CN107490610B - A kind of chirality MOF- graphene hybrid material and its preparation method and application - Google Patents
A kind of chirality MOF- graphene hybrid material and its preparation method and application Download PDFInfo
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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
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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 to detect the application of enantiomers of chiral drugs the invention discloses a kind of chirality MOF- graphene hybrid material and preparation method thereof and based on the hybrid material, belongs to nanocomposite, polymer-based composite, graphene-based composite material and chiral sensing detection technical field.It has main steps that the alkaline aqueous solution of L-Aspartic acid is blended with copper nitrate-graphene oxide aqueous solution after, the ethanol solution of 4,4 '-bipyridyls is added, after standing overnight, centrifuge separation, dry is made washing.The chiral MOF- graphene hybrid material sensor constructed using the hybrid material, the Sensitive Detection for R-2- amino -3- phenylpropionic acid and S-2- amino -3- phenylpropionic acid Enantiomeric excess.
Description
Technical field
The present invention relates to a kind of chirality MOF- graphene hybrid material and its preparation method and application, belong to nano material,
Metal organic complex nano material and chiral sensing detection technical field.
Background technique
Chirality is one of nature essential attribute, and the property that certain compound molecule and its mirror image can not overlap completely is known as hand
Property.Chiral phenomenon is widely present in nature, such as people's vivo acid is L-configuration, glucose in plant in nature
With the presence of D configuration.Many drugs, nutrient and healthcare products and pesticide etc. are most of with one group of enantiomer in mirror symmetry, 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 drug of entitled Thalidomide has the function of mitigating pregnancy reaction, but since chiral drug at that time is in people
Difference bioactivity understanding is insufficient in vivo, leads to 1.2 ten thousand baby's teratogenesis.Drug R configuration has sedation, and S configuration pair
Fetus has the effect of teratogenesis shape.More than half in the best-selling drug in the whole world has chirality according to statistics.Therefore, how to identify single
Chiral material is always one of the problem that numerous quiral products productions and exploitation must solve.
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, has
The characteristics of inorganic material and organic material.Metal ion and chiral organic ligand molecule based on synthesis MOFs material are abundant more
The chiral amorphous metal organic framework materials of coloured silk, a large amount of structure novels have been assembled, and chiral MOFs is in Heterogeneous asymmetric catalysis, choosing
The fields such as the identification of selecting property and separation and chiral sensing are applied.
Graphene is a kind of allotrope of carbon, it be by single layer of carbon atom it is tightly packed at 2D honeycomb structure material
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 substrate on graphene oxide
Base and epoxy functionality, the carboxyl functional group of edge) increase its hydrophily and dispersibility in the solution.Aoxidize stone
The common presence of functional group and the fragrance domain sp2 on black alkene participates in MOFs so that graphene oxide can be used as structure node
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
The growth of MOFs is led, in nature, MOFs and graphene oxide will play synergistic effect.
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 miscellaneous to provide a kind of chirality MOF- graphene
Change 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 industrial application
Prospect.
The two of technical assignment of the invention are to provide a kind of purposes of chirality MOF- graphene hybrid material, i.e., by the chirality
Polyaniline-graphite alkene composite material is used for efficient detection R-2- amino -3- phenylpropionic acid and S-2- amino -3- phenylpropionic acid mapping
The content of body, the detecting instrument is at low cost, analysis efficiency is high, easy to operate, and operating technology requires low.
Technical scheme is as follows:
1. a kind of chirality MOF- graphene hybrid material, the hybrid material are by the graphene oxide-loaded hand of nano-sheet
Property Metal-organic frame MOF crystal composition, the chemical formula of MOF is [Cu (L-Asp) (4,4 '-Bipy)2] n, it is asymmetric
One structural unit is by a Cu2+, L-Aspartic acid anion L-Asp and two 4,4 '-Bipy molecular compositions, 4,4
'-Bipy is 4,4 '-bipyridyls；
MOF average crystal grain diameter is 120-160nm, and single layer loads on sheet graphene oxide.
