framework material according to an embodiment of the present invention.

[0051] Figure 8 This is a Fourier transform infrared spectrum of a two-dimensional metal polyphenol framework material in one embodiment of the present invention.

[0052] Figure 9 This is a curve showing the relationship between the ABTS•+ scavenging rate and antioxidant properties of two-dimensional metal polyphenol framework material therapeutic agents of different concentrations and their concentrations in one embodiment of the present invention.

[0053] Figure 10 This is a digital photograph of a two-dimensional metal polyphenol framework material after being incubated for 48 hours in three simulated physiological solutions: phosphate buffer, cell culture medium, and physiological saline, according to one embodiment of the present invention.

[0054] Figure 11 This describes the cytotoxicity of different concentrations of two-dimensional metal polyphenol framework material therapeutic agents after co-incubation with mouse ovarian granulosa cells for 48 and 72 hours, as described in one embodiment of the present invention.

[0055] Figure 12 This is a TEM image of a two-dimensional metal polyphenol framework material prepared by changing the reaction time and stirring speed in one embodiment of the present invention.

[0056] Figure 13 These are TEM images of the polymers synthesized in a pair of proportions according to the present invention. Detailed Implementation

[0057] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. Experimental methods in the following embodiments that do not specify specific conditions are generally determined according to national standards. Experimental materials in the following embodiments that do not specify their source are all commercially available raw materials. The equipment used in each step of the following embodiments is conventional equipment. If there is no corresponding national standard, it is carried out according to general international standards, conventional conditions, or conditions recommended by the manufacturer. Unless otherwise stated, all parts are parts by weight, and all percentages are percentages by mass. Unless otherwise defined or stated, all professional and scientific terms used in the present invention have the same meaning as those skilled in the art. In addition, any methods and materials similar or equivalent to those described can be applied to the methods of the present invention.

[0058] It should be noted that, unless otherwise specified, the embodiments and features described in the present invention can be combined with each other. The present invention will be further described below with reference to the accompanying drawings and specific embodiments, but this is not intended to limit the scope of the invention.

[0059] The reagents used in the following embodiments of the present invention are all commercially available.

[0060] In one specific embodiment of the present invention, the two-dimensional metal polyphenol framework material is a type of sheet-like nanosheet with an average size tunable in the range of 200-800 nm and good dispersibility, exhibiting good biocompatibility and physiological stability. The ligand molecules of the two-dimensional metal polyphenol framework material are at least one selected from catechin, quercetin, rosin, trihydroxyflavone, luteolin, salicumin, tannic acid, gallic acid, and pyrogallol, endowing it with potential anti-inflammatory, antioxidant, and antitumor properties. The two-dimensional metal polyphenol framework material possesses a unique two-dimensional morphology, resulting in a high specific surface area and abundant hydroxyl groups on its surface, making it easy to modify and functionalize.

[0061] In one specific embodiment of the present invention, the two-dimensional metal polyphenol framework material is synthesized using a green and efficient aqueous phase synthesis method. The synthesis process is simple, pollution-free, yields high quantities, and is low in cost, showing excellent clinical application prospects in the biomedical field. The following exemplarily illustrates the two-dimensional metal polyphenol framework material provided by the present invention.

[0062] In a specific embodiment of the present invention, the preparation method of the two-dimensional polyphenol framework material includes the following steps: 1) A certain amount of hydrated metal salt is dissolved in a certain volume of deionized water to obtain a metal ion solution. The hydrated metal salt can be ferrous chloride tetrahydrate, zinc nitrate hexahydrate, zirconium chloride hexahydrate, magnesium chloride hexahydrate, aluminum chloride hexahydrate, etc. The concentration of metal ions in the solution can be 10-200 mmol / L. 2) A certain amount of flavonoid polyphenol molecules are dissolved in a certain volume of alcohol solvent to obtain a flavonoid polyphenol alcohol solution. The flavonoid polyphenol molecules can be quercetin, rosin, trihydroxyflavone, luteolin, salicumin, etc.; the concentration of the flavonoid polyphenol alcohol solution can be 5-100 mmol / L; the alcohol solvent includes methanol or anhydrous ethanol. 3) Take a certain volume of metal ion solution and add it dropwise to a certain amount of phosphate buffer solution with a certain pH. Stir at 800-1200 rpm for a period of time at room temperature to form a stable dispersion system. The concentration of the phosphate buffer solution is 10-20 mM. The volume ratio of the metal salt ion solution to the phosphate buffer solution is (1-2):20, and the pH is 4-8. 4) The flavonoid polyphenol alcohol solution was added dropwise to the above dispersion system and stirred at 800-1200 rpm for a certain time at room temperature. The product after the reaction was washed and centrifuged multiple times with deionized water and alcohol solvent. Finally, the sample was freeze-dried to obtain two-dimensional metal polyphenol framework material powder. The molar ratio of metal salt ions to flavonoid polyphenols was (5-20):1.

