CN110243897A - A kind of preparation of polyethyleneimine/chirality peptide modified glassy carbon electrode and its application in Tryptophan enantiomer Selective recognition - Google Patents
A kind of preparation of polyethyleneimine/chirality peptide modified glassy carbon electrode and its application in Tryptophan enantiomer Selective recognition Download PDFInfo
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Abstract
The present invention relates to a kind of preparation of polyethyleneimine/chirality peptide modified glassy carbon electrode and its applications in Tryptophan enantiomer Selective recognition.The following steps are included: first preparing polyethyleneimine modified glassy carbon electrode, polyethyleneimine modified glassy carbon electrode is immersed in a kind of chiral peptide (BGAc) solution again and is further modified, polyethyleneimine/chirality peptide modified glassy carbon electrode is obtained, electrochemical recognition Tryptophan enantiomer is used for.Effect of the invention are as follows: polyethyleneimine/chirality peptide modified electrode preparation process is simple, and environmental protection, at low cost and modified electrode tryptophan enantiomer has apparent recognition effect.
Description
Technical field
The present invention relates to a kind of preparation of polyethyleneimine/chirality peptide modified glassy carbon electrode and its it is applied to tryptophan mapping
The Selective recognition of body, belongs to electrochemical analysis and field of biotechnology.
Background technique
Amino acid provides important material base, Ke Yizuo for metabolism, vital movement and the growth and development of biology
For the important biomolecule marker of various metabolic diseases.Amino acid isomers configuration has D type and L-type, in practical applications, often one
Kind of enantiomer can play pharmacological action to human body and another enantiomer is invalid or have serious side effect even toxic effect.So
The Study of recognition of opponent's acidic amino acid is in pharmacy, bioanalysis, drug screening, seem in the fields such as Analyze & separate it is especially important and
It is significant.The deficiencies of that there is sensitivity is low for existing some spectra methods, complicated for operation, and analysis cost is high, so finding one
The analysis method that kind has good prospect is vital.Electrochemical analysis method has that high sensitivity, response time be fast, behaviour
Make simplicity, and the advantages that distinguishing different aminoacids enantiomer can be reached by regulating and controlling the chiral interface of modified electrode, therefore
Electrochemical Detection based on chiral Recognition is with good application prospect.
Summary of the invention
In the present invention, using the electrostatic interaction of polyethyleneimine and chiral peptide, by polyethyleneimine and chiral peptide in glass
Self assembly forms a film on carbon electrode.By the good filming ability of polyethyleneimine, Tryptophan enantiomer is distinguished in conjunction with chiral peptide.
A kind of preparation of polyethyleneimine/chirality peptide modified glassy carbon electrode and its selectivity applied to Tryptophan enantiomer
Identification, comprising the following steps:
A, it prepares polyethyleneimine modified electrode: preparing polyethylenimine solution, glass-carbon electrode is immersed into polyethyleneimine
In solution, certain time is impregnated, polyethyleneimine modified electrode is obtained；
B, it prepares polyethyleneimine/chirality peptide modified electrode: preparing chiral peptide solution, polyethyleneimine modified electrode is used
Certain time in chiral peptide solution is immersed after water cleaning, is taken out room temperature and is dried, obtains polyethyleneimine/chirality peptide modified electrode；
C, electrochemical recognition Tryptophan enantiomer: polyethyleneimine/chirality peptide modified electrode is working electrode, Ag/AgCl
Electrode is reference electrode, and platinum electrode is that the three-electrode system is immersed the L- tryptophan prepared or D-trp is molten to electrode
In liquid, it is incubated for after a certain period of time, is tested using pulse voltammetry.
Further, the aqueous solution that polyethyleneimine amine concentration is 1~3mg/mL in step a, soaking time are 20~60min.
Further, chiral peptide is BGAc in step b, and the concentration of chiral peptide is the aqueous solution of 0.1~1mg/mL, soaking time
For 10~30min.