2. a kind of preparation method of chirality MOF- graphene hybrid material, be by the alkaline aqueous solution of L-Aspartic acid with
After copper nitrate-graphene oxide aqueous solution is blended, the ethanol solution of 4,4 '-bipyridyls is added, after standing overnight, centrifugation point
From dry to be made with ethanol washing 3 times；
The alkaline aqueous solution of the L-Aspartic acid is by 0.0200-0.035 g sodium hydroxide 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 is after 0.53-0.73 g copper nitrate is dissolved in 6-8 mL water, to add
Enter 0.010-0.020 g graphene oxide, 30 min of ultrasound are made；
The ethanol solution of 4, the 4- bipyridyl is that 4,4 '-bipyridyl of 0.050-0.66 g is dissolved in 0.75-1.25 mL
Ethyl alcohol is made.
3. application of the chirality MOF- graphene hybrid material as described above as electrochemical sensing detection enantiomer, step
It is as follows:
(1) chirality MOF- graphene sensor working electrode is prepared
It has polished in alumina powder, the basal electrode glassy carbon electrode surface of water and ethyl alcohol cleaning, drop coating 6uL is chiral
MOF- graphene solution, room temperature are dried, and the working sensor electrode of chiral MOF- graphene hybrid material modification has been obtained；
The chirality MOF- graphene hybrid material solution is by 3 mg chirality MOF- graphene hybrid materials and 250 uL
Isopropanol, 720 uL water, 30 uL Nafion are blended ultrasound 10-15min and are made；
(2) chirality MOF- graphene electrochemistry chiral sensor is prepared
By working electrode, reference electrode made from step (1) and electrode is connected on electrochemical workstation, hand has been made
Property MOF- graphene electrochemistry chiral sensor；
The reference electrode is saturated calomel electrode, is platinum electrode to electrode；
(3) R-2- amino -3- phenylpropionic acid and S-2- amino -3- phenylpropionic acid enantiomer are detected
With pH 7.0,0.1 mol L-1PBS buffer solution, using chirality MOF- graphene made from step (2)
Electrochemistry chiral sensor measures the R-2- amino -3- phenylpropionic acid and S- of various concentration using differential pulse voltammetry respectively
The current value of 2- amino -3- phenylpropionic acid standard solution draws the R- based on chiral MOF- graphene electrochemistry chiral sensor
2- amino -3- phenylpropionic acid and S-2- amino -3- phenylpropionic acid enantiomer working curve；The solution of sample to be tested is replaced into R-2-
Amino -3- phenylpropionic acid and S-2- amino -3- phenylpropionic acid standard solution, carry out sample in R-2- amino -3- phenylpropionic acid and
The detection of S-2- amino -3- phenylpropionic acid content.
Inspection of the chiral sensor to R-2- amino -3- phenylpropionic acid and S-2- amino -3- phenylpropionic acid mapping liquid solution
Survey range is 0.1-1.0 × 10-10g/mL。
The beneficial technical effect of the present invention is as follows:
(1) preparation of chirality MOF- graphene hybrid material of the invention, due to joined chiral ligand L- in preparation process
Aspartic acid, induction MOF- graphene hybrid material generate chiral；Preparation process one kettle way ambient operation, simple process are easy to
Industrialization.
(2) the present invention provides a kind of electrochemistry chiral sensor based on chiral MOF- graphene hybrid material, the biographies
Sensor is simply to modify chiral MOF- graphene hybrid material to be made in glassy carbon electrode surface, and preparation method is simple, easy to operate.
