CN110483798A - A kind of preparation method and application of graphene oxide@chirality Ni-MOF hybrid material - Google Patents
A kind of preparation method and application of graphene oxide@chirality Ni-MOF hybrid material Download PDFInfo
- Publication number
- CN110483798A CN110483798A CN201910813212.4A CN201910813212A CN110483798A CN 110483798 A CN110483798 A CN 110483798A CN 201910813212 A CN201910813212 A CN 201910813212A CN 110483798 A CN110483798 A CN 110483798A
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- chirality
- mof
- hybrid material
- chiral
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 81
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000013099 nickel-based metal-organic framework Substances 0.000 title claims abstract description 62
- 239000000463 material Substances 0.000 title claims abstract description 49
- 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 32
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 28
- VVNCNSJFMMFHPL-GSVOUGTGSA-N L-penicillamine Chemical compound CC(C)(S)[C@H](N)C(O)=O VVNCNSJFMMFHPL-GSVOUGTGSA-N 0.000 claims abstract description 20
- 238000001514 detection method Methods 0.000 claims abstract description 15
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 11
- 239000000725 suspension Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 230000005518 electrochemistry Effects 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 239000012621 metal-organic framework Substances 0.000 claims description 9
- 229960004441 tyrosine Drugs 0.000 claims description 8
- 238000002604 ultrasonography Methods 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 239000012086 standard solution Substances 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 5
- 238000012986 modification 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
- 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
- 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
- 150000001412 amines Chemical class 0.000 claims description 3
- 230000001413 cellular effect Effects 0.000 claims description 3
- 238000010276 construction 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
- 239000000126 substance Substances 0.000 claims description 3
- -1 Tyr anions Chemical class 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 150000001450 anions Chemical class 0.000 claims 1
- 229940079593 drug Drugs 0.000 abstract description 6
- 239000003814 drug Substances 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 2
- 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 1
- 239000002114 nanocomposite Substances 0.000 abstract 1
- 238000011896 sensitive detection Methods 0.000 abstract 1
- 238000004458 analytical method Methods 0.000 description 3
- 238000013507 mapping Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 241000446313 Lamella Species 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 125000003798 L-tyrosyl group Chemical group [H]N([H])[C@]([H])(C(=O)[*])C([H])([H])C1=C([H])C([H])=C(O[H])C([H])=C1[H] 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000857 drug effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000007689 inspection 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
- 229960001639 penicillamine Drugs 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920002338 polyhydroxyethylmethacrylate Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- G—PHYSICS
- G01—MEASURING; TESTING
- 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
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
-
- G—PHYSICS
- G01—MEASURING; TESTING
- 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
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Molecular Biology (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
It is used to detect the application of enantiomers of chiral drugs the invention discloses a kind of graphene oxide@chirality Ni-MOF hybrid material and preparation method thereof and based on the hybrid material, belongs to nanocomposite, chiral sensing detection technical field.It has main steps that l-tyrosine aqueous slkali is blended with nickel nitrate-graphene oxide suspension after, reacted under normal temperature condition overnight be made graphene oxide@chirality Ni-MOF hybrid material.Chiral sensor is constructed using the hybrid material, for the Sensitive Detection to L- penicillamine and Beracilline Enantiomeric excess.The chiral sensor, method is simple, operation is convenient, and chiral detection effect is good.
Description
Technical field
The present invention relates to a kind of graphene oxide@chirality Ni-MOF hybrid materials and its preparation method and application, belong to and receive
Rice material, Metal-organic frame nano-hybrid material and chiral sensing detection technical field.
Background technique
Chiral metal organic framework materials (MOFs) are to be led to by chiral organic bridge ligand with metal ion or metal cluster
Porous crystalline material periodically ordered made of self-assembles is crossed, synthetic operation is relatively easy, and reaction condition is mild.Currently
Chiral MOFs has been applied in Heterogeneous asymmetric catalysis, the fields such as chirality sensing.
Graphene oxide resistivity about 10-6Ω cm, it is lower than copper, silver, be currently it has been found that the smallest object of resistivity
Matter；Its electron mobility is more than 15000 cm under room temperature2/ Vs is much higher than carbon nanotubes and silicon crystal.Just since its is low
Resistivity, the electron transfer rate being exceedingly fast, size is thinner, electronic device exploitation of new generation, potentiality are huge faster for conductive speed
Greatly.
