CN110483798B - Preparation method and application of graphene oxide @ chiral Ni-MOF hybrid material - Google Patents
Preparation method and application of graphene oxide @ chiral Ni-MOF hybrid material Download PDFInfo
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 85
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- 239000013099 nickel-based metal-organic framework Substances 0.000 title claims abstract description 63
- 239000000463 material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 claims abstract description 47
- VVNCNSJFMMFHPL-GSVOUGTGSA-N L-penicillamine Chemical compound CC(C)(S)[C@H](N)C(O)=O VVNCNSJFMMFHPL-GSVOUGTGSA-N 0.000 claims abstract description 35
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229960004441 tyrosine Drugs 0.000 claims abstract description 19
- 238000001514 detection method Methods 0.000 claims abstract description 15
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 229960001639 penicillamine Drugs 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000012621 metal-organic framework Substances 0.000 claims description 11
- 239000002131 composite material Substances 0.000 claims description 8
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 5
- 239000012086 standard solution Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- LJRDOKAZOAKLDU-UDXJMMFXSA-N (2s,3s,4r,5r,6r)-5-amino-2-(aminomethyl)-6-[(2r,3s,4r,5s)-5-[(1r,2r,3s,5r,6s)-3,5-diamino-2-[(2s,3r,4r,5s,6r)-3-amino-4,5-dihydroxy-6-(hydroxymethyl)oxan-2-yl]oxy-6-hydroxycyclohexyl]oxy-4-hydroxy-2-(hydroxymethyl)oxolan-3-yl]oxyoxane-3,4-diol;sulfuric ac Chemical class OS(O)(=O)=O.N[C@@H]1[C@@H](O)[C@H](O)[C@H](CN)O[C@@H]1O[C@H]1[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](N)C[C@@H](N)[C@@H]2O)O[C@@H]2[C@@H]([C@@H](O)[C@H](O)[C@@H](CO)O2)N)O[C@@H]1CO LJRDOKAZOAKLDU-UDXJMMFXSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 229920000557 Nafion® Polymers 0.000 claims description 3
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000001903 differential pulse voltammetry Methods 0.000 claims description 3
- 239000008151 electrolyte solution Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
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- 239000003814 drug Substances 0.000 abstract description 7
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- HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 239000002114 nanocomposite Substances 0.000 abstract 1
- 238000011896 sensitive detection Methods 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 3
- -1 D-penicillamine enantiomers Chemical class 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
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- 239000011248 coating agent Substances 0.000 description 1
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- 230000007547 defect Effects 0.000 description 1
- 238000003821 enantio-separation Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
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- C08K3/042—Graphene or derivatives, e.g. graphene oxides
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
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- G01N27/28—Electrolytic cell components
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- G—PHYSICS
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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Abstract
The invention discloses a graphene oxide @ chiral Ni-MOF hybrid material, a preparation method thereof and application of the hybrid material in detection of chiral drug enantiomers, and belongs to the technical fields of nano composite materials and chiral sensing detection. The method mainly comprises the steps of blending an L-tyrosine alkali solution and a nickel nitrate-graphene oxide turbid liquid, and reacting overnight at normal temperature to obtain the graphene oxide @ chiral Ni-MOF hybrid material. The hybrid material is adopted to construct a chiral sensor for sensitive detection of the content of L-penicillamine and D-penicillamine enantiomers. The chiral sensor is simple in method, convenient and fast to operate and good in chiral detection effect.
Description
Technical Field
The invention relates to a graphene oxide @ chiral Ni-MOF hybrid material and a preparation method and application thereof, and belongs to the technical field of nano materials, metal organic framework nano hybrid materials and chiral sensing detection.
Background
Chiral metal organic framework Materials (MOFs) are periodically ordered porous crystalline materials which are formed by self-assembling chiral organic bridging ligands and metal ions or metal clusters, and the synthesis operation is relatively simple and the reaction conditions are mild. Currently, chiral MOFs are applied in the fields of heterogeneous asymmetric catalysis, chiral sensing and the like.
