CN107490610A - A kind of chiral MOF graphene hybrid materials and its preparation method and application - Google Patents
A kind of chiral MOF graphene hybrid materials and its preparation method and application Download PDFInfo
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- 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
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- 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
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- 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
- G01N27/36—Glass electrodes
Abstract
It is used for the application for detecting enantiomers of chiral drugs the invention discloses a kind of chiral MOF graphene hybrid materials and preparation method thereof and based on the hybrid material, belongs to nano composite material, polymer-based composite, graphene-based composite and chiral sensing detection technical field.After it has main steps that the aqueous solution blending by the alkaline aqueous solution of L aspartic acids and copper nitrate graphene oxide, the ethanol solution of 4,4 ' bipyridyls is added, after standing overnight, centrifuged, washing, dried and be made.The chiral MOF graphene hybrid materials sensor built using the hybrid material, the Sensitive Detection for the phenylpropionic acid of 2 amino of R 3 and the phenylpropionic acid Enantiomeric excess of 2 amino of S 3.
Description
Technical field
The present invention relates to a kind of chiral MOF- graphene hybrid materials and its preparation method and application, belong to nano material,
Metal organic complex nano material and chiral sensing detection technical field.
Background technology
Chirality is one of nature essential attribute, and certain compound molecule is referred to as hand with the property that its mirror image can not overlap completely
Property.Chiral phenomenon is widely present in nature, such as people's vivo acid is L-configuration, glucose in plant in nature
Exist with D configurations.Many medicines, nutrient and healthcare products and agricultural chemicals etc. are most of to have one group of enantiomer in specular, so
And these enantiomers typically exhibit different bioactivity and pharmacological reaction.For example, " the reaction occurred the fifties in last century
Stop " in event, the medicine of entitled Thalidomide has the function that to mitigate pregnancy reaction, but because chiral medicine at that time is in people
Different bioactivity understanding deficiency in vivo, causes 1.2 ten thousand baby's teratogenesis.Medicine R configurations have a sedation, and S configurations pair
Fetus has the effect of teratogenesis shape.More than half in the best-selling medicine in the whole world has chirality according to statistics.Therefore, how to identify single
Chiral material is always one of problem that numerous quiral products productions and exploitation must solve.
Chiral metal organic framework materials（MOFs）It is to be led to by chiral organic bridge ligand with metal ion or metal cluster
The periodically ordered porous crystalline material that self-assembles form is crossed, its synthetic operation is relatively easy, and reaction condition is gentle, possesses
The characteristics of inorganic material and organic material.Metal ion and chiral organic ligand molecule based on synthesis MOFs materials are abundant more
Coloured silk, the novel chiral amorphous metal organic framework materials of a large amount of structures have been assembled, and chiral MOFs is in Heterogeneous asymmetric catalysis, choosing
Selecting property identifies and the field such as separation and chiral sensing is applied.
Graphene is a kind of allotrope of carbon, it be by single layer of carbon atom it is tightly packed into 2D alveolate texture materials
Material.Property of the graphene with brilliance, such as high specific surface area (2630m2/g), the local aromatic structure gripped altogether, superelevation
Translucency (97.7%), high chemistry and electrochemical stability.Many oxygen-containing functional group (hydroxyls on base material on graphene oxide
Base and epoxy functionality, the carboxyl functional group of edge) add its hydrophily and dispersiveness in the solution.Aoxidize stone
The common presence of functional group and fragrant sp2 domains on black alkene so that graphene oxide can be used as structure node, participate in MOFs
Bonding action.Meanwhile carboxylic acid on graphene or nitrogen-containing functional group are capable of the coordination of oxidation reinforced graphene and MOFs, and lure
MOFs growth is led, in nature, MOFs and graphene oxide will play synergy.
The content of the invention
One of technical assignment of the present invention is to make up the deficiencies in the prior art, there is provided a kind of chiral MOF- graphenes are miscellaneous
Change material and preparation method thereof, the raw materials used cost of this method is low, and preparation technology is simple, and energy consumption of reaction is low, has commercial Application
Prospect.
