CN112280054B - Yttrium-based metal-organic framework material and application thereof - Google Patents
Yttrium-based metal-organic framework material and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 56
- 229910052727 yttrium Inorganic materials 0.000 title claims abstract description 54
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 53
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 title claims abstract description 42
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000011282 treatment Methods 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 17
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 13
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical compound C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 claims abstract description 12
- AOJJSUZBOXZQNB-TZSSRYMLSA-N Doxorubicin Chemical compound O([C@H]1C[C@@](O)(CC=2C(O)=C3C(=O)C=4C=CC=C(C=4C(=O)C3=C(O)C=21)OC)C(=O)CO)[C@H]1C[C@H](N)[C@H](O)[C@H](C)O1 AOJJSUZBOXZQNB-TZSSRYMLSA-N 0.000 claims abstract description 10
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- -1 yttrium ions Chemical class 0.000 claims description 12
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- JDFUJAMTCCQARF-UHFFFAOYSA-N tatb Chemical compound NC1=C([N+]([O-])=O)C(N)=C([N+]([O-])=O)C(N)=C1[N+]([O-])=O JDFUJAMTCCQARF-UHFFFAOYSA-N 0.000 description 1
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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 Y 4 (M) 2 ·(DMF) 3.5 ·(H 2 O), 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) simultaneously 2+ ，Fe 2+ Etc.) and drug molecules (methotrexate, busulfan, adriamycin, etc.), has the effects of magnetic resonance imaging, chemodynamic therapy and chemodrug therapy, can detect the therapeutic 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, and the method has the advantages of simple and safe operation, easily obtained raw materials and mild conditions.
Description
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 therapy is the inherent Fe in tumor cells 2+ ,Mn 2+ ,Ti 2+ ,Cu 2+ Catalyzing H under the action of plasma 2 O 2 Generating strong oxidationA novel tumor treatment technology for inducing tumor cell apoptosis by using sexual hydroxyl group (. OH). 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 advanced medical imaging technology and chemical dynamic therapy means are combined based on a carrier material, diagnosis and treatment can be integrated and the treatment effect is 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+ ,Fe 2+ Etc.) and drug molecules (methotrexate, busulfan, doxorubicin, etc.), making it possible in magnetic resonance imaging, chemodynamic therapy, and chemotherapeutic drug therapy, etc.
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+ ,Fe 2+ 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 is 4 (M) 2 ·(DMF) 3.5 ·(H 2 O), 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-carboxyphenyl) -1,3, 5-triazine (H) 3 TATB), 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) is a porous structure, has good biocompatibility and water stability, and can be used as a carrier material for loading metal ions (Mn) simultaneously 2+ ，Fe 2+ 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 further described in 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 do not limit the invention.
In a first aspect, the present invention provides a yttrium-based metal-organic framework material (Y-MOF) having the formula: y is 4 (M) 2 ·(DMF) 3.5 ·(H 2 O), 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 Y 4 (C 24 N 3 H 12 O 10.5 ) 2 ·(DMF) 3.5 ·(H 2 O); when M is 2,4, 6-tris (4-pyridine) 1,3, 5-triazine, the yttrium-based metal-organic framework material has the chemical formula Y 4 (C 18 N 6 H 9 ) 2 ·(DMF) 3.5 ·(H 2 O); when M is pyridine 1,3, 5-tribenzoate, the yttrium-based metal-organic framework material has a chemical formula of Y 4 (C 26 NH 12 O 10.5 ) 2 ·(DMF) 3.5 ·(H 2 O)。
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 ) 3 Dissolved in 1.8mL of an aqueous solution to prepare Y (NO) having a molar ratio of 0.044mol/L 3 ) 3 An 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 ) 3 Putting the aqueous solution and 12mL of organic ligand solution into a reaction kettle, performing ultrasonic treatment for 8min at an ultrasonic frequency of 25KHz, then placing the solution at 105 ℃ for 48h, cooling the solution to normal temperature, filtering the solution, washing the solid particles obtained after filtering the solid particles by using N, N-dimethylformamide, and drying the solid particles to obtain the yttrium-based metal-organic framework material (Y-MOF) which has a chemical formula: y is 4 (C 24 N 3 H 12 O 10.5 ) 2 ·(DMF) 3.5 ·(H 2 O)。
Example 2:
(1) 19.8mg of yttrium nitrate Y (NO) 3 ) 3 Dissolved in 1.8mL of waterIn the liquid, Y (NO) with a molar ratio of 0.040mol/L is prepared 3 ) 3 An 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 of 0.004mol/L and the molar concentration of o-fluorobenzoic acid of 0.200 mol/L.
