CN103208635A - Poly(4-vinylpyridine-co-acrylonitrile)-based pH-sensitive electrochemical switch and application thereof - Google Patents
Poly(4-vinylpyridine-co-acrylonitrile)-based pH-sensitive electrochemical switch and application thereof Download PDFInfo
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- CN103208635A CN103208635A CN2013101079482A CN201310107948A CN103208635A CN 103208635 A CN103208635 A CN 103208635A CN 2013101079482 A CN2013101079482 A CN 2013101079482A CN 201310107948 A CN201310107948 A CN 201310107948A CN 103208635 A CN103208635 A CN 103208635A
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Abstract
The invention discloses a poly(4-vinylpyridine-co-acrylonitrile)-based pH-sensitive electrochemical switch and an application thereof, belonging to the technical field of bioelectrocatalysis controlled by macromolecule-based intelligent switches. The electrochemical switch comprises an electrode system taking a phosphate buffered solution containing a negative charge probe as an electrolyte and a poly(4-vinylpyridine-co-acrylonitrile) film modified electrode as a working electrode. Cyclic voltammetry proves that the poly(4-vinylpyridine-co-acrylonitrile) film modified electrode has the performance of the switch sensitive to the pH value of the negative charge probe, and the control for the process for electrocatalytic oxidation of glucose by using glucose oxidase by using the negative charge probe as an oxidoreduction mediator is realized after the glucose oxidase is fixed on the poly(4-vinylpyridine-co-acrylonitrile) film modified working electrode.
Description
Technical field
The invention belongs to the technical field of polymer-based intelligent switch regulation and control biological electro catalysis.
Background technology
In recent years, the research of adjustable biological electro catalysis has caused a lot of researchers' interest.The controllable biological electro-catalysis is applied to aspects such as biology sensor, biological fuel cell and all has extraordinary development prospect.Such as, if can realize the adjustable of enzyme biological fuel cell anode biological electro catalysis process, just can realize the intellectuality control discharge of biological fuel cell, can enough provide power supply to implanted electronics microdevice intelligently according to the concrete physiological requirement of human body, can prolong the useful life of battery like this, can make biological fuel cell have very big advantage aspect medical diagnosis on disease and the treatment like this.
Realize controlled biological electro catalysis, at first must select the proper polymer material to come modified electrode.This macromolecular material externally environment (as current potential, pH, temperature etc.) stimulates the variation that produces corresponding properties (as conductivity, swelling/contraction state, permeability etc.) down, thereby influence electric transmission in the biological electro catalysis process, material diffusion etc., can realize controlled biological electro catalysis like this.
Summary of the invention
The objective of the invention is to propose a kind of responsive electrochemistry switch of the pH based on poly-(tetrem thiazolinyl pyridine-co-acrylonitrile) that can regulate and control the biological electro catalysis process.
The PBS that electrochemistry switch of the present invention comprises containing the negative electrical charge probe is electrolyte, and the electrode that comprises being modified with poly-(tetrem thiazolinyl pyridine-co-acrylonitrile) film at least is the electrode system of work electrode.
Negative electrical charge probe wherein can be electronegative electroactive probes such as the potassium ferricyanide or carboxylic acid ferrocene.
The random copolymer that the present invention selects for use poly-(tetrem thiazolinyl pyridine-co-acrylonitrile) combines the film forming of poly 4 vinyl pyridine good hydrophilicity, biocompatibility and polyacrylonitrile excellence, good physical and mechanical properties, chemical stability are the good material of modified electrode.And containing alkalescent group pyridine ring in poly-(tetrem thiazolinyl pyridine-co-acrylonitrile) structure, its protonated degree can change along with the variation of pH, so it has the pH sensitive natur.Adopt cyclic voltammetry to prove that poly-(tetrem thiazolinyl pyridine-co-acrylonitrile) film modified electrode has the pH sentive switch performance to the negative electrical charge probe:
When pH=3.0, the response of the cyclic voltammetric of probe is very big, and is intimate reversible, and this moment, poly-(tetrem thiazolinyl pyridine-co-acrylonitrile) film was in "open" state to probe; When pH=7.0, the response of the cyclic voltammetric of probe almost detect less than, this moment, poly-(tetrem thiazolinyl pyridine-co-acrylonitrile) film was in "off" state to probe, and poly-(tetrem thiazolinyl pyridine-co-acrylonitrile) membrane electrode has invertibity to this pH sentive switch performance of probe.