[0063] In one embodiment of the present invention, a two-dimensional metal polyphenol framework material is dispersed in physiological saline or phosphate buffer to obtain a therapeutic agent of a certain concentration. The preparation method involves freeze-drying the two-dimensional metal polyphenol framework material and then resuspending it in a certain volume of physiological saline solution to obtain a therapeutic agent of two-dimensional metal polyphenol framework material with adjustable concentration.

[0064] The present invention will be further illustrated below with examples. It should also be understood that the following examples are for further explanation only and should not be construed as limiting the scope of protection of the present invention. Non-essential improvements and adjustments made by those skilled in the art based on the above description of the present invention are all within the scope of protection of the present invention. The specific process parameters, etc., in the following examples are merely examples within a suitable range; that is, those skilled in the art can make appropriate selections within the appropriate range based on the description herein, and are not intended to be limited to the specific values ​​in the examples below.

[0065] Example 1: Preparation of two-dimensional metal polyphenol framework material (Zn-Fis) The two-dimensional metal polyphenol framework material described in this invention relates to the utilization of metal ions Fe 2+ Cu 2+ Mn2+ Zn 2+ Zr 4 + Al 3+ Two-dimensional metal polyphenol framework materials synthesized by arbitrary coordination with flavonoid polyphenol molecules such as catechin, quercetin, rosin, trihydroxyflavone, luteolin, and succinin are described below using the metal ion Zn. 2+ Taking the flavonoid polyphenol rosin as an example, we carried out specific preparation and characterization.

[0066] This embodiment relates to the two-dimensional metal polyphenol framework material of the present invention, specifically the metal ion Zn. 2+ The synthesis of a two-dimensional metal polyphenol framework material through coordination with laccasein specifically includes the following steps: Dissolving 30 mg of Zn(NO3)2·6H2O in 2 mL of deionized water yields clarified Zn. 2+ Aqueous solution A; Dissolve 4.5 mg of flavonoid powder in 1 mL of methanol to obtain a clear flavonoid alcohol solution B; Take 1.6 mL of Zn 2+ Aqueous solution A was added dropwise to 20 mL of phosphate buffer (10 mM, pH = 7.4), and stirred at 1100 rpm for 30 min at room temperature to form a stable dispersion. 0.6 mL of flavonoid alcohol solution B was added to the dispersion, and stirring was continued at 1100 rpm for 30 min at room temperature. After the reaction was completed, the sample was collected by centrifugation at 9000 g, washed at least 3 times with deionized water and methanol, the precipitate was collected and freeze-dried to obtain two-dimensional metal polyphenol framework material (Zn-Fis) powder.

