CN112280054A - Yttrium-based metal-organic framework material and application thereof - Google Patents

Yttrium-based metal-organic framework material and application thereof Download PDF

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CN112280054A
CN112280054A CN202011185373.2A CN202011185373A CN112280054A CN 112280054 A CN112280054 A CN 112280054A CN 202011185373 A CN202011185373 A CN 202011185373A CN 112280054 A CN112280054 A CN 112280054A
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林文鑫
黄霞娟
余世桨
王岩
陈建军
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Zhejiang University of Technology ZJUT
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Abstract

The invention discloses a yttrium-based metal-organic framework material and application thereof. The yttrium-based metal-organic framework material (Y-MOF) has a chemical formula of Y4(M)2·(DMF)3.5·(H2O), wherein M is 2,4, 6-tris (4-carboxyphenyl) -1,3, 5-triazine, 2,4, 6-tris (4-pyridine) 1,3, 5-triazine or 1,3, 5-pyridine tribenzoate. The yttrium-based metal-organic framework material (Y-MOF) prepared by the invention is of a porous structure, has good biocompatibility and water stability, and can be used as a carrier material for loading metal ions (Mn) simultaneously2+,Fe2+Etc.) and drug molecules (formazan)Aminopterin, busulfan, adriamycin and the like) has the effects of magnetic resonance imaging, chemodynamic therapy and chemopharmacotherapy, can detect the treatment effect and reduce the treatment cost while treating, and the yttrium-based metal-organic framework material (Y-MOF) is prepared by adopting a solvothermal method, so that the method is simple and safe to operate, the raw materials are easy to obtain, and the condition is mild.

Description

Yttrium-based metal-organic framework material and application thereof
Technical Field
The invention relates to a porous metal organic framework material, in particular to a yttrium-based metal-organic framework material (Y-MOF) and application thereof.
Background
With the development of medical technology, the treatment level of cancer is greatly improved, and common clinical cancer treatment methods mainly comprise chemotherapy, surgery, radiotherapy and the like, but have the defects of long treatment time, high treatment cost, incomplete treatment effect and the like. Thermotherapy, photodynamic therapy, chemical photodynamic therapy and the like are some methods for treating cancers which are started in recent years, and the chemical photodynamic therapy is concerned about due to simple conditions, good effect and targeting. The chemodynamic treatment is the intrinsic Fe in tumor cells2+,Mn2+,Ti2+,Cu2+Catalyzing H under the action of plasma2O2A novel tumor therapy technique for generating strong oxidative hydroxyl groups (. OH) to induce apoptosis of tumor cells. In addition, the diagnosis and treatment are relatively independent in clinic, the optimal treatment time is usually missed, and the accurate positioning and real-time monitoring of pathological tissues in the treatment process cannot be realized, so that the effective evaluation of clinical treatment means is influenced. If the advanced medical imaging technology and the chemical dynamic treatment means are combined based on a carrier material, diagnosis and treatment can be integrated and the treatment effect can be improved.
Metal-organic framework Materials (MOFs) are porous crystalline materials formed by self-assembling metal ions or metal clusters and organic ligands in a coordination manner, and have the advantages of high porosity, large specific surface area, material size adjustability, diversity of material components, thermal stability and chemical stability, functional modification, mild synthesis conditions and the like, so that the metal-organic framework materials become novel porous materials which are widely concerned and researched by people. The yttrium-based metal-organic framework material (Y-MOF) can be used as a carrier material and is loaded with metal ions (Mn)2+,Fe2+Etc.) and drug molecules (methotrexate, busulfan, doxorubicin, etc.), making it possible in magnetic resonance imaging, chemodynamic therapy, and chemotherapeutic drug therapy, among others.
Disclosure of Invention
The invention aims to provide a method for preparing yttrium-based metal-organic framework material (Y-MOF), which has good biocompatibility, can be used as a carrier material and is loaded with metal ions (Mn)2+,Fe2+Etc.) and drug molecules (methotrexate, busulfan, doxorubicin, etc.), can achieve the purposes of magnetic resonance imaging, chemodynamic therapy and chemo-drug therapy based on the system, so that patients do not miss the optimal treatment opportunity, the treatment cost is reduced, and the treatment effect can be detected while treating.