As the production and application percentage of quiral products such as chiral medicinal increasingly increase, people more and more recognize
In serious consequence single chiral drug important drug effect and will lead to using racemic modification drug.In recent years, it was
Solve the problems, such as some brought by racemic modification drug, many developed countries constantly promulgate the guiding performance of related chiral drug exploitation
Guide or policy.Currently, chiral chromatogram has been widely used for separation analysis chipal compounds, but there is certain lack in this method
Point, such as instrument cost are high, and analysis time is long, are particularly difficult to realize in situ and on-line checking etc..Electrochemical sensor is because of its system
The advantages that standby simple, at low cost, recognition efficiency is high, is extensively studied value for identifying that chiral material has very much.
Based on chiral MOFs, the unique structure of graphene oxide and property, it is multiple to develop a kind of graphene oxide@chirality MOFs
The preparation method of condensation material, and drug enantiomter is identified for highly sensitive electrochemical sensing, have great importance.
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 chiral to provide a kind of graphene oxide
Ni-MOF hybrid material and preparation method thereof, this method is raw materials used at low cost, and 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 the purposes of the graphene oxide chirality Ni-MOF hybrid material, i.e.,
Graphene oxide@chirality Ni-MOF hybrid material is used for the content of efficient detection L- penicillamine and Beracilline enantiomer,
The detection sensor is at low cost, analysis efficiency is high, high sensitivity, easy to operate, and operating technology requires low.
To achieve the above object, technical scheme is as follows:
1. a kind of preparation method of graphene oxide@chirality Ni-MOF hybrid material
0.30-0.60 g nickel nitrate is dissolved in 5-10 mL water, while 0.1-0.3 g graphene oxide is added, 180 W water-baths
Middle ultrasound 5-10 min, obtained nickel nitrate-graphene oxide mixing suspension；
The l-tyrosine of 0.50 mmol and 0.50-0.58 mmol sodium hydroxide are dissolved in 5-8 mL water, obtained clear
L-tyrosine aqueous slkali；
L-tyrosine aqueous slkali is added in nickel nitrate-graphene oxide mixing suspension, 4-5 h is stirred at room temperature, is filtered, 80
It is DEG C dry to constant weight, the composite material of graphene oxide-loaded chirality Ni-MOF is made, i.e. graphene oxide@chirality Ni-MOF is miscellaneous
Change material.
The chirality Ni-MOF, belongs to Metal-organic frame, and chemical formula is [Ni (Tyr)2·2H2O] ·H2O, Tyr are
L-tyrosine anion；A cellular construction of Ni-MOF, by Ni (II) ion center, two Tyr anions and two
A main body hydrone and an object hydrone are constituted.
The graphene oxide is commercial product, and for graphene film with a thickness of 0.5-1.0 nm, lamella diameter is 0.5-5 μ
m。
2. the graphene oxide@chirality Ni-MOF hybrid material of the preparation of preparation method described in as above 1 is passed for electrochemistry
The application of sense detection penicillamine enantiomer
(1) graphene oxide@chirality Ni-MOF working sensor electrode is prepared
Diameter is after the glass-carbon electrode of 4 mm is polished with alumina powder, and water and ethyl alcohol clean the surface pipette 10 μ L graphite oxides
Alkene@chirality Ni-MOF hybrid material solution is coated on glass-carbon electrode, and room temperature is dried, and graphene oxide@chirality Ni- is obtained
The working sensor electrode of MOF hybrid material modification；
The graphene oxide@chirality Ni-MOF hybrid material solution is by 6 mg graphene oxide@chirality Ni-MOF hydridization materials
Ultrasound 10-15 min is blended with 250 μ L ethyl alcohol, 720 μ L water and 30 μ L Nafion and is made for material；
(2) L- penicillamine and Beracilline enantiomer are detected
Working electrode made from step (1), Ag-AgCl reference electrode and platinized platinum are connected on electrochemical workstation electrode,
Chiral Ni-MOF@graphene oxide electrochemistry chiral sensor has been made；
With 0.1 molL-1KOH solution be electrolyte solution, it is chiral using graphene oxide@chirality Ni-MOF electrochemistry
Sensor measures the L- penicillamine of various concentration and the electric current of Beracilline standard solution using differential pulse voltammetry respectively
Value draws L- penicillamine and Beracilline enantiomer work based on graphene oxide@chirality Ni-MOF electrochemistry chiral sensor
Make curve；The solution of sample to be tested is replaced into L- penicillamine and Beracilline standard solution, carries out L- penicillamine and D- in sample
The detection of mould amine content.