[0067] Example 2: Physicochemical characterization of two-dimensional high-valence metallic framework materials To confirm that the prepared two-dimensional high-valence metal framework material is a two-dimensional structure, this embodiment characterizes the two-dimensional metal polyphenol framework material (Zn-Fis) prepared in Example 1 at the microscopic level and with respect to its chemical composition, as detailed below: (a) Structural characterization The microstructure and crystal structure of the two-dimensional high-valence metallic framework material prepared in Example 1 were characterized using transmission electron microscopy (TEM) and atomic force microscopy (AFM). The results are as follows: Figures 1-4 As shown: TEM images show that the material has a clear layered structure with a lateral dimension of approximately 300 nm. Figure 1 High-resolution transmission electron microscopy (HRTEM) images further revealed that the material has clear lattice fringes with a lattice spacing of 2.7 Å, indicating its good crystallinity. Figure 2The selected electron diffraction (SAED) pattern revealed a six-fold symmetrical diffraction pattern, further confirming that the Zn-Fis in Example 1 is a hexagonal crystal system. Figure 3 AFM characterization and TEM structure are consistent, showing that the material has a flat surface and uniform thickness. Figure 4 (a) portion), the measured thickness is approximately 2 nm ( Figure 4 Part (b) shows that Zn-Fis was successfully prepared, and the material in Example 1 has a high-quality layered structure, good crystallinity and uniform size; (ii) Elemental characterization The elemental composition of the two-dimensional metal polyphenol framework material in Example 1 was characterized using energy dispersive spectroscopy (EDS) elemental surface mapping, and the results are as follows: Figure 5 As shown, Figure 5 This visually demonstrates that Zn, C, and O elements are uniformly distributed in the layered structure of the material; (III) Chemical state analysis The chemical states of each element in Zn-Fis in Example 1 were further analyzed using X-ray photoelectron spectroscopy (XPS). Figure 6 The XPS full spectrum shown quantitatively reveals the contents of Zn, C, and O in the Zn-Fis prepared in Example 1, which are 11.1%, 24.9%, and 51.28%, respectively. Further high-resolution XPS spectroscopy analysis was used to analyze the chemical state of Zn, and the results are as follows: Figure 7 As shown, Zn mainly exists in a divalent form, with a binding energy of 1022.5 eV (2p). 3 / 2 ) and 1046 eV (2p 1 / 2 ); (iv) Functional group representation The Zn-Fis functional groups prepared in Example 1 were characterized using Fourier transform infrared spectroscopy. The results are as follows: Figure 8 As shown, it is located at 3511 cm. -1 The intensity of the OH stretching vibration peak decreased and broadened, indicating that the hydroxyl group underwent deprotonation and participated in coordination; meanwhile, the peak originally located at 1095 cm⁻¹... -1 The characteristic absorption of the CO bond at this location is enhanced by coordination and undergoes a high-frequency shift to 1107 cm⁻¹. -1 These changes prove Zn 2+ It successfully formed a complex with laccoside.

[0068] Characterization results show that the Zn-Fis prepared in Example 1 has a thickness of only 2 nm, which is only a few atomic layers thick, indicating that the material has a typical two-dimensional sheet structure. This ultrathin morphology gives it significant advantages in several aspects: the two-dimensional structure endows it with an extremely high theoretical specific surface area, allowing more drug molecules to be adsorbed or loaded per unit mass of material, thus improving drug loading potential; the extremely thin thickness means that reaction substrates do not need to diffuse into the material interior, but can directly interact with the fully exposed metal nodes and polyphenol ligands on the surface, improving reaction efficiency; the flexible nanosheets can form large-area "surface contact" when interacting with cells, bacteria, or viruses, which is more biocompatible than the "point contact" of spherical nanoparticles; the crystalline two-dimensional framework has a long-range ordered coordination network, and its thermodynamic stability is higher than that of amorphous coordination polymers, allowing it to better maintain structural integrity in physiological environments; in summary, Zn-Fis, with its ultrathinness, high specific surface area, full exposure of surface sites, and excellent structural stability, shows significant advantages in drug loading, interfacial reactions, and biological applications.

