CN112552522A - Adenine and terephthalic acid with Zn2+Constructed MOFs material and preparation method thereof - Google Patents
Adenine and terephthalic acid with Zn2+Constructed MOFs material and preparation method thereof Download PDFInfo
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Abstract
The invention provides adenine, terephthalic acid and Zn2+The constructed MOFs material and the preparation method thereof belong to the technical field of metal organic framework materials. Adenine and terephthalic acid with Zn2+The crystallinity of the constructed MOFs material is good, and the grain size is 10-100 μm. The preparation method of the MOFs material comprises the steps of respectively dissolving zinc salt, adenine and terephthalic acid in a solvent to prepare a stock solution, and then mixing according to Zn2+The mass ratio of the ions adenine to terephthalic acid is (1.5-3.5) mol, (0.6-1.2) mol, (1-2.5) mol, the stock solution is mixed and then is subjected to a sealed reaction, and the metal organic framework material with a novel structure is obtained. According to the invention, the regulation of the MOF structure can be realized by introducing terephthalic acid as a second ligand, and the material has high porosity and good stability.
Description
Technical Field
The present invention belongs to the field of metal-organic frame material technologyField of adenine and terephthalic acid with Zn2+Constructed MOFs materials and a preparation method thereof.
Background
The metal organic frameworks (also called porous co-polymers, MOFs) are a new type of crystalline porous material, and are one of the hot spots of material research in recent years due to their unique properties and broad application prospects. The material is constructed by organic ligands and inorganic metal units, an extended and regular network structure is formed by metal ions/clusters and organic connectors through coordination bonds, so that a highly functionalized pore space is generated in crystal lattices, and the material has the characteristics of high porosity, low density, large specific surface area, regular pore channels, adjustable pore diameter, diversity of topological structures and the like, and is widely applied to the fields of gas adsorption, separation, purification, storage, sensing, catalysis and the like.
At present, the research of metal-organic framework materials is still in an initial stage, the classes of the biologically applicable MOFs are few, most of the metal-organic framework materials take organic matters containing benzene rings as ligands, the biocompatibility of the materials is not researched too much, and the main problem at present is to expand the classes of the biological MOFs and widen the application of the biological MOFs in the biological field.
Research shows that the nucleobase has rich self-assembly characteristic and may be used in structure assembly and function design of coordination polymer. The application of nucleobases as organic linkers has significant features and allows the construction of a wide variety of bioMOFs. Adenine is used as a component of human nucleic acid, and has good biocompatibility; meanwhile, the adenine is used as a rigid ligand, so that the stability of the material can be greatly improved; in addition, adenine has multiple coordination sites, providing multiple possibilities for MOF structures. However, because adenine has low symmetry, it is difficult to obtain a material with more symmetry and larger pores, so it is considered that the symmetry of the material can be improved by introducing a second ligand with high symmetry. Jihyun An et al synthesized Bio-MOF-1(An J, Geib S J, Rosi N L.Caption-triggered drug release from a pore zinc-adenate metallic-organic frame, 2009,131(24):8376-7.) using biphenyldicarboxylic acid as the second ligand, zinc ion as the central ion, and specific surface of the material as the main ligandUp to 1700m2Per g, over Na+Triggering the release of the procainamide drug. Edwin A. Giles-Maz Lo n, etc. synthesized the MOF structure with Zn ion as the center ion, adenine as the main ligand, and 1,3, 5-isophthalic acid as the second ligand (Giles-Maz Lo n, Edwin A, Germ a n-Ramos, Iv a n, Romero-Romero F, et al. Synthesis and catalysis of a Bio-MOF based on mixed addition/tricarboxylate ligand and catalysis [ J]Inorganica Chimica Acta,2018: S0020169317307867.), a synthetic metal-organic framework pair N2And CO2Has poor adsorption and desorption effects, and the BET test result is only 16.7m2/g。
The structure of the terephthalic acid is symmetrical, the formed pore channel is more regular, the adjustment of the MOF pore size can be realized by introducing the second ligand, and the material synthesized by the second ligand has good structural symmetry and stability. Meanwhile, the terephthalic acid serving as a drug intermediate also has certain biocompatibility, and is expected to serve as a second ligand to construct a brand new biocompatible MOF structure. In addition, the zinc element is used as an essential trace element of a human body, has a great effect on the health of the human body, and the lack of zinc can cause symptoms of low immunity, poor appetite and the like. And the daily maximum intake of zinc element is relatively high, so Zn is adopted2+The central ion is preferably selected.