In order to achieve the purpose, the technical scheme of the invention is as follows:
yttrium-base metal-organic frame material (Y-MOF)
The yttrium-based metal-organic framework material (Y-MOF) has a chemical formula as follows: y is4(M)2·(DMF)3.5·(H2O), wherein M is 2,4, 6-tris (4-carboxyphenyl) -1,3, 5-triazine, 2,4, 6-tris (4-pyridine) 1,3, 5-triazine or 1,3, 5-pyridine tribenzoate.
Secondly, a preparation method of yttrium-based metal-organic framework material (Y-MOF), which comprises the following steps:
(1) respectively providing an aqueous solution of trivalent yttrium ions and an organic ligand solution containing an organic ligand L and o-fluorobenzoic acid.
(2) And (2) mixing the aqueous solution of trivalent yttrium ions in the step (1) with an organic ligand solution containing an organic ligand L and o-fluorobenzoic acid, reacting for 2-3 days under the conditions of sealing and 120 ℃, and then sequentially cooling, carrying out solid-liquid separation, washing with an organic solvent and drying to obtain the yttrium-based metal-organic framework material (Y-MOF).
The trivalent yttrium ions adopt yttrium nitrate or yttrium chloride, and the molar concentration of the trivalent yttrium ions is 0.04-0.05 mol/L.
The organic ligand L is 2,4, 6-tri (4-carboxyl benzene)Radical) -1,3, 5-triazine (H)3TATB), 2,4, 6-tris (4-pyridine) 1,3, 5-triazine or 1,3, 5-triphenylcarboxylic acid pyridine.
The organic solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide or N, N-diethylformamide.
In the step (2), the mass ratio of the trivalent yttrium ions to the organic ligand L is 1-3: 1-2.
In the organic ligand solution, the molar concentrations of the organic ligand L and the o-fluorobenzoic acid are 0.004-0.006mol/L and 0.200-0.210mol/L respectively.
In the step (2), ultrasonic mixing is adopted for mixing.
In the ultrasonic mixing, the ultrasonic frequency is 20-30KHz, and the ultrasonic time is 5-10 min.
The yttrium-based metal-organic framework material (Y-MOF) is applied to magnetic resonance imaging, preparation of chemodynamic treatment drugs and preparation of chemodynamic treatment drugs.
The invention has the beneficial effects that:
(1) the yttrium-based metal-organic framework material (Y-MOF) provided by the invention is of a porous structure, has good biocompatibility and water stability, and can be used as a carrier material for loading metal ions (Mn) simultaneously2+,Fe2+Etc.) and drug molecules (methotrexate, busulfan, doxorubicin, etc.), have magnetic resonance imaging, chemodynamic therapy, and chemotherapeutic effects, enabling detection of therapeutic effects while treating and reducing treatment costs.
(2) The yttrium-based metal-organic framework material (Y-MOF) provided by the invention is prepared by adopting a solvothermal method, and the method is simple and safe to operate, easy to obtain raw materials and mild in condition.
Drawings
FIG. 1 is the UV absorption spectrum of ZJU-16 after loading with metal ions.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In a first aspect, the present invention provides a yttrium-based metal-organic framework material (Y-MOF) having the formula: y is4(M)2·(DMF)3.5·(H2O), wherein M is 2,4, 6-tris (4-carboxyphenyl) -1,3, 5-triazine, 2,4, 6-tris (4-pyridine) 1,3, 5-triazine or 1,3, 5-pyridine tribenzoate.