[0069] The 2D MFPNS prepared by this invention exhibits a two-dimensional sheet-like morphology, which is generally determined by the planar structure of the ligand molecules, the geometry of the metal ligands, and the specific regulatory effect of phosphate ions. (1) Planar rigid structure of ligand molecules: Taking lacquer xanthophyll as an example, lacquer xanthophyll is a typical flavonoid compound. Its skeleton is mainly composed of two benzene rings (ring A and ring B) and one oxygen-containing heterocycle (ring C). The entire molecule has a highly conjugated system and presents a flat rigid planar structure. This planar structure makes it easy for lacquer xanthophyll molecules to stack in layers through π-π conjugation interactions. This stacking tends to provide an intrinsic driving force for the formation of two-dimensional sheet-like structures. (2) Directional growth of metal-organic coordination polymers: Zn 2+ Zn forms a metal-organic coordination polymer or a metal polyphenol network with rutin through coordination bonds. 2+ It usually chelates with the 3-hydroxy-4-carbonyl or 3',4'-o-dihydroxy (catechol group on ring B) of lacquer xanthophyll. Since lacquer xanthophyll is planar, when Zn... 2+ When these planar molecules are connected as nodes, if steric hindrance restricts growth in the vertical direction, the coordination network tends to extend infinitely in the XY plane, while growth is restricted in the Z axis (vertical direction), thus forming two-dimensional sheets. (3) The role of phosphate ions: Phosphate ions not only regulate pH but also act as strong ligands. Phosphate ions specifically adsorb onto certain crystal planes of the crystal nucleus (usually crystal planes perpendicular to the layer plane), inhibiting crystal growth in that direction (Z-axis) and forcing the crystal to grow only laterally (XY plane). This anisotropic growth directly leads to the formation of ultrathin lamellar structures; Zn2+ Zinc phosphate, which readily forms a layered structure (α-Hopeite structure) with phosphate ions, acts as a framework, with rosin molecules embedded or adsorbed between these layers, forming a two-dimensional structure. (4) Self-assembly kinetics: In solution, in order to reduce the surface energy of the system, the hydrophobic aromatic rings (lactoxanthin skeleton) tend to aggregate together, while the hydrophilic groups (with Zn) 2+ The coordinated portion and phosphate group are exposed to the outside. This arrangement is conducive to the formation of large-area membranes or sheet-like micelle structures to maximize internal hydrophobic interactions and maintain interfacial stability.

[0070] Example 3: Evaluation of the oxidation resistance and stability of two-dimensional high-valence metal framework materials In this embodiment, the two-dimensional metal polyphenol framework material (Zn-Fis) prepared in Example 1 was dispersed in physiological saline to simulate a therapeutic agent, and its antioxidant properties and stability were tested. Specifically, the following steps were performed: (I) Preparation of therapeutic agents The Zn-Fis prepared in Example 1 were dispersed in physiological saline (0.9 wt% NaCl aqueous solution) to obtain concentrations of 0 µg / mL. -1 0.06 µg mL -1 0.12 µg mL -1 0.25 µg mL -1 0.5 µg mL -1 1 µg mL -1 2µg mL -1 Therapeutic agents.

[0071] (ii) Evaluation of antioxidant performance: The total antioxidant performance of the two-dimensional metal polyphenol framework material (Zn-Fis) in Example 1 was evaluated using the ABTS method.

[0072] Stable ABTS radical cations (ABTS•) were prepared by reacting ABTS with potassium persulfate. + (Stock solution; different concentrations of Zn-Fis therapeutic agents are mixed with ABTS diluted to a specific absorbance.) + The working solutions were mixed and reacted at room temperature in the dark for 10 minutes. After the reaction, the absorbance of the solution was measured at 734 nm using a UV spectrophotometer, compared to ABTS without the addition of the sample. + The solution was used as a blank control. The clearance rate of Zn-Fis against ABTS was calculated according to the formula: Scavenging rate (%) = [(A0-A1) / A0] × 100%. + The clearance rate is given by A0, where A0 is the absorbance of the blank control group and A1 is the absorbance of the sample group.

[0073] The results are as follows Figure 9 As shown, the Zn-Fis prepared in Example 1 is effective against ABTS• + It exhibits significant scavenging activity, and the scavenging rate increases with increasing concentration. When the concentration of Zn-Fis is 2 µg / mL... -1 At that time, the scavenging rate reached 100%. The results show that the Zn-Fis prepared in Example 1 has good in vitro antioxidant activity.