The two of the technical assignment of the present invention are to provide a kind of purposes of chiral MOF- graphene hybrid materials, will the chirality
Polyaniline-graphite alkene composite is used for efficient detection R-2- amino -3- phenylpropionic acids and S-2- amino -3- phenylpropionic acid mappings
The content of body, the detecting instrument cost is low, analysis efficiency is high, easy to operate, and operating technology requires low.
Technical scheme is as follows：
1. a kind of chiral MOF- graphene hybrid materials, the hybrid material is by the graphene oxide-loaded chiral gold of nano-sheet
Belong to organic framework MOF crystal composition, MOF chemical formula is [Cu (L-Asp) (4,4 '-Bipy)2] n, its asymmetric one
Construction unit, it is by a Cu2+, L-Aspartic acid anion L-Asp and two 4,4 '-Bipy molecular compositions, 4,4 '-
Bipy is 4,4 '-bipyridyl；
MOF average crystal grain diameters are 120-160nm, and individual layer loads on sheet graphene oxide.
2. a kind of preparation method of chiral MOF- graphene hybrid materials, be by the alkaline aqueous solution of L-Aspartic acid with
After the aqueous solution blending of copper nitrate-graphene oxide, 4 are added, the ethanol solution of 4 '-bipyridyl, after standing overnight, centrifugation divides
From, washed 3 times with ethanol, it is dry to be made；
The alkaline aqueous solution of the L-Aspartic acid, it is by 0.0200-0.035 g sodium hydroxides and 0.0200-0.0340 g
L-Aspartic acid is dissolved in 1-1.5 mL water and is made；
The aqueous solution of the copper nitrate-graphene oxide, it is after 0.53-0.73 g copper nitrates are dissolved in into 6-8 mL water, adds
0.010-0.020 g graphene oxides, 30 min of ultrasound are made；
The ethanol solution of 4, the 4- bipyridyls, it is by 0.050-0.66 g 4,4 '-bipyridyl is dissolved in 0.75-1.25 mL ethanol
It is made.
3. application of the chiral MOF- graphene hybrid materials as described above as electrochemical sensing detection enantiomer, step
It is as follows：
（1）Prepare chiral MOF- graphene sensors working electrode
Polish in alumina powder, the basal electrode glassy carbon electrode surface of water and ethanol cleaning, drop coating 6uL chiralitys MOF-
Graphene solution, room temperature are dried, that is, the working sensor electrode of chiral MOF- graphene hybrid materials modification has been made；
The chiral MOF- graphene hybrid materials solution, it is by 3 mg chirality MOF- graphene hybrid materials and 250 uL isopropyls
Alcohol, 720 uL water, 30 uL Nafion are blended ultrasonic 10-15min and are made；
（2）Prepare chiral MOF- graphenes electrochemistry chiral sensor
By step（1）Obtained working electrode, reference electrode and electrode is connected on electrochemical workstation, chirality has been made
MOF- graphene electrochemistry chiral sensors；
The reference electrode is saturated calomel electrode, is platinum electrode to electrode；
（3）Detect R-2- amino -3- phenylpropionic acids and S-2- amino -3- phenylpropionic acid enantiomers
With pH 7.0,0.1 mol L-1PBS cushioning liquid, using step（2）Obtained chiral MOF- graphenes electrification
Chiral sensor is learned, using the R-2- amino -3- phenylpropionic acids and S-2- ammonia of differential pulse voltammetry, respectively measure various concentrations
The current value of base -3- phenylpropionic acid standard liquids, draw the R-2- ammonia based on chiral MOF- graphenes electrochemistry chiral sensor
Base -3- phenylpropionic acids and S-2- amino -3- phenylpropionic acid enantiomer working curves；The solution of testing sample is replaced into R-2- ammonia
Base -3- phenylpropionic acids and S-2- amino -3- phenylpropionic acid standard liquids, carry out R-2- amino -3- phenylpropionic acids and S- in sample
The detection of 2- amino -3- phenylpropionic acid contents.