The structural formula of the BGAc are as follows:
Further, the concentration of L-/D- tryptophan solution is 0.01~0.8mM in step c, scanning current potential be 0.4~
1V, incubation time are 1~30min.
What the present invention obtained has the beneficial effect that
The present invention identification of self assembly film forming as chiral amino acid on glass-carbon electrode by polyethyleneimine and chiral peptide
Material, the composite film material modified electrode is compared with single polyethyleneimine or chiral peptide modified electrode, Tryptophan enantiomer
Recognition effect significantly improve, and the preparation method is cheap, environmental protection, simply.
Detailed description of the invention
Fig. 1 is that polyethyleneimine (PEI) film (A), chiral peptide (D-BGAc) (B), PEI/D-BGAc composite membrane (C) are swept
Retouch electron microscope.
Fig. 2 is that bare glassy carbon electrode schemes the DPV that L-/D- Tryptophan enantiomer identifies.
Fig. 3 is that PEI modified glassy carbon electrode schemes the DPV that L-/D- Tryptophan enantiomer identifies.
Fig. 4 is that chiral peptide (D-BGAc) modified glassy carbon electrode schemes the DPV that L-/D- Tryptophan enantiomer identifies.
Fig. 5 is the DPV figure that PEI/D-BGAc adorns that glass-carbon electrode identifies L-/D- Tryptophan enantiomer.
Fig. 6 is the relationship that PEI/D-BGAc modified glassy carbon electrode measures different L-Trp contents and electric current in mixed solution
Figure.
Specific embodiment
Presently in connection with specific implementation the present invention will be further described, following embodiment be intended to illustrate invention rather than it is right
The present invention further limits.
Embodiment one:
PEI/D-BGAc is prepared to characterize for scanning electron microscope
A, 50mg PEI is weighed, is dissolved in 50mL deionized water and 1mg/mLPEI solution is made.
B, 25mgD-BGAc chirality peptide is weighed, the method bibliography [1] of D-BGAc is prepared, is scattered in 50mL deionized water
In be made 0.5mg/mLD-BGAc solution.
C, silicon wafer is cleaned and is used and is dried with nitrogen, is placed in the PEI solution of 1mg/mL, impregnated 15min and obtain PEI modification silicon
Piece.
D, PEI obtained in step c modification silicon wafer is cleaned with deionized water, is immersed after being dried with nitrogen and contains 0.5mg/
In the D-BGAc solution of mL, 15min is impregnated, room temperature is taken out and dries, obtain PEI/D-BGAc film.
Embodiment two:
PEI modified electrode, D-BGAc modified electrode and PEI/D-BGAc modified glassy carbon electrode are prepared respectively for electrochemistry
Identify that steps are as follows for Tryptophan enantiomer:
It prepares PEI modified electrode: preparing 4mL 1mg/mLPEI solution, glass-carbon electrode is immersed in PEI solution, impregnate
30min obtains the glass-carbon electrode of PEI modification.
It prepares D-BGAc modified electrode: preparing 4mL 0.5mg/mLD-BGAc solution, it is molten that glass-carbon electrode is immersed D-BGAc
In liquid, 30min is impregnated, obtains the glass-carbon electrode of D-BGAc modification.
It prepares PEI/D-BGAc modified electrode: the PEI obtained glass-carbon electrode modified being cleaned with deionized water, nitrogen is blown
It is immersed in the D-BGAc solution containing 0.5mg/mL after dry, impregnates 15min and obtain the glass-carbon electrode of PEI/D-BGAc modification.
It is working electrode by PEI modified electrode, D-BGAc modified electrode or PEI/D-BGAc the modification glass carbon of above-mentioned preparation,
Ag/AgCl electrode is reference electrode, and platinum electrode is to electrode, and by the three-electrode system, being immersed in 10mL contains 0.05mM simultaneously
In the PBS solution of L-Trp or the pH=7 containing 0.05mMD- tryptophan, incubation time 2min.In the electrochemical window of 0.4~1V
DPV test is carried out in mouthful, compares electric current difference.