Graphene oxide resistivity is only about 10-6Ω · cm, lower than copper, silver, is the substance for which the resistivity has been found to be the smallest at present; its electron mobility exceeds 15000 cm at normal temperature2The V.s is far higher than that of the carbon nano-tube and the silicon crystal. Due to its low resistivity and extremely fast electron transfer speed, the potential is huge in the development of a new generation of electronic devices with thinner size and faster conduction speed.
With the increasing production and use of chiral products, such as chiral pharmaceuticals, there is an increasing awareness
The important pharmacological effects of a single chiral drug and the serious consequences of the use of racemic drugs. In recent years, many developed countries have continually promulgated guidelines or policies regarding the development of chiral drugs in order to solve some of the problems associated with racemic drugs. At present, chiral chromatography 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 realization of 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.
Based on the unique structures and properties of chiral MOFs and graphene oxide, the preparation method of the graphene oxide @ chiral MOFs composite material is developed, and the graphene oxide @ chiral MOFs composite material is used for high-sensitivity electrochemical sensing identification of drug enantiomers and has important significance.
Disclosure of Invention
One of the technical tasks of the invention is to make up for the defects of the prior art and provide a graphene oxide @ chiral Ni-MOF hybrid material and a preparation method thereof.
The second technical task of the invention is to provide the application of the graphene oxide @ chiral Ni-MOF hybrid material, namely the graphene oxide @ chiral Ni-MOF hybrid material is used for efficiently detecting the contents of L-penicillamine and D-penicillamine enantiomers.
In order to achieve the purpose, the technical scheme of the invention is as follows:
1. preparation method of graphene oxide @ chiral Ni-MOF hybrid material
Dissolving 0.30-0.60 g of nickel nitrate in 5-10 mL of water, simultaneously adding 0.1-0.3 g of graphene oxide, and carrying out ultrasonic treatment in a 180W water bath for 5-10 min to obtain a nickel nitrate-graphene oxide mixed suspension;
dissolving 0.50 mmol of L-tyrosine and 0.50-0.58 mmol of sodium hydroxide in 5-8 mL of water to obtain a clear L-tyrosine alkali solution;
adding the L-tyrosine aqueous solution into the nickel nitrate-graphene oxide mixed turbid liquid, stirring for 4-5 h at room temperature, carrying out suction filtration, and drying at 80 ℃ to constant weight to obtain the graphene oxide supported chiral Ni-MOF composite material, namely the graphene oxide @ chiral Ni-MOF hybrid material.
The chiral Ni-MOF belongs to a metal-organic framework and has a chemical formula of [ Ni (Tyr)2·2H2O] ·H2O and Tyr are L-tyrosine negative ions; the unit structure of the Ni-MOF is composed of a Ni (II) ion center, two Tyr negative ions, two host water molecules and a guest water molecule.
The graphene oxide is a commercial product, the thickness of a graphene sheet is 0.5-1.0 nm, and the diameter of the sheet layer is 0.5-5 mu m.
2. Application of graphene oxide @ chiral Ni-MOF hybrid material prepared by the preparation method in 1 in electrochemical sensing detection of penicillamine enantiomer
(1) Preparation of graphene oxide @ chiral Ni-MOF sensor working electrode
Polishing a glassy carbon electrode with the diameter of 4 mm by using alumina powder, cleaning the surface by using water and ethanol, transferring 10 mu L of graphene oxide @ chiral Ni-MOF hybrid material solution to coat the glassy carbon electrode, and airing at room temperature to obtain a graphene oxide @ chiral Ni-MOF hybrid material modified sensor working electrode;
the graphene oxide @ chiral Ni-MOF hybrid material solution is prepared by blending 6 mg of graphene oxide @ chiral Ni-MOF hybrid material with 250 muL of ethanol, 720 muL of water and 30 muL of Nafion and performing ultrasonic treatment for 10-15 min;
(2) detection of L-and D-penicillamine enantiomers
Connecting the working electrode, the Ag-AgCl reference electrode and the platinum sheet counter electrode which are prepared in the step (1) to an electrochemical workstation to prepare a chiral Ni-MOF @ graphene oxide electrochemical chiral sensor;
at 0.1 mol. L-1The KOH solution is an electrolyte solution, a graphene oxide @ chiral Ni-MOF electrochemical chiral sensor is adopted, and a differential pulse voltammetry method is adopted to respectively measure L-penicillamine and D-penicillamine with different concentrationsDrawing an L-penicillamine and D-penicillamine enantiomer working curve of the electrochemical chiral sensor based on graphene oxide @ chiral Ni-MOF according to the current value of the standard solution; and (3) replacing the standard solution of the L-penicillamine and the D-penicillamine with the solution of the sample to be detected, and detecting the content of the L-penicillamine and the D-penicillamine in the sample.