[0074] (3) Evaluation of physiological stability To evaluate the in vitro physiological stability of Zn-Fis in Example 1, the Zn-Fis therapeutic agent was placed in simulated physiological solutions such as phosphate buffer (10 mM, pH 7.4), cell culture medium (DMEM), and physiological saline (0.9 wt%), and incubated at 37 ℃ for 48 hours. The results are as follows: Figure 10 As shown, in the above-mentioned simulated physiological fluid, Zn-Fis maintained no significant change in appearance within 48 hours and did not exhibit precipitation, demonstrating good stability and dispersibility.

[0075] Example 4: Biocompatibility Evaluation of Two-Dimensional High-Valuation Metal Framework Materials In this embodiment, the two-dimensional metal polyphenol framework material (Zn-Fis) prepared in Example 1 was dispersed in a culture medium and co-cultured with cells to simulate a therapeutic agent and to evaluate its biocompatibility. Specifically, the following steps were performed: (I) Preparation of therapeutic agents The Zn-Fis prepared in Example 1 were dispersed in DMEM high-glucose complete medium to obtain concentrations of 0 µg / mL. -1 12 µg mL -1 25 µg mL -1 50 µg mL -1 100 µg mL -1 Therapeutic agents.

[0076] (ii) Biocompatibility evaluation: The biocompatibility of the above-mentioned Zn-Fis therapeutic agents was evaluated using mouse ovarian granulosa cells.

[0077] Mouse ovarian granulosa cells were seeded into 96-well plates and cultured for 24 hours. Different concentration gradients of Zn-Fis therapeutic agents were then added, and the cells were cultured for another 48 and 72 hours, respectively. Cell viability was then assessed using the CCK-8 assay.

[0078] The results are as follows Figure 11 As shown in Table 1, at 100 µg mL -1 Within the specified concentration range, there was no significant difference in cell viability between the Zn-Fis-treated group and the control group.

[0079] Table 1. Effects of Zn-Fis treatment duration on mouse ovarian granulosa cell viability Example 5: Size control of fabrication conditions for two-dimensional high-valence metallic framework materials This embodiment involves a comparative experiment on the effects of reaction time and stirring speed on the size of the synthesized two-dimensional metal polyphenol framework material during the synthesis process of the present invention, specifically involving the metal ion Zn 2+ The synthesis of a two-dimensional metal polyphenol framework material through coordination with laccasein specifically includes the following steps: Dissolving 30 mg of Zn(NO3)2·6H2O in 2 mL of deionized water yields clarified Zn. 2+ Aqueous solution A; Dissolve 4.5 mg of flavonoid powder in 1 mL of methanol to obtain a clear flavonoid alcohol solution B; Take 1.6 mL of Zn 2+ Aqueous solution A was added dropwise to 20 mL of phosphate buffer (10 mM, pH = 7.4), and stirred at 1100 rpm for 30 min at room temperature to form a stable dispersion. 0.6 mL of flavonoid alcohol solution B was added to the dispersion, and stirring was continued at 800 rpm for 120 min at room temperature. After the reaction was completed, the sample was collected by centrifugation at 9000 g, washed at least 3 times with deionized water and methanol, the precipitate was collected and freeze-dried to obtain two-dimensional metal polyphenol framework material (Zr-Fis) powder.

[0080] The Zr-Fis powder obtained in Example 5 was characterized using electron transmission microscopy, and the results were as follows: Figure 12 The TEM image shown indicates that the material prepared in this embodiment has a clear layered structure, with a size of approximately 500-600 nm, which differs from the two-dimensional metal polyphenol framework material prepared in Example 1 under the same proportions and components. This suggests that the control of 2D MFPNs mainly depends on controlling the reaction time and stirring speed of the system. At a stirring speed of 800 rpm, after 1 h of reaction, the material size is approximately 500-600 nm, which is different from the Zn-Fis two-dimensional metal polyphenol framework material with a size of approximately 300 nm formed in Example 1 under the condition of stirring at 1100 rpm for 30 min.