Since chiral MOF- graphene hybrid material is by the graphene oxide-loaded chiral metal organic framework MOF crystal group of nano-sheet
At MOF average crystal grain diameter is 120-160nm, and single layer loads on sheet graphene oxide, nano-sheet graphene oxide
More and different active sites is exposed with MOF crystal, has played the synergistic effect of chiral MOF and graphene, so that base
In the chiral sensor of composite material preparation, R-2- amino -3- phenylpropionic acid and S-2- amino -3- phenylpropionic acid mapping are detected
The content of body chiral enantiomer has the characteristics that wide quick response, detection range, high sensitivity, easy to operate, 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 chirality MOF- graphene hybrid material of embodiment 1
After the alkaline aqueous solution of L-Aspartic acid is blended with copper nitrate-graphene oxide aqueous solution, 4,4 '-connection are added
The ethanol solution of pyridine, after standing overnight, centrifuge separation is dry to be made with ethanol washing 3 times；
The alkaline aqueous solution of the L-Aspartic acid is by 0.0200-g sodium hydroxide and 0.0200 g L-Aspartic acid
1 mL water is dissolved in be made；
The aqueous solution of the copper nitrate-graphene oxide is to be added 0.010 after 0.53 g copper nitrate is dissolved in 6 mL water
G graphene oxide, 30 min of ultrasound are made；
The ethanol solution of 4, the 4- bipyridyl is that 0.050 g, 4,4 '-bipyridyl is dissolved in 0.75 mL ethyl alcohol to be made.
A kind of preparation method of the chirality MOF- graphene hybrid material of embodiment 2.
After the alkaline aqueous solution of L-Aspartic acid is blended with copper nitrate-graphene oxide aqueous solution, 4,4 '-connection are added
The ethanol solution of pyridine, after standing overnight, centrifuge separation is dry to be made with ethanol washing 3 times；
The alkaline aqueous solution of the L-Aspartic acid is by 0.035 g sodium hydroxide and 0.0340 g L-Aspartic acid
1.5 mL water are dissolved in be made；
The aqueous solution of the copper nitrate-graphene oxide is to be added 0.020 after 0.73 g copper nitrate is dissolved in 8 mL water
G graphene oxide, 30 min of ultrasound are made；
The ethanol solution of 4, the 4- bipyridyl is that 0.66 g, 4,4 '-bipyridyl is dissolved in 1.25 mL ethyl alcohol to be made.
A kind of preparation method of the chirality MOF- graphene hybrid material of embodiment 3.
After the alkaline aqueous solution of L-Aspartic acid is blended with copper nitrate-graphene oxide aqueous solution, 4,4 '-connection are added
The ethanol solution of pyridine, after standing overnight, centrifuge separation is dry to be made with ethanol washing 3 times；
The alkaline aqueous solution of the L-Aspartic acid is that 0.028 g sodium hydroxide and 0.027 g L-Aspartic acid is molten
It is made in 1.3 mL water；
The aqueous solution of the copper nitrate-graphene oxide is to be added 0.015 after 0.60 g copper nitrate is dissolved in 7 mL water
G graphene oxide, 30 min of ultrasound are made；
The ethanol solution of 4, the 4- bipyridyl is that 0.058 g, 4,4 '-bipyridyl is dissolved in 1.0 mL ethyl alcohol to be made.
The graphene oxide that 4. embodiment 1-3 of embodiment is used, preparation step are as follows
In the 40 mL concentrated sulfuric acids, 1.0g graphite powder is added, under magnetic agitation, 0.60g NaNO is added3, cooling in ice bath
Stir 1h；Divide 4 addition 4.0g KMnO4Afterwards, continue ice bath stirring 1h, be warming up to 35 DEG C, keep the temperature 30min；
Into 46 mL water, it is added with stirring above-mentioned mixed liquor, raw temperature keeps the temperature 40min to 98 DEG C；100 mL water are added,
It is slowly added to the H that 10 mL mass fractions are 30%2O2, observing solution colour from dark brown becomes glassy yellow, and solution is depressurized and is filtered,
The hydrochloric acid for being 3% with mass fraction, water successively wash, dry, and graphene oxide is made.
Embodiment 5.