The chiral sensor has a detection range of 0.01-7.8 x 10 for L-penicillamine and D-penicillamine enantiomer solutions-8 g/mL。
Advantageous technical effects of the invention
(1) The preparation of the graphene oxide @ chiral Ni-MOF hybrid material is that the chiral Ni-MOF grows on the surface of the graphene oxide in a self-assembly manner, so that the prepared graphene oxide @ chiral Ni-MOF hybrid material has chirality;
(2) the preparation process has low raw material cost, simple and easily-controlled process and wide application prospect;
(3) the invention provides an electrochemical chiral sensor based on a graphene oxide @ chiral Ni-MOF hybrid material, which is prepared by coating the graphene oxide @ chiral Ni-MOF hybrid material on the surface of a glassy carbon electrode, and is simple in preparation method and easy to operate. The chiral Ni-MOF crystal is loaded on the surface of graphene, more active sites are exposed, the graphene oxide increases the material conductivity, and the synergistic effect of the MOF and the graphene oxide is exerted, so that the chiral sensor prepared based on the composite material can detect the content of chiral enantiomers of L-penicillamine and D-penicillamine, and has the characteristics of quick response, wide detection range, high sensitivity, simplicity in operation, time saving and the like.
Detailed Description
The invention will now be further described with reference to the following examples, but the scope of the invention is not limited to the practice thereof
For example, variations of the present invention that may be made by a person skilled in the art are intended to fall within the scope of the present invention.
Embodiment 1 preparation method of graphene oxide @ chiral Ni-MOF hybrid material
Dissolving 0.30 g of nickel nitrate in 5 mL of water, simultaneously adding 0.1 g of graphene oxide, and carrying out ultrasonic treatment in a 180W water bath for 5min to obtain a nickel nitrate-graphene oxide mixed suspension;
dissolving 0.50 mmol of L-tyrosine and 0.50 mmol of sodium hydroxide in 5 mL of water to obtain a clear L-tyrosine alkali solution;
adding the L-tyrosine aqueous solution into the nickel nitrate-graphene oxide mixed turbid liquid, stirring for 45 h at room temperature, performing suction filtration, and drying at 80 ℃ to constant weight to prepare the graphene oxide supported chiral Ni-MOF composite material, namely the graphene oxide @ chiral Ni-MOF hybrid material.
The composition of the chiral Ni-MOF belongs to a metal-organic framework with a chemical formula of [ Ni (Tyr)2·2H2O] ·H2O and Tyr are L-tyrosine negative ions; the unit structure of the Ni-MOF is composed of a Ni (II) ion center, two Tyr negative ions, two host water molecules and a guest water molecule;
the graphene oxide is a commercial product, the thickness of a graphene sheet is 0.5-1.0 nm, and the diameter of the sheet layer is 0.5-5 mu m.
Embodiment 2 preparation method of graphene oxide @ chiral Ni-MOF hybrid material
Dissolving 0.45 g of nickel nitrate in 7 mL of water, simultaneously adding 0.2 g of graphene oxide, and carrying out ultrasonic treatment in a 180W water bath for 7 min to obtain a nickel nitrate-graphene oxide mixed suspension;
dissolving 0.50 mmol of L-tyrosine and 0.54 mmol of sodium hydroxide in 6 mL of water to obtain a clear L-tyrosine alkali solution;
adding the L-tyrosine aqueous solution into the nickel nitrate-graphene oxide mixed turbid liquid, stirring for 4.5 h at room temperature, performing suction filtration, and drying at 80 ℃ to constant weight to prepare the graphene oxide supported chiral Ni-MOF composite material, namely the graphene oxide @ chiral Ni-MOF hybrid material.