The invention provides a metal organic framework material which takes adenine as a main ligand, terephthalic acid as a second ligand and zinc ions as central ions, can greatly improve the biocompatibility and stability of the material, has good prospect in the field of drug controlled release, and is hopefully applied to the aspects of gas adsorption, catalysis and the like.
Disclosure of Invention
In view of the above, the present invention provides a method for preparing adenine, terephthalic acid and Zn with environmental protection, simplicity and low cost2+Constructed MOFs materials and a preparation method thereof.
The metal-organic framework material is characterized by using Zn2+As central ion, adenine as main ligand and terephthalic acid as secondary ligand; good crystallinity and grain sizeInch at 10-100 μm.
The invention also provides a preparation method of the organic metal framework material, which comprises the following steps:
(1) weighing 0.05-0.15 g of adenine, dissolving the adenine in 5-35 mL of organic solvent to obtain a solution A with the concentration of 0.03-0.08 mol/L, weighing 0.10-0.50 g of terephthalic acid, dissolving the terephthalic acid in 5-20 mL of organic solvent to obtain a solution B with the concentration of 0.1-0.6 mol/L, weighing 0.20-1.20 g of zinc salt, dissolving the zinc salt in 10-35 mL of organic solvent to obtain a solution C with the concentration of 0.03-0.28 mol/L;
(2) measuring 5-35 mL of solution A and 5-30 mL of solution B, mixing, adding 5-15 mL of ethanol and 1-5 mL of H2O to obtain a solution D;
(3) weighing 10-35 mL of solution C, mixing with the solution D obtained in the step (2), and stirring for 10-15 s by using a glass rod to obtain a uniform reaction solution;
(4) transferring the reaction liquid obtained in the step (3) into a polytetrafluoroethylene lining reaction kettle to perform closed reaction for 24-48 hours at the temperature of 80-120 ℃;
(5) and cooling to room temperature after the reaction is finished, separating to obtain a precipitate, washing with N, N-2-methylformamide for 3-5 times, washing with absolute ethyl alcohol for 3-5 times, and drying at 100-170 ℃ for 5-10 hours to obtain a product.
The zinc salt in the step (1) is zinc acetate or zinc nitrate, preferably zinc acetate.
The organic solvent in step (1) comprises N, N-2-methylformamide or dimethyl sulfoxide, preferably N, N-2-methylformamide.
The invention has the beneficial effects that:
(1) according to the preparation method, adenine is used as a main ligand, and terephthalic acid is used as a second ligand to prepare the MOF structure, so that the structural adjustability of the material can be realized and the porosity can be improved compared with the method that adenine is used as a single ligand.
(2) Selected central ion (Zn) of the invention2+) The metal organic framework material is a metal organic framework material which has biocompatibility and structural stability.
(3) The metal organic framework material synthesized by the invention can become a sustained and controlled release drug carrier material with good biocompatibility and stable structure.
Description of the drawings:
FIG. 1 is an XRD spectrum of the powder prepared in example 2 of the present invention.
FIG. 2 is an SEM spectrum of the powder prepared in example 2 of the present invention.
The specific implementation mode is as follows:
the invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the invention defined by the appended claims.
