CN106018517B - The preparation of a kind of complex film modified electrode of tartaric acid-graphene quantum dot and applied to identification Tryptophan enantiomer - Google Patents

The preparation of a kind of complex film modified electrode of tartaric acid-graphene quantum dot and applied to identification Tryptophan enantiomer Download PDF

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CN106018517B
CN106018517B CN201610321006.8A CN201610321006A CN106018517B CN 106018517 B CN106018517 B CN 106018517B CN 201610321006 A CN201610321006 A CN 201610321006A CN 106018517 B CN106018517 B CN 106018517B
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electrode
tartaric acid
quantum dot
graphene quantum
complex film
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CN106018517A (en
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孔泳
于茵
欧洁
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Changzhou University
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    • G01N27/26Investigating 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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    • GPHYSICS
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    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating 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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Abstract

The present invention relates to a kind of preparation of complex film modified electrode of tartaric acid graphene quantum dot and applied to identification Tryptophan enantiomer.Include the following steps:The preparation of graphene quantum dot, the preparation of the complex film modified electrode of tartaric acid graphene quantum dot, electrochemical process identify Tryptophan enantiomer.The beneficial effects of the invention are as follows:The complex film modified electrode preparation method of tartaric acid graphene quantum dot is simple, it makes full use of tartaric acid that there is chiral environment (being respectively L (+) tartaric acid and D () tartaric acid) this characteristic, the excellent complex film modified electrode of tartaric acid graphene quantum dot of recognition performance is prepared in conjunction with graphene quantum dot.The complex film modified electrode possesses more excellent recognition effect than single tartaric acid or modified by graphene quantum dot electrode.