Inspection of the chiral sensor to R-2- amino -3- phenylpropionic acids and S-2- amino -3- phenylpropionic acid mapping liquid solutions
Survey scope is 0.1-1.0 × 10-10g/mL。
The beneficial technique effect of the present invention is as follows：
（1）The preparation of the chiral MOF- graphene hybrid materials of the present invention, due to adding chiral ligand L- asparagus ferns in preparation process
Propylhomoserin, induction MOF- graphene hybrid materials produce chiral；Preparation process one kettle way ambient operation, technique is simple, is easy to industry
Change.
（2）The invention provides a kind of electrochemistry chiral sensor based on chiral MOF- graphene hybrid materials, the biography
Sensor is simply to modify chiral MOF- graphene hybrid materials to be made in glassy carbon electrode surface, and preparation method is simple, easy to operate.
Because chiral MOF- graphene hybrid materials are by the graphene oxide-loaded chiral metal organic framework MOF crystal groups of nano-sheet
Into MOF average crystal grain diameters are 120-160nm, and individual layer loads on sheet graphene oxide, nano-sheet graphene oxide
More and different avtive spots is exposed with MOF crystal, has played chiral MOF and graphene synergy so that base
In chiral sensor prepared by the composite, R-2- amino -3- phenylpropionic acids and S-2- amino -3- phenylpropionic acid mappings are detected
The content of body chiral enantiomer, there is wide quick response, detection range, high sensitivity, simple to operate, time saving.
Embodiment
With reference to embodiment, the invention will be further described, but protection scope of the present invention is not only limited to implement
Example, the change that professionals in the field is made to technical solution of the present invention, all should belong in protection scope of the present invention.
A kind of preparation method of chiral MOF- graphene hybrid materials of embodiment 1
After the blending of the aqueous solution of the alkaline aqueous solution of L-Aspartic acid and copper nitrate-graphene oxide, 4 are added, 4 '-bipyridyl
Ethanol solution, after standing overnight, centrifuge, wash 3 times with ethanol, dry obtained；
The alkaline aqueous solution of the L-Aspartic acid, it is to be dissolved in 0.0200-g sodium hydroxides and 0.0200 g L-Aspartic acids
1 mL water is made；
The aqueous solution of the copper nitrate-graphene oxide, it is after 0.53 g copper nitrates are dissolved in into 6 mL water, adds 0.010 g oxygen
Graphite alkene, 30 min of ultrasound are made；
The ethanol solution of 4, the 4- bipyridyls, it is by 0.050 g 4,4 '-bipyridyl is dissolved in 0.75 mL ethanol and is made.
A kind of preparation method of chiral MOF- graphene hybrid materials of embodiment 2.
After the blending of the aqueous solution of the alkaline aqueous solution of L-Aspartic acid and copper nitrate-graphene oxide, 4 are added, 4 '-bipyridyl
Ethanol solution, after standing overnight, centrifuge, wash 3 times with ethanol, dry obtained；
The alkaline aqueous solution of the L-Aspartic acid, it is to be dissolved in 0.035 g sodium hydroxides and 0.0340 g L-Aspartic acids
1.5 mL water are made；
The aqueous solution of the copper nitrate-graphene oxide, it is after 0.73 g copper nitrates are dissolved in into 8 mL water, adds 0.020 g oxygen
Graphite alkene, 30 min of ultrasound are made；
The ethanol solution of 4, the 4- bipyridyls, it is by 0.66 g 4,4 '-bipyridyl is dissolved in 1.25 mL ethanol and is made.
A kind of preparation method of chiral MOF- graphene hybrid materials of embodiment 3.
After the blending of the aqueous solution of the alkaline aqueous solution of L-Aspartic acid and copper nitrate-graphene oxide, 4 are added, 4 '-bipyridyl
Ethanol solution, after standing overnight, centrifuge, wash 3 times with ethanol, dry obtained；
The alkaline aqueous solution of the L-Aspartic acid, it is to be dissolved in 0.028 g sodium hydroxides and 0.027 g L-Aspartic acids
1.3 mL water are made；
The aqueous solution of the copper nitrate-graphene oxide, it is after 0.60 g copper nitrates are dissolved in into 7 mL water, adds 0.015 g oxygen
Graphite alkene, 30 min of ultrasound are made；
The ethanol solution of 4, the 4- bipyridyls, it is by 0.058 g 4,4 '-bipyridyl is dissolved in 1.0 mL ethanol and is made.