The preparation method who is modified with the electrode of poly-(tetrem thiazolinyl pyridine-co-acrylonitrile) film of the present invention is: will gather (tetrem thiazolinyl pyridine-co-acrylonitrile) and N, the mixed solution of dinethylformamide drips and is applied to the substrate working electrode surface, treat N, namely modify at the substrate working electrode surface after the dinethylformamide volatilization and gathered (tetrem thiazolinyl pyridine-co-acrylonitrile) film.
The mass fraction of poly-(tetrem thiazolinyl pyridine-co-acrylonitrile) is 0.1%-5% in the above mixed solution, and the mole proportioning of monomer 4-vinylpridine and acrylonitrile is 1:1 in described poly-(tetrem thiazolinyl pyridine-co-acrylonitrile).
The method that the present invention prepares the glass-carbon electrode that is modified with poly-(tetrem thiazolinyl pyridine-co-acrylonitrile) film is simple, good stability.
The present invention also proposes the application based on the responsive electrochemistry switch of the pH that gathers (tetrem thiazolinyl pyridine-co-acrylonitrile) of preparation method's preparation:
Adopt inorganic cation clay laponite fixing glucose oxidase (GOD) at the work electrode that is modified with poly-(tetrem thiazolinyl pyridine-co-acrylonitrile) (P (4VP-co-AN)) film, construct and obtain GOD/laponite/ P (4VP-co-AN)/GCE electrode, it is the redox mediator that this bioelectrode can be used for the negative electrical charge probe, the process of glucose oxidase catalytic oxidation glucose.
The GOD/laponite/ P (4VP-co-AN) that the present invention constructs/GCE intelligence biological electrode can be used as biological fuel cell anode, thereby provides a new way for the intellectuality of biological fuel cell.
Description of drawings
Fig. 1 is the poly-cyclic voltammetric response diagram of (tetrem thiazolinyl pyridine-co-acrylonitrile) membrane electrode in containing the different pH PBSs of potassium ferricyanide probe.
Fig. 2 for poly-(tetrem thiazolinyl pyridine-co-acrylonitrile) membrane electrode in the PBS that contains potassium ferricyanide probe the cyclic voltammetric oxidation peak current and the graph of a relation of pH value of buffer solution.
Fig. 3 alternately places pH3.0 and pH7.0 to contain the oxidation peak current figure of the cushioning liquid of potassium ferricyanide probe for poly-(tetrem thiazolinyl pyridine-co-acrylonitrile) membrane electrode.
Fig. 4 is containing 1mM K for GOD/laponite/ P (4VP-co-AN)/GCE electrode
3Fe (CN)
6, the ampere response diagram in the different pH cushioning liquid of 100mg/dl glucose.
Embodiment
One, by solution polymerization process preparation poly-(tetrem thiazolinyl pyridine-co-acrylonitrile):
Measure 3.77ml 4VP(4-vinylpyridine), 2.1ml the AN(acrylonitrile), 10ml toluene mixes in flask, system vacuumizes, and adds 0.016g initiator A IBN(azodiisobutyronitrile then under nitrogen atmosphere), be warming up to 70 ℃, obtain product behind the reaction 2h, repeatedly behind the washing and filtering, place 50 ℃ of vacuumizes of vacuum drying chamber with toluene and ether, namely getting monomer mole ratio is the random copolymer poly-(tetrem thiazolinyl pyridine-co-acrylonitrile) of 1:1.
Two, preparation is modified with the work electrode of poly-(tetrem thiazolinyl pyridine-co-acrylonitrile) film:
To gather (tetrem thiazolinyl pyridine-co-acrylonitrile) and be dissolved in N, in the dinethylformamide (DMF), be mixed with that to contain poly-(tetrem thiazolinyl pyridine-co-acrylonitrile) mass fraction be 0.1%～5% mixed solution.
Mixed solution dripped be applied to the glass-carbon electrode surface, place drier then, treat that solvent DMF is volatilized fully after, namely obtain being modified with the work electrode of poly-(tetrem thiazolinyl pyridine-co-acrylonitrile) film.
