CN107442170A - A kind of chiral MOF composite catalysts and its preparation method and application - Google Patents
A kind of chiral MOF composite catalysts and its preparation method and application Download PDFInfo
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- 239000012924 metal-organic framework composite Substances 0.000 title claims abstract description 52
- 239000003054 catalyst Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000007864 aqueous solution Substances 0.000 claims abstract description 31
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- QIVBCDIJIAJPQS-SECBINFHSA-N D-tryptophane Chemical compound C1=CC=C2C(C[C@@H](N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-SECBINFHSA-N 0.000 claims abstract description 19
- QIVBCDIJIAJPQS-VIFPVBQESA-N L-tryptophane Chemical class C1=CC=C2C(C[C@H](N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-VIFPVBQESA-N 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
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- 238000001514 detection method Methods 0.000 claims abstract description 15
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- 239000000243 solution Substances 0.000 claims description 18
- 239000010949 copper Substances 0.000 claims description 12
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 10
- 239000004094 surface-active agent Substances 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 230000005518 electrochemistry Effects 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 239000012621 metal-organic framework Substances 0.000 claims description 8
- 229930182827 D-tryptophan Natural products 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 229960004799 tryptophan Drugs 0.000 claims description 6
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- 239000013078 crystal Substances 0.000 claims description 5
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical class CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 3
- 229920000557 Nafion® Polymers 0.000 claims description 3
- 239000006035 Tryptophane Substances 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
- 230000001413 cellular effect Effects 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000010276 construction Methods 0.000 claims description 3
- 238000001903 differential pulse voltammetry Methods 0.000 claims description 3
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- 238000001548 drop coating Methods 0.000 claims description 3
- 239000002135 nanosheet Substances 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- 238000000034 method Methods 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 4
- 230000003213 activating effect Effects 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 abstract 1
- 239000002114 nanocomposite Substances 0.000 abstract 1
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- 238000001914 filtration Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- UEJJHQNACJXSKW-UHFFFAOYSA-N 2-(2,6-dioxopiperidin-3-yl)-1H-isoindole-1,3(2H)-dione Chemical compound O=C1C2=CC=CC=C2C(=O)N1C1CCC(=O)NC1=O UEJJHQNACJXSKW-UHFFFAOYSA-N 0.000 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 description 2
- 102000004160 Phosphoric Monoester Hydrolases Human genes 0.000 description 2
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- 239000007787 solid Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
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- 229960003433 thalidomide Drugs 0.000 description 2
- DWNBOPVKNPVNQG-LURJTMIESA-N (2s)-4-hydroxy-2-(propylamino)butanoic acid Chemical compound CCCN[C@H](C(O)=O)CCO DWNBOPVKNPVNQG-LURJTMIESA-N 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
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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
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Abstract
It is used for the application for detecting chiral enantiomer the invention discloses a kind of chiral MOF composite catalysts and preparation method thereof and based on the composite, belongs to nano composite material, Metal-organic frame material and chiral sensing detection technical field.It, which will have main steps that, to be stored at room temperature, centrifuge after the aqueous solution blending of the alkaline aqueous solution of chiral ligand and copper acetate surface of graphene oxide activating agent, water washing, dry and be made.The chiral sensor built using the composite, it is notable for the detection of D (+) tryptophan and L () Tryptophan enantiomer content, simple, easy to operate, the chiral Detection results of method.
Description
Technical field
The present invention relates to a kind of chiral MOF composite catalysts and its preparation method and application, belong to nano material, gold
Belong to organic framework nano material and chiral sensing detection technical field.
Background technology
Chirality is one of essential attribute of nature, has a pair of chiral enantiomers, its chemical property is identical, thing
Rationality matter is also identical in addition to optical direction is opposite, but the bioactivity of enantiomer is entirely different.For chiral medicine,
An isomers in enantiomer may have drug effect, and another isomers may be invalid or even harmful.Sand profit in medical history
Amine event is spent, be about born more than 12,000 lopsided baby, and it is that Thalidomide molecule has two kinds of structures of R and S to trace it to its cause
Type enantiomer, the Thalidomide of wherein R configurations has neuroleptic effect, and the molecule of S configurations then has strong teratogenesis.This
A pair of enantiomers without fractionation put goods on the market into huge numbers of families, result in the generation of tragedy.