The chiral sensor is 0 .01-7.8 × 10 to the detection range of L- penicillamine and Beracilline mapping liquid solution-8
g/mL。
The beneficial technical effect of the present invention
(1) preparation of graphene oxide@chirality Ni-MOF hybrid material is chiral Ni-MOF in surface of graphene oxide self assembly
Growth, so that graphene oxide@chirality Ni-MOF hybrid material obtained has chirality；
(2) preparation process cost of material is low, and simple process is easily-controllable, has broad application prospects；
(3) the present invention provides a kind of electrochemistry chiral sensors based on graphene oxide@chirality Ni-MOF hybrid material, should
Sensor is that graphene oxide@chirality Ni-MOF hybrid material is coated to glassy carbon electrode surface, and preparation method is simple, easily grasps
Make.Chiral Ni-MOF crystal load on the surface of graphene, exposes more active sites, and graphene oxide increases material
Electric conductivity has played the synergistic effect of MOF and spiral polyaniline, so that the chiral sensor based on composite material preparation, inspection
The content of L- penicillamine and Beracilline chiral enantiomer is surveyed, there is wide quick response, detection range, high sensitivity, operation letter
The features such as single, time saving.
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.
A kind of preparation method of the graphene oxide@chirality Ni-MOF hybrid material of embodiment 1
0.30 g nickel nitrate is dissolved in 5 mL water, while 0.1 g graphene oxide is added, 5 min of ultrasound in 180 W water-baths,
Obtained nickel nitrate-graphene oxide mixing suspension；
The l-tyrosine of 0.50 mmol and 0.50 mmol sodium hydroxide are dissolved in 5 mL water, clear l-tyrosine is obtained
Aqueous slkali；
L-tyrosine aqueous slkali is added in nickel nitrate-graphene oxide mixing suspension, 45 h are stirred at room temperature, is filtered, 80
It is DEG C dry to constant weight, the composite material of graphene oxide-loaded chirality Ni-MOF is made, i.e. graphene oxide@chirality Ni-MOF is miscellaneous
Change material.
The composition of the chirality Ni-MOF, belongs to Metal-organic frame, and chemical formula is [Ni (Tyr)2·2H2O] ·H2O,
Tyr is l-tyrosine anion；A cellular construction of Ni-MOF, by Ni (II) ion center, two Tyr bear from
Son and two main body hydrones and an object hydrone are constituted；
The graphene oxide is commercial product, and for graphene film with a thickness of 0.5-1.0 nm, lamella diameter is 0.5-5 μm.
A kind of preparation method of the graphene oxide@chirality Ni-MOF hybrid material of embodiment 2
0.45 g nickel nitrate is dissolved in 7 mL water, while 0.2 g graphene oxide is added, 7 min of ultrasound in 180 W water-baths,
Obtained nickel nitrate-graphene oxide mixing suspension；
The l-tyrosine of 0.50 mmol and 0.54 mmol sodium hydroxide are dissolved in 6 mL water, clear l-tyrosine is obtained
Aqueous slkali；
L-tyrosine aqueous slkali is added in nickel nitrate-graphene oxide mixing suspension, 4.5 h are stirred at room temperature, is filtered, 80
It is DEG C dry to constant weight, the composite material of graphene oxide-loaded chirality Ni-MOF is made, i.e. graphene oxide@chirality Ni-MOF is miscellaneous
Change material.
The composition of the chirality Ni-MOF and the source of graphene oxide and property are the same as embodiment 1.
A kind of preparation method of the graphene oxide@chirality Ni-MOF hybrid material of embodiment 3
0.60 g nickel nitrate is dissolved in 10 mL water, while 0.3 g graphene oxide is added, ultrasound 10 in 180 W water-baths
Min, obtained nickel nitrate-graphene oxide mixing suspension；
The l-tyrosine of 0.50 mmol and 0.58 mmol sodium hydroxide are dissolved in 8 mL water, clear l-tyrosine is obtained
Aqueous slkali；
L-tyrosine aqueous slkali is added in nickel nitrate-graphene oxide mixing suspension, 4-5 h is stirred at room temperature, is filtered, 80
It is DEG C dry to constant weight, the composite material of graphene oxide-loaded chirality Ni-MOF is made, i.e. graphene oxide@chirality Ni-MOF is miscellaneous
Change material；
The composition of the chirality Ni-MOF and the source of graphene oxide and property are the same as embodiment 1.
