CN108645902A - A kind of preparation method of Chiral Calixarenes Derivatives Modified Electrodes for electrochemical process identification Tryptophan enantiomer - Google Patents
A kind of preparation method of Chiral Calixarenes Derivatives Modified Electrodes for electrochemical process identification Tryptophan enantiomer Download PDFInfo
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Abstract
The present invention relates to a kind of preparation methods for the Chiral Calixarenes Derivatives Modified Electrodes identifying Tryptophan enantiomer for electrochemical process, include the following steps：It prepares Chiral Calixarenes derivative, prepare Chiral Calixarenes Derivatives Modified Electrodes, electrochemical process identification Tryptophan enantiomer.The beneficial effects of the invention are as follows：Preparing Chiral Calixarenes Derivatives Modified Electrodes, method is simple, and preparation process is environment friendly and pollution-free, and the modified electrode can efficiently identify Tryptophan enantiomer.
Description
Technical field
The present invention relates to a kind of Chiral Calixarenes Derivatives Modified Electrodes identifying Tryptophan enantiomer for electrochemical process
Preparation method, belong to electrochemical analysis and biotechnology.
Technical background
L-Trp is a kind of amino acid needed by human, it all plays vital work in all physiological activities
With, and be the important component of most protein and the precursor of neurotransmitters seratonin serotonin.D-trp
With the physicochemical properties closely similar with L-Trp, however, non-protein amino acid D-trp is not involved in life system
Metabolism.Therefore, the chiral Recognition of tryptophan enantiomer is very important.In Tryptophan enantiomer for identification
In technology, the advantages of electrochemical method is at low cost due to easy to operate, accuracy and high sensitivity, extensive concern is caused.
Calixarenes is the novel host molecule after crown ether and cyclodextrin, it is easier to realize that chemistry is repaiied by derivatization
Decorations.Since its structure is special, when being performed the derivatization to it, can directly be synthesized by introducing group with optical activation
Chiral Calixarenes derivative.Calixarene Derivatives detect in analysis, are concentrated and separated, are catalyzed the fields such as bionical, environmental protection and have
Good application prospect focuses primarily upon supermolecule of the development with specific function to the research of Calixarene Derivatives in recent years
System.But in the document delivered at present, for the use of Chiral Calixarenes Derivatives Modified Electrodes carry out electrochemistry chiral Recognition
Report it is fresh few.
Invention content
The purpose of the present invention is to provide a kind of Chiral Calixarenes derivatives identifying Tryptophan enantiomer for electrochemical process
The preparation method of object modified electrode, the Chiral Calixarenes Derivatives Modified Electrodes can efficiently identify Tryptophan enantiomer.
A kind of Chiral Calixarenes Derivatives Modified Electrodes for electrochemical process identification Tryptophan enantiomer of the present invention
Preparation method, include the following steps：
A, Chiral Calixarenes derivative is prepared：L-phenylalanine methyl ester hydrochloride and triethylamine are added in dichloromethane,
Ice bath reaction a period of time, then chloracetyl chloride is added dropwise, after being stirred to react overnight, product is obtained into (R)-N- by column chromatography for separation
(2- chloracetyls) phenyalanine methyl ester；With 4- tertiary butyls p tertButylcalixarene and (R)-N- (2- chloracetyls) phenyalanine methyl ester
It for raw material, is stirred to react under alkaline condition after suitable solvent is added, synthesis of chiral Calixarene Derivatives；
B, Chiral Calixarenes Derivatives Modified Electrodes are prepared：By Chiral Calixarenes derivative ultrasonic disperse in ultra-pure water,
The Chiral Calixarenes derivative dispersant liquid drop is applied to glassy carbon electrode surface, is dried at room temperature, Chiral Calixarenes derivative is obtained
Object modified electrode；
C, electrochemical process identifies Tryptophan enantiomer：Using three-electrode system, Chiral Calixarenes Derivatives Modified Electrodes are
Working electrode, platinum plate electrode are to electrode, and saturated calomel electrode is reference electrode, which is immersed to preparation respectively
In L-/D- tryptophan solutions, after standing a period of time, differential pulse test is carried out with certain speed of sweeping, will be repaiied after having surveyed every time
Cyclic voltammetric is swept in the phosphate buffer solution of decorations electrode immersion pH=7.0, for restoring electrode activity.
Further, L-phenylalanine methyl ester hydrochloride, triethylamine and chloracetyl chloride mol ratio are 1 in step a:2.5:
1.05。
Further, the amount that dichloromethane is added in step a is 50mL, and the ice bath reaction time is 20~60min.
Further, 4- tertiary butyls p tertButylcalixarene and (R)-N- (2- chloracetyls) phenyalanine methyl ester mole are matched in step a
Than being 1：1.
Further, solvent is absolute methanol in step a, and mixing time is 10~14h.
