CN105067686B - The Selective recognition of poly- L glutamic acid/amylose modified glassy carbon electrode tryptophan enantiomer - Google Patents
The Selective recognition of poly- L glutamic acid/amylose modified glassy carbon electrode tryptophan enantiomer Download PDFInfo
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Abstract
The present invention relates to the Selective recognition of poly- L glutamic acid/amylose modified glassy carbon electrode tryptophan enantiomer.Comprise the following steps：Prepare poly- L glutamic acid modified glassy carbon electrode, prepare poly- L glutamic acid/amylose modified glassy carbon electrode, the Selective recognition of tryptophan enantiomer.The beneficial effects of the invention are as follows：The preparation method of poly- L glutamic acid/amylose modified glassy carbon electrode is simple, convenient, pollution-free, and the modified electrode tryptophan enantiomer has preferable recognition effect.This is attributed to the stereoselectivity of amylose tryptophan enantiomer.
Description
Technical field
The present invention relates to the Selective recognition of L-glutamic acid/amylose modified glassy carbon electrode tryptophan enantiomer,
Belong to electrochemical sensor and molecular recognition field.
Technical background
Material such as protein, polysaccharide, nucleic acid, the amino acid etc. constituted in real life in vital movement nearly all has
Chiral.For chipal compounds, when in the absence of outside chiral environment, two enantiomers are in addition to optical activity, with complete
Identical chemical and physical features, it shows as identical fusing point, solubility, infrared spectrum, nuclear magnetic resoance spectrum, in gas phase and liquid
Also there is identical retention time in phase chromatogram.But when chipal compounds are in chiral environment, two optical isomers are just
The different behavior of performance, causes different performances.Such as chiral drug, because its spatial configuration is different, the phase interaction between acceptor
With also there is different pharmacology and medicine efficacy relation；The stereoselectivity of biochemical reaction process, all kinds of natural organic chiral chemical combination
The spatial configuration all with chiral molecules such as the spatial configuration of thing, spatial configuration of high polymer material, bioactivity are relevant, it is seen then that
The research of chiral Recognition is with important theory and practical study meaning.At present, chiral Recognition research method mainly includes chirality
Chromatogram, spectrum and electrochemistry chiral sensor.Wherein chromatographic process has been widely used for separation analysis chipal compounds, and
It is proved to be a kind of effective chiral analysis method, but this method is there is also certain shortcoming, for example, be easier to cause biology
The change of configuration or inactivation of class chiral selector and analysis of compounds, and instrument cost is high, and analysis time is long, is particularly difficult to reality
Existing in situ and on-line checking etc..Electrochemical sensor prepares the advantages of simple, cost is low, recognition efficiency is high because of it, for recognizing
Chiral material has is extensively studied value very much.
Amino acid chiral is recognized to protein chemistry, biochemistry and whole life science and product development, matter
Amount control and production management etc. are significant.Amino acid has close relationship, big polyamino with biological vital movement
Acid has chiral isomer.The physiological action of D- types and L-type enantiomer is totally different, and L-type amino acid is amino acid needed by human body, and
Excess intake D- types amino acid can cause poisoning.D- types do not appear to meaning in nutrition, but its extremely medical personal
Favor, in such as amino acids antibiotic, D- type amino acid is difficult to by bacterial degradation, and will not develop immunity to drugs.This undoubtedly will
More wide prospect is provided for utilizing for antibiotic.All these fractionation problems for being directed to chiral amino acid, are prepared pure
Chipal compounds be respectively provided with significance in fields such as life science, pharmaceutical chemistry, fine chemistries, enjoy chemist, life
The attention of scholar.Therefore use appropriate technology accurately to be recognized, separated to it and purification is particularly important.
Amylose, is polymeric carbohydrate, is a kind of natural polysaccharide.Amylose is the ring glucose of D- six warp
α-Isosorbide-5-Nitrae-glycosidic bond composition, is double-spiral structure.Starch is widely used in food, change as a kind of important raw material of industry
In the industries such as work, weaving and building materials.Amylose has good film forming, and its molecule has abundant-OH, so that directly
Chain starch has the effect such as ion chelating, absorption, amylose and its derivative to many ions, organic matter and biomolecule
It can be used as chiral Recognition material.
The content of the invention
For problem present in technical background, the purpose of the present invention is to modify glass by L-glutamic acid/amylose
The Selective recognition of carbon electrode tryptophan enantiomer.