As shown in Figure 2, naked glass carbon modified electrode D-/L- tryptophan electric current ratio at 0.74V is 1.
From the figure 3, it may be seen that PEI modified electrode D-/L- tryptophan electric current at 0.80V essentially coincides, electric current ratio is 1.
As shown in Figure 4, D-BGAc modified electrode D-/L- tryptophan electric current ratio is 1.56.
As shown in Figure 5, PEI/D-BGAc modified electrode D-/L- tryptophan electric current ratio at 0.75V is 3.4, illustrates PEI/
D-BGAc modified electrode tryptophan enantiomer obtains recognition efficiency and significantly improves.
Embodiment three:
Prepare PEI/D-BGAc modified electrode step such as example two.It is working electrode, Ag/ by the modified electrode of preparation
AgCl electrode is reference electrode, and platinum electrode is that the three-electrode system is immersed in 10mL respectively and contains different L- colors to electrode
In the PBS solution of the mixed proportion of propylhomoserin and D-trp.DPV test is carried out in the potential window of 0.4~1V, obtains electric current
With L-Trp content change diagram.As shown in Figure 6: electric current and L- tryptophane are in a linear relationship.
[1]Li C,Jin X,Zhao T,Zhou J,Duan P.Optically active quantum dots with
induced circularly polarized luminescence in amphiphilic peptide dendron
hydrogel. Nanoscale Advances 2019,1,508-512. 。
Claims (5)
1. a kind of polyethyleneimine/application of the chirality peptide modified glassy carbon electrode in Tryptophan enantiomer Selective recognition, special
Sign is that steps are as follows:
A, it prepares polyethyleneimine modified electrode: preparing polyethylenimine solution, glass-carbon electrode is immersed into polyethylenimine solution
In, certain time is impregnated, polyethyleneimine modified electrode is obtained；
B, it prepares polyethyleneimine/chirality peptide modified electrode: preparing chiral peptide solution, the step a polyethyleneimine prepared is repaired
It is immersed in certain time in chiral peptide solution after decorations electrode water cleaning, room temperature is taken out and dries, obtain polyethyleneimine/chirality peptide
Modified electrode；
C, electrochemical recognition Tryptophan enantiomer: using polyethyleneimine/chirality peptide modified electrode as working electrode, Ag/AgCl electricity
Extremely reference electrode, platinum electrode are to immerse the three-electrode system in the L-/D- tryptophan solution of preparation simultaneously to electrode,
It is incubated for after a certain period of time, is tested using pulse voltammetry.
2. polyethyleneimine/chirality peptide modified glassy carbon electrode is in Tryptophan enantiomer Selective recognition according to claim 1
In application, it is characterised in that: in the step a concentration of polyethylenimine solution be 1~3mg/mL, soaking time be 20~
60min。
3. polyethyleneimine/chirality peptide modified glassy carbon electrode is in Tryptophan enantiomer Selective recognition according to claim 1
In application, it is characterised in that: chiral peptide is BGAc in the step b, and chiral peptide solution concentration is 0.1~1mg/mL, is impregnated
Time is 10~30min.
4. polyethyleneimine/chirality peptide modified glassy carbon electrode is in Tryptophan enantiomer Selective recognition according to claim 1
In application, it is characterised in that: the concentration of L-/D- tryptophan is 0.01~0.8mM in the step c.