(2) 1.8mL of Y (NO) as described above 3 ) 3 Placing 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 is 4 (C 18 N 6 H 9 ) 2 ·(DMF) 3.5 ·(H 2 O)。
Example 3:
(1) 27.5mg of yttrium chloride YCl 3 Dissolved in 2.0mL of aqueous solution to prepare YCl with a molar ratio of 0.050mol/L 3 An 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 YCl 3 Putting 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 is 4 (C 24 N 3 H 12 O 10.5 ) 2 ·(DMF) 3.5 ·(H 2 O)。
Example 4:
(1) 25.8mg of yttrium nitrate Y (NO) 3 ) 3 Dissolved in 2.0mL of an aqueous solution to prepare Y (NO) with a molar ratio of 0.047mol/L 3 ) 3 An aqueous solution; 25.2mg of pyridine 1,3, 5-tribenzoate 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 pyridine 1,3, 5-tribenzoate 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 above 3 ) 3 Placing 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 is 4 (C 26 NH 12 O 10.5 ) 2 ·(DMF) 3.5 ·(H 2 O)。
Example 5:
(1) 23.3mg of YCl 3 Dissolving in 1.8mL of aqueous solution to obtain YCl with a molar ratio of 0.047mol/L 3 An 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 YCl 3 Putting the aqueous solution and 12mL of organic ligand solution into a reaction kettle, performing ultrasonic treatment for 6min at the ultrasonic frequency of 25KHz, then placing the mixture at 105 ℃ for 60h, cooling the mixture to room temperature, filtering the mixture, washing the solid particles obtained after filtering the mixture by using N, N-dimethylacetamide, and drying the solid particles to obtain the yttrium-based metal-organic framework material (Y-MOF) which has the chemical formula: y is 4 (C 18 N 6 H 9 ) 2 ·(DMF) 3.5 ·(H 2 O)。
Test example
Metal ions (Mn) are added by a simple immersion method 2+ ，Fe 2+ Etc.) loading into Y obtained in example 3 4 (C 24 N 3 H 12 O 10.5 ) 2 ·(DMF) 3.5 ·(H 2 O), 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 on 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 metal ions, and it can be seen from the figure that the material after loading metal ions has a significant promoting effect on the degradation of MB, the UV absorption peak drops sharply at 5min, and the MB solution is completely degraded at 60 min. That is, the material is capable of promoting H 2 O 2 Generating . 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, Mn 2+ ，Fe 2+ 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 (8)
1. Use of a yttrium-based metal-organic framework material, characterized in that: the chemical formula of the yttrium-based metal-organic framework material Y-MOF is as follows: y is 4 (M) 2 ·(DMF) 3.5 ·(H 2 O), wherein M is 2,4, 6-tri (4-pyridine) 1,3, 5-triazine; the yttrium-based metal-organic framework material Y-MOF is loaded with metal ions or drugsThe substance molecule, metal ion being Mn in particular 2+ Or Fe 2+ The drug molecules are methotrexate, busulfan or adriamycin, and the loading is carried out by loading metal ions and the drug molecules into yttrium-based metal-organic framework material Y-MOF through a soaking method;
the yttrium-based metal-organic framework material is used for magnetic resonance imaging, chemodynamic treatment drug preparation and chemotherapy.
2. Use of a yttrium-based metal-organic framework material according to claim 1, characterized in that: the preparation method of the yttrium-based metal-organic framework material comprises the following steps:
(1) respectively providing an aqueous solution of trivalent yttrium ions and an organic ligand solution containing an organic ligand 2,4, 6-tri (4-pyridine) 1,3, 5-triazine and o-fluorobenzoic acid;
(2) mixing the aqueous solution of trivalent yttrium ions in the step (1) and the organic ligand solution containing the organic ligand and the o-fluorobenzoic acid, then reacting for 2-3 days under the conditions of sealing and 120 ℃, and then sequentially cooling, solid-liquid separating, washing with an organic solvent and drying to finally obtain the yttrium-based metal-organic framework material Y-MOF.
3. Use of a yttrium-based metal-organic framework material according to claim 2, characterized in that: 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. Use of a yttrium-based metal-organic framework material according to claim 2, characterized in that: the organic solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide or N, N-diethylformamide.
5. Use of a yttrium-based metal-organic framework material according to claim 2, characterized in that: in the step (2), the mass ratio of the trivalent yttrium ions to the organic ligand is 1-3: 1-2.
6. Use of a yttrium-based metal-organic framework material according to claim 2, characterized in that: in the organic ligand solution, the molar concentrations of the organic ligand and the o-fluorobenzoic acid are 0.004-0.006mol/L and 0.200-0.210mol/L respectively.
7. Use of a yttrium-based metal-organic framework material according to claim 2, characterized in that: in the step (2), ultrasonic mixing is adopted for mixing.
8. Use of a yttrium-based metal-organic framework material according to claim 7, characterized in that: in the ultrasonic mixing, the ultrasonic frequency is 20-30KHz, and the ultrasonic time is 5-10 min.
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