According to incompletely statistics, current more than 2/3 medicine developed is chiral drug, the chiral drug of in the market 40%
It is individual isomer.2002, chiral drug market was up to 159,000,000,000 dollars.Amino acid is the elementary cell of constitutive protein matter,
Very important effect is played in human body and animal life activity.Optics pure amino acid is synthesis polypeptide and lactams antibiosis
The important intermediate of the medicines such as element, in exploitation of pharmaceutical synthesis, new material synthesis, food additives and fine chemicals etc.
All there is huge application value.However, artificial synthesized amino acid is racemic modification mostly.Therefore, develop detecting instrument into
This is low, analysis efficiency is high, easy to operate, and operating technology requires the identifying and analyzing method of low amino acid enantiomer, has important
Meaning.
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 composites
The preparation method of catalyst, the raw materials used cost of this method is low, and preparation technology is simple, and energy consumption of reaction is low, before having commercial Application
Scape.
The two of the technical assignment of the present invention are to provide the purposes of the chiral MOF composite catalysts, will the chirality
MOF composites are used for the content of efficient catalytic detection D- (+)-tryptophan and L- (-)-Tryptophan enantiomer, the testing cost
It is low, analysis efficiency is high, easy to operate, operating technology require it is low.
Technical scheme is as follows：
A kind of 1. chiral MOF composite catalysts
The catalyst is made up of the graphene oxide-loaded chiral metal organic framework MOF crystal of nano-sheet, and crystal is footpath
Wide 80-110 nm nanometer rods, its chemical formula are [(CuL)2 H2O]n；Crystal one cellular construction of asymmetry, by two Cu
(II) ion center, two asymmetric chiral ligand H2L L (II) ions and a H2O molecules are formed, the structure of L (II) ion
It is as follows to make formula：
。
2. the preparation method of above-described chiral MOF composite catalysts, step are as follows：
By chiral ligand H2After L alkaline aqueous solution is blended with the aqueous solution of copper acetate-graphene oxide-surfactant, room
Temperature stand 2-10 min centrifuge, water washing three times, be dried to obtain；Yield 70-75 %；
The chiral ligand H2L alkaline aqueous solution, it is by 0.185-0.205g parts H2L, add 10mL, mass fraction is
The 0.20-0.30 % LiOH aqueous solution, dissolving are made；
The aqueous solution of the copper acetate-graphene oxide-surfactant, it is by 0.15-0.25 g CuAc2·H2O、9-11
ML water, the polyethylene glycol and 5-7 mg graphene oxides that 0.2-0.3 mL molecular weight is 6000, ultrasonic 5-10 min are made；
The chiral ligand H2L, preparation method are as follows：By 15 mmol ALANINEs and 18 mL, the water containing 0.84 g KOH
Solution blending is pyrolyzed, and adds 16 mL, the ethanol solution containing 1.8 g salicylides, after 30 min are stirred at room temperature, ice bath is cooled to 0-5
DEG C, 9mL, the aqueous solution containing 0.69 g NaBH4 are added, after yellow disappears, is neutralized to the watery hydrochloric acid that mass fraction is 18%
PH is 3.5-5.0, the filtering of obtained solid, wash three times with ethanol, then with volume ratio is 1：1 water and ethyl alcohol recrystallization, mistake
Filter, dry and be made after being washed with cold ethanol；
The graphene oxide is bought in chemical reagent company, or is prepared as follows：
Concentrated sulfuric acid 120mL and phosphatase 11 3.3mL is blended, nitration mixture is made；By 1.0 g graphite and 6.0g KMnO4After blending, stirring
Under, nitration mixture is added, heating water bath continues to stir 12h to 50 DEG C；Mixed liquor ice-water bath is cooled to room temperature, add 1.5mL,
30%H2O2The aqueous solution；Mixture is centrifuged and pours out supernatant, is precipitated, then successively with water, 30% hydrochloric acid, second
Alcohol washs twice respectively, dries, and graphene oxide is made.