The specific implementation mode is as follows:
example 1
Dissolving 0.0006mol of adenine (0.0811g) in 10mLN, N-2 methylformamide, heating to 140 ℃ while magnetically stirring until the adenine is completely dissolved in the N, N-2 methylformamide, and cooling to room temperature to obtain a solution A with the concentration of 0.06 mol/L; dissolving 0.0001mol of terephthalic acid (0.1660g) in 10ml of N, N-2 methyl formamide, and carrying out magnetic stirring for a period of time until the terephthalic acid is completely dissolved in the N, N-2 methyl formamide to obtain a solution B with the concentration of 0.1 mol/L; dissolving 0.002mol of zinc acetate (0.4390g) in 40mLN, N-2 methyl formamide, and carrying out magnetic stirring for a period of time until the zinc acetate is completely dissolved in the N, N-2 methyl formamide to obtain a solution C with the concentration of 0.05 mol/L; firstly, measuring 10mL of solution A and 9mL of solution B by using a pipette, and mixing to obtain solution D; sequentially adding 4mL of ethanol and 1mL of water into the solution D to obtain a solution E; mixing 30mL of the solution C with the solution E, uniformly stirring to obtain a reaction solution, and transferring the reaction solution to a polytetrafluoroethylene lining reaction kettle; putting the polytetrafluoroethylene lining reaction kettle into an oven, heating to 90 ℃, and then heating at 90 ℃ for 36 hours; after heating is finished, after the reaction liquid is cooled to room temperature, opening the lining reaction kettle to pour out supernatant, adding an organic solvent N, N-2 methylformamide into the residual white precipitate, performing suction filtration treatment for 3 times, washing for 3 times by using absolute ethyl alcohol, after centrifugation is finished, placing the obtained product in a drying oven, drying for 8 hours at 100 ℃, and after subsequent treatment is finished, obtaining material powder.
Example 2
Dissolving 0.0005mol of adenine (0.0676g) in 10mLN, N-2 methylformamide, heating to 140 ℃ while magnetically stirring until the adenine is completely dissolved in the N, N-2 methylformamide, and cooling to room temperature to obtain a solution A with the concentration of 0.05 mol/L; dissolving 0.0001mol of terephthalic acid (0.1660g) in 10ml of N, N-2 methyl formamide, and carrying out magnetic stirring for a period of time until the terephthalic acid is completely dissolved in the N, N-2 methyl formamide to obtain a solution B with the concentration of 0.1 mol/L; dissolving 0.0015mol of zinc acetate (0.3293g) in 30mLN, N-2-methylformamide, and carrying out magnetic stirring for a period of time until the zinc acetate is completely dissolved in the N, N-2-methylformamide to obtain a solution C with the concentration of 0.05 mol/L; firstly, measuring 10mL of solution A and 10mL of solution B, and mixing to obtain solution D; sequentially adding 4mL of ethanol and 1mL of water into the solution D to obtain a solution E; taking a pipette to measure 25mL of solution C and solution E, mixing, uniformly stirring to obtain a reaction solution, and transferring the reaction solution to a polytetrafluoroethylene lining reaction kettle; putting the polytetrafluoroethylene lining reaction kettle into an oven, heating to 90 ℃, and then heating at 90 ℃ for 36 hours; after heating is finished, after the reaction liquid is cooled to room temperature, opening the lining reaction kettle to pour out supernatant, adding an organic solvent N, N-2 methyl formamide into the residual white precipitate, performing suction filtration treatment for 3 times, washing for 3 times by using absolute ethyl alcohol, after centrifugation is finished, placing the obtained product in a drying box, drying for 6 hours at 110 ℃, and after subsequent treatment is finished, obtaining material powder.