The graphene oxide that the embodiment 1-3 of embodiment 4. is used, preparation process are as follows
In the 40 mL concentrated sulfuric acids, 1.0g graphite powders are added, under magnetic agitation, add 0.60g NaNO3, in ice bath cooling and stirring
1h；Divide 4 times and add 4.0g KMnO4Afterwards, continue ice bath stirring 1h, be warming up to 35 DEG C, be incubated 30min；
Into 46 mL water, the lower above-mentioned mixed liquor of addition is stirred, raw temperature is incubated 40min to 98 DEG C；100 mL water are added, slowly
Add the H that 10 mL mass fractions are 30%2O2, observe solution colour and be changed into glassy yellow from dark brown, solution decompression is filtered, uses matter
Measure hydrochloric acid, water that fraction is 3% to wash successively, dry, graphene oxide is made.
Embodiment 5.
Embodiment 1-3 chiral MOF- graphene hybrid materials, it is organic by the graphene oxide-loaded chiral metal of nano-sheet
Framework thing MOF crystal forms, and MOF chemical formula is [Cu (L-Asp) (4,4 '-Bipy)2] n, its asymmetric structure list
Member, it is by a Cu2+, L-Aspartic acid anion L-Asp and two 4,4 '-Bipy molecular compositions, 4,4 '-Bipy are 4,
4 '-bipyridyl；MOF average crystal grain diameters are 120-160nm, and individual layer loads on sheet graphene oxide.
Embodiment 6
The application of chiral MOF- graphene hybrid materials prepared by embodiment 1 as electrochemical sensing detection enantiomer, step is such as
Under：
（1）Prepare chiral MOF- graphene sensors working electrode
Polish in alumina powder, the basal electrode glassy carbon electrode surface of water and ethanol cleaning, drop coating 6uL chiralitys MOF-
Graphene solution, room temperature are dried, that is, the working sensor electrode of chiral MOF- graphene hybrid materials modification has been made；
The chiral MOF- graphene hybrid materials solution, it is by 3 mg chirality MOF- graphene hybrid materials and 250 uL isopropyls
Alcohol, 720 uL water, 30 uL Nafion are blended ultrasonic 10-15min and are made；
（2）Prepare chiral MOF- graphenes electrochemistry chiral sensor
By step（1）Obtained working electrode, reference electrode and electrode is connected on electrochemical workstation, chirality has been made
MOF- graphene electrochemistry chiral sensors；
The reference electrode is saturated calomel electrode, is platinum electrode to electrode；
（3）Detect R-2- amino -3- phenylpropionic acids and S-2- amino -3- phenylpropionic acid enantiomers
With pH 7.0,0.1 mol L-1PBS cushioning liquid, using step（2）Obtained chiral MOF- graphenes electrification
Chiral sensor is learned, using the R-2- amino -3- phenylpropionic acids and S-2- ammonia of differential pulse voltammetry, respectively measure various concentrations
The current value of base -3- phenylpropionic acid standard liquids, draw the R-2- ammonia based on chiral MOF- graphenes electrochemistry chiral sensor
Base -3- phenylpropionic acids and S-2- amino -3- phenylpropionic acid enantiomer working curves；The solution of testing sample is replaced into R-2- ammonia
Base -3- phenylpropionic acids and S-2- amino -3- phenylpropionic acid standard liquids, carry out R-2- amino -3- phenylpropionic acids and S- in sample
The detection of 2- amino -3- phenylpropionic acid contents.
Embodiment 7
For step with embodiment 6, the chiral MOF- graphene hybrid materials for only preparing embodiment 1 replace with prepared by embodiment 2
Chiral MOF- graphene hybrid materials.
Embodiment 8
For step with embodiment 6, the chiral MOF- graphene hybrid materials for only preparing embodiment 1 replace with prepared by embodiment 3
Chiral MOF- graphene hybrid materials.