The technical solution adopted for the present invention to solve the technical problems is：L-glutamic acid/amylose modification glass carbon electricity
The Selective recognition of pole tryptophan enantiomer, comprises the following steps：
A, prepare L-glutamic acid modified glassy carbon electrode：Preparing Pidolidone solution, (solvent is 0.1~0.3M biphosphates
Sodium, pH=6~7), glassy carbon electrode surface is deposited onto using cyclic voltammetry, L-glutamic acid modified glassy carbon electrode is obtained.
B, prepare L-glutamic acid/amylose modified glassy carbon electrode：By the L-glutamic acid modified glassy carbon electrode of preparation
Immerse in 20~30mL amylose solutions, 18~28h of self assembly at 8 DEG C, obtain L-glutamic acid/amylose modification glass
Carbon electrode.
C, tryptophan enantiomer Selective recognition：Tryptophan enantiomer is recognized using differential pulse method, by poly- L-
20~30mL Tryptophan enantiomers that glutamic acid/amylose modified glassy carbon electrode is rested under different temperatures (2~42 DEG C) are molten
In liquid (30~90s of time of repose), speed is swept in the range of 0.4~1.0V (vs.SCE) electrochemical window with 0.1~0.5V/s
Carry out differential pulse, surveyed every time rear modified electrode 20~30mL blank solutions (0.1~0.3M sodium dihydrogen phosphates, pH=6~
7) steady recovery electrode activity is swept in.
Further, the concentration of Pidolidone is 0.03~0.06M in step a.
Further, the concentration of amylose is 1~3mg/mL in step b.
Further, the concentration of Tryptophan enantiomer is 0.2~1mM in step c.
The beneficial effects of the invention are as follows：The preparation method of L-glutamic acid/amylose modified glassy carbon electrode is simply, just
Prompt, pollution-free, the modified electrode tryptophan enantiomer has preferable recognition effect.This is attributed to amylose tryptophan
The stereoselectivity of enantiomer.
Brief description of the drawings
This experiment is further illustrated below in conjunction with the accompanying drawings.
Fig. 1 is the cyclic voltammogram of different modifying electrode in embodiment one；A in Fig. 1:Glass-carbon electrode, b:L-glutamic acid
Modified glassy carbon electrode, c:L-glutamic acid/amylose modified glassy carbon electrode.
Fig. 2 is L-glutamic acid modified glassy carbon electrode (a) and the poly-L-glutamic acid prepared at different temperatures in embodiment two
The cyclic voltammogram of acid/amylose modified glassy carbon electrode；b:4 DEG C, c:8 DEG C, d:12 DEG C, e:20℃.
Fig. 3 is influence of the different self assembly times to identification in embodiment three.
Fig. 4 is influence of the temperature to identification in example IV.
Fig. 5 is the block diagram of four kinds of different modifying electrode pair Tryptophan enantiomer oxidation peak current ratio in comparative example one,
A:Glass-carbon electrode, B:L-glutamic acid modified glassy carbon electrode, C:Amylose modified glassy carbon electrode, D:L-glutamic acid/straight chain
Starch modified glassy carbon electrode.
Embodiment
Presently in connection with specific embodiment, the invention will be further described, following examples be intended to illustrate invention rather than
Limitation of the invention further.
Embodiment one：
(1) 2mg/mL amylose solutions are prepared (solvent is ultra-pure water).
(2) 0.05mM Pidolidones solution (solvent is 0.1M sodium dihydrogen phosphates, pH=7) is prepared, using cyclic voltammetry
Pidolidone is deposited on glassy carbon electrode surface, potential range is -0.6~2.0V, it is 0.1V/s to sweep speed, the scanning number of turns is 20
Circle, obtains L-glutamic acid modified glassy carbon electrode.
(3) by the L-glutamic acid modified glassy carbon electrode that step 2 is prepared rest on that step 1 prepares at 8 DEG C it is molten
Self assembly 24h in liquid, obtains L-glutamic acid/amylose modified glassy carbon electrode.
(4) electrode for preparing step 2,3 is rested in 5mM potassium ferricyanide solutions, is carried out using cyclic voltammetry
Characterize, potential range is -0.2~0.6V, it is 0.1V/s to sweep speed, the scanning number of turns is 20 circles, and its result is as shown in Figure 1.