3. application of the above-described chiral MOF composite catalysts as electrochemical sensing detection enantiomer, step
It is as follows：
（1）Prepare chiral MOF composites working sensor electrode
Polish in alumina powder, the basal electrode glassy carbon electrode surface of water and ethanol cleaning, the uL chiralitys MOF of drop coating 6
Composite solution, room temperature are dried, and the working sensor electrode of chiral MOF composites structure is made；
The chiral MOF composites solution, it is by 3 mg chirality MOF composites and 250 uL isopropanols, 720 uL water, 30
UL Nafion are blended ultrasonic 10-15min and are made；
（2）Prepare chiral MOF composites electrochemistry chiral sensor
By step（1）Obtained working electrode, reference electrode and electrode is connected on electrochemical workstation, chirality has been made
MOF composite electrochemistry chiral sensors；
The reference electrode is saturated calomel electrode, is platinum electrode to electrode；
（3）Detect D- (+)-tryptophan and L- (-)-Tryptophan enantiomer
With pH 5.0,0.1 mol L-1PBS cushioning liquid, using step（2）Obtained chiral MOF composites electricity
Chemical chiral sensor, using D- (+)-tryptophan and L- (-)-color ammonia of differential pulse voltammetry, respectively measure various concentrations
The current value of sour standard liquid, draw the D- based on chiral MOF composites electrochemistry chiral sensor（+）- tryptophan and L-
（-）- Tryptophan enantiomer working curve；The solution of testing sample is replaced into D-（+）- tryptophan or L-（-）- tryptophan standards are molten
Liquid, carry out D- in sample（+）- tryptophan and L-（-）The detection of-tryptophane.
The chiral sensor is to D-（+）- tryptophan and L-（-）The detection range of-tryptophan solution is 0.1-1.0 × 10- 9g/mL。
The beneficial technique effect of the present invention：
（1）The preparation of the chiral MOF composites of the present invention, due to adding chiral ligand H in preparation process2L, induction MOF are answered
Condensation material produces chiral；Due to having used the polyethylene glycol that molecular weight is 6000, chiral MOF crystal is in obtained composite
The wide 80-110 nm in footpath nanometer rods, if the not effect of the surface-active, chiral MOF crystal footpath in obtained composite
A width of 1-5um；And the preparation process one kettle way ambient operation, technique is simple, is easy to industrialize.
（2）The invention provides a kind of chiral MOF composite catalysts answering as electrochemical sensing detection enantiomer
With the detection is simply to modify the solution of chiral MOF composites to be made in glassy carbon electrode surface, and preparation method is simple, easy
Operation.Due to exposing more and different avtive spots in chiral MOF and graphene oxide composite material, chirality has been played
MOF and graphene oxide synergy so that the chiral sensor prepared based on the composite, successfully detect D-（+）- color
Propylhomoserin and L-（-）The content of-tryptophan solution chiral enantiomer, and with quick response, detection range is wide, high sensitivity,
The features such as 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 composite catalysts of embodiment 1
By chiral ligand H2After L alkaline aqueous solution is blended with the aqueous solution of copper acetate-graphene oxide-surfactant, room
Temperature stand 2 min centrifuge, water washing three times, be dried to obtain；The % of yield 70；
The chiral ligand H2L alkaline aqueous solution, it is by 0.185g parts H2L, add 10mL, mass fraction is 0.20 %
The LiOH aqueous solution, dissolving are made；
The aqueous solution of the copper acetate-graphene oxide-surfactant, it is by 0.15 g CuAc2·H2O, 9 mL water, 0.2
ML molecular weight is 6000 polyethylene glycol and 5 mg graphene oxides, and 5 min of ultrasound are made.
A kind of preparation method of chiral MOF composite catalysts of embodiment 2
By chiral ligand H2After L alkaline aqueous solution is blended with the aqueous solution of copper acetate-graphene oxide-surfactant, room
Temperature stand 10 min centrifuge, water washing three times, be dried to obtain；The % of yield 75；
The chiral ligand H2L alkaline aqueous solution, it is by 0.205g parts H2L, add 10mL, mass fraction is 0.30 %
The LiOH aqueous solution, dissolving are made；
The aqueous solution of the copper acetate-graphene oxide-surfactant, it is by 0.25 g CuAc2·H2O, 11 mL water,
0.3 mL molecular weight is 6000 polyethylene glycol and 7 mg graphene oxides, and 10 min of ultrasound are made.