Description

A kind of preparation of the complex film modified electrode of tartaric acid-graphene quantum dot and it is applied to Identify Tryptophan enantiomer
Technical field
The present invention relates to a kind of preparation of complex film modified electrode of tartaric acid-graphene quantum dot and applied to identification color ammonia Sour enantiomer belongs to biotechnology and electrochemical research field.
Technical background
Amino acid is a kind of organic compound beneficial to human body, for example, inside protein just containing there are many amino acid at Part.The effect of amino acid, adjusts function of human body with the protein needed for effect mainly supplement human life, resistance building, It sustains life.It can be seen that amino acid is the first element of human body.Tryptophan is neurotransmitter -5- hydroxyl colors important in human body The precursor of amine is one of amino acid needed by human, and there are two types of the chiral enantiomers of various configuration, respectively L-Trp and D- Tryptophan.Different stereochemical structures will produce different pharmacological action and reaction, so identification L-/D- tryptophans are most important. The method of detection tryptophan has high performance liquid chromatography, ultraviolet spectroscopy, fluorescent spectrometry etc. at present, but at these method samples Reason process is cumbersome.
Graphene is two-dimensional structure, there is its unique performance.Its specific surface area is larger, have high current-carrying mobility, It is very thin and dense, in biological cell the features such as nontoxicity.It is that quasi-zero dimension is received for graphene quantum dot is compared to graphene Rice material, and have the property of graphene, size is in 10nm hereinafter, therefore its quantum confined effect and boundary effect are brighter It is aobvious.Due to quantum confined effect and boundary effect, the shapes and sizes of graphene quantum dot by determine they electricity, optics, Magnetic and chemical characteristic.It is mainly used in solar cell, electronic equipment, optical dye, biomarker and multiple microparticles system Etc..
The present invention selects tartaric acid enantiomer as chiral material, and tartaric acid is a kind of carboxylic acid, is present in various plants, It is also one of main organic acid in grape wine.L-/D- tartaric acid contains a large amount of hydroxyls with coordination ability, provides chiral work Property site, can with the amino in tryptophan formed hydrogen bond, be theoretically utilized in electrochemical recognition Tryptophan enantiomer.The present invention It is combined tartaric acid enantiomer to form the composite membrane with stereoselectivity with graphene quantum dot, can identify tryptophan with mapping Isomers.
Invention content
The present invention is intended to provide a kind of preparation method of the complex film modified electrode of tartaric acid-graphene quantum dot, and by its Tryptophan enantiomer is identified applied to electrochemical process.By L- (+)-tartaric acid-graphene quantum dot composite membrane or D- (-)-winestone The complex film modified efficiency that mapping identification L-/D- tryptophans can be effectively improved after glass-carbon electrode of acid-graphene quantum dot.
A kind of preparation of complex film modified electrode of tartaric acid-graphene quantum dot of the present invention and applied to identification color ammonia Sour enantiomer, includes the following steps:
A, graphene quantum dot is prepared:Citric acid is added in crucible, is heated in program-controlled cabinet-type electric furnace, reaction knot Solid sample is taken out after beam, yellow transparent solution is filtered to obtain, in room temperature after product fully dissolves with ultra-pure water ultrasonic dissolution Under be kept in dark place;
B, the complex film modified electrode of tartaric acid-graphene quantum dot is prepared:It tests using three-electrode system, glass-carbon electrode is Working electrode, platinum plate electrode are to electrode, and saturated calomel electrode is reference electrode, is dipped in graphene quantum dot solution, Within the scope of the electrochemical window of 0V~1.0V (vs.SCE), carries out cyclic voltammetry scan and obtains modified by graphene quantum dot electrode, The modified electrode is immersed in prepared L- (+)-tartaric acid or D- (-)-tartaric acid solution again, potentiostatic method is prepared into winestone The complex film modified electrode of acid-graphene quantum dot;
C, electrochemical process identifies Tryptophan enantiomer:Experiment uses three-electrode system, L- (+)-tartaric acid-graphene quantum Point or D- (-)-tartaric acid-complex film modified electrode of graphene quantum dot are working electrode, and platinum plate electrode is to electrode, and saturation is sweet Mercury electrode is reference electrode, it is immersed respectively in the L-/D- tryptophan solutions configured, and differential pulse is carried out after standing and is swept It retouches.
A kind of preparation of complex film modified electrode of tartaric acid-graphene quantum dot of the present invention and applied to identification color ammonia Sour enantiomer, further technical solution can also be in the step a that citric acid quality is 0.1~15.0g, reaction temperature It it is 50~400 DEG C, the reaction time is 0.1~3h.
A kind of preparation of complex film modified electrode of tartaric acid-graphene quantum dot of the present invention and applied to identification color ammonia Sour enantiomer, further technical solution can also be in the step b that glass-carbon electrode scans in graphene quantum dot solution The number of turns is 4~100 circles, configures the tartaric acid solution of 0.1g/mL, and sedimentation potential is+1.0V, and electrodeposition time is 10~1000s.
A kind of preparation of complex film modified electrode of tartaric acid-graphene quantum dot of the present invention and applied to identification color ammonia Sour enantiomer, further technical solution can also be in the step c, L- (+)-tartaric acid-graphene quantum dot or D- The complex film modified electrode of (-)-tartaric acid-graphene quantum dot immerse respectively L-/D- tryptophan solutions a concentration of 0.1~ 10mmol/L。
The beneficial effects of the invention are as follows:The complex film modified electrode preparation method of tartaric acid-graphene quantum dot is simple, fully There is chiral environment (being respectively L- (+)-tartaric acid and D- (-)-tartaric acid) this characteristic using tartaric acid, in conjunction with graphene amount Sub- point prepares the excellent complex film modified electrode of tartaric acid-graphene quantum dot of recognition performance.The complex film modified electrode is than single One tartaric acid or modified by graphene quantum dot electrode possess more excellent recognition effect.
Description of the drawings
The following further describes the present invention with reference to the drawings.
Fig. 1 is the transmission electron microscope picture of graphene quantum dot in embodiment one, two;
Fig. 2 is the complex film modified electrode tryptophan enantiomer of L- (+)-tartaric acid-graphene quantum dot in embodiment one Recognition effect figure;
