CN111413379A - Preparation method and application of chiral Ni-MOF/NiSR core-shell composite material - Google Patents
Preparation method and application of chiral Ni-MOF/NiSR core-shell composite material Download PDFInfo
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Abstract
The invention discloses a preparation method of a chiral Ni-MOF/NiSR core-shell composite material and application of the material in detecting chiral enantiomers, and belongs to the technical fields of nano catalysis, chiral sensing and the like.
Description
Technical Field
The invention relates to a preparation method and application of a chiral Ni-MOF/NiSR core-shell composite material, and belongs to the technical fields of nano materials, metal organic complex polymers, catalysis and the like.
Background
Chirality is a common phenomenon in nature and one of essential attributes of human survival, various biochemical reaction processes occurring in the life process are closely related to chiral recognition and change, and in recent years, people's understanding and research on the problem of chirality have been advanced from simple molecular chirality to the chiral research field at the level of more diversified supramolecular chirality and the like. Except the common chiral assembly phenomenon in the nature, the chiral assembly structure with wide variety and multiple functions is constructed through manual design.
Chiral assembly refers to chiral or achiral molecules that are bound together through intermolecular interactions, such as hydrogen bonds, van der waals forces, coordination bonds, static electricity, stacking, and the like, to form chiral aggregates with definite microstructures and functional characteristics, which exhibit unique properties that a single molecule does not have, such as good thermal stability, optical activity, easy chemical modification, and the like, and are widely used in asymmetric synthesis, enantiomer recognition and separation, photoelectric material sensors, and the like. Therefore, the assembly of the novel chiral aggregate and the technical development of the application are the research directions with application prospects and challenges, and the method has important significance for scientific exploration of high-tech products in the fields of chemical engineering, biomedicine, nanotechnology and the like in the future.
The increasing proportion of chiral products, such as pharmaceuticals, produced and used today requires that efficient, rapid and convenient methods for detecting and identifying chiral drugs must be sought. In recent years, many developed countries have been promulgating guidelines or policies for the development of chiral drugs in order to solve some of the problems associated with racemic drugs. Therefore, the identification of the chiral drug has important significance for researching the reasonable and accurate use of the chiral drug, controlling the quality of the chiral drug and the like. The chiral identification research method mainly comprises chiral chromatography, spectrum and electrochemical chiral sensors. Among them, the chromatographic method has been widely used for separating and analyzing chiral compounds, but the method has certain disadvantages, such as high instrument cost, long analysis time, and particularly difficult in-situ and on-line detection. The electrochemical sensor has the advantages of simple preparation, low cost, high identification efficiency and the like, and has wide research value when being used for identifying chiral substances.
Disclosure of Invention
One of the technical tasks of the invention is to make up the defects of the prior art and provide a preparation method of a chiral Ni-MOF/NiSR core-shell composite material, and the method has the advantages of low cost of used raw materials, simple preparation process, low reaction energy consumption and industrial application prospect.
The second technical task of the invention is to provide the application of the chiral Ni-MOF/NiSR core-shell composite material, namely, the chiral Ni-MOF/NiSR core-shell composite material is used for detecting the content of L-histidine and D-histidine enantiomers, and the detection instrument has the advantages of low cost, high analysis efficiency, convenient operation and low operation technical requirement.
The technical scheme of the invention is as follows:
1. preparation method of chiral Ni-MOF/NiSR core-shell composite material
Mixing 5-7 mmol of nickel chloride hexahydrate and 3-5mmol of m-benzenetricarboxylic acid with 7-10 m of L water, adding 2-4 m of L and 3-5mmol of NaOH solution, carrying out ultrasonic treatment at room temperature of 180W for 3 min, continuously adding 5-10 m of L ethanol, carrying out ultrasonic treatment at room temperature of 180W for 3 min, carrying out centrifugal separation, and washing with water for 3 times to obtain Ni-MOF;
adding 10-15m L and 0.2 mol L into the prepared Ni-MOF-1Magnetically stirring the D-penicillamine aqueous solution for 1 h, centrifugally separating, washing with water for 3 times, and drying at 85 ℃ to constant weight to prepare the chiral Ni-MOF/NiSR core-shell composite material.