Three, make up the electrochemistry switch, and measure poly-(tetrem thiazolinyl pyridine-co-acrylonitrile) membrane electrode respectively at pH3.0, the cyclic voltammetric to the negative electrical charge probe potassium ferricyanide in 4.0,5.0,6.0,7.0 the cushioning liquid responds:
Cushioning liquid is PBS: by dipotassium hydrogen phosphate (0.1mol dm
-3) and potassium dihydrogen phosphate (0.1mol dm
-3) preparation, and regulate pH by dripping phosphoric acid solution, obtain the pH value respectively and be 3.0,4.0,5.0,6.0 and 7.0 PBS.
The cyclic voltammetric potential range is set is-0.2 ~ 0.8 V, sweep speed is 100 mv/s.
Adding solution in five electrolytic cells respectively is the PBS that comprises the 1mM potassium ferricyanide and the different pH of 0.01M potassium chloride.
1, in above five different electrolytic cell, with identical cyclic voltammetric potential voltage and the cyclic voltammetric response of poly-(the tetrem thiazolinyl pyridine-co-acrylonitrile) membrane electrode of sweep speed test in the cushioning liquid of the different pH values that contain the negative electrical charge probe potassium ferricyanide, the result as shown in Figure 1, 2.
Fig. 1 has shown poly-(tetrem thiazolinyl pyridine-co-acrylonitrile) membrane electrode to the pH sentive switch performance of potassium ferricyanide probe, and to be respectively the pH value of PBS be that poly-(tetrem thiazolinyl pyridine-co-acrylonitrile) membrane electrode responds the cyclic voltammetric of potassium ferricyanide probe in 3.0,4.0,5.0,6.0 and 7.0 5 electrolytic cells for curve a, b, c, d, e among the figure.
Fig. 2 has shown under the different pH, the poly-cyclic voltammetric oxidation peak current of (tetrem thiazolinyl pyridine-co-acrylonitrile) membrane electrode in the PBS that contains potassium ferricyanide probe.
By Fig. 1,2 as seen, and in the PBS of pH=3.0, probe has a pair of reversible redox peak, and peak current is very big, and this moment, poly-(tetrem thiazolinyl pyridine-co-acrylonitrile) film was in "open" state to probe.Along with the increase of pH, peak current sharply reduces.In the PBS of pH=7.0, almost do not observe the redox peak, this moment, poly-(tetrem thiazolinyl pyridine-co-acrylonitrile) film was in "off" state to probe.
2, will gather (tetrem thiazolinyl pyridine-co-acrylonitrile) membrane electrode alternately places pH3.0 and pH7.0 to contain the PBS of potassium ferricyanide probe, can find that oxidation peak current alternately changes between maximum and minimum value, as shown in Figure 3, illustrate that the pH sentive switch based on poly-(tetrem thiazolinyl pyridine-co-acrylonitrile) is reversible.
Four, use:
At poly-(tetrem thiazolinyl pyridine-co-acrylonitrile) (P (4VP-co-AN)) membrane electrode surface inorganic cation clay laponite fixing glucose oxidase (GOD), be built into GOD/laponite/ P (4VP-co-AN)/GCE electrode, tested the pH regulation and control electrocatalysis characteristic of this bioelectrode then by the ampere method.
As shown in Figure 4, in the pH that contains probe is 3.0 cushioning liquid, add glucose after, response current is very big, the glucose oxidase catalytic oxidation has been described glucose, the biological electro catalysis process is in "open" state; And place pH be 7.0 contain probe cushioning liquid, almost do not observe response current after dripping glucose, the biological electro catalysis process is in "off" state.
Above experimental phenomena explanation: can be used for the potassium ferricyanide based on the responsive electrochemistry switch of the pH of poly-(tetrem thiazolinyl pyridine-co-acrylonitrile) is the redox mediator, the process of glucose oxidase catalytic oxidation glucose, the GOD/laponite/ P (4VP-co-AN) that herein constructs/GCE intelligence biological electrode can be used as the biological fuel cell anode intelligent switch, thereby provides a new way for the intellectuality that realizes biological fuel cell.
Claims (5)
1. responsive electrochemistry switch of the pH based on poly-(tetrem thiazolinyl pyridine-co-acrylonitrile), the PBS that it is characterized in that comprising containing the negative electrical charge probe is electrolyte, and the electrode that comprises being modified with poly-(tetrem thiazolinyl pyridine-co-acrylonitrile) film at least is the electrode system of work electrode.