The chiral MOF- graphene hybrid material of embodiment 1-3, by the graphene oxide-loaded chiral metal of nano-sheet
Organic framework MOF crystal composition, the chemical formula of MOF are [Cu (L-Asp) (4,4 '-Bipy)2] n, an asymmetric knot
Structure unit is by a Cu2+, L-Aspartic acid anion L-Asp and two 4,4 '-Bipy molecular compositions, 4,4 '-Bipy
It is 4,4 '-bipyridyls；MOF average crystal grain diameter is 120-160nm, and single layer loads on sheet graphene oxide.
Embodiment 6
The application of chiral MOF- graphene hybrid material prepared by embodiment 1 as electrochemical sensing detection enantiomer, step
It is rapid as follows:
(1) chirality MOF- graphene sensor working electrode is prepared
It has polished in alumina powder, the basal electrode glassy carbon electrode surface of water and ethyl alcohol cleaning, drop coating 6uL is chiral
MOF- graphene solution, room temperature are dried, and the working sensor electrode of chiral MOF- graphene hybrid material modification has been obtained；
The chirality MOF- graphene hybrid material solution is by 3 mg chirality MOF- graphene hybrid materials and 250 uL
Isopropanol, 720 uL water, 30 uL Nafion are blended ultrasound 10-15min and are made；
(2) chirality MOF- graphene electrochemistry chiral sensor is prepared
By working electrode, reference electrode made from step (1) and electrode is connected on electrochemical workstation, hand has been made
Property MOF- graphene electrochemistry chiral sensor；
The reference electrode is saturated calomel electrode, is platinum electrode to electrode；
(3) R-2- amino -3- phenylpropionic acid and S-2- amino -3- phenylpropionic acid enantiomer are detected
With pH 7.0,0.1 mol L-1PBS buffer solution, using chirality MOF- graphene made from step (2)
Electrochemistry chiral sensor measures the R-2- amino -3- phenylpropionic acid and S- of various concentration using differential pulse voltammetry respectively
The current value of 2- amino -3- phenylpropionic acid standard solution draws the R- based on chiral MOF- graphene electrochemistry chiral sensor
2- amino -3- phenylpropionic acid and S-2- amino -3- phenylpropionic acid enantiomer working curve；The solution of sample to be tested is replaced into R-2-
Amino -3- phenylpropionic acid and S-2- amino -3- phenylpropionic acid standard solution, carry out sample in R-2- amino -3- phenylpropionic acid and
The detection of S-2- amino -3- phenylpropionic acid content.
Embodiment 7
With embodiment 6, the chiral MOF- graphene hybrid material for only preparing embodiment 1 replaces with embodiment 2 and makes step
Standby chiral MOF- graphene hybrid material.
Embodiment 8
With embodiment 6, the chiral MOF- graphene hybrid material for only preparing embodiment 1 replaces with embodiment 3 and makes step
Standby chiral MOF- graphene hybrid material.
Embodiment 9
6-8 chiral sensor made from embodiment, to R-2- amino -3- phenylpropionic acid and S-2- amino -3- phenylpropionic acid
The detection range of mapping liquid solution is 0.1-1.0 × 10-10g/mL。
Claims (7)
1. a kind of chirality MOF- graphene hybrid material, which is characterized in that the hybrid material is by nano-sheet graphene oxide
Loaded chiral Metal-organic frame MOF crystal composition, the chemical formula of MOF are [Cu (L-Asp) (4,4 '-Bipy)2] n, no
A symmetrical structural unit is by a Cu2+, a L-Aspartic acid anion L-Asp2-With two 4,4 '-Bipy molecules
Composition, 4,4 '-Bipy are 4,4 '-bipyridyls.
2. the preparation method of chirality MOF- graphene hybrid material as described in claim 1, which is characterized in that be by L- asparagus fern
After the alkaline aqueous solution of propylhomoserin is blended with copper nitrate-graphene oxide aqueous solution, the ethanol solution of 4,4 '-bipyridyls is added,
After standing overnight, centrifuge separation is dry to be made with ethanol washing 3 times.
3. the preparation method of chirality MOF- graphene hybrid material as claimed in claim 2, which is characterized in that the L- asparagus fern
The alkaline aqueous solution of propylhomoserin is that 0.0200-0.0350g sodium hydroxide and 0.0200-0.0340g L-Aspartic acid are dissolved in 1-
1.5mL water is made.