Specifically, when M is 2,4, 6-tris (4-carboxyphenyl) -1,3, 5-triazine, the yttrium-based metal-organic framework material has the formula Y4(C24N3H12O10.5)2·(DMF)3.5·(H2O); when M is 2,4, 6-tris (4-pyridine) 1,3, 5-triazine, the yttrium-based metal-organic framework material has the chemical formula Y4(C18N6H9)2·(DMF)3.5·(H2O); when M is pyridine 1,3, 5-tribenzoate, the yttrium-based metal-organic framework material has a chemical formula of Y4(C26NH12O10.5)2·(DMF)3.5·(H2O)。
In a second aspect, the present invention provides a method for preparing a yttrium-based metal-organic framework material (Y-MOF), comprising the steps of:
(1) respectively providing an aqueous solution of trivalent yttrium ions and an organic ligand solution containing an organic ligand L and o-fluorobenzoic acid;
(2) and (2) mixing the aqueous solution of trivalent yttrium ions in the step (1) with an organic ligand solution containing an organic ligand L and o-fluorobenzoic acid, reacting for 2-3 days under the conditions of sealing and 120 ℃, and then sequentially cooling, carrying out solid-liquid separation, washing with an organic solvent and drying to obtain the yttrium-based metal-organic framework material (Y-MOF).
Wherein the organic ligand L is 2,4, 6-tri (4-carboxyphenyl) -1,3, 5-triazine, 2,4, 6-tri (4-pyridine) 1,3, 5-triazine or 1,3, 5-pyridine tribenzoate.
The specific embodiment of the invention is as follows:
example 1:
(1) 22mg of yttrium nitrate Y (NO)3)3Dissolved in 1.8mL of an aqueous solution to prepare Y (NO) having a molar ratio of 0.044mol/L3)3An aqueous solution; 24mg of 2,4, 6-tris (4-carboxyphenyl) -1,3, 5-triazine and 346.2mg of o-fluorobenzoic acid are dissolved in 12mL of N, N-dimethylformamide to prepare an organic ligand solution with the molar concentration of 2,4, 6-tris (4-carboxyphenyl) -1,3, 5-triazine being 0.0042mol/L and the molar concentration of o-fluorobenzoic acid being 0.201 mol/L.
(2) The above 1.8mL of Y (NO)3)3Placing the aqueous solution and 12mL of organic ligand solution in a reaction kettle, performing ultrasonic treatment at the ultrasonic frequency of 25KHz for 8min, then placing at 105 ℃ for 48h, cooling to normal temperature, filtering, washing the solid particles obtained after filtering with N, N-dimethylformamide, and drying to obtain an yttrium-based metal-organic framework material (Y-MOF) with the chemical formula: y is4(C24N3H12O10.5)2·(DMF)3.5·(H2O)。
Example 2:
(1) 19.8mg of yttrium nitrate Y (NO)3)3Dissolved in 1.8mL of an aqueous solution to prepare Y (NO) with a molar ratio of 0.040mol/L3)3An aqueous solution; 21mg of 2,4, 6-tri (4-pyridine) 1,3, 5-triazine and 334.8 mg of o-fluorobenzoic acid are dissolved in 12mL of N, N-dimethylacetamide to prepare an organic ligand solution with the molar concentration of 2,4, 6-tri (4-pyridine) 1,3, 5-triazine being 0.004mol/L and the molar concentration of o-fluorobenzoic acid being 0.200 mol/L.
(2) The above 1.8mL of Y (NO)3)3Placing the aqueous solution and 12mL of organic ligand solution in a reaction kettle, performing ultrasonic treatment at the ultrasonic frequency of 30KHz for 7min, then placing at 110 ℃ for 48h, cooling to normal temperature, filtering, washing the solid particles obtained after filtering with N, N-dimethylacetamide, and drying to obtain an yttrium-based metal-organic framework material (Y-MOF) with the chemical formula: y is4(C18N6H9)2·(DMF)3.5·(H2O)。
Example 3:
(1) 27.5mg of yttrium chloride YCl3Dissolved in 2.0mLIn the aqueous solution of (3), YCl with a molar ratio of 0.050mol/L is prepared3An aqueous solution; 25.8mg of 2,4, 6-tris (4-carboxyphenyl) -1,3, 5-triazine and 337.45mg of o-fluorobenzoic acid are dissolved in 11.8mL of N, N-diethylformamide to prepare an organic ligand solution with the molar concentration of 2,4, 6-tris (4-carboxyphenyl) -1,3, 5-triazine of 0.005mol/L and the molar concentration of o-fluorobenzoic acid of 0.205 mol/L.