[0081] Example 6: Preparation of two-dimensional metal polyphenol framework material (Fe-Que) This embodiment relates to the characterization of the two-dimensional metal polyphenol framework material and structure of the present invention, specifically the metal ion Fe. 2+ The synthesis of two-dimensional metal polyphenol framework materials through coordination with quercetin specifically includes the following steps: 20 mg FeCl2 4H2O dissolved in 2 mL of deionized water yields pale green Fe. 2+ Aqueous solution A; Dissolve 3.4 mg of quercetin powder in 1 mL of anhydrous ethanol to obtain a yellow quercetin alcohol solution B; Take 1.0 mL of Fe 2+ Aqueous solution A was added dropwise to 20 mL of phosphate buffer (10 mM, pH = 7.4), and stirred at 1000 rpm for 20 min at room temperature to form a stable dispersion. 0.8 mL of quercetin alcohol solution B was added to the dispersion, and stirring was continued at 1000 rpm for 40 min at room temperature. After the reaction was completed, the sample was collected by centrifugation at 9000 g, washed at least 3 times with deionized water and methanol, the precipitate was collected and freeze-dried to obtain dark green two-dimensional iron-quercetin framework material (Fe-Que) powder.

[0082] Example 7: Preparation of two-dimensional metal polyphenol framework material (Cu-Lut) This embodiment relates to the two-dimensional metal polyphenol framework material of the present invention, specifically the metal ion Cu. 2+ The synthesis of a two-dimensional metal polyphenol framework material through coordination with luteolin specifically includes the following steps: 34 mg CuCl2 Cu is obtained by dissolving 2H2O in 2 mL of deionized water. 2+ Aqueous solution A; Dissolve 5.7 mg of luteolin in 1 mL of methanol to obtain luteolin alcohol solution B; Take 2.0 mL of Cu 2+ Aqueous solution A was added dropwise to 30 mL of phosphate buffer (20 mM, pH = 7.4), and stirred at 1200 rpm for 30 min at room temperature to form a stable dispersion. 1.0 mL of luteolin alcohol solution B was added to the dispersion, and stirring was continued at 1200 rpm for 60 min at room temperature. After the reaction was completed, the sample was collected by centrifugation at 10000 g, washed at least three times with deionized water and methanol, the precipitate was collected and freeze-dried to obtain yellow-green two-dimensional copper-luteolin framework material (Cu-Lut) powder.

[0083] Example 8: Preparation of two-dimensional metal polyphenol framework material (Zr-Cat) This embodiment relates to the two-dimensional metal polyphenol framework material of the present invention, specifically the metal ion Zr 4+ The synthesis of two-dimensional metal polyphenol framework materials through coordination with catechins specifically includes the following steps: 46 mg ZrOCl2 Zr is obtained by dissolving 8H2O in 2 mL of deionized water.4+ Aqueous solution A; Dissolve 2.9 mg of catechin in 1 mL of methanol to obtain catechin alcohol solution B; Take 1.6 mL of Zr 4+ Aqueous solution A was added dropwise to 20 mL of phosphate buffer (20 mM, pH = 6.0), and stirred at 800 rpm for 30 min at room temperature to form a stable dispersion (considering Zr). 4+ (Easily hydrolyzed, slightly lower pH and stir at a slow speed); add 0.6 mL of catechin alcohol solution B to the dispersion system and continue stirring at 800 rpm for 120 min at room temperature; after the reaction is complete, centrifuge at 9000 g to collect the sample, wash with deionized water and methanol at least 3 times, collect the precipitate and freeze-dry to obtain a light yellow two-dimensional zirconium-catechin framework material (Zr-Cat) powder.

[0084] Comparative Example 1 The preparation process of the metal polyphenol framework material in Comparative Example 1 was the same as in Example 1, except that the solvent methanol in solution B was replaced with deionized water, while other conditions remained unchanged. The metal polyphenol framework material that was stably dispersed in Example 1 was not formed.