4. the preparation method of chirality MOF- graphene hybrid material as claimed in claim 2, which is characterized in that the nitric acid
Copper-graphene oxide aqueous solution is that 0.010-0.020g oxidation is added after 0.53-0.73g copper nitrate is dissolved in 6-8mL water
Graphene, ultrasonic 30min are made.
5. the preparation method of chirality MOF- graphene hybrid material as claimed in claim 2, which is characterized in that described 4,4 '-
The ethanol solution of bipyridyl is that 4,4 '-bipyridyl of 0.050-0.660g is dissolved in 0.75-1.25mL ethyl alcohol to be made.
6. application of the chirality MOF- graphene hybrid material as described in claim 1 as electrochemical sensing detection enantiomer.
7. the application of electrochemical sensing detection enantiomer as claimed in claim 6, which is characterized in that steps are as follows:
(1) chirality MOF- graphene sensor working electrode is prepared
It has polished in alumina powder, the basal electrode glassy carbon electrode surface of water and ethyl alcohol cleaning, drop coating 6uL chirality MOF-
Graphene solution, room temperature are dried, and the working sensor electrode of chiral MOF- graphene hybrid material modification has been obtained；
The chirality MOF- graphene hybrid material solution is by 3mg chirality MOF- graphene hybrid material and 250uL isopropyl
Alcohol, 720uL water, 30uL Nafion are blended ultrasound 10-15min and are made；
(2) chirality MOF- graphene electrochemistry chiral sensor is prepared
By working electrode, reference electrode made from step (1) and electrode is connected on electrochemical workstation, chirality has been made
MOF- graphene electrochemistry chiral sensor；
The reference electrode is saturated calomel electrode, is platinum electrode to electrode；
(3) R-2- amino -3- phenylpropionic acid and S-2- amino -3- phenylpropionic acid enantiomer are detected
With pH 7.0,0.1molL-1PBS buffer solution, learned to do using chirality MOF- graphene electrification made from step (2)
Property sensor the R-2- amino -3- phenylpropionic acid and S-2- amino-of various concentration measured using differential pulse voltammetry respectively
The current value of 3- phenylpropionic acid standard solution draws the R-2- amino-based on chiral MOF- graphene electrochemistry chiral sensor
3- phenylpropionic acid and S-2- amino -3- phenylpropionic acid enantiomer working curve；The solution of sample to be tested is replaced into R-2- amino -3-
Phenylpropionic acid and S-2- amino -3- phenylpropionic acid standard solution carry out R-2- amino -3- phenylpropionic acid and S-2- ammonia in sample
The detection of base -3- phenylpropionic acid content.
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| CN107589159B (en) * | 2017-09-05 | 2019-06-25 | 济南大学 | A kind of preparation method and application of chirality MOF nanofiber-graphene hybrid material |
| CN109916973B (en) * | 2019-02-28 | 2020-05-19 | 华中科技大学 | Ball-milled graphene-MOFs composite material, and preparation and application thereof |
| CN110483798B (en) * | 2019-08-30 | 2021-08-17 | 济南大学 | Preparation method and application of graphene oxide @ chiral Ni-MOF hybrid material |
| CN110361432B (en) * | 2019-08-30 | 2021-05-14 | 济南大学 | Preparation method and application of chiral spiral polyaniline @ MOF nanocomposite |
| CN110841720B (en) * | 2019-11-29 | 2022-11-18 | 河南师范大学 | Graphene adsorption multi-component chiral catalyst and application thereof in asymmetric hydrogenation |
| CN111413380A (en) * | 2020-03-12 | 2020-07-14 | 济南大学 | Preparation method and application of HKUST-1-based chiral composite material |
| CN111398381A (en) * | 2020-04-17 | 2020-07-10 | 济南大学 | Electrochemical identification method for identifying non-electroactive amino acid enantiomer |
| 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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