The composition of the chiral Ni-MOF and the source and properties of the graphene oxide were the same as in example 1.
Embodiment 3 preparation method of graphene oxide @ chiral Ni-MOF hybrid material
Dissolving 0.60 g of nickel nitrate in 10 mL of water, simultaneously adding 0.3 g of graphene oxide, and carrying out ultrasonic treatment in a 180W water bath for 10 min to obtain a nickel nitrate-graphene oxide mixed suspension;
dissolving 0.50 mmol of L-tyrosine and 0.58 mmol of sodium hydroxide in 8 mL of water to obtain a clear L-tyrosine alkali solution;
adding an L-tyrosine alkali solution into a nickel nitrate-graphene oxide mixed suspension, stirring at room temperature for 4-5 h, performing suction filtration, and drying at 80 ℃ to constant weight to prepare a graphene oxide supported chiral Ni-MOF composite material, namely a graphene oxide @ chiral Ni-MOF hybrid material;
the composition of the chiral Ni-MOF and the source and properties of the graphene oxide were the same as in example 1.
Example 4 application of graphene oxide @ chiral Ni-MOF hybrid material to electrochemical sensing detection of penicillamine enantiomer
(1) Preparation of graphene oxide @ chiral Ni-MOF sensor working electrode
After the glassy carbon electrode is polished by alumina powder, water and ethanol are used for cleaning the surface, 10 mu L of graphene oxide @ chiral Ni-MOF hybrid material solution is transferred and coated on the glassy carbon electrode, and the glassy carbon electrode is dried at room temperature to obtain a graphene oxide @ chiral Ni-MOF hybrid material modified sensor working electrode;
the graphene oxide @ chiral Ni-MOF hybrid material solution is prepared by blending 6 mg of the graphene oxide @ chiral Ni-MOF hybrid material prepared in example 1 or example 2 or example 3 with 250 muL of ethanol, 720 muL of water and 30 muL of Nafion and performing ultrasonic treatment for 13 min;
(2) detection of L-and D-penicillamine enantiomers
Connecting the working electrode, the Ag-AgCl reference electrode and the platinum sheet counter electrode which are prepared in the step (1) to an electrochemical workstation to prepare a chiral Ni-MOF @ graphene oxide electrochemical chiral sensor;
at 0.1 mol. L-1The KOH of the method is an electrolyte solution, a graphene oxide @ chiral Ni-MOF electrochemical chiral sensor is adopted, the current values of L-penicillamine and D-penicillamine standard solutions with different concentrations are respectively measured by adopting a differential pulse voltammetry method, and the working curves of L-penicillamine and D-penicillamine enantiomers based on the graphene oxide @ chiral Ni-MOF electrochemical chiral sensor are drawn; replacing the solution of the sample to be tested for the L-penicillamine and D-penicillamine standardsA solution for detecting the contents of L-penicillamine and D-penicillamine in a sample;
the chiral sensor has a detection range of 0.01-7.8 x 10 for L-penicillamine and D-penicillamine enantiomer solutions-8 g/mL。
Claims (4)
1. A preparation method of a graphene oxide @ chiral Ni-MOF hybrid material is characterized by comprising the following steps:
dissolving 0.30-0.60 g of nickel nitrate in 5-10 mL of water, simultaneously adding 0.1-0.3 g of graphene oxide, and carrying out ultrasonic treatment in a 180W water bath for 5-10 min to obtain a nickel nitrate-graphene oxide mixed suspension;
dissolving 0.50 mmol of L-tyrosine and 0.50-0.58 mmol of sodium hydroxide in 5-8 mL of water to obtain a clear L-tyrosine alkali solution;
adding the L-tyrosine aqueous solution into the nickel nitrate-graphene oxide mixed turbid liquid, stirring for 4-5 h at room temperature, carrying out suction filtration, and drying at 80 ℃ to constant weight to obtain the graphene oxide supported chiral Ni-MOF composite material, namely the graphene oxide @ chiral Ni-MOF hybrid material.