(2) Mixing the above 2.0mL of YCl3Putting the aqueous solution and 11.8mL of organic ligand solution into a reaction kettle, carrying out ultrasonic treatment for 10min at the ultrasonic frequency of 20KHz, then putting the mixture at 105 ℃ for 60h, cooling the mixture to normal temperature, filtering the mixture, washing the solid particles obtained after filtering by using N, N-diethylformamide, and drying the solid particles to obtain an yttrium-based metal-organic framework material (Y-MOF), wherein the chemical formula of the yttrium-based metal-organic framework material is as follows: y is4(C24N3H12O10.5)2·(DMF)3.5·(H2O)。
Example 4:
(1) 25.8mg of yttrium nitrate Y (NO)3)3Dissolved in 2.0mL of an aqueous solution to prepare Y (NO) with a molar ratio of 0.047mol/L3)3An aqueous solution; 25.2mg of 1,3, 5-tribenzoic acid pyridine and 346.52 mg of o-fluorobenzoic acid are dissolved in 11.8mL of N, N-dimethylformamide to prepare an organic ligand solution with the molar concentration of 1,3, 5-tribenzoic acid pyridine of 0.0048mol/L and the molar concentration of o-fluorobenzoic acid of 0.207 mol/L.
(2) 2.0mL of Y (NO) as described above3)3Placing the aqueous solution and 11.8mL of organic ligand solution in a reaction kettle, performing ultrasonic treatment for 8min at the ultrasonic frequency of 25KHz, then placing the mixture at 110 ℃ for 60h, cooling the mixture to room temperature, filtering the mixture, washing the solid particles obtained after filtering the mixture by using N, N-dimethylformamide, and drying the solid particles to obtain an yttrium-based metal-organic framework material (Y-MOF), wherein the chemical formula of the yttrium-based metal-organic framework material is as follows: y is4(C26NH12O10.5)2·(DMF)3.5·(H2O)。
Example 5:
(1) 23.3mg of YCl3Dissolving in 1.8mL of aqueous solution to obtain YCl with a molar ratio of 0.047mol/L3An aqueous solution; 25.2mg of 2,4, 6-tri (4-pyridine) 1,3, 5-triazine and 336.5mg of o-fluorobenzoic acid are dissolved in 12mL of N, N-dimethylacetamide to prepare an organic ligand solution with the molar concentration of 2,4, 6-tri (4-pyridine) 1,3, 5-triazine being 0.0048mol/L and the molar concentration of o-fluorobenzoic acid being 0.201 mol/L.
(2) Mixing the above 1.8mL of YCl3Placing the aqueous solution and 12mL of organic ligand solution in a reaction kettle, performing ultrasonic treatment at the ultrasonic frequency of 25KHz for 6min, then placing at 105 ℃ for 60h, cooling to room temperature, filtering, washing the solid particles obtained after filtering with N, N-dimethylacetamide, and drying to obtain an yttrium-based metal-organic framework material (Y-MOF) with the chemical formula: y is4(C18N6H9)2·(DMF)3.5·(H2O)。
Test example
Metal ions (Mn) are added by a simple immersion method2+,Fe2+Etc.) loading into Y obtained in example 34(C24N3H12O10.5)2·(DMF)3.5·(H2O), putting the material into the prepared MB solution, placing the MB solution into a 37 ℃ water bath box, taking out the solution at different time points to test the height of the ultraviolet absorption peak of the MB solution, and measuring the ultraviolet absorption peak generated by the material at different time points according to the degradation condition of the material to the MB solution.The rate of OH, and thereby its inhibitory effect on the survival rate of tumor cells.
FIG. 1 is the UV absorption spectrum of ZJU-16 after loading with metal ions, from which it can be seen that the material after loading with metal ions has a significant promoting effect on the degradation of MB, the UV absorption peak drops sharply at 5min, and the MB solution has been completely degraded at 60 min. That is, the material is capable of promoting H2O2Generating.OH can kill cancer cells.