Example 3
Dissolving 0.0015mol of adenine (0.2027g) in 30mLN, N-2 methylformamide, heating to 140 ℃ while magnetically stirring until the adenine is completely dissolved in the N, N-2 methylformamide, and cooling to room temperature to obtain a solution A with the concentration of 0.05 mol/L; dissolving 0.0025mol of terephthalic acid (0.4153g) in 10mLN, N-2-methylformamide, and carrying out magnetic stirring for a period of time until the terephthalic acid is completely dissolved in the N, N-2-methylformamide to obtain a solution B with the concentration of 0.25 mol/L; dissolving 0.005mol of zinc acetate (1.0975g) in 20mLN, N-2 methyl formamide, and carrying out magnetic stirring for a period of time until the zinc acetate is completely dissolved in the N, N-2 methyl formamide to obtain a solution C with the concentration of 0.25 mol/L; firstly, measuring 25mL of solution A and 10mL of solution B, and mixing to obtain solution D; adding 10mL of ethanol and 2.5mL of water into the solution D in sequence to obtain a solution E; taking a pipette to measure 10mL of solution C and solution E, mixing, uniformly stirring to obtain a reaction solution, and transferring the reaction solution to a polytetrafluoroethylene lining reaction kettle; putting the polytetrafluoroethylene lining reaction kettle into an oven, heating to 110 ℃, and then heating for 30h at 110 ℃; after heating is finished, after the reaction liquid is cooled to room temperature, opening the lining reaction kettle to pour out supernatant, adding an organic solvent N, N-2 methyl formamide into the residual white precipitate, performing suction filtration treatment for 3 times, washing for 3 times by using absolute ethyl alcohol, after centrifugation is finished, placing the obtained product in a drying box, drying for 6 hours at 120 ℃, and after subsequent treatment is finished, obtaining material powder.
Example 4
Dissolving 0.001mol of adenine (0.1352g) in 20ml of N, N-2-methylformamide, heating to 140 ℃ while magnetically stirring until the adenine is completely dissolved in the N, N-2-methylformamide, and cooling to room temperature to obtain a solution A with the concentration of 0.05 mol/L; dissolving 0.002mol of terephthalic acid (0.3323g) in 10mLN, N-2 methyl formamide, and carrying out magnetic stirring for a period of time until the terephthalic acid is completely dissolved in the N, N-2 methyl formamide to obtain a solution B with the concentration of 0.2 mol/L; dissolving 0.003mol of zinc acetate (0.6585g) in 20mLN, N-2 methyl formamide, and carrying out magnetic stirring for a period of time until the zinc acetate is completely dissolved in the N, N-2 methyl formamide to obtain a solution C with the concentration of 0.15 mol/L; firstly, measuring 20mL of solution A and 7.5mL of solution B by using a pipette, and mixing to obtain a solution D; adding 8mL of ethanol and 2mL of water into the solution D in sequence to obtain a solution E; taking a pipette to measure 17mL of solution C and solution E, mixing, uniformly stirring to obtain a reaction solution, and transferring the reaction solution to a polytetrafluoroethylene lining reaction kettle; putting the polytetrafluoroethylene lining reaction kettle into an oven, heating to 90 ℃, and then heating at 90 ℃ for 36 hours; after heating is finished, after the reaction liquid is cooled to room temperature, opening the lining reaction kettle, pouring out supernatant, adding an organic solvent N, N-2 methylformamide into the residual white precipitate, performing suction filtration treatment for 3 times, washing for 3 times by using absolute ethyl alcohol, after centrifugation is finished, placing the obtained product in a drying oven, drying for 5 hours at 130 ℃, and after subsequent treatment is finished, obtaining material powder.
Example 5
Dissolving 0.0007mol of adenine (0.0946g) in 10mLN, N-2 methylformamide, heating to 140 ℃ while magnetically stirring until the adenine is completely dissolved in the N, N-2 methylformamide, and cooling to room temperature to obtain a solution A with the concentration of 0.07 mol/L; dissolving 0.0015mol of terephthalic acid (0.2492g) in 10mLN, N-2-methylformamide, and carrying out magnetic stirring for a period of time until the terephthalic acid is completely dissolved in the N, N-2-methylformamide to obtain a solution B with the concentration of 0.15 mol/L; dissolving 0.0025mol of zinc acetate (0.5488g) in 25mLN, N-2-methylformamide, and carrying out magnetic stirring for a period of time until the zinc acetate is completely dissolved in the N, N-2-methylformamide to obtain a solution C with the concentration of 0.1 mol/L; firstly, measuring 10mL of solution A and 9mL of solution B by using a pipette, and mixing to obtain solution D; sequentially adding 4mL of ethanol and 1mL of water into the solution D to obtain a solution E; mixing 21mL of the solution C with the solution E, uniformly stirring to obtain a reaction solution, and transferring the reaction solution to a polytetrafluoroethylene lining reaction kettle; putting the polytetrafluoroethylene lining reaction kettle into an oven, heating to 120 ℃, and then heating at 120 ℃ for 24 hours; after heating is finished, after the reaction liquid is cooled to room temperature, opening the lining reaction kettle to pour out supernatant, adding an organic solvent N, N-2 methylformamide into the residual white precipitate, performing suction filtration treatment for 3 times, washing for 3 times by using absolute ethyl alcohol, after centrifugation is finished, placing the obtained product in a drying oven, drying for 5 hours at 150 ℃, and after subsequent treatment is finished, obtaining material powder.
