阅读说明：本技术 一种手性mof超分子复合材料的制备方法及其识别青霉胺对映体的应用 (A kind of preparation method of chirality MOF supermolecule composite material and its application for identifying penicillamine enantiomer ) 是由 赵璐 王志玲 于 2019-08-30 设计创作，主要内容包括：本发明公开了手性MOF超分子复合材料的制备及其对青霉胺对映体高效电化学识别的应用,属于纳米材料、电化学手性识别、金属有机框架物材料技术领域。其主要步骤是利用十六烷基二酸与谷氨酸二乙酯合成手性L-谷氨酸双头基两亲分子L-HDGA,继续以乙醇和水为溶剂制得螺旋型排列的L-HDGA模板,采用自组装方法,制得ZIF-67纳米颗粒负载在L-HDGA螺旋结构表面的复合材料,采用该材料电化学手性识别青霉胺对映体,工艺简单,响应快,电化学识别范围大,具有应用前景。(Application the invention discloses the preparation of chiral MOF supermolecule composite material and its to the identification of penicillamine enantiomer high-efficiency electrochemical, belongs to nano material, electrochemistry chiral Recognition, Metal-organic frame material technical field.It, which has main steps that, utilizes cetyl diacid and glutamate diethyl ester synthesis of chiral Pidolidone Bolaamphiphile L-HDGA, continue the L-HDGA template that screw type arrangement is made using second alcohol and water as solvent, using self-assembling method, the composite material that ZIF-67 nano particle is supported on L-HDGA helical structure surface is made, using the material electrochemical chiral Recognition penicillamine enantiomer, simple process, response is fast, electrochemical recognition range is big, has application prospect.)

1. a kind of preparation method of chirality MOF supermolecule composite material, which is characterized in that steps are as follows:

2.0-2.4 g cobalt nitrate is dissolved in 10-20 mL water, it is ultrasonic to obtain cobalt nitrate red, transparent solution；

2.2-2.6 g methylimidazole is dissolved in 10-20 mL water, it is ultrasonic to obtain methylimidazole colourless transparent solution；

80-120 μ L cobalt nitrate solution is taken to be added in chiral helical L-HDGA clear gel, 10 min of ultrasound keep its dispersion equal It is even, 80-120 μ L methylimidazole solution is added, 10 min of ultrasound are filtered and are supported on L- up to ZIF-67 nanocrystal Composite [email protected] ZIF-67 of HDGA helical surface, i.e. chirality MOF supermolecule composite material.

2. the preparation method of chirality MOF supermolecule composite material as described in claim 1, which is characterized in that the chirality spiral shell L-HDGA is revolved, structural formula is as follows:

。

3. the preparation method of chirality MOF supermolecule composite material as described in claim 1, which is characterized in that the chirality spiral shell L-HDGA clear gel is revolved, the preparation method is as follows:

It takes 4-6 mg L-HDGA powder to be dissolved in 0.5 mL dehydrated alcohol and 0.5 mL water, is heated to 70 DEG C and is placed on -4 DEG C of ice 2-4 min forms clear gel under case environment, and chiral helical L-HDGA clear gel is made.

4. a kind of chirality MOF supermolecule composite material of preparation method preparation as described in claim 1 is as identification penicillamine The application of enantiomer.

Technical field

Electrochemistry is used for the present invention relates to a kind of preparation method of chirality MOF supermolecule composite material and based on the material The application for identifying penicillamine enantiomer belongs to nano material, electrochemistry chirality sensing, Metal-organic frame material technology neck Domain.

Background technique

Chirality is most basic in all organisms and one of the property of most attraction, and chirality is also typically present in pharmacy In chemical industry.In general, a pair of of enantiomer with mirror-image structure, one kind showing required biochemical activity, conveyance System and metabolism behavior, and it is alternatively possible cause side effect even serious toxicity.Therefore, exploitation can measure single in sample The effective ways of enantiomer are of great significance, and this method depends on very small between enantiomer and the chiral selector of application Interaction.Therefore, chiral Recognition is considered as one of highest form, and most difficult measurement of molecular recognition.