The SR has the following structural formula:
the Ni-MOF of the formula Ni3(BTC)2·12H2O, a metal-organic framework, one structural unit of which is composed of 3 Ni2+And 2 BTCs3-And 12 water molecules; BTC3-Is the m-benzene tricarboxylic acid (III) negative ion.
2. The chiral Ni-MOF/NiSR core-shell composite material prepared by the preparation method is applied to electrochemical sensing and enantiomer detection.
(1) Preparation of working electrode of chiral sensor
Dripping 6 mu L chiral Ni-MOF/NiSR core-shell composite material suspension on the surface of a 4 mm glassy carbon electrode which is polished by alumina powder and cleaned by water and ethanol, and airing at room temperature to prepare a working electrode of the Ni-MOF/NiSR chiral sensor;
the chiral Ni-MOF/NiSR core-shell composite material suspension is prepared by blending 3 mg of chiral Ni-MOF/NiSR core-shell composite material with 250 mu L isopropanol, 720 mu L water and 30 mu L Nafion and carrying out ultrasonic treatment in a water bath of 180W for 10-15 min;
(2) construction of chiral electrochemical sensors
Connecting a working electrode of the Ni-MOF/NiSR chiral sensor, a saturated calomel reference electrode and a platinum wire counter electrode on an electrochemical workstation to prepare the Ni-MOF/NiSR chiral electrochemical sensor;
(3) detection of L-histidine and D-histidine enantiomers
At a pH of 7.0, 0.1 mol. L-1The PBS buffer solution is electrolyte, the chiral electrochemical sensor prepared in the step (2) is adopted, current values of L-histidine and D-histidine standard solutions with different concentrations are respectively measured by adopting a differential pulse voltammetry method, working curves of L-histidine amine and D-histidine enantiomer based on the Ni-MOF/NiSR chiral composite material are drawn, the solution of a sample to be detected replaces L-histidine and D-histidine standard solutions, and the content of L-histidine and D-histidine in the sample is detected;
the detection range of the Ni-MOF/NiSR chiral electrochemical sensor on L-tyrosine and D-tyrosine enantiomer solutions is 0.1-1 × 10-9mmol·mL-1。
The beneficial technical effects of the invention are as follows:
(1) the chiral D-penicillamine is added in the preparation process of the chiral Ni-MOF/NiSR core-shell composite material, and sulfydryl and carboxyl in the chiral penicillamine and Ni on the surface of Ni-MOF crystal2+NiSR is generated, so that the generated Ni-MOF/NiSR core-shell composite material generates chirality.
(2) The preparation of the chiral Ni-MOF/NiSR core-shell composite material is carried out by one-pot room temperature operation, the process is simple, the operation cost is low, and the industrialization is easy.
(3) The chiral Ni-MOF/NiSR core-shell composite material prepared by the invention is a core-shell composite material taking Ni-MOF as a core and taking NiSR as a shell, and is beneficial to further exposing more different active sites on the surface of the composite material and improving the mass transfer performance.
(4) The electrochemical chiral sensor of the chiral Ni-MOF/NiSR core-shell composite material provided by the invention is simple in method and easy to operate, detects the content of L-histidine and D-histidine enantiomers, and has the characteristics of quick response, wide detection range, high sensitivity, simplicity in operation, time saving and the like.
Detailed Description
The present invention is further described with reference to the following examples, but the scope of the present invention is not limited to the examples, and modifications made by those skilled in the art to the technical solutions of the present invention should fall within the scope of the present invention.
Embodiment 1 preparation method of chiral Ni-MOF/NiSR core-shell composite material
Mixing 5mmol of nickel chloride hexahydrate and 3 mmol of m-benzenetricarboxylic acid with 7 m of L water, adding 2 m of L and 3-5mmol of NaOH solution, carrying out ultrasonic treatment at room temperature of 180W for 3 min, continuously adding 5m of L ethanol, carrying out ultrasonic treatment at room temperature of 180W for 3 min, carrying out centrifugal separation, and washing with water for 3 times to obtain Ni-MOF;
to the prepared Ni-MOF was added 10 m L, 0.2 mol L-1Magnetically stirring the D-penicillamine aqueous solution for 1 h, centrifugally separating, washing with water for 3 times, and drying at 85 ℃ to constant weight to prepare the chiral Ni-MOF/NiSR core-shell composite material.