Fig. 3 is the complex film modified electrode tryptophan enantiomer of D- (-)-tartaric acid-graphene quantum dot in embodiment two Recognition effect figure;
Fig. 4 is the recognition effect figure of modified by graphene quantum dot electrode tryptophan enantiomer in comparative example one;
Fig. 5 is the recognition effect figure of L- (+)-tartaric acid modified electrode tryptophan enantiomer in comparative example two;
Fig. 6 is the recognition effect figure of D- (-)-tartaric acid modified electrode tryptophan enantiomer in comparative example three.
Specific implementation mode
Presently in connection with specific embodiment, the present invention will be further described, following embodiment be intended to illustrate invention rather than Limitation of the invention further.
Embodiment one:
It includes following steps to prepare L- (+)-complex film modified electrode of tartaric acid-graphene quantum dot:
(1) 2.0g citric acids are weighed to be added in 10mL crucibles, heat reaction under the conditions of 200 DEG C in program-controlled cabinet-type electric furnace 30min takes out solid sample, with ultra-pure water ultrasonic dissolution after reaction.After product fully dissolves, filter yellow is saturating Bright solution, is kept in dark place at normal temperatures.
(2) it is working electrode that experiment, which uses three-electrode system, glass-carbon electrode (diameter 3mm), and platinum plate electrode is to satisfy to electrode It is reference electrode with calomel electrode (SCE), is dipped in graphene quantum dot solution, in the electrification of 0V~1.0V (vs.SCE) It learns in window ranges, cyclic voltammetric 50 is swept with the speed of 0.1V/s and is enclosed, modified by graphene quantum dot electrode is obtained.Again by the modification Electrode immerses in 0.1g/mL L- (+)-tartaric acid solution prepared, with the potential deposition 400s of potentiostatic method application+1.0V, system It is standby to obtain L- (+)-tartaric acid-complex film modified electrode of graphene quantum dot.
L- (+)-tartaric acid of preparation-complex film modified electrode of graphene quantum dot is immersed into a concentration of of configuration respectively In 0.5mmol/L L-/D- tryptophan solutions, the recognition effect figure of Tryptophan enantiomer is shown in Fig. 2, it can be seen that L- (+)-wine Stone acid-complex film modified electrode of graphene quantum dot has preferable recognition effect, I to D-trpD/ILIt is 2.47.
Embodiment two:
It includes following steps to prepare D- (-)-complex film modified electrode of tartaric acid-graphene quantum dot:
(1) 2.0g citric acids are weighed to be added in 10mL crucibles, heat reaction under the conditions of 200 DEG C in program-controlled cabinet-type electric furnace 30min takes out solid sample, with ultra-pure water ultrasonic dissolution after reaction.After product fully dissolves, filter yellow is saturating Bright solution, is kept in dark place at normal temperatures.
(2) it is working electrode that experiment, which uses three-electrode system, glass-carbon electrode (diameter 3mm), and platinum plate electrode is to satisfy to electrode It is reference electrode with calomel electrode (SCE), is dipped in graphene quantum dot solution, in the electrification of 0V~1.0V (vs.SCE) It learns in window ranges, cyclic voltammetric 50 is swept with the speed of 0.1V/s and is enclosed, modified by graphene quantum dot electrode is obtained.Again by the modification Electrode immerses in 0.1g/mL D- (-)-tartaric acid solution prepared, with the potential deposition 400s of potentiostatic method application+1.0V, system It is standby to obtain D- (-)-tartaric acid-complex film modified electrode of graphene quantum dot.
D- (-)-tartaric acid of preparation-complex film modified electrode of graphene quantum dot is immersed into a concentration of of configuration respectively In 0.5mmol/L L-/D- tryptophan solutions, the recognition effect figure of Tryptophan enantiomer is shown in Fig. 3, it can be seen that D- (-)-wine Stone acid-complex film modified electrode of graphene quantum dot is more preferable to the recognition effect of L-Trp, IL/IDIt is 2.71.
Comparative example one:
Modified by graphene quantum dot electrode is prepared, preparation process is as follows:
(1) 2.0g citric acids are weighed to be added in 10mL crucibles, heat reaction under the conditions of 200 DEG C in program-controlled cabinet-type electric furnace 30min takes out solid sample, with ultra-pure water ultrasonic dissolution after reaction.After product fully dissolves, filter yellow is saturating Bright solution, is kept in dark place at normal temperatures.
(2) it is working electrode that experiment, which uses three-electrode system, glass-carbon electrode (diameter 3mm), and platinum plate electrode is to satisfy to electrode It is reference electrode with calomel electrode (SCE), is dipped in graphene quantum dot solution, in the electrification of 0V~1.0V (vs.SCE) It learns in window ranges, cyclic voltammetric 50 is swept with the speed of 0.1V/s and is enclosed, modified by graphene quantum dot electrode is obtained.
The modified by graphene quantum dot electrode of preparation is used for the identification of Tryptophan enantiomer, which is immersed respectively In a concentration of 0.5mmol/L L-/D- tryptophan solutions of configuration, as shown in figure 4, IL/IDIt is 1.03.
Comparative example two:
L- (+)-tartaric acid modified electrode is prepared, preparation process is as follows:
It is working electrode that experiment, which uses three-electrode system, glass-carbon electrode (diameter 3mm), and platinum plate electrode is to electrode, saturation Calomel electrode (SCE) is reference electrode, is dipped in prepared 0.1g/mL L- (+)-tartaric acid solution, uses potentiostatic method L- (+)-tartaric acid modified electrode is prepared in the potential deposition 400s of application+1.0V.
The L- (+) of preparation-tartaric acid modified electrode is used for the identification of Tryptophan enantiomer, which is immersed respectively In a concentration of 0.5mmol/L L-/D- tryptophan solutions of configuration, as shown in figure 5, ID/ILIt is 1.34.
Comparative example three:
D- (-)-tartaric acid modified electrode is prepared, preparation process is as follows:
It is working electrode that experiment, which uses three-electrode system, glass-carbon electrode (diameter 3mm), and platinum plate electrode is to electrode, saturation Calomel electrode (SCE) is reference electrode, is dipped in prepared 0.1g/mL D- (-)-tartaric acid solution, uses potentiostatic method D- (-)-tartaric acid modified electrode is prepared in the potential deposition 400s of application+1.0V.
The D- (-) of preparation-tartaric acid modified electrode is used for the identification of Tryptophan enantiomer, which is immersed respectively In a concentration of 0.5mmol/L L-/D- tryptophan solutions of configuration, as shown in fig. 6, IL/IDIt is 1.28.
The present invention make full use of tartaric acid have chiral environment (be respectively L- (+)-tartaric acid and D- (-)-tartaric acid) this One characteristic prepares the excellent complex film modified electrode of tartaric acid-graphene quantum dot of recognition performance in conjunction with graphene quantum dot.It should Complex film modified electrode possesses more excellent recognition effect than single tartaric acid or modified by graphene quantum dot electrode.