Currently, having developed the chiral Recognition method that series is of great significance, including gas-chromatography, high-efficient liquid phase color Spectrum, photoelectron circular dichroism spectra (CD), Surface enhanced Raman scattering (SERS) spectrum and nuclear magnetic resonance (NMR) etc..However, still needing Want highly sensitive, inexpensive, easy-operating instrument and easy timesaving method.Electrochemistry chiral sensor table in these areas Reveal special advantage.However, there is effective site and to the novel of the selectivity efficients of certain enantiomers designing and constructing There are still improved challenge is needed on chiral sensor, this is the core of sensing process.

In contemporary electrochemical sensing, due to ultra-high surface area, the crystal structure of high-sequential, uniform and come-at-able position Point and adjustable structure, metal organic frame (MOF) or composite material based on MOF are more and more concerned.Importantly, making There is redox active for the metal ion of coordination center in MOF, and there is the organic ligand of abundant active site can pass through Hydrogen bond, p-p interaction and Van der Waals force and analyte form specific interaction.In addition, the porosity of MOF allows properly Analyte be selectively entered and pass through MOF chamber, which greatly improves MOF to the detection efficiency of target molecule.However, at present The composite material of many achirality MOF and some functional materials composition are developed, the functional material includes metal nano Particle, carbon nano-structured, polymer and biomolecule, these sensing materials are in quantitative judge polysaccharide, C reactive protein, blood coagulation Enzyme, H₂O₂, glucose, dopamine and uric acid etc. there is highly sensitive and selectivity.But for chirality MOF, at present only Two kinds of research for Enantioselective recognition is reported.2017, Kuang et al. illustrated a kind of the pure of no object for the first time Homotype chirality Cu-MOF sensing interface, successfully carried out Alpha-Methyl benzylamine enantiomer differentiation [Kuang, R., Zheng, L. Y., Chi, Y. H., Shi, J. M., Chen, X. X., Zhang, C. C., 2017. RSC Advance. 7, 11701-11706.].The same year, Deng et al. report chiral cyclodextrin MOF(CD-MOF), to realize α-and β-pine alkene pair Reflect differentiation [Deng, C. H., Li, T., Chen, J. H., Ma, the J. G., Cheng, P., 2017. of body Dalton Trans. 46, 6830-6834.].It is identified compared to achirality, the high cost of chiral MOF and stablizes the available of MOF Property, so that being extremely restricted in terms of sensing identification, because they are usually synthesized by expensive homochiral ligand, and in exposure It is not able to maintain its original physics and chemical property after aqueous solution.Therefore, by low cost chiral presoma assembling based on The identification sensor of MOF is particularly attractive and has good development prospect.

Summary of the invention

Technical assignment of the invention first is that in order to make up for the deficiencies of the prior art, it is multiple to provide a kind of screw type chirality MOF Condensation material, the i.e. preparation method of [email protected] self assembly spiral supermolecule nano pipe, the raw materials used cost of this method Low, preparation process is simple, and energy consumption of reaction is low, has prospects for commercial application.

The two of technical assignment of the invention are to provide a kind of purposes of screw type chirality MOF composite material, i.e., should L-HDGA ZIF-67 self assembly spiral supermolecule nano pipe is used for efficient qualitative, quantitative electrochemical recognition penicillamine enantiomerism Body, the catalyst have very excellent recognition effect and stability.

To achieve the above object, The technical solution adopted by the invention is as follows:

1. a kind of preparation method of chirality MOF supermolecule composite material, steps are as follows:

2.0-2.4 g cobalt nitrate is dissolved in 10-20 mL water, it is ultrasonic to obtain cobalt nitrate red, transparent solution；

2.2-2.6 g methylimidazole is dissolved in 10-20 mL water, it is ultrasonic to obtain methylimidazole colourless transparent solution；

80-120 μ L cobalt nitrate solution is taken to be added in chiral helical L-HDGA clear gel, 10 min of ultrasound keep its dispersion equal It is even, 80-120 μ L methylimidazole solution is added, 10 min of ultrasound are filtered and are supported on L- up to ZIF-67 nanocrystal Composite [email protected] ZIF-67 of HDGA helical surface, i.e. chirality MOF supermolecule composite material.