The SR has the following structural formula:
the Ni-MOF of the formula Ni3(BTC)2·12H2O, a metal-organic framework, one structural unit of which is composed of 3 Ni2+And 2 BTCs3-And 12 water molecules; BTC3-Is the m-benzene tricarboxylic acid (III) negative ion.
Embodiment 2 preparation method of chiral Ni-MOF/NiSR core-shell composite material
Mixing 6 mmol of nickel chloride hexahydrate and 4 mmol of m-benzenetricarboxylic acid with 8 m L of water, adding 3 m L and 4 mmol of NaOH solution, carrying out ultrasonic treatment at room temperature of 180W for 3 min, continuously adding 7 m L of ethanol, carrying out ultrasonic treatment at room temperature of 180W for 3 min, carrying out centrifugal separation, and washing with water for 3 times to obtain Ni-MOF;
to the prepared Ni-MOF was added 12 m L, 0.2 mol L-1Magnetically stirring the D-penicillamine aqueous solution for 1 h, centrifugally separating, washing with water for 3 times, and drying at 85 ℃ to constant weight to prepare the chiral Ni-MOF/NiSR core-shell composite material.
The structure and properties of the SR, Ni-MOF are the same as those of example 1.
Embodiment 3 preparation method of chiral Ni-MOF/NiSR core-shell composite material
Mixing 7 mmol of nickel chloride hexahydrate and 5mmol of m-benzenetricarboxylic acid with 10 m L of water, adding 4 m L and 5mmol of NaOH solution, carrying out ultrasonic treatment at room temperature of 180W for 3 min, continuously adding 10 m L of ethanol, carrying out ultrasonic treatment at room temperature of 180W for 3 min, carrying out centrifugal separation, and washing with water for 3 times to obtain Ni-MOF;
adding 15m L, 0.2 mol L to the prepared Ni-MOF-1Magnetically stirring the D-penicillamine aqueous solution for 1 h, centrifugally separating, washing with water for 3 times, and drying at 85 ℃ to constant weight to prepare the chiral Ni-MOF/NiSR core-shell composite material.
The structure and properties of the SR, Ni-MOF are the same as those of example 1.
Example 4 application of chiral Ni-MOF/NiSR core-shell composite material for detecting enantiomer by electrochemical sensing
(1) Preparation of working electrode of chiral sensor
Dripping 6 mu L chiral Ni-MOF/NiSR core-shell composite material suspension on the surface of a 4 mm glassy carbon electrode which is polished by alumina powder and cleaned by water and ethanol, and airing at room temperature to prepare a working electrode of the Ni-MOF/NiSR chiral sensor;
the chiral Ni-MOF/NiSR core-shell composite material suspension is prepared by blending 3 mg of the chiral Ni-MOF/NiSR core-shell composite material prepared in the example 1 or the example 2 or the example 3 with 250 mu L isopropanol, 720 mu L water and 30 mu L Nafion and performing ultrasonic treatment in a water bath of 180W for 10-15 min;
(2) construction of chiral electrochemical sensors
Connecting a working electrode of the Ni-MOF/NiSR chiral sensor, a saturated calomel reference electrode and a platinum wire counter electrode on an electrochemical workstation to prepare the Ni-MOF/NiSR chiral electrochemical sensor;
(3) detection of L-histidine and D-histidine enantiomers
At a pH of 7.0, 0.1 mol. L-1The PBS buffer solution is used as electrolyte, the chiral electrochemical sensor prepared in the step (2) is adopted, current values of L-histidine and D-histidine standard solutions with different concentrations are respectively measured by adopting a differential pulse voltammetry method, working curves of the L-histidine and D-histidine enantiomers based on the Ni-MOF/NiSR chiral composite material are drawn, and the solution of a sample to be detected replaces the L-histidine and D-histidine standard solutions to detect the content of L-histidine and D-histidine in the sample.
The detection range of the Ni-MOF/NiSR chiral electrochemical sensor on L-tyrosine and D-tyrosine enantiomer solutions is 0.1-1 × 10-9mmol·mL-1。
Claims (5)
1. A preparation method of a chiral Ni-MOF/NiSR core-shell composite material is characterized by comprising the following steps:
mixing 5-7 mmol of nickel chloride hexahydrate and 3-5mmol of m-benzenetricarboxylic acid with 7-10 m of L water, adding 2-4 m of L and 3-5mmol of NaOH solution, carrying out ultrasonic treatment at room temperature of 180W for 3 min, continuously adding 5-10 m of L ethanol, carrying out ultrasonic treatment at room temperature of 180W for 3 min, carrying out centrifugal separation, and washing with water for 3 times to obtain Ni-MOF;
adding 10-15m L and 0.2 mol L into the prepared Ni-MOF-1Magnetically stirring the D-penicillamine aqueous solution for 1 h, centrifugally separating, washing with water for 3 times, and drying at 85 ℃ to constant weight to prepare the chiral Ni-MOF/NiSR core-shell composite material.