Claims (6)
1. Adenine and terephthalic acid with Zn2+The constructed MOFs material is characterized by comprising the following components: with Zn2+As the central ion, adenine is the main ligand and terephthalic acid is the secondary ligand.
2. Adenine and terephthalic acid as in claim 1 and Zn2+Constructed MOFs materials characterized by Zn2+The mass ratio of the ions adenine and terephthalic acid is (1.5-3.5) mol, (0.6-1.2) mol, (1-2.5) mol.
3. Adenine and terephthalic acid as in claim 1 and Zn2+The constructed MOFs material is characterized by good crystallinity and grain size of 10-100 μm.
4. Adenine and terephthalic acid as in claim 1 and Zn2+The preparation method of the constructed MOFs material is characterized by comprising the following steps:
(1) weighing 0.05-0.15 g of adenine, dissolving the adenine in 5-35 mL of organic solvent to obtain a solution A with the concentration of 0.03-0.08 mol/L, weighing 0.10-0.50 g of terephthalic acid, dissolving the terephthalic acid in 5-20 mL of organic solvent to obtain a solution B with the concentration of 0.1-0.6 mol/L, weighing 0.20-1.20 g of zinc salt, dissolving the zinc salt in 10-35 mL of organic solvent to obtain a solution C with the concentration of 0.03-0.28 mol/L;
(2) measuring 5-35 mL of solution A and 5-30 mL of solution B, mixing, adding 5-15 mL of ethanol and 1-5 mL of H2O to obtain a solution D;
(3) weighing 10-35 mL of solution C, mixing with the solution D obtained in the step (2), and stirring for 10-15 s by using a glass rod to obtain a uniform reaction solution;
(4) transferring the reaction liquid obtained in the step (3) into a polytetrafluoroethylene lining reaction kettle to perform closed reaction for 24-48 hours at the temperature of 80-120 ℃;
(5) and cooling to room temperature after the reaction is finished, separating to obtain a precipitate, washing for 3-5 times by using N, N-2-methylformamide, washing for 3-5 times by using absolute ethyl alcohol, and drying for 5-10 hours at the temperature of 100-170 ℃ to obtain a product.
5. Adenine and terephthalic acid as in claim 4 and Zn2+The preparation method of the constructed MOFs material is characterized by comprising the following steps: the organic solvent in the step (1) is N, N-2-methylformamide or dimethyl sulfoxide, and preferably N, N-2-methylformamide.
6. Adenine and terephthalic acid as in claim 4 and Zn2+The preparation method of the constructed MOFs material is characterized by comprising the following steps: the zinc salt in the step (1) is zinc acetate or zinc nitrate, preferably zinc acetate.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113426489A (en) * | 2021-07-09 | 2021-09-24 | 常州大学 | adenine/UiO-66 composite catalyst for piezoelectric degradation of rhodamine B in dark state and preparation method thereof |
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| CN111635537A (en) * | 2020-07-08 | 2020-09-08 | 浙江理工大学 | Metal-organic framework material and preparation method and application thereof |
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| CN108384025A (en) * | 2018-04-08 | 2018-08-10 | 东华大学 | A kind of biological MOF and preparation method thereof based on adenine |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113426489A (en) * | 2021-07-09 | 2021-09-24 | 常州大学 | adenine/UiO-66 composite catalyst for piezoelectric degradation of rhodamine B in dark state and preparation method thereof |
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Application publication date: 20210326 |