1) the chiral helical L-HDGA clear gel, the preparation method is as follows:

It takes 4-6 mg L-HDGA powder to be dissolved in 0.5 mL dehydrated alcohol and 0.5 mL water, is heated to 70 DEG C and is placed on -4 DEG C of ice 2-4 min forms clear gel under case environment, and chiral helical L-HDGA clear gel is made.

2) the L-HDGA powder, the preparation method is as follows:

0. 855 g cetyl diacid are dissolved in 30 mL petroleum ethers, until it is sub- that 3 mL dichloros are added dropwise dropwise after starting reflux Sulfone, flow back 8h, obtains colourless oil liquid；

0.475 mg Pidolidone diethyl ester hydrochloride is added to the mixed solution of 3 mL triethylamines and 10 mL methylene chloride In, 0.645 g colourless oil liquid is added under ice-water bath after 30 min are stirred at room temperature, 3h is stirred at room temperature;

Mixed solution is used respectively 10 mL distillation washing 3 times, 10 mL 2M HCl are washed once, and 10 mL saturated sodium bicarbonates are molten Liquid is washed once, and 10 mL distillation washing is primary；

Dichloromethane solvent in mixed solution is distilled, white solid is obtained, it is molten that 10 mL 3M sodium hydroxides are added Liquid, and 3h is stirred at 40 DEG C, it is 1 that 6 M HCl of gained clear solution, which adjust PH, dry after suction filtration.

3) L-HDGA, structural formula are as follows:

。

2. a kind of chirality MOF supermolecule composite material as described above is as electrochemical recognition penicillamine chiral enantiomer Application, steps are as follows:

1) chiral sensor working electrode is prepared

After the glass-carbon electrode that diameter is 4 mm is polished with alumina powder, water and ethyl alcohol clean surface, and it is chiral to pipette 10 μ L MOF supermolecule composite material solution, room temperature are dried, and MOF supermolecule composite material chiral sensor working electrode is obtained；

The chirality MOF supermolecule composite material solution, be by 6 mg chirality MOF supermolecule composite materials and 250 μ L ethyl alcohol, 720 μ L water and 30 μ L Nafion are blended, and 180W ultrasound 10-15min is made；

2) chiral enantiomer is detected

By working electrode made from step 1), Ag/AgCl reference electrode and platinized platinum (mm × 0.1 of 5 mm × 5 mm) auxiliary electrode It is connected on electrochemical workstation, chirality MOF supermolecule composite material chiral sensor is made；

With 0.5 molL^-1KOH be that electrolyte solution using differential pulse voltammetry utilizes MOF supermolecule composite material Chiral sensor measures the L- penicillamine of various concentration and the current value of Beracilline standard solution respectively, draws super based on MOF The L- penicillamine and Beracilline enantiomer working curve of molecular composite material chiral sensor；The solution of sample to be tested is replaced L- penicillamine and Beracilline standard solution carry out the detection of L- penicillamine and Beracilline content in sample.

The chiral sensor is 1.0 × 10 to the detection range of L- penicillamine and Beracilline mapping liquid solution^-2-2.7× 10^-10 g/mL。

Beneficial technical effect of the invention:

1. a kind of chirality MOF supermolecule composite material produced by the present invention is that ZIF-67 nano particle room temperature self-assembled growth exists L-HDGA helical structure surface and obtain.Preparation process simple process, it is simple and easy to control, it is easy to industrialize.

2. L-HDGA used in the present invention belongs to end Pidolidone Bolaamphiphile spiral-shaped structure, chiral MOF For supermolecule composite material, due to being that ZIF-67 nano-particles self assemble is grown in the L-HDGA helical structure Surface Creation Composite material not only has the active site of L-HDGA, and there are also ZIF-67 nanocrystals and the helical configuration of formation to penicillamine The synergistic effect of enantiomer, to form efficient electrochemistry chiral Recognition.

Specific embodiment

The present invention will be further described below with reference to examples, but protection scope of the present invention is not only limited to implement Example, professionals in the field change to made by technical solution of the present invention, are within the scope of protection of the invention interior.