2. according to the described electrochemistry switch of claim 1, it is characterized in that described negative electrical charge probe is the potassium ferricyanide or carboxylic acid ferrocene.
3. according to the described electrochemistry switch of claim 1, it is characterized in that the described preparation method who is modified with the electrode of poly-(tetrem thiazolinyl pyridine-co-acrylonitrile) film is: will gather (tetrem thiazolinyl pyridine-co-acrylonitrile) and N, the mixed solution of dinethylformamide drips and is applied to the substrate working electrode surface, treat N, namely modify at the substrate working electrode surface after the dinethylformamide volatilization and gathered (tetrem thiazolinyl pyridine-co-acrylonitrile) film.
4. according to the described electrochemistry switch of claim 3, the mass fraction that it is characterized in that poly-(tetrem thiazolinyl pyridine-co-acrylonitrile) in the described mixed solution is 0.1%-5%, and the mole proportioning of monomer 4-vinylpridine and acrylonitrile is 1:1 in described poly-(tetrem thiazolinyl pyridine-co-acrylonitrile).
5. one kind according to claim 1 based on the application of the responsive electrochemistry switch of pH of poly-(tetrem thiazolinyl pyridine-co-acrylonitrile), it is characterized in that behind fixing glucose oxidase on the work electrode that is modified with poly-(tetrem thiazolinyl pyridine-co-acrylonitrile) film, being used for the negative electrical charge probe is the redox mediator, the process of glucose oxidase catalytic oxidation glucose.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103878027A (en) * | 2014-04-16 | 2014-06-25 | 扬州大学 | Preparation method of 4-vinylpyridine-co-acrylonitrile and platinum composite nanowire |
| CN104833715A (en) * | 2015-05-21 | 2015-08-12 | 扬州大学 | Electrode based on poly (styrene-co-acrylic acid) as well as preparation method and application thereof |
| CN110534753A (en) * | 2019-08-22 | 2019-12-03 | 浙江大学 | The glucose fuel cell for having homogeneous auxiliary catalysis |
Citations (2)
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|---|---|---|---|---|
| US20050137372A1 (en) * | 2003-12-15 | 2005-06-23 | Council Of Scientific And Industrial Research | pH sensitive polymer and process for preparation thereof |
| CN101768281A (en) * | 2009-12-28 | 2010-07-07 | 江南大学 | Preparation method of segmented copolymer capable of forming different micelles by self assembly under condition of different pH values |
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2013
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050137372A1 (en) * | 2003-12-15 | 2005-06-23 | Council Of Scientific And Industrial Research | pH sensitive polymer and process for preparation thereof |
| CN101768281A (en) * | 2009-12-28 | 2010-07-07 | 江南大学 | Preparation method of segmented copolymer capable of forming different micelles by self assembly under condition of different pH values |
Non-Patent Citations (3)
| Title |
|---|
| TZONKA GODJEVARGOVA等: "Immobilization of glucose oxidase by acrylonitrile copolymer coated silica supports", 《JOURNAL OF MOLECULAR CATALYSIS B：ENZYMATIC》 * |
| YAN LIANG等: "Triply switchable bioelectrocatalysis based on poly(N,N-diethylacrylamide-co-4-vinylpyridine) copolymer hydrogel films with immobilized glucose oxidase", 《ELECTROCHIMICA ACTA》 * |
| 贺园园: "多孔高分子膜的制备及其在生物传感器中的应用", 《中国优秀硕士学位论文全文数据库》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103878027A (en) * | 2014-04-16 | 2014-06-25 | 扬州大学 | Preparation method of 4-vinylpyridine-co-acrylonitrile and platinum composite nanowire |
| CN103878027B (en) * | 2014-04-16 | 2015-09-16 | 扬州大学 | 4-vinylpridine-co-acrylonitrile and platinum composite nano-line preparation method |
| CN104833715A (en) * | 2015-05-21 | 2015-08-12 | 扬州大学 | Electrode based on poly (styrene-co-acrylic acid) as well as preparation method and application thereof |
| CN110534753A (en) * | 2019-08-22 | 2019-12-03 | 浙江大学 | The glucose fuel cell for having homogeneous auxiliary catalysis |
| CN110534753B (en) * | 2019-08-22 | 2021-02-12 | 浙江大学 | Glucose fuel cell with homogeneous auxiliary catalysis |
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Application publication date: 20130717 |