2. A preparation method of a chiral Ni-MOF/NiSR core-shell composite material is characterized in that the SR has the following structural formula:
3. the preparation method of the chiral Ni-MOF/NiSR core-shell composite material of claim 1, wherein the chemical formula of the Ni-MOF is Ni3(BTC)2·12H2O, belongs toThe metal-organic framework is composed of 3 Ni structural units2+And 2 BTCs3-And 12 water molecules; BTC3-Is the m-benzene tricarboxylic acid anion.
4. The application of the chiral Ni-MOF/NiSR core-shell composite material prepared by the preparation method of claim 1 in the detection of enantiomers through electrochemical sensing.
5. The use of electrochemical sensing for the detection of an enantiomer in accordance with claim 4, comprising the steps of:
(1) preparation of working electrode of chiral sensor
Dripping 6 mu L chiral Ni-MOF/NiSR core-shell composite material suspension on the surface of a 4 mm glassy carbon electrode which is polished by alumina powder and cleaned by water and ethanol, and airing at room temperature to prepare a working electrode of the Ni-MOF/NiSR chiral sensor;
the chiral Ni-MOF/NiSR core-shell composite material suspension is prepared by blending 3 mg of chiral Ni-MOF/NiSR core-shell composite material with 250 mu L isopropanol, 720 mu L water and 30 mu L Nafion and performing ultrasonic treatment in a water bath of 180W for 10-15 min;
(2) construction of chiral electrochemical sensors
Connecting a working electrode of the Ni-MOF/NiSR chiral sensor, a saturated calomel reference electrode and a platinum wire counter electrode on an electrochemical workstation to prepare the Ni-MOF/NiSR chiral electrochemical sensor;
(3) detection of L-histidine and D-histidine enantiomers
At a pH of 7.0, 0.1 mol. L-1The PBS buffer solution is used as electrolyte, the chiral electrochemical sensor prepared in the step (2) is adopted, current values of L-histidine and D-histidine standard solutions with different concentrations are respectively measured by adopting a differential pulse voltammetry method, working curves of L-histidine amine and D-histidine enantiomer based on the Ni-MOF/NiSR chiral composite material are drawn, and the solution of a sample to be detected replaces L-histidine and D-histidine standard solutions to detect the content of L-histidine and D-histidine in the sample.
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| CN109107609A (en) * | 2018-08-29 | 2019-01-01 | 济南大学 | A kind of preparation method and application of the MOF catalyst of gluconic acid enhancing catalytic activity |
| CN109675639A (en) * | 2019-02-12 | 2019-04-26 | 济南大学 | A kind of preparation method and application of Ni-MOF/NiF bifunctional catalyst that is while preparing hydrogen and glucaric acid |
| CN110483798A (en) * | 2019-08-30 | 2019-11-22 | 济南大学 | A kind of preparation method and application of graphene oxide@chirality Ni-MOF hybrid material |
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- 2020-03-12 CN CN202010171485.6A patent/CN111413379A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106442686A (en) * | 2016-09-12 | 2017-02-22 | 济南大学 | Chiral metal organic framework polymer sensor as well as preparation and application thereof |
| CN109107609A (en) * | 2018-08-29 | 2019-01-01 | 济南大学 | A kind of preparation method and application of the MOF catalyst of gluconic acid enhancing catalytic activity |
| CN109675639A (en) * | 2019-02-12 | 2019-04-26 | 济南大学 | A kind of preparation method and application of Ni-MOF/NiF bifunctional catalyst that is while preparing hydrogen and glucaric acid |
| CN110483798A (en) * | 2019-08-30 | 2019-11-22 | 济南大学 | A kind of preparation method and application of graphene oxide@chirality Ni-MOF hybrid material |
Non-Patent Citations (1)
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Application publication date: 20200714 |