[0085] Organic solvents (such as methanol) play a dual role as both "solvent" and "kinetic regulator" in the synthesis of two-dimensional metal-polyphenol framework materials. Compared with deionized water systems, their advantages lie in both thermodynamic dissolution and kinetic control. (1) Thermodynamic solubility: Flavonoid polyphenols (such as rosin) have a hydrophobic aromatic ring skeleton and strong intermolecular π-π stacking interaction. They are almost insoluble in water and easily form micron-sized aggregates. This results in metal ions being able to coordinate with ligands only at the solid-liquid interface, making it difficult to construct long-range ordered structures. Methanol can destroy the intermolecular stacking interaction of ligands, allowing them to disperse in a single-molecule form, laying the foundation for homogeneous reaction to achieve stoichiometric coordination and subsequent self-assembly. (2) Kinetic Regulation: The essence of this method is "solvent-antisolvent" induced self-assembly. When the lacquer xanthocyanin methanol solution is added dropwise to the aqueous phase PBS, a high degree of supersaturation is formed locally. At the same time, methanol reduces the surface tension and polarity of the mixed solvent, slowing down the nucleation rate and prolonging the nucleation induction period. This allows the ligand molecules to arrange themselves in an orderly manner along the two-dimensional plane under the guidance of metal ions, rather than rapidly agglomerating. The pure water system, due to its high polarity and large surface tension, is prone to explosive nucleation and rapid agglomeration, and can only form amorphous aggregates.

[0086] Therefore, methanol not only solved the ligand dissolution problem, but also guided the system from disordered aggregation to ordered two-dimensional crystal growth by regulating nucleation and growth kinetics, thus achieving structure-controllable synthesis.

[0087] Comparative Example 2 The preparation process of the metal polyphenol framework material in Comparative Example 2 is the same as that in Example 1, except that the pH of the phosphate buffer is 3, and other conditions remain unchanged.

[0088] Referring to Example 2, the structure of the material prepared in Comparative Example 2 was characterized using transmission electron microscopy (TEM). The microstructure of the polymer prepared in Comparative Example 2 is as follows: Figure 13 As shown, by Figure 13 It can be seen that the metal polyphenol framework material prepared in Comparative Example 2 is unevenly dispersed and the particles are prone to agglomeration.

[0089] pH acts as a "chemical switch" and "kinetic regulator" for the synthesis of two-dimensional metal-polyphenol frameworks. The weakly acidic to weakly basic pH range of 4-8 precisely regulates the balance between ligand deprotonation and metal ion hydrolysis, thereby driving the formation of ordered two-dimensional structures.

[0090] When the pH is too low (e.g., pH=3), high concentrations of H+ + This competitively inhibits the deprotonation of phenolic hydroxyl groups, making it difficult for flavonoid polyphenols (such as flavonoids) to provide the oxygen anions required for coordination. Therefore, metal ions (Zn²⁺) + Unable to effectively bind to ligands, the system can only form disordered aggregates through non-covalent interactions, failing to construct an ordered framework. However, within the pH range of 4-8, the phenolic hydroxyl groups are in a moderately deprotonated state, ensuring sufficient coordination activity while avoiding excessively high pH levels that could trigger metal ion hydrolysis or excessively rapid reactions. This window allows the coordination reaction to proceed at an appropriate rate, providing kinetic space for the ordered arrangement of molecules. The ligands, due to their planar rigidity, can bind to Zn²⁺ ions. + With the assistance of nodes and phosphate ions, π-π stacking and coordination assembly occur along the two-dimensional direction to form an ultrathin sheet structure.

[0091] Therefore, phosphate buffer solutions within this pH range play a dual role: first, stabilizing the pH of the reaction system, neutralizing protons released during coordination, and ensuring a uniform and controllable process; second, allowing phosphate ions to selectively adsorb onto specific crystal faces, inhibiting crystal growth along the thickness direction, thereby promoting two-dimensional anisotropic expansion. Once the pH deviates from this range (e.g., due to strong acids or bases), the buffering and guiding effects fail, leading to the collapse of the two-dimensional structure and the formation of disordered precipitates. Thus, pH 4-8 not only activates the thermodynamic driving force of the coordination reaction but also, by regulating reaction kinetics and the interfacial environment, enables the controllable growth from disordered aggregates to ordered two-dimensional crystals.

[0092] The above description is merely a preferred embodiment of the present invention and does not limit the implementation and protection scope of the present invention. Those skilled in the art should realize that any equivalent substitutions and obvious changes made based on the description and illustrations of the present invention should be included within the protection scope of the present invention.