Claims (4)

1. a kind of preparation method of the complex film modified electrode of tartaric acid-graphene quantum dot of Tryptophan enantiomer for identification, It is characterized in that:Steps are as follows:
A, graphene quantum dot is prepared:Citric acid is added in crucible, is heated in program-controlled cabinet-type electric furnace, after reaction Solid sample is taken out, yellow transparent solution is filtered to obtain after product is fully dissolved with ultra-pure water ultrasonic dissolution, kept away at normal temperatures Light preserves;
B, the complex film modified electrode of tartaric acid-graphene quantum dot is prepared:Experiment uses three-electrode system, and glass-carbon electrode is work Electrode, platinum plate electrode are to electrode, and saturated calomel electrode is reference electrode, and it is molten which is immersed graphene quantum dot In liquid, within the scope of the electrochemical window of 0V~1.0V, carries out cyclic voltammetry scan and obtain modified by graphene quantum dot electrode, then will The modified electrode immerses in prepared L- (+)-tartaric acid or D- (-)-tartaric acid solution, and potentiostatic method is prepared into tartaric acid- The complex film modified electrode of graphene quantum dot;
C, electrochemical process identifies Tryptophan enantiomer:Experiment use three-electrode system, L- (+)-tartaric acid-graphene quantum dot or D- (-)-tartaric acid-complex film modified electrode of graphene quantum dot is working electrode, and platinum plate electrode is to electrode, saturation calomel electricity Extremely reference electrode immerses the three-electrode system in prepared L-/D- tryptophan solutions respectively, and difference arteries and veins is carried out after standing Punching scanning.
2. a kind of tartaric acid of Tryptophan enantiomer for identification-graphene quantum dot composite membrane is repaiied according to claim 1 The preparation method of electrode is adornd, it is characterized in that:Citric acid quality is 0.1~15.0g in the step a, and reaction temperature is 50~400 DEG C, the reaction time is 0.1~3h.
3. a kind of tartaric acid of Tryptophan enantiomer for identification-graphene quantum dot composite membrane is repaiied according to claim 1 The preparation method of electrode is adornd, it is characterized in that:It is 4 that glass-carbon electrode scans the number of turns in graphene quantum dot solution in the step b ~100 circles prepare the tartaric acid solution of 0.1g/mL, and sedimentation potential is+1.0V, and electrodeposition time is 10~1000s.
4. a kind of tartaric acid of Tryptophan enantiomer for identification-graphene quantum dot composite membrane is repaiied according to claim 1 The preparation method of electrode is adornd, it is characterized in that:L- (+)-tartaric acid-graphene quantum dot or D- (-)-tartaric acid-graphene quantum The complex film modified electrode of point immerses a concentration of 0.1~10mmol/L of L-/D- tryptophan solutions respectively.
CN201610321006.8A 2016-05-16 2016-05-16 The preparation of a kind of complex film modified electrode of tartaric acid-graphene quantum dot and applied to identification Tryptophan enantiomer Expired - Fee Related CN106018517B (en)

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CN106928434B (en) * 2017-03-07 2019-02-15 常州大学 A kind of method and its application by adulterating tartrate ion synthesis of chiral conducting polymer
CN108375617B (en) * 2018-02-09 2020-05-19 华中科技大学 Double-nanoenzyme modified carbon fiber composite material, and preparation method and application thereof
CN108445064B (en) * 2018-03-05 2019-12-31 常州大学 Preparation method of graphene quantum dot-bovine serum albumin composite material applicable to electrochemical chiral recognition
CN109908765B (en) * 2019-03-14 2021-12-03 闽江学院 L-tartaric acid modified self-made microporous polymer membrane and preparation method thereof

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