Further, in step b Chiral Calixarenes derivative a concentration of 1~5mg/mL, take 10 μ L Chiral Calixarenes derive
Object dispersant liquid drop is applied to electrode surface.
Further, Chiral Calixarenes Derivatives Modified Electrodes immerse a concentration of the 0.5 of L-/D- tryptophan solutions in step c
~1.5mM, time of repose are 60~120s.
Further, the number of turns of modified electrode scan cycle volt-ampere in phosphate buffer solution is 3~15 circles in step c,
It is 8mV/s to sweep speed.
The beneficial effects of the invention are as follows：Preparing Chiral Calixarenes Derivatives Modified Electrodes, method is simple, prepared
Journey is environment friendly and pollution-free, and the modified electrode can efficiently identify Tryptophan enantiomer.
Description of the drawings
This experiment is further illustrated below in conjunction with the accompanying drawings.
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of Chiral Calixarenes derivative.
Fig. 2 is the differential pulse voltammetry that Chiral Calixarenes Derivatives Modified Electrodes identify Tryptophan enantiomer in embodiment one
Figure.
Fig. 3 is the differential pulse volt that the calixarenes modified electrode without derivatization identifies Tryptophan enantiomer in comparative example one
Antu.
Specific implementation mode
Presently in connection with specific embodiment, the invention will be further described, following embodiment be intended to illustrate invention rather than
Limitation of the invention further.
It is of the present invention to be known as follows by Chiral Calixarenes Derivatives Modified Electrodes tryptophan enantiomer
Not：
RL/D=IL/ID
Δ E=ED-EL
In formula, RL/DIndicate that Tryptophan enantiomer peak current ratio, Δ E indicate Tryptophan enantiomer spike potential difference, ILWith
IDL-Trp and D-trp peak current, E are indicated respectivelyLAnd EDL-Trp and D-trp spike potential are indicated respectively.
Embodiment one：
It includes following step that Chiral Calixarenes Derivatives Modified Electrodes, which are prepared, for electrochemical recognition Tryptophan enantiomer
Suddenly：
(1) 0.50gL- phenylalanine methyl ester hydrochlorides and 0.58g triethylamines are added in 50mL dichloromethane, ice bath is anti-
30min is answered, then 0.27g chloracetyl chlorides are added dropwise, after being stirred to react overnight, product is obtained into (R)-N- (2- by column chromatography for separation
Chloracetyl) phenyalanine methyl ester；It is original with 4- tertiary butyls p tertButylcalixarene and (R)-N- (2- chloracetyls) phenyalanine methyl ester
Material, mol ratio 1：1, it is stirred to react 12h after 50mL absolute methanols and sodium hydroxide solution is added, synthesis of chiral calixarenes spreads out
Biology.
(2) by Chiral Calixarenes derivative ultrasonic disperse in ultra-pure water, the Chiral Calixarenes for being configured to 3mg/mL derive
Object dispersion liquid takes 10 μ L Chiral Calixarenes derivative dispersant liquid drops to be applied to glassy carbon electrode surface, dries at room temperature, obtain chirality
Calixarene Derivatives modified electrode.
(3) it is working electrode that experiment, which uses three-electrode system, Chiral Calixarenes Derivatives Modified Electrodes, and platinum plate electrode is pair
Electrode, saturated calomel electrode are reference electrode, which is immersed to the 1.0mM L-/D- tryptophan solutions of preparation respectively
In, after standing 90s, in the potential range of 0.4~1.2V, differential pulse test is carried out with the speed of sweeping of 8mV/s, after having surveyed every time
It is enclosed cyclic voltammetric 5 is swept in the phosphate buffer solution of modified electrode immersion pH=7.0, for restoring electrode activity.Tryptophan
The recognition effect figure of enantiomer is shown in attached drawing 2, IL/IDIt is 20.14.
Comparative example one：
It prepares the calixarenes modified electrode without derivatization and is used for electrochemical recognition Tryptophan enantiomer, including is following
Step：
(1) 4- tertiary butyl p tertButylcalixarenes are pulverized into last ultrasonic disperse in ultra-pure water, is configured to uncle 4- of 3mM
Butyl cup [4] aromatic hydrocarbons dispersion liquid.It takes the 10 μ L dispersant liquid drops to be applied to glassy carbon electrode surface, dries at room temperature, obtain the tertiary fourths of 4-
Base cup [4] aromatic hydrocarbons modified electrode.
(2) it is working electrode that experiment, which uses three-electrode system, 4- tertiary butyl p tertButylcalixarene modified electrodes, and platinum plate electrode is
To electrode, saturated calomel electrode is reference electrode, and the 1.0mM L-/D- tryptophans which is immersed to preparation respectively are molten
In liquid, after standing 90s, in the potential range of 0.4~1.2V, differential pulse test is carried out with the speed of sweeping of 8mV/s, has been surveyed every time
Cyclic voltammetric 5 will be swept in the phosphate buffer solution of modified electrode immersion pH=7.0 afterwards to enclose, for restoring electrode activity.Uncle 4-
The recognition effect figure of butyl cup [4] aromatic hydrocarbons modified electrode tryptophan enantiomer is shown in attached drawing 3, IL/IDIt is 7.65.