Embodiment two：
In order to investigate L-glutamic acid/amylose modified glassy carbon electrode tryptophan prepared by different self assembly temperature
The difference of recognition capability.Therefore, the time of self assembly is respectively adopted 4 DEG C, 8 DEG C, 12 DEG C and 20 DEG C.Its result is shown in Fig. 2, it is seen that when
When the temperature of self assembly is 8 DEG C, the electric current of its cyclic voltammogram is minimum, caused by this is due to the weak electric conductivity of amylose.Can
See, the amount that amylose is loaded into above electrode when the temperature of self assembly is 8 DEG C is most.
Embodiment three：
In order to investigate L-glutamic acid/amylose modified glassy carbon electrode tryptophan prepared by the different self assembly times
The difference of recognition capability.Therefore, 8h, 12h, 15h, 18h, 20h, 22h, 24h and 26h is respectively adopted in the time of self assembly.It is tied
Fruit sees Fig. 3, it is seen that when the time of self assembly is 24h, the oxidation peak current ratio of L-/D- tryptophans reaches maximum, when from group
When ETL estimated time of loading is shorter, the amount that amylose is self-assembled on electrode is small, causes recognition capability relatively low.With the increasing of self assembly time
Plus, the amount that amylose is self-assembled on electrode gradually increases, when the time of self assembly is 24h, amylose self assembly amount
Saturation is reached, Tryptophan enantiomer can be effectively recognized.But as the self assembly time continues to increase, amylose self assembly amount mistake
Many, excessive amylose causes the breakage of poly-L-glutamic acid sorrel, so as to be unfavorable for identification.
Example IV：
In order to investigate L-glutamic acid/amylose modified glassy carbon electrode tryptophan recognition capability at different temperature
Difference.Therefore, 2 DEG C, 4 DEG C, 8 DEG C, 12 DEG C, 15 DEG C, 20 DEG C, 25 DEG C, 30 DEG C, 35 DEG C, 37 DEG C and 42 DEG C are respectively adopted.It is tied
Fruit sees Fig. 4, it is seen that when temperature is 37 DEG C, the oxidation peak current ratio of L-/D- tryptophans reaches maximum.When 4 DEG C, due to water
Molecule self-interaction, so as to limit its motion, makes based on the hydrogen bond that system main water mutually forms, to suppress straight chain
The formation of hydrogen bond between starch and tryptophan, causes the system recognition efficiency relatively low.Raised when with temperature, hydrone phase interaction
With gradually weakening, the hydrogen bond between hydrone is caused gradually to start destruction, the gradually shape of hydrogen bond between hydrone and D-trp
Into recognition efficiency gradually rises.Compared with L-Trp, when 8 DEG C, stable single hydrogen is formed between hydrone and D-trp
Key, D-trp is more difficult to penetrate amylose helical structure arrival electrode surface, therefore has obtained higher recognition effect.When with
When temperature and continuing to be increased to 37 DEG C, highest recognition effect is reached, this is due to be formed between hydrone and D-trp
Stable dihydrogen bond.But as temperature continues to raise, stable dihydrogen bond is destroyed, and causes host-guest interaction to weaken,
Recognition efficiency declines.
Comparative example one：
Prepare glass-carbon electrode, L-glutamic acid modified glassy carbon electrode, amylose modified glassy carbon electrode and L-glutamic acid/
Amylose modified glassy carbon electrode, compares the recognition capability of these four electrode pair Tryptophan enantiomers.
Its result is shown in Fig. 5, it can be seen that glass-carbon electrode and L-glutamic acid modified glassy carbon electrode tryptophan enantiomer are several
Without recognition effect.The oxidation peak current ratio of amylose modified glassy carbon electrode tryptophan enantiomer is 1.42, and this can
It can be due to that amount of the amylose absorption on glass-carbon electrode is less, cause recognition effect relatively low.But this problem can pass through
Pidolidone is modified on glass-carbon electrode and is resolved.L-glutamic acid/amylose modified glassy carbon electrode tryptophan pair
The oxidation peak current ratio for reflecting body reaches 2.67.Compared with amylose-D-trp, amylose-L-Trp has higher
Electric current, this explanation have more L-Trps penetrate amylose helical structure reach electrode surface.Amylose-D- colors
The lower electric current of propylhomoserin illustrates when the indolyl radical of tryptophan enters the helical structure of amylose, compared with L-Trp,
Due to the less steric hindrance of D-trp ,-the NH on D-trp2Stabilization can be formed with the crystallization water in amylose
Hydrogen bond, the inclusion for making it be more beneficial for D-trp.Just because of this, D-trp is more difficult to penetrate the helical structure of amylose
Electrode surface is reached, causes lower electric current.The order of each modified electrode electrochemical recognition Tryptophan enantiomer is：Poly- L- paddy
Propylhomoserin/amylose modified glassy carbon electrode>Amylose modified glassy carbon electrode>L-glutamic acid modified glassy carbon electrode ≈ glass carbon electricity
Pole.