2. The preparation method of graphene oxide @ chiral Ni-MOF hybrid material of claim 1, wherein the chiral Ni-MOF belongs to metal-organic framework and has chemical formula [ Ni (Tyr) ]2·2H2O] ·H2O and Tyr are L-tyrosine negative ions; the unit structure of the Ni-MOF is composed of a Ni (II) ion center, two Tyr negative ions, two host water molecules and a guest water molecule.
3. The application of the graphene oxide @ chiral Ni-MOF hybrid material prepared by the preparation method of claim 1 in electrochemical sensing detection of penicillamine enantiomer.
4. The use of electrochemical sensing for the detection of the penicillamine enantiomer according to claim 3, comprising the steps of:
(1) preparation of graphene oxide @ chiral Ni-MOF sensor working electrode
Polishing a glassy carbon electrode with the diameter of 4 mm by using alumina powder, cleaning the surface by using water and ethanol, transferring 10 mu L of graphene oxide @ chiral Ni-MOF hybrid material solution to coat the glassy carbon electrode, and airing at room temperature to obtain a graphene oxide @ chiral Ni-MOF hybrid material modified sensor working electrode;
the graphene oxide @ chiral Ni-MOF hybrid material solution is prepared by blending 6 mg of graphene oxide @ chiral Ni-MOF hybrid material with 250 muL of ethanol, 720 muL of water and 30 muL of Nafion and performing ultrasonic treatment for 10-15 min;
(2) detection of L-and D-penicillamine enantiomers
Connecting the working electrode, the Ag-AgCl reference electrode and the platinum sheet counter electrode which are prepared in the step (1) to an electrochemical workstation to prepare a graphene oxide @ chiral Ni-MOF electrochemical chiral sensor;
at 0.1 mol. L-1The KOH solution is an electrolyte solution, a graphene oxide @ chiral Ni-MOF electrochemical chiral sensor is adopted, the current values of L-penicillamine and D-penicillamine standard solutions with different concentrations are respectively measured by adopting a differential pulse voltammetry method, and the L-penicillamine and D-penicillamine enantiomer working curves based on the graphene oxide @ chiral Ni-MOF electrochemical chiral sensor are drawn; and (3) replacing the standard solution of the L-penicillamine and the D-penicillamine with the solution of the sample to be detected, and detecting the content of the L-penicillamine and the D-penicillamine in the sample.
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| CN111440286A (en) * | 2020-03-12 | 2020-07-24 | 济南大学 | Preparation method and application of chiral Co-MOF/CoSR/PU core-shell composite material |
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| EP2072116A1 (en) * | 2007-12-19 | 2009-06-24 | Universität Potsdam | Metal-peptide frameworks (MPFs) |
| CN105203612A (en) * | 2014-06-10 | 2015-12-30 | 中国科学院大连化学物理研究所 | Biosensor based on metal organic skeleton material and application thereof |
| CN107490610A (en) * | 2017-09-05 | 2017-12-19 | 济南大学 | A kind of chiral MOF graphene hybrid materials and its preparation method and application |
| CN107589159A (en) * | 2017-09-05 | 2018-01-16 | 济南大学 | A kind of preparation method and application of chiral MOF nanofibers graphene hybrid material |
| CN109265698A (en) * | 2018-08-30 | 2019-01-25 | 济南大学 | A kind of MOF/ carbon dots chiral hybrid material and its preparation method and application |
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| GB201013307D0 (en) * | 2010-08-09 | 2010-09-22 | Univ St Andrews | Anti-microbial metal organic framework |
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| EP2072116A1 (en) * | 2007-12-19 | 2009-06-24 | Universität Potsdam | Metal-peptide frameworks (MPFs) |
| CN105203612A (en) * | 2014-06-10 | 2015-12-30 | 中国科学院大连化学物理研究所 | Biosensor based on metal organic skeleton material and application thereof |
| CN107490610A (en) * | 2017-09-05 | 2017-12-19 | 济南大学 | A kind of chiral MOF graphene hybrid materials and its preparation method and application |
| CN107589159A (en) * | 2017-09-05 | 2018-01-16 | 济南大学 | A kind of preparation method and application of chiral MOF nanofibers graphene hybrid material |
| CN109265698A (en) * | 2018-08-30 | 2019-01-25 | 济南大学 | A kind of MOF/ carbon dots chiral hybrid material and its preparation method and application |
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