阅读说明：本技术 基于5-(4-咪唑-1-苯基)-1H-四唑的Zn(Ⅱ)手性MOF材料 (Zn (II) chiral MOF materials based on 5- (4-imidazole-1-phenyl) -1H-tetrazoles ) 是由 王军杰 马志敏 李雷 张仁春 张道军 张有娟 于 2019-10-16 设计创作，主要内容包括：本发明公开了一种基于5-(4-咪唑-1-苯基)-1H-四唑的Zn(II)手性金属有机骨架材料,该Zn(II)手性金属有机骨架材料是以L组氨酸(L-His)为模板剂,将5-(4-咪唑-1-苯基)-1H-四唑(HL)与Zn(NO<Sub>3</Sub>)<Sub>2</Sub>·6H<Sub>2</Sub>O溶于DMF(N,N-二甲基甲酰胺)中,用浓硫酸调节溶液pH值,而后采用溶剂热方法获得,将该Zn(II)手性金属有机骨架材料用作色谱法手性拆分实验的手性固定相材料拆分丙氨酸,对丙氨酸具有良好的分离效果。(The invention discloses a Zn (II) chiral metal organic framework material based on 5- (4-imidazole-1-phenyl) -1H-tetrazole, wherein the Zn (II) chiral metal organic framework material takes L-histidine (L-His) as a template agent, and 5- (4-imidazole-1-phenyl) -1H-tetrazole (HL) and Zn (NO) 3 ) 2 ·6H 2 Dissolving O in DMF (N, N-dimethylformamide), adjusting pH with concentrated sulfuric acid, and separating alanine with Zn (II) chiral metal organic framework material as chiral stationary phase material for chromatography chiral separation experimentThe acid has good separation effect.)

1. The Zn (II) chiral metal organic framework material based on 5- (4-imidazole-1-phenyl) -1H-tetrazole is characterized in that the Zn (II) chiral metal organic framework material is obtained by a solvothermal method by using 5- (4-imidazole-1-phenyl) -1H-tetrazole and Zn (II) ions and taking L histidine as a template agent.

2. The 5- (4-imidazol-1-phenyl) -1H-tetrazole based zn (ii) chiral metal-organic framework material of claim 1, wherein the structure of the zn (ii) chiral metal-organic framework material is: the metal organic framework material comprises a half Zn (II) ion, a deprotonated 5- (4-imidazole-1-phenyl) -1H-tetrazole and a free L-histidine molecule in an asymmetric unit; each Zn (II) ion forms a four-coordinate with four N atoms of four 5- (4-imidazol-1-phenyl) -1H-tetrazole ligands, exhibiting a distorted tetrahedral coordination configuration; by bridging of the 5- (4-imidazole-1-phenyl) -1H-tetrazole ligand, the adjacent Zn (II) ions form a two-dimensional 4⁴The network structure, free L histidine molecule is occupied in one-dimensional pore channel.

3. The preparation method of 5- (4-imidazole-1-phenyl) -1H-tetrazole-based Zn (II) chiral metal-organic framework material as claimed in claim 1, comprising the following steps:

mixing 5- (4-imidazole-1-phenyl) -1H-tetrazole, L-histidine and Zn (NO)₃)₂·6H₂Dissolving the mixture of O in DMF (N, N-dimethylformamide), adjusting the pH value of the solution to 3 ~ 4 with concentrated sulfuric acid, ultrasonically dissolving the obtained solution, placing the solution in a reaction bottle, placing the reaction bottle in a drying box at 100 ~ 110 ℃ for constant temperature of 48 ~ 60 hours, washing with ethanol, and drying to obtain the crystal of the Zn (II) chiral metal organic framework material.

4. The method for preparing 5- (4-imidazole-1-phenyl) -1H-tetrazole based Zn (II) chiral metal-organic framework material of claim 3, wherein the 5- (4-imidazole-1-phenyl) -1H-tetrazole, the L-histidine and the Zn (NO)₃)₂·6H₂The molar ratio of O is 2 ~ 3: 2: 1.

5. The 5- (4-imidazol-1-phenyl) -1H-tetrazole based zn (ii) chiral metal organic framework material of claim 1, wherein the zn (ii) chiral metal organic framework material is used as a chiral stationary phase material for chromatography chiral resolution experiments.

6. The 5- (4-imidazol-1-phenyl) -1H-tetrazole based Zn (II) chiral metal-organic framework material of claim 5, wherein the Zn (II) chiral metal-organic framework material is used as a chiral stationary phase material for chromatography chiral resolution experiments for resolution of alanine.

Technical Field

The invention belongs to the technical field of metal organic framework materials, and particularly relates to a Zn (II) chiral Metal Organic Framework (MOF) material based on 5- (4-imidazole-1-phenyl) -1H-tetrazole, and a preparation method and application thereof.