Claims

1. A two-dimensional metal polyphenol framework material, characterized in that, The framework material is a two-dimensional sheet-like structure material formed by the coordination of metal ions and flavonoid polyphenol molecules; Wherein, the molar ratio of the metal ions to the flavonoid polyphenols is 5-20:1; and the particle size of the two-dimensional metal polyphenol framework material is 200-800 nm; and the thickness of the two-dimensional metal polyphenol framework material is 2-10 nm.

2. The two-dimensional metal polyphenol framework material according to claim 1, characterized in that, The metal ions are selected from Fe. 2+ Cu 2+ Mn 2+ Zn 2+ Zr 4+ Al 3+ At least one of them; And / or, the flavonoid polyphenol molecules are selected from at least one of catechin, quercetin, flavonoid, trihydroxyflavone, luteolin, and succinate.

3. A method for preparing a two-dimensional metal polyphenol framework material, used to prepare the two-dimensional metal polyphenol framework material as described in any one of claims 1 to 2, characterized in that, Includes the following steps: 1) Dissolve the metal salt in water to obtain a metal ion solution; 2) Dissolve flavonoid polyphenol molecules in an alcohol solvent to obtain a flavonoid polyphenol alcohol solution; 3) Add the metal ion solution dropwise to the phosphate buffer solution and stir until homogeneous to form a dispersion system; 4) The flavonoid polyphenol alcohol solution was added dropwise to the dispersion system, and the reaction was stirred at room temperature. After post-treatment, the two-dimensional metal polyphenol framework material was obtained.

4. The preparation method according to claim 3, characterized in that, The metal salt is a hydrated metal salt, including any one of ferrous chloride tetrahydrate, copper chloride dihydrate, manganese chloride tetrahydrate, zinc nitrate hexahydrate, zirconium oxychloride octahydrate, and aluminum chloride hexahydrate; And / or, in the metal ion solution, the concentration of the metal ion is 10-200 mmol / L; And / or, the alcohol solvent includes either methanol or ethanol; And / or, in the flavonoid polyphenol alcohol solution, the concentration of flavonoid polyphenols is 5-100 mmol / L; And / or, the phosphate buffer solution has a concentration of 10-20 mM and a pH of 4-8; And / or, the volume ratio of the metal salt ion solution to the phosphate buffer solution is (1-2):20; And / or, in the dispersion system, the molar ratio of metal salt ions to flavonoid polyphenols is (5-20):1; And / or, the stirring is performed at 800-1200 rpm for 10-60 min; And / or, the post-processing includes centrifugation, washing, and drying.

5. The preparation method according to claim 4, characterized in that, In the centrifugation, the centrifugation speed is 8000-12000 g; And / or, the washing includes washing with deionized water and methanol.

6. A product containing a two-dimensional metal polyphenol framework material, characterized in that, The product includes the two-dimensional metal polyphenol framework material as described in any one of claims 1 to 2 or the two-dimensional metal polyphenol framework material prepared by any one of the preparation methods described in claims 3 to 5.

7. The product according to claim 6, characterized in that, The product is a therapeutic agent prepared by dispersing the two-dimensional metal polyphenol framework material in a solvent.

8. The product according to claim 7, characterized in that, The solvent is a biocompatible solvent, including any one of phosphate buffer solution, physiological saline, and culture medium; And / or, the concentration of the two-dimensional metal polyphenol framework material in the solvent is 1-2000 µg / mL.

9. An application of a two-dimensional metal polyphenol framework material, characterized in that, The two-dimensional metal polyphenol framework material is the two-dimensional metal polyphenol framework material as described in any one of claims 1 to 2, or the two-dimensional metal polyphenol framework material prepared by any one of the preparation methods described in claims 3 to 5, or the product as described in any one of claims 6 to 8.

10. The application according to claim 9, characterized in that, The application is selected from at least one of the following applications: applications for preparing drug-loaded materials, applications for preparing antioxidant biomaterials, and applications for preparing biocompatible materials.

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