4 graphene oxide@chirality Ni-MOF hybrid material of embodiment is for electrochemical sensing detection penicillamine enantiomer
Using
(1) graphene oxide@chirality Ni-MOF working sensor electrode is prepared
After glass-carbon electrode is polished with alumina powder, water and ethyl alcohol clean the surface pipette 10 μ L graphene oxide@chirality Ni-
MOF hybrid material solution is coated on glass-carbon electrode, and room temperature is dried, and graphene oxide@chirality Ni-MOF hybrid material is obtained
The working sensor electrode of modification；
The graphene oxide@chirality Ni-MOF hybrid material solution, is to make 6 mg embodiments 1 or embodiment 2 or embodiment 3
Ultrasound is blended with 250 μ L ethyl alcohol, 720 μ L water and 30 μ L Nafion in standby graphene oxide@chirality Ni-MOF hybrid material
13 min are made；
(2) L- penicillamine and Beracilline enantiomer are detected
Working electrode made from step (1), Ag-AgCl reference electrode and platinized platinum are connected on electrochemical workstation electrode,
Chiral Ni-MOF@graphene oxide electrochemistry chiral sensor has been made；
With 0.1 mol L-1KOH be electrolyte solution, using graphene oxide@chirality Ni-MOF electrochemistry chirality sense
Device is measured the L- penicillamine of various concentration and the current value of Beracilline standard solution respectively, is drawn using differential pulse voltammetry
Make L- penicillamine and Beracilline mapping body running song based on graphene oxide chirality Ni-MOF electrochemistry chiral sensor
Line；The solution of sample to be tested is replaced into L- penicillamine and Beracilline standard solution, carries out L- penicillamine and D- mould in sample
The detection of amine content；
The chiral sensor is 0 .8 × 10 .01-7 to the detection range of L- penicillamine and Beracilline mapping liquid solution-8 g/
mL。
Claims (4)
1. a kind of preparation method of graphene oxide@chirality Ni-MOF hybrid material, which is characterized in that steps are as follows:
0.30-0.60 g nickel nitrate is dissolved in 5-10 mL water, while 0.1-0.3 g graphene oxide is added, 180 W water-baths
Middle ultrasound 5-10 min, obtained nickel nitrate-graphene oxide mixing suspension；
The l-tyrosine of 0.50 mmol and 0.50-0.58 mmol sodium hydroxide are dissolved in 5-8 mL water, obtained clear
L-tyrosine aqueous slkali；
L-tyrosine aqueous slkali is added in nickel nitrate-graphene oxide mixing suspension, 4-5 h is stirred at room temperature, is filtered, 80
It is DEG C dry to constant weight, the composite material of graphene oxide-loaded chirality Ni-MOF is made, i.e. graphene oxide@chirality Ni-MOF is miscellaneous
Change material.
2. a kind of preparation method of graphene oxide@chirality Ni-MOF hybrid material as described in claim 1, feature exist
In the chirality Ni-MOF belongs to Metal-organic frame, and chemical formula is [Ni (Tyr)2·2H2O] ·H2O, Tyr are L- junket ammonia
Sour anion；A cellular construction of Ni-MOF, by Ni (II) ion center, two Tyr anions and two main bodys
Hydrone and an object hydrone are constituted.
3. the graphene oxide@chirality Ni-MOF hybrid material of preparation method preparation as described in claim 1 is used for electrochemistry
The application of sensing detection penicillamine enantiomer.