Claims (4)
1. a kind of preparation method of Chiral Calixarenes Derivatives Modified Electrodes for electrochemical process identification Tryptophan enantiomer, step
It is rapid as follows：
A, Chiral Calixarenes derivative is prepared：L-phenylalanine methyl ester hydrochloride and triethylamine are added in dichloromethane, ice bath
Reaction a period of time, then chloracetyl chloride is added dropwise, after being stirred to react overnight, product is obtained into (R)-N- (2- by column chromatography for separation
Chloracetyl) phenyalanine methyl ester；It is original with 4- tertiary butyls p tertButylcalixarene and (R)-N- (2- chloracetyls) phenyalanine methyl ester
Material, is stirred to react, synthesis of chiral Calixarene Derivatives under alkaline condition after suitable solvent is added；
B, Chiral Calixarenes Derivatives Modified Electrodes are prepared：By Chiral Calixarenes derivative ultrasonic disperse in ultra-pure water, this is taken
Chiral Calixarenes derivative dispersant liquid drop is applied to glassy carbon electrode surface, dries at room temperature, obtains Chiral Calixarenes derivative and repaiies
Adorn electrode；
C, electrochemical process identifies Tryptophan enantiomer：Using three-electrode system, Chiral Calixarenes Derivatives Modified Electrodes are work
Electrode, platinum plate electrode are to electrode, and saturated calomel electrode is reference electrode, by the three-electrode system immerse respectively the L- of preparation/
In D-trp solution, after standing a period of time, differential pulse test is carried out with certain speed of sweeping, it will modification electricity after having surveyed every time
Cyclic voltammetric is swept in the phosphate buffer solution of pole immersion pH=7.0, for restoring electrode activity.
2. a kind of Chiral Calixarenes Derivatives Modified for electrochemical process identification Tryptophan enantiomer according to claim 1
The preparation method of electrode, it is characterized in that：L-phenylalanine methyl ester hydrochloride in the step a, triethylamine and chloracetyl chloride rub
Your proportioning is 1:2.5:1.05, the amount that dichloromethane is added is 50mL, and the ice bath reaction time is 20~60min；4- tert-butyl-calixes
[4] mol ratio of aromatic hydrocarbons and (R)-N- (2- chloracetyls) phenyalanine methyl ester is 1：1, solvent is absolute methanol, when stirring
Between be 10~14h.
3. a kind of Chiral Calixarenes Derivatives Modified for electrochemical process identification Tryptophan enantiomer according to claim 1
The preparation method of electrode, it is characterized in that：A concentration of 1~5mg/mL of Chiral Calixarenes derivative in the step b takes 10 μ L hands
Property Calixarene Derivatives dispersant liquid drop is applied to electrode surface.
4. a kind of Chiral Calixarenes Derivatives Modified for electrochemical process identification Tryptophan enantiomer according to claim 1
The preparation method of electrode, it is characterized in that：A concentration of 0.5~the 1.5mM for the L-/D- tryptophan solutions prepared in the step c, it is quiet
It is 60~120s to set the time, and differential pulse test, the scan cycle volt-ampere in phosphate buffer solution are carried out with the speed of sweeping of 8mV/s
The number of turns be 3~15 circle.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109959690A (en) * | 2019-04-12 | 2019-07-02 | 常州大学 | A kind of preparation method of the cyclohexane cyclohexanedimethanodibasic Derivatives Modified Electrodes for electrochemical recognition Tryptophan enantiomer |
| CN111257388A (en) * | 2020-02-19 | 2020-06-09 | 常州大学 | Preparation method of chiral supramolecular gel modified electrode for electrochemical recognition of tryptophan enantiomer |
| CN113203778A (en) * | 2021-04-12 | 2021-08-03 | 北京理工大学 | MoS recognizing tryptophan enantiomers2-IL @ CS electrochemical chiral sensor and application thereof |
| CN113702464A (en) * | 2021-09-23 | 2021-11-26 | 上海大学 | P-tau detection immunosensor and preparation and application methods thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109959690A (en) * | 2019-04-12 | 2019-07-02 | 常州大学 | A kind of preparation method of the cyclohexane cyclohexanedimethanodibasic Derivatives Modified Electrodes for electrochemical recognition Tryptophan enantiomer |
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| CN113203778A (en) * | 2021-04-12 | 2021-08-03 | 北京理工大学 | MoS recognizing tryptophan enantiomers2-IL @ CS electrochemical chiral sensor and application thereof |
| CN113702464A (en) * | 2021-09-23 | 2021-11-26 | 上海大学 | P-tau detection immunosensor and preparation and application methods thereof |
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Application publication date: 20181012 |