5. polyethyleneimine/chirality peptide modified glassy carbon electrode is in Tryptophan enantiomer Selective recognition according to claim 1
In application, it is characterised in that: in the step c incubation time be 1~30min, scanning current potential be 0.4~1.0V.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112595769A (en) * | 2020-12-07 | 2021-04-02 | 常州大学 | Method for amplifying and identifying tryptophan enantiomer by using PEI-Fc in-situ generated nano silver |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070138007A1 (en) * | 2005-11-03 | 2007-06-21 | Ramot At Tel Aviv University Ltd. | Peptide nanostructure-coated electrodes |
| CN106226381A (en) * | 2016-07-11 | 2016-12-14 | 常州大学 | The preparation of a kind of Thermo-sensitive quinine chiral sensor and be applied to electrochemical recognition Tryptophan enantiomer |
| CN106908507A (en) * | 2017-02-22 | 2017-06-30 | 常州大学 | A kind of preparation and its application of phenylalanine dipeptide Chitosan Composites |
| WO2018153918A1 (en) * | 2017-02-22 | 2018-08-30 | Roche Diagnostics Gmbh | Polymer-coating of electrodes for sensor devices |
| CN108562628A (en) * | 2018-04-18 | 2018-09-21 | 常州大学 | A kind of preparation for the alpha-cyclodextrin inclusion glutathione composite material modified electrode can be applied to electrochemistry chiral Recognition |
| CN108645900A (en) * | 2018-04-18 | 2018-10-12 | 常州大学 | A kind of preparation method for the glutathione modified electrode can be applied to electrochemistry chiral Recognition |
| CN109975379A (en) * | 2019-04-30 | 2019-07-05 | 常州大学 | A kind of chitosan/CT-DNA Modified Gold Electrode preparation method for electrochemical recognition Tryptophan enantiomer |
-
2019
- 2019-07-10 CN CN201910617961.XA patent/CN110243897B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070138007A1 (en) * | 2005-11-03 | 2007-06-21 | Ramot At Tel Aviv University Ltd. | Peptide nanostructure-coated electrodes |
| CN106226381A (en) * | 2016-07-11 | 2016-12-14 | 常州大学 | The preparation of a kind of Thermo-sensitive quinine chiral sensor and be applied to electrochemical recognition Tryptophan enantiomer |
| CN106908507A (en) * | 2017-02-22 | 2017-06-30 | 常州大学 | A kind of preparation and its application of phenylalanine dipeptide Chitosan Composites |
| WO2018153918A1 (en) * | 2017-02-22 | 2018-08-30 | Roche Diagnostics Gmbh | Polymer-coating of electrodes for sensor devices |
| CN108562628A (en) * | 2018-04-18 | 2018-09-21 | 常州大学 | A kind of preparation for the alpha-cyclodextrin inclusion glutathione composite material modified electrode can be applied to electrochemistry chiral Recognition |
| CN108645900A (en) * | 2018-04-18 | 2018-10-12 | 常州大学 | A kind of preparation method for the glutathione modified electrode can be applied to electrochemistry chiral Recognition |
| CN109975379A (en) * | 2019-04-30 | 2019-07-05 | 常州大学 | A kind of chitosan/CT-DNA Modified Gold Electrode preparation method for electrochemical recognition Tryptophan enantiomer |
Non-Patent Citations (5)
| Title |
|---|
| CHENGXI LI 等: ""Optically active quantum dots with induced circularly polarized luminescence in amphiphilic peptide dendron hydrogel"", 《NANOSCALE ADV.》 * |
| JINYI SONG 等: ""Voltammetric chiral discrimination of tryptophan using a multilayer nanocomposite with implemented amino-modified β-cyclodextrin as recognition element"", 《MICROCHIM ACTA》 * |
| WORAPOT PRONGMANEE 等: ""Hydroxyapatite/Graphene oxide composite for electrochemical detection of L-Tryptophan"", 《JOURNAL OF THE TAIWAN INSTITUTE OF CHEMICAL ENGINEERS》 * |
| YI-XIN SUN 等: ""Electrochemical recognition of tryptophan enantiomers based on the selfassembly of polyethyleneimine and chiral peptides"", 《JOURNAL OF ELECTROANALYTICAL CHEMISTRY》 * |
| 何家辉 等: ""聚乙烯亚胺和手性肽自组装膜用于电化学区分色氨酸对映体"", 《现代化工》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112595769A (en) * | 2020-12-07 | 2021-04-02 | 常州大学 | Method for amplifying and identifying tryptophan enantiomer by using PEI-Fc in-situ generated nano silver |
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