In addition, the metal organic framework material has the advantages of large pore channel, high specific surface area, good biocompatibility, size structure adjustability and the like, so that the metal organic framework material can be used for loading drugs to achieve the effect of chemical drug therapy. Meanwhile, Mn2+,Fe2+And the metal organic framework material has a magnetic effect, and can be used for magnetic resonance imaging after being loaded with metal ions. The system can achieve the purposes of magnetic resonance imaging, chemical dynamic therapy and drug therapy, so that patients do not miss the optimal therapy opportunity, the therapy cost is reduced, and the therapy effect can be detected during therapy.
The foregoing embodiments may be modified in many different ways by those skilled in the art without departing from the spirit and scope of the invention, which is defined by the appended claims and all changes that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.

Claims (10)

1. A yttrium-based metal-organic framework material, characterized by: the chemical formula of the yttrium-based metal-organic framework material Y-MOF is as follows: y is4(M)2·(DMF)3.5·(H2O), wherein M is 2,4, 6-tris (4-carboxyphenyl) -1,3, 5-triazine, 2,4, 6-tris (4-pyridine) 1,3, 5-triazine or 1,3, 5-pyridine tribenzoate.
2. A method of preparing a yttrium-based metal-organic framework material according to claim 1, wherein: the method comprises the following steps:
(1) respectively providing an aqueous solution of trivalent yttrium ions and an organic ligand solution containing an organic ligand L and o-fluorobenzoic acid;
(2) and (2) mixing the aqueous solution of trivalent yttrium ions in the step (1) with the organic ligand solution containing the organic ligand L and the o-fluorobenzoic acid, reacting for 2-3 days under the conditions of sealing and 120 ℃, and then sequentially cooling, carrying out solid-liquid separation, washing with an organic solvent and drying to obtain the yttrium-based metal-organic framework material Y-MOF.
3. The method of claim 2, wherein the metal-organic framework is prepared by the following steps: the trivalent yttrium ions adopt yttrium nitrate or yttrium chloride, and the molar concentration of the trivalent yttrium ions is 0.04-0.05 mol/L.
4. A method of preparing a yttrium-based metal-organic framework material according to claim 3, wherein: the organic ligand L is 2,4, 6-tri (4-carboxyphenyl) -1,3, 5-triazine (H)3TATB), 2,4, 6-tris (4-pyridine) 1,3, 5-triazine or 1,3, 5-triphenylcarboxylic acid pyridine.
5. The method of claim 2, wherein the metal-organic framework is prepared by the following steps: the organic solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide or N, N-diethylformamide.
6. The method of claim 2, wherein the metal-organic framework is prepared by the following steps: in the step (2), the mass ratio of the trivalent yttrium ions to the organic ligand L is 1-3: 1-2.
7. The method of claim 2, wherein the metal-organic framework is prepared by the following steps: in the organic ligand solution, the molar concentrations of the organic ligand L and the o-fluorobenzoic acid are 0.004-0.006mol/L and 0.200-0.210mol/L respectively.
8. The method of claim 2, wherein the metal-organic framework is prepared by the following steps: in the step (2), ultrasonic mixing is adopted for mixing.
9. The method of claim 8, wherein the metal-organic framework is prepared by: in the ultrasonic mixing, the ultrasonic frequency is 20-30KHz, and the ultrasonic time is 5-10 min.
10. Use of a yttrium-based metal-organic framework material Y-MOF prepared by the preparation method according to any one of claims 2 to 9, wherein: the yttrium-based metal-organic framework material is applied to magnetic resonance imaging, preparation of chemodynamic treatment drugs and preparation of chemodynamic treatment drugs.
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CN114034656A (en) * 2021-11-10 2022-02-11 国网四川省电力公司电力科学研究院 Probe for detecting fluorine ions, preparation method and application of probe
CN114645379A (en) * 2022-03-29 2022-06-21 昆明理工大学 Preparation method of covalent triazine organic framework composite film
WO2024074141A1 (en) * 2022-10-08 2024-04-11 华为技术有限公司 Porous material and application thereof

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