Background

Chirality is a common phenomenon in nature and is one of the essential attributes by which humans live, most macromolecules in a living system only play a role in a chiral enantiomer form, and a molecular recognition system of the chirality has extremely strong chiral recognition capability. For example, a chiral drug enters a living organism, often only one enantiomer is effective, while its mirror molecule either has no effect at all, or has the opposite effect, or has toxic side effects. In addition to drugs, modern research also shows that enantiomers of chiral compounds such as food, spices, pheromones, herbicides, pesticides and the like often show obvious differences in biological activity and physiological activity when acting with biological receptors; therefore, the research on the method for obtaining single enantiomer molecules and the application thereof becomes one of the frontiers and hot spots of the contemporary chemical research; at present, the chromatographic resolution method is the most common chiral resolution method with wide application, and although great progress is made in the separation of chiral drug enantiomers, the application of the chiral stationary phase material suitable for chromatographic resolution is limited due to the shortage of the chiral stationary phase material.

Disclosure of Invention

In view of the shortcomings of the prior art, the present invention aims to provide a Zn (II) chiral Metal Organic Framework (MOF) material based on 5- (4-imidazole-1-phenyl) -1H-tetrazole, which has good separation effect on DL alanine (DL-Ala) as a chiral stationary phase material for chromatographic resolution.

In order to achieve the purpose, the technical scheme of the invention is as follows:

a Zn (II) chiral metal organic framework material based on 5- (4-imidazole-1-phenyl) -1H-tetrazole is obtained by a solvothermal method by using 5- (4-imidazole-1-phenyl) -1H-tetrazole (HL) and Zn (II) ions and taking L-histidine (L-His) as a template agent.

Further, the structure of the Zn (II) chiral metal-organic framework material is as follows: the metal organic framework material comprises half Zn (II) ion, a deprotonated 5- (4-imidazole-1-phenyl) -1H-tetrazole (HL) and a free L-histidine (L-His) molecule in an asymmetric unit; each Zn (II) ion forms a four-coordinate with four N atoms of four 5- (4-imidazol-1-phenyl) -1H-tetrazole ligands, exhibiting a distorted tetrahedral coordination configuration; by bridging of the 5- (4-imidazole-1-phenyl) -1H-tetrazole ligand, the adjacent Zn (II) ions form a two-dimensional 4⁴The network structure, free L histidine (L-His) molecules are occupied in one-dimensional pore channels.

Further, the preparation method of the Zn (II) chiral metal-organic framework material specifically comprises the following steps:

mixing 5- (4-imidazole-1-phenyl) -1H-tetrazole (HL), L-histidine (L-His) and Zn (NO)₃)₂·6H₂Dissolving the mixture of O in DMF (N, N-dimethylformamide), adjusting the pH value of the solution to 3 ~ 4 with concentrated sulfuric acid, ultrasonically dissolving the obtained solution, placing the solution in a reaction bottle, placing the reaction bottle in a drying box at 100 ~ 110 ℃ for constant temperature of 48 ~ 60 hours, washing with ethanol, and drying to obtain the colorless crystal of the Zn (II) chiral metal organic framework material.

Further, the 5- (4-imidazole-1-phenyl) -1H-tetrazole (HL), L-histidine (L-His), and Zn (NO)₃)₂·6H₂The molar ratio of O is 2 ~ 3: 2: 1.

Further, the Zn (II) chiral metal organic framework material is used as a chiral stationary phase material for chromatographic chiral resolution experiments.

Further, the Zn (II) chiral metal organic framework material is used as a chiral stationary phase material for chromatographic chiral resolution experiments for resolving DL-alanine.

Wherein, the molecular structural formula of the 5- (4-imidazole-1-phenyl) -1H-tetrazole (HL) is as follows:

。

the invention has the advantages of

The invention takes the L histidine (L-His) with single chirality as a template, Zn (II) as a central metal atom and 5- (4-imidazole-1-phenyl) -1H-tetrazole (HL) as a ligand to synthesize the Zn (II) chiral metal organic framework material by adopting a solvothermal method, the synthesis method of the material is simple, and the synthesis conditions are controllable; the chiral complex has stable chiral environment and pore structure, large specific surface area, good chemical stability and thermal stability, can fully interact with guest chiral molecules, and realizes high enantioselectivity to the guest molecules.

The Zn (II) chiral metal organic framework material is used as a chiral stationary phase resolution material, shows excellent separation effect in the separation of DL-alanine (DL-Ala) by capillary gas chromatography, and has potential application value in the aspect of chiral stationary phase materials for chiral separation of alanine.

Drawings

FIG. 1 is a diagram of coordination environment of a Zn (II) chiral metal-organic framework material of the present invention.

FIG. 2 is a structural diagram of a two-dimensional network structure of a Zn (II) chiral metal-organic framework material of the present invention.

FIG. 3 is a separation chromatogram of DL-alanine (DL-Ala) using Zn (II) chiral metal-organic framework material of the present invention as capillary gas chromatography stationary phase material.

Detailed Description

The technical scheme of the invention is further described in the following with reference to the drawings and specific examples, and all reagents and solvents used in the experiment are commercially available and are not directly used after any treatment.