A kind of preparation method of chiral MOF composite catalysts of embodiment 3
By chiral ligand H2After L alkaline aqueous solution is blended with the aqueous solution of copper acetate-graphene oxide-surfactant, room
Temperature stand 6 min centrifuge, water washing three times, be dried to obtain；The % of yield 73；
The chiral ligand H2L alkaline aqueous solution, it is by 0.195 g parts H2L, add 10mL, mass fraction is 0.25 %
The LiOH aqueous solution, dissolving are made；
The aqueous solution of the copper acetate-graphene oxide-surfactant, it is by 0.20 g CuAc2·H2O, 10 mL water,
0.25 mL molecular weight is 6000 polyethylene glycol and 6 mg graphene oxides, and 7 min of ultrasound are made.
Chiral MOF composite catalysts made from the embodiment 1-3 of embodiment 4., by nano-sheet graphene oxide
Loaded chiral Metal-organic frame MOF crystal forms, and crystal is the wide 80-110 nm in footpath nanometer rods, and its chemical formula is
[(CuL)2 H2O]n；Crystal one cellular construction of asymmetry, by two Cu (II) ion centers, two asymmetric chiral ligands
H2L L (II) ions and a H2O molecules are formed, and the structural formula of L (II) ion is as follows：
。
The chiral ligand H that the embodiment 1-3 of embodiment 5. is used2L, preparation method are as follows：
15 mmol ALANINEs and 18 mL, the aqueous solution containing 0.84 g KOH are blended and are pyrolyzed, add 16 mL, containing 1.8 g
The ethanol solution of salicylide, after 30 min are stirred at room temperature, ice bath is cooled to 0-5 DEG C, adds 9mL, the water containing 0.69 g NaBH4
Solution, after yellow disappears, it is 3.5-5.0 that the watery hydrochloric acid for being 18% with mass fraction, which is neutralized to pH, obtained solid filtering, is used
Ethanol wash three times, then with volume ratio be 1：1 water and ethyl alcohol recrystallization, filtering, dry and be made after being washed with cold ethanol.
The graphene oxide that the embodiment 1-3 of embodiment 6. is used is bought in chemical reagent company, or is made as follows
It is standby：
Concentrated sulfuric acid 120mL and phosphatase 11 3.3mL is blended, nitration mixture is made；By 1.0 g graphite and 6.0g KMnO4After blending, stirring
Under, nitration mixture is added, heating water bath continues to stir 12h to 50 DEG C；Mixed liquor ice-water bath is cooled to room temperature, add 1.5mL,
30%H2O2The aqueous solution；Mixture is centrifuged and pours out supernatant, is precipitated, then successively with water, 30% hydrochloric acid, second
Alcohol washs twice respectively, dries, and graphene oxide is made.
Chiral MOF composite catalysts prepared by the embodiment 1 of embodiment 7. are as electrochemical sensing detection enantiomer
Using step is as follows：
（1）Prepare chiral MOF composites working sensor electrode
Polish in alumina powder, the basal electrode glassy carbon electrode surface of water and ethanol cleaning, the uL chiralitys MOF of drop coating 6
Composite solution, room temperature are dried, and the working sensor electrode of chiral MOF composites structure is made；
The chiral MOF composites solution, it is by 3 mg chirality MOF composites and 250 uL isopropanols, 720 uL water, 30
UL Nafion are blended ultrasonic 10-15min and are made；
（2）Prepare chiral MOF composites electrochemistry chiral sensor
By step（1）Obtained working electrode, reference electrode and electrode is connected on electrochemical workstation, chirality has been made
MOF composite electrochemistry chiral sensors；
The reference electrode is saturated calomel electrode, is platinum electrode to electrode；
（3）Detect D- (+)-tryptophan and L- (-)-Tryptophan enantiomer
With pH 5.0,0.1 mol L-1PBS cushioning liquid, using step（2）Obtained chiral MOF composites electricity
Chemical chiral sensor, using D- (+)-tryptophan and L- (-)-color ammonia of differential pulse voltammetry, respectively measure various concentrations
The current value of sour standard liquid, draw the D- based on chiral MOF composites electrochemistry chiral sensor（+）- tryptophan and L-
（-）- Tryptophan enantiomer working curve；The solution of testing sample is replaced into D-（+）- tryptophan or L-（-）- tryptophan standards are molten
Liquid, carry out D- in sample（+）- tryptophan and L-（-）The detection of-tryptophane.