The selectivity that the present invention is prepared for L-glutamic acid/amylose modified glassy carbon electrode tryptophan enantiomer is known
Not.As a result show, be 0.5mM in the concentration of Tryptophan enantiomer, the self assembly time is 24h, and self assembly temperature is 8 DEG C, identification
Temperature is under conditions of 37 DEG C, recognition efficiency reaches maximum.
Claims (4)
1. based on the Selective recognition of L-glutamic acid/amylose modified glassy carbon electrode tryptophan enantiomer, step is as follows：
A, prepare L-glutamic acid modified glassy carbon electrode：Phosphate buffer solutions of the pH for 6~7 Pidolidone is prepared, is used
Cyclic voltammetry is deposited onto glassy carbon electrode surface, obtains L-glutamic acid modified glassy carbon electrode；
B, prepare L-glutamic acid/amylose modified glassy carbon electrode：The L-glutamic acid modified glassy carbon electrode of preparation is immersed
In 20~30mL amylose solutions, 18~28h of self assembly at 8 DEG C obtains L-glutamic acid/amylose modification glass carbon electricity
Pole；
C, tryptophan enantiomer Selective recognition：Tryptophan enantiomer is recognized using differential pulse method, by poly-L-glutamic acid
Acid/amylose modified glassy carbon electrode rest on 20~30mL temperature be 30 in 2~42 DEG C of Tryptophan enantiomer solution~
90s, carries out differential pulse with 0.1~0.5V/s speed of sweeping in 0.4~1.0V potential range, rear modified electrode has been surveyed every time
Steady recovery electrode activity is swept in 20~30mL pH is 6~7 phosphate buffer solutions.
2. the choosing according to claim 1 based on L-glutamic acid/amylose modified glassy carbon electrode tryptophan enantiomer
The identification of selecting property, it is characterized in that：In the step a, the concentration of Pidolidone is 0.03~0.06M.
3. the choosing according to claim 1 based on L-glutamic acid/amylose modified glassy carbon electrode tryptophan enantiomer
The identification of selecting property, it is characterized in that：In the step b, the concentration of amylose is 1~3mg/mL.
4. the choosing according to claim 1 based on L-glutamic acid/amylose modified glassy carbon electrode tryptophan enantiomer
The identification of selecting property, it is characterized in that：In the step c, the concentration of Tryptophan enantiomer is 0.2~1mM.
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| CN106226381B (en) * | 2016-07-11 | 2018-10-19 | 常州大学 | A kind of preparation of Thermo-sensitive quinine chiral sensor and it is applied to electrochemical recognition Tryptophan enantiomer |
| CN106290536B (en) * | 2016-07-29 | 2019-04-02 | 广西师范学院 | The method for detecting aspartic acid concentration in solution |
| CN106053584B (en) * | 2016-07-29 | 2019-04-02 | 广西师范学院 | The method for detecting acrylamide concentration in solution |
| CN106908500B (en) * | 2017-02-22 | 2019-06-04 | 常州大学 | A kind of preparation and its application of the phenylalanine dipeptide self assembly chiral sensor based on CTAB induction |
| CN108844982B (en) * | 2018-06-26 | 2021-01-29 | 常州大学 | Method for identifying tryptophan enantiomer based on ternary self-assembly system |
| CN110220959A (en) * | 2019-06-19 | 2019-09-10 | 长沙理工大学 | A kind of Pidolidone detection method and sensor based on polymerization film modified electrode |
| CN116574414B (en) * | 2023-05-16 | 2024-05-28 | 内江师范学院 | Graphite powder/starch chiral selector, glassy carbon electrode, preparation method and application |
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