Embodiment 9
6-8 chiral sensors made from embodiment, to R-2- amino -3- phenylpropionic acids and S-2- amino -3- phenylpropionic acid mappings
The detection range of liquid solution is 0.1-1.0 × 10-10g/mL。
Claims (7)
1. a kind of chiral MOF- graphene hybrid materials, it is characterised in that the hybrid material is by nano-sheet graphene oxide
Loaded chiral Metal-organic frame MOF crystal forms, and MOF chemical formula is [Cu (L-Asp) (4,4 '-Bipy)2] n, it is not
A symmetrical construction unit, it is by a Cu2+, a L-Aspartic acid anion L-Asp2-With two 4,4 '-Bipy molecules
Composition, 4,4 '-Bipy are 4,4 '-bipyridyl.
2. the preparation method of chiral MOF- graphene hybrid materials as claimed in claim 1, it is characterised in that be by L- asparagus ferns
After the alkaline aqueous solution of propylhomoserin is blended with the aqueous solution of copper nitrate-graphene oxide, addition 4, the ethanol solution of 4 '-bipyridyl,
After standing overnight, centrifuge, washed 3 times with ethanol, dry and be made.
3. the preparation method of chiral MOF- graphene hybrid materials as claimed in claim 2, it is characterised in that described L- days
The alkaline aqueous solution of winter propylhomoserin, it is that 0.0200-0.035 g sodium hydroxides and 0.0200-0.0340 g L-Aspartic acids is molten
It is made in 1-1.5 mL water.
4. the preparation method of chiral MOF- graphene hybrid materials as claimed in claim 2, it is characterised in that the nitric acid
The aqueous solution of copper-graphene oxide, it is after 0.53-0.73 g copper nitrates are dissolved in into 6-8 mL water, adds 0.010-0.020 g oxygen
Graphite alkene, 30 min of ultrasound are made.
5. the preparation method of chiral MOF- graphene hybrid materials as claimed in claim 2, it is characterised in that described 4,4 '-
The ethanol solution of bipyridyl, it is by 0.050-0.66 g 4,4 '-bipyridyl is dissolved in 0.75-1.25 mL ethanol and is made.
6. chiral MOF- graphene hybrid materials prepared by preparation method as claimed in claim 1 detect as electrochemical sensing
The application of enantiomer.
7. the application of electrochemical sensing detection enantiomer as claimed in claim 6, it is characterised in that step is as follows：
（1）Prepare chiral MOF- graphene sensors working electrode
Polish in alumina powder, the basal electrode glassy carbon electrode surface of water and ethanol cleaning, the uL of drop coating 6 is chiral
MOF- graphene solutions, room temperature are dried, that is, the working sensor electrode of chiral MOF- graphene hybrid materials modification has been made；
The chiral MOF- graphene hybrid materials solution, it is by 3 mg chirality MOF- graphene hybrid materials and 250 uL isopropyls
Alcohol, 720 uL water, 30 uL Nafion are blended ultrasonic 10-15min and are made；
（2）Prepare chiral MOF- graphenes electrochemistry chiral sensor
By step（1）Obtained working electrode, reference electrode and electrode is connected on electrochemical workstation, chirality has been made
MOF- graphene electrochemistry chiral sensors；
The reference electrode is saturated calomel electrode, is platinum electrode to electrode；
（3）Detect R-2- amino -3- phenylpropionic acids and S-2- amino -3- phenylpropionic acid enantiomers
With pH 7.0,0.1 mol L-1PBS cushioning liquid, using step（2）Obtained chiral MOF- graphenes electrification
Chiral sensor is learned, using the R-2- amino -3- phenylpropionic acids and S-2- ammonia of differential pulse voltammetry, respectively measure various concentrations
The current value of base -3- phenylpropionic acid standard liquids, draw the R-2- ammonia based on chiral MOF- graphenes electrochemistry chiral sensor
Base -3- phenylpropionic acids and S-2- amino -3- phenylpropionic acid enantiomer working curves；The solution of testing sample is replaced into R-2- ammonia
Base -3- phenylpropionic acids and S-2- amino -3- phenylpropionic acid standard liquids, carry out R-2- amino -3- phenylpropionic acids and S- in sample
The detection of 2- amino -3- phenylpropionic acid contents.
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| CN115248244A (en) * | 2021-12-30 | 2022-10-28 | 兰州理工大学 | Method for synthesizing chiral polymer by inducing chiral nanochannels based on MOF and application |
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