4. the application of electrochemical sensing detection penicillamine enantiomer as claimed in claim 3, which is characterized in that steps are as follows:
(1) graphene oxide@chirality Ni-MOF working sensor electrode is prepared
Diameter is after the glass-carbon electrode of 4 mm is polished with alumina powder, and water and ethyl alcohol clean the surface pipette 10 μ L graphite oxides
Alkene@chirality Ni-MOF hybrid material solution is coated on glass-carbon electrode, and room temperature is dried, and graphene oxide@chirality Ni- is obtained
The working sensor electrode of MOF hybrid material modification；
The graphene oxide@chirality Ni-MOF hybrid material solution is by 6 mg graphene oxide@chirality Ni-MOF hydridization materials
Ultrasound 10-15min is blended with 250 μ L ethyl alcohol, 720 μ L water and 30 μ L Nafion and is made for material；
(2) L- penicillamine and Beracilline enantiomer are detected
Working electrode made from step (1), Ag-AgCl reference electrode and platinized platinum are connected on electrochemical workstation electrode,
Chiral Ni-MOF@graphene oxide electrochemistry chiral sensor has been made；
With 0.1 molL-1KOH solution be electrolyte solution, it is chiral using graphene oxide@chirality Ni-MOF electrochemistry
Sensor measures the L- penicillamine of various concentration and the electric current of Beracilline standard solution using differential pulse voltammetry respectively
Value draws L- penicillamine and Beracilline enantiomer work based on graphene oxide@chirality Ni-MOF electrochemistry chiral sensor
Make curve；The solution of sample to be tested is replaced into L- penicillamine and Beracilline standard solution, carries out L- penicillamine and D- in sample
The detection of mould amine content.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910813212.4A CN110483798B (en) | 2019-08-30 | 2019-08-30 | Preparation method and application of graphene oxide @ chiral Ni-MOF hybrid material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910813212.4A CN110483798B (en) | 2019-08-30 | 2019-08-30 | Preparation method and application of graphene oxide @ chiral Ni-MOF hybrid material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110483798A true CN110483798A (en) | 2019-11-22 |
| CN110483798B CN110483798B (en) | 2021-08-17 |
Family
ID=68555384
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910813212.4A Expired - Fee Related CN110483798B (en) | 2019-08-30 | 2019-08-30 | Preparation method and application of graphene oxide @ chiral Ni-MOF hybrid material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110483798B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110927135A (en) * | 2019-12-25 | 2020-03-27 | 无锡市疾病预防控制中心 | Method for rapidly and visually distinguishing different chiral penicillamine and racemic penicillamine in sample |
| CN111413379A (en) * | 2020-03-12 | 2020-07-14 | 济南大学 | Preparation method and application of chiral Ni-MOF/NiSR core-shell composite material |
| 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 |
| CN113311036A (en) * | 2021-05-23 | 2021-08-27 | 山东化工职业学院 | MOFs/GO composite gas sensitive material and preparation method and application thereof |
| CN113406183A (en) * | 2021-06-29 | 2021-09-17 | 宁波大学 | Method for efficiently identifying penicillamine chiral enantiomer based on ion mobility mass spectrometer |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2072116A1 (en) * | 2007-12-19 | 2009-06-24 | Universität Potsdam | Metal-peptide frameworks (MPFs) |
| US20130171228A1 (en) * | 2010-08-09 | 2013-07-04 | University Court Of The University Of St. Andrews | Anti-microbial metal organic framework |
| 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 |
-
2019
- 2019-08-30 CN CN201910813212.4A patent/CN110483798B/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2072116A1 (en) * | 2007-12-19 | 2009-06-24 | Universität Potsdam | Metal-peptide frameworks (MPFs) |
| US20130171228A1 (en) * | 2010-08-09 | 2013-07-04 | University Court Of The University Of St. Andrews | Anti-microbial metal organic framework |
| 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 |
Non-Patent Citations (2)
| Title |
|---|
| BO ZHOU ET AL.: ""CoII/ZnII–(L-Tyrosine) Magnetic Metal–Organic Frameworks"", 《EUR. J. INORG. CHEM》 * |
| LIU ZHAOXUAN ET AL.: ""Electrochemical enantioselective recognition penicillamine isomers based on chiral C-dots/MOF hybrid arrays"", 《JOURNAL OF ELECTROANALYTICAL CHEMISTRY》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110927135A (en) * | 2019-12-25 | 2020-03-27 | 无锡市疾病预防控制中心 | Method for rapidly and visually distinguishing different chiral penicillamine and racemic penicillamine in sample |