Chiral MOF composite catalysts in embodiment 7 are only replaced with implementation by the method for embodiment 8. with embodiment 7
Chiral MOF composite catalysts prepared by example 2.
Chiral MOF composite catalysts in embodiment 7 are only replaced with implementation by the method for embodiment 9. with embodiment 7
Chiral MOF composite catalysts prepared by example 3.
Chiral MOF composite catalysts prepared by the embodiment 7-9 of embodiment 10. detect mapping as electrochemical sensing
The application of body, to D-（+）- tryptophan and L-（-）The detection range of-tryptophan solution is 0.1-1.0 × 10-9g/mL。
Claims (6)
1. a kind of chiral MOF composite catalysts, it is characterised in that the catalyst is graphene oxide-loaded by nano-sheet
Chiral metal organic framework MOF crystal forms, and crystal is the wide 80-110 nm in footpath nanometer rods, and its chemical formula is [(CuL)2
H2O]n；Crystal one cellular construction of asymmetry, by two Cu (II) ion centers, two asymmetric chiral ligand H2L L (II)
Ion and a H2O molecules are formed, and the structural formula of L (II) ion is as follows：
。
2. the preparation method of chiral MOF composite catalysts as claimed in claim 1, it is characterised in that by chiral ligand
H2L alkaline aqueous solution is with after the aqueous solution blending of copper acetate-graphene oxide-surfactant, being stored at room temperature 2-10 min
Centrifuge, water washing three times, be dried to obtain；Yield 70-75 %.
3. the preparation method of chiral MOF composite catalysts as claimed in claim 2, it is characterised in that the chirality is matched somebody with somebody
Body H2L alkaline aqueous solution, it is by 0.185-0.205g parts H2L, add 10mL, mass fraction is 0.20-0.30 % LiOH
The aqueous solution, dissolving are made.
4. the preparation method of chiral MOF composite catalysts as claimed in claim 2, it is characterised in that the acetic acid
The aqueous solution of copper-graphene oxide-surfactant, it is by 0.15-0.25 g CuAc2·H2O, 9-11 mL water, 0.2-0.3
ML molecular weight is 6000 polyethylene glycol and 5-7 mg graphene oxides, and ultrasonic 5-10 min are made.
5. chiral MOF composite catalysts prepared by preparation method as claimed in claim 1 detect as electrochemical sensing
The application of enantiomer.
6. electrochemical sensing as claimed in claim 6 detects enantiomer, it is characterised in that step is as follows：
（1）Prepare chiral MOF composites working sensor electrode
Polish in alumina powder, the basal electrode glassy carbon electrode surface of water and ethanol cleaning, the uL chiralitys MOF of drop coating 6
Composite solution, room temperature are dried, and the working sensor electrode of chiral MOF composites structure is made；
The chiral MOF composites solution, it is by 3 mg chirality MOF composites and 250 uL isopropanols, 720 uL water, 30
UL Nafion are blended ultrasonic 10-15min and are made；
（2）Prepare chiral MOF composites electrochemistry chiral sensor
By step（1）Obtained working electrode, reference electrode and electrode is connected on electrochemical workstation, chirality has been made
MOF composite electrochemistry chiral sensors；
The reference electrode is saturated calomel electrode, is platinum electrode to electrode；
（3）Detect D- (+)-tryptophan and L- (-)-Tryptophan enantiomer
With pH 5.0,0.1 mol L-1PBS cushioning liquid, using step（2）Obtained chiral MOF composites electrification
Chiral sensor is learned, using D- (+)-tryptophan and L- (-)-tryptophan of differential pulse voltammetry, respectively measure various concentrations
The current value of standard liquid, draw the D- based on chiral MOF composites electrochemistry chiral sensor（+）- tryptophan and L-
（-）- Tryptophan enantiomer working curve；The solution of testing sample is replaced into D-（+）- tryptophan or L-（-）- tryptophan standards are molten
Liquid, carry out D- in sample（+）- tryptophan and L-（-）The detection of-tryptophane.
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