| CN110927135B (en) * | 2019-12-25 | 2023-12-29 | 无锡市疾病预防控制中心 | Method for rapidly and visually distinguishing different chiral penicillamine and racemic penicillamine in sample |
| CN111413379A (en) * | 2020-03-12 | 2020-07-14 | 济南大学 | Preparation method and application of chiral Ni-MOF/NiSR core-shell composite material |
| 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 |
| CN113311036A (en) * | 2021-05-23 | 2021-08-27 | 山东化工职业学院 | MOFs/GO composite gas sensitive material and preparation method and application thereof |
| CN113311036B (en) * | 2021-05-23 | 2024-01-12 | 山东化工职业学院 | MOFs/GO composite gas-sensitive material and preparation method and application thereof |
| CN113406183A (en) * | 2021-06-29 | 2021-09-17 | 宁波大学 | Method for efficiently identifying penicillamine chiral enantiomer based on ion mobility mass spectrometer |
| CN113406183B (en) * | 2021-06-29 | 2024-04-23 | 常州磐诺仪器有限公司 | Method for efficiently identifying penicillamine chiral enantiomer based on ion mobility mass spectrometer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110483798B (en) | 2021-08-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110483798A (en) | A kind of preparation method and application of graphene oxide@chirality Ni-MOF hybrid material | |
| Gao et al. | Facile synthesis of copper oxide nanostructures and their application in non-enzymatic hydrogen peroxide sensing | |
| CN109100404B (en) | Hydrotalcite-like nanosheet @ ZIF-67 composite material modified electrode and preparation method and detection application thereof | |
| Lin et al. | Layer-by-layer construction of multi-walled carbon nanotubes, zinc oxide, and gold nanoparticles integrated composite electrode for nitrite detection | |
| CN109307700B (en) | Method for determining rutin by using cobalt-based metal organic framework material/three-dimensional graphene nanocomposite modified electrode | |
| CN101458225B (en) | Electrochemical gas sensors | |
| Xiao et al. | Sensitive and selective electrochemical sensing of l-cysteine based on a caterpillar-like manganese dioxide–carbon nanocomposite | |
| Chen et al. | MOF derived porous carbon modified rGO for simultaneous determination of hydroquinone and catechol | |
| Zhang et al. | An ultrasensitive sensor based on polyoxometalate and zirconium dioxide nanocomposites hybrids material for simultaneous detection of toxic clenbuterol and ractopamine | |
| Ni et al. | In-situ growth of Co 3 O 4 nanoparticles on mesoporous carbon nanofibers: a new nanocomposite for nonenzymatic amperometric sensing of H 2 O 2 | |
| Lin et al. | Simultaneous determination for toxic ractopamine and salbutamol in pork sample using hybrid carbon nanotubes | |
| CN108144620A (en) | Foamed nickel supported composite Nano metal oxide electrode material preparation method | |
| Salimi et al. | Cobalt oxide nanostructure-modified glassy carbon electrode as a highly sensitive flow injection amperometric sensor for the picomolar detection of insulin | |
| CN108970642A (en) | A kind of carbon dots adulterate the preparation method and application of rich nitrogen MOF nano-chip arrays catalyst | |
| Yuan et al. | Layered titanate nanosheets as an enhanced sensing platform for ultrasensitive stripping voltammetric detection of mercury (II) | |
| CN109265698A (en) | A kind of MOF/ carbon dots chiral hybrid material and its preparation method and application | |
| Baloach et al. | An amperometric sensitive dopamine biosensor based on novel copper oxide nanostructures | |
| Rezaei et al. | Electrochemical determination of papaverine on Mg-Al layered double hydroxide/graphene oxide and CNT modified carbon paste electrode | |
| CN203083964U (en) | Screen-printed electrode sensor prepared by nitrogen doped graphene and used for detecting bisphenol A | |
| CN109187678A (en) | Utilize the nitrite detection device of nanogold graphene modified electrochemical method | |
| Wei et al. | A novel electrochemical sensor based on DUT-67/ZnCo2O4-MWCNTs modified glassy carbon electrode for the simultaneous sensitive detection of dopamine and uric acid | |
| Wang et al. | A Novel Electrochemical Sensor for Detection of Baicalein in Human Serum Based on DUT‐9/Mesoporous Carbon Composite | |
| Wang et al. | Electrochemical study of hydrogen peroxide detection on MnO2 micromaterials | |
| CN109580747B (en) | Electrochemical sensor for detecting dopamine | |
| CN114058025A (en) | Preparation method and application of copper simple substance/copper-based metal organic framework material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20210817 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |