CN102262114A - Electrochemical preparation method of electrode modified by polypyrrole-chitosan-enzyme composite film - Google Patents
Electrochemical preparation method of electrode modified by polypyrrole-chitosan-enzyme composite film Download PDFInfo
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- CN102262114A CN102262114A CN2011101013378A CN201110101337A CN102262114A CN 102262114 A CN102262114 A CN 102262114A CN 2011101013378 A CN2011101013378 A CN 2011101013378A CN 201110101337 A CN201110101337 A CN 201110101337A CN 102262114 A CN102262114 A CN 102262114A
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Abstract
The invention relates to an electrochemical preparation method of an electrode modified by a polypyrrole-chitosan-enzyme composite film, and the preparation method comprises the following steps: 1) dissolving chitosan in a 0.01-1 mol/L nitric acid solution to obtain a solution A, wherein the mass percentage concentration of chitosan in the solution A is 0.5-5%; 2) adding a pyrrole monomer to the solution A to obtain a solution B, wherein the concentration of the pyrrole monomer in the solution B is 0.1-0.4 mol/L; 3) adding an enzyme to the solution B and ultrasonically treating for 10-30 minutes to obtain a solution C, wherein the concentration of the enzyme in the solution C is 0.01-1 mg/mL; and 4) placing a cathode in the solution C, electrifying for electrochemical synthesis so that polypyrrole, chitosan and the enzyme are attached to the surface of the cathode, thus obtaining the electrode modified by the polypyrrole-chitosan-enzyme composite film. The preparation method provided by the invention has the advantages of simple preparation conditions, easiness in operation, controllable thickness of the polypyrrole-chitosan-enzyme composite film and controllable enzyme immobilization amount.
Description
Technical field
The present invention relates to the preparation method of modified electrode, particularly relate to the electrochemical preparation method of a kind of polypyrrole-shitosan-enzyme composite membrane modified electrode.
Background technology
Conducting polymer is a new research field that grows up the seventies in last century, because its special structure and good physical and chemical performance, make it wide application prospect be arranged at aspects such as electrode material, modified electrode, enzyme electrode, electromagnetism demonstrations, the conducting polymer polypyrrole that wherein has conjugated double bond is owing to synthetic convenience, antioxygenic property are good, compare with other conducting polymers, because of have higher, the easy film forming of conductivity, softness, advantage such as nontoxic is subjected to people day by day and pays close attention to.The enzyme electrode of polypyrrole modifying is the focus of biology sensor research, and has developed multiple preparation method.
Shitosan is that natural chitin connects the derivant that obtains through partially deacetylated back by β-1,4 glycosidic bond, is that a class formation is similar to the big molecule of cellulosic glycosaminoglycan.Active aminos a large amount of in the chitosan molecule can be protonated under sour environment, makes it be dissolved in acid solution.Shitosan has good biocompatibility, cheap, advantage such as the source is abundant, is the environment renewable resource, has become widely used enzyme immobilization carrier.
Modified electrode is as the vitals in the biology sensor, and its preparation method has very big influence to the performance of biology sensor.The sensitivity of enzyme modified electrode is to estimate the important indicator of enzyme electrode performance with stability, and the controllability of enzyme modified electrode preparation process is the principal element of decision enzyme electrode practical application.The selection of enzyme fixing means is fast, highly sensitive for preparation response, the sensor of good stability, long service life is most important.But enzyme modified electrode preparation technology is generally complicated in the prior art, and manufacturing cycle is long.
Summary of the invention
Problem to be solved by this invention is the electrochemical preparation method of a kind of polypyrrole-shitosan-enzyme composite membrane modified electrode of proposing at above-mentioned existing deficiency, and this method technology is simple, operation easily, manufacturing cycle are short.
The present invention for the solution that problem adopts of the above-mentioned proposition of solution is: the electrochemical preparation method of polypyrrole-shitosan-enzyme composite membrane modified electrode includes following steps:
1) shitosan is dissolved in the 0.01-1mol/L salpeter solution, obtains solution A, the mass percent concentration of shitosan is 0.5-5% in the solution A;
2) add pyrrole monomer in solution A, obtain solution B, the concentration of pyrrole monomer in solution B is 0.1-0.4mol/L;
3) in solution B, add enzyme, ultrasonic 10-30 minute, obtain solution C, the concentration of enzyme in solution C is 0.01-1mg/mL;
4) negative electrode is placed solution C, it is synthetic that galvanochemistry is carried out in energising, and polypyrrole, shitosan and enzyme promptly obtain polypyrrole-shitosan-enzyme composite membrane modified electrode attached to cathode surface.
Press such scheme, described working electrode is gold, platinum, glass carbon or indium tin oxide-coated glass;
Press such scheme, when the described galvanochemistry of step 4) is synthetic cathode potential be-0.5～-2V;
Press such scheme, the synthetic generated time of the described galvanochemistry of step 4) is 1-30 minute;
Press such scheme, described enzyme is peroxidase, glucose oxidase, Lactate Oxidase, lipase or cholesterol oxidase.
The present invention is compound as the immobilized carrier of a kind of novel enzyme with polypyrrole and shitosan, place the mixed solution of shitosan, pyrrole monomer and enzyme to switch on negative electrode, nitrate ion in the solution and hydrogen ion get electron reaction and generate the NO+ ion near cathode electrodes.The NO+ ion has strong oxidizing property, and then the oxidation pyrrole monomer becomes polypyrrole and is deposited on cathode surface.Meanwhile, near the pH value the negative electrode is consumed along with hydrogen ion and increases, and causes shitosan to become insoluble state and also is deposited on cathode surface.Shitosan, polypyrrole combine with enzyme like this, can obtain the modified electrode of polypyrrole-shitosan-enzyme composite membrane in the cathode surface electro-deposition.
Compared with the prior art, the technique effect that the present invention has reached: the shitosan source is abundant, has excellent biological compatibility, is good enzyme immobilization carrier.And on the preparation method, the negative electrode polymerization of polypyrrole is combined with the electro-deposition electricity of shitosan, single stage method has obtained polypyrrole-shitosan-enzyme composite membrane at cathode surface.Polypyrrole-shitosan-enzyme composite membrane can make enzyme have good biologically active and help taking place the electrochemical catalysis reaction.Preparation method's condition of the present invention is simple, operation easily, and polypyrrole-shitosan-enzyme composite membrane controllable thickness, the enzyme fixed amount is controlled.
Embodiment
For a better understanding of the present invention, further illustrate content of the present invention, but content of the present invention not only is confined to the following examples below in conjunction with embodiment.
Embodiment 1:
1) shitosan is dissolved in the 0.1mol/L salpeter solution, obtains solution A, the mass percent concentration of shitosan is 0.5% in the solution A;
2) add pyrrole monomer in solution A, obtain solution B, the concentration of pyrrole monomer in solution B is 0.1mol/L;
3) in solution B, add the peroxidase enzyme, ultrasonic 10 minutes, obtain solution C, the concentration of peroxidase enzyme in solution C is 0.1mg/mL
4) gold electrode is placed solution C as negative electrode, it is synthetic that galvanochemistry is carried out in energising, and cathode potential is-0.6V, and the galvanochemistry generated time is 5 minutes, and polypyrrole, shitosan and enzyme promptly obtain polypyrrole-shitosan-enzyme composite membrane modified electrode attached to cathode surface.
Embodiment 2:
1) shitosan is dissolved in the 0.3mol/L salpeter solution, obtains solution A, the mass percent concentration of shitosan is 1% in the solution A;
2) add pyrrole monomer in solution A, obtain solution B, the concentration of pyrrole monomer in solution B is 0.2mol/L;
3) in solution B, add glucose oxidase, ultrasonic 20 minutes, obtain solution C, the concentration of glucose oxidase in solution C is 0.5mg/mL;
4) platinum electrode is placed solution C as negative electrode, it is synthetic that galvanochemistry is carried out in energising, and cathode potential is-0.8V, and the galvanochemistry generated time is 10 minutes, and polypyrrole, shitosan and enzyme promptly obtain polypyrrole-shitosan-enzyme composite membrane modified electrode attached to cathode surface.
Embodiment 3:
1) shitosan is dissolved in the 0.5mol/L salpeter solution, obtains solution A, the mass percent concentration of shitosan is 2% in the solution A;
2) add pyrrole monomer in solution A, obtain solution B, the concentration of pyrrole monomer in solution B is 0.3mol/L;
3) in solution B, add Lactate Oxidase, ultrasonic 15 minutes, obtain solution C, the concentration of Lactate Oxidase in solution C is 0.4mg/mL;
4) glass-carbon electrode is placed solution C as negative electrode, it is synthetic that galvanochemistry is carried out in energising, and cathode potential is-1.2V that the galvanochemistry generated time is 10 minutes, polypyrrole, shitosan and enzyme promptly obtain polypyrrole-shitosan-enzyme composite membrane modified electrode attached to cathode surface.
Embodiment 4:
1) shitosan is dissolved in the 0.05mol/L salpeter solution, obtains solution A, the mass percent concentration of shitosan is 1% in the solution A;
2) add pyrrole monomer in solution A, obtain solution B, the concentration of pyrrole monomer in solution B is 0.25mol/L;
3) in solution B, add lipase, ultrasonic 30 minutes, obtain solution C, the concentration of lipase in solution C is 0.5mg/mL;
4) the indium tin oxide-coated glass electrode is placed solution C as negative electrode, it is synthetic that galvanochemistry is carried out in energising, and cathode potential is-1.0V that the galvanochemistry generated time is 15 minutes, polypyrrole, shitosan and enzyme promptly obtain polypyrrole-shitosan-enzyme composite membrane modified electrode attached to cathode surface.
Embodiment 5:
1) shitosan is dissolved in the 0.08mol/L salpeter solution, obtains solution A, the mass percent concentration of shitosan is 0.6% in the solution A;
2) add pyrrole monomer in solution A, obtain solution B, the concentration of pyrrole monomer in solution B is 0.15mol/L;
3) in solution B, add cholesterol oxidase, ultrasonic 20 minutes, obtain solution C, the concentration of cholesterol oxidase in solution C is 0.1mg/mL;
4) the indium tin oxide-coated glass electrode is placed solution C as negative electrode, it is synthetic that galvanochemistry is carried out in energising, and cathode potential is-0.7V that the galvanochemistry generated time is 25 minutes, polypyrrole, shitosan and enzyme promptly obtain polypyrrole-shitosan-enzyme composite membrane modified electrode attached to cathode surface.
Embodiment 6:
1) shitosan is dissolved in the 0.4mol/L salpeter solution, obtains solution A, the mass percent concentration of shitosan is 2.5% in the solution A;
2) add pyrrole monomer in solution A, obtain solution B, the concentration of pyrrole monomer in solution B is 0.3mol/L;
3) in solution B, add Lactate Oxidase, ultrasonic 30 minutes, obtain solution C, the concentration of Lactate Oxidase in solution C is 0.6mg/mL;
4) gold electrode is placed solution C as negative electrode, it is synthetic that galvanochemistry is carried out in energising, and cathode potential is-0.8V, and the galvanochemistry generated time is 15 minutes, and polypyrrole, shitosan and enzyme promptly obtain polypyrrole-shitosan-enzyme composite membrane modified electrode attached to cathode surface.
Each cited raw material of the present invention can both be realized the present invention, and the bound value of each raw material, interval value can both realize the present invention; Do not enumerate embodiment one by one at this.Bound value, the interval value of technological parameter of the present invention (as temperature, time etc.) can both be realized the present invention, do not enumerate embodiment one by one at this.
Claims (5)
1. the electrochemical preparation method of polypyrrole-shitosan-enzyme composite membrane modified electrode includes following steps:
1) shitosan is dissolved in the 0.01-1mol/L salpeter solution, obtains solution A, the mass percent concentration of shitosan is 0.5-5% in the solution A;
2) add pyrrole monomer in solution A, obtain solution B, the concentration of pyrrole monomer in solution B is 0.1-0.4mol/L;
3) in solution B, add enzyme, ultrasonic 10-30 minute, obtain solution C, the concentration of enzyme in solution C is 0.01-1mg/mL;
4) negative electrode is placed solution C, it is synthetic that galvanochemistry is carried out in energising, and polypyrrole, shitosan and enzyme promptly obtain polypyrrole-shitosan-enzyme composite membrane modified electrode attached to cathode surface.
2. by the electrochemical preparation method of the described polypyrrole-shitosan of claim 1-enzyme composite membrane modified electrode, it is characterized in that described working electrode is gold, platinum, glass carbon or indium tin oxide-coated glass.
3. by the electrochemical preparation method of claim 1 or 2 described polypyrrole-shitosans-enzyme composite membrane modified electrode, when it is characterized in that the described galvanochemistry of step 4) is synthetic cathode potential be-0.5～-2V.
4. by the electrochemical preparation method of the described polypyrrole-shitosan of claim 3-enzyme composite membrane modified electrode, it is characterized in that the synthetic generated time of the described galvanochemistry of step 4) is 1-30 minute.
5. by the electrochemical preparation method of claim 1 or 2 described polypyrrole-shitosans-enzyme composite membrane modified electrode, it is characterized in that described enzyme is peroxidase, glucose oxidase, Lactate Oxidase, lipase or cholesterol oxidase.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103954660A (en) * | 2014-04-14 | 2014-07-30 | 华南理工大学 | Enzyme biosensor for detecting cholesterol as well as preparation method and application of biosensor |
| CN104034778A (en) * | 2014-06-18 | 2014-09-10 | 武汉工程大学 | Chitosan-ionic liquid-graphene-enzyme composite membrane modified electrode and preparation method thereof |
| CN104049016A (en) * | 2014-06-18 | 2014-09-17 | 武汉工程大学 | Graphene-polypyrrole-ion liquid-enzyme composite film modified electrode and preparation method thereof |
| CN105645523A (en) * | 2016-01-07 | 2016-06-08 | 西安建筑科技大学 | Method for preparing polypyrrole/chitosan composite electrode |
| CN107033349A (en) * | 2017-03-30 | 2017-08-11 | 青岛科技大学 | A kind of preparation method and applications of polypyrrole/nano platinum particle composite |
| CN110411951A (en) * | 2019-08-13 | 2019-11-05 | 信阳师范学院 | A kind of preparation method of the Photoelectrochemistrbiosensor biosensor for the double Applications of Cardiac Markers of detection simultaneously |
| WO2019218562A1 (en) * | 2018-05-17 | 2019-11-21 | 华南理工大学 | Glucose sensor electrode, preparation method therefor and use thereof |
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| US20100116691A1 (en) * | 2008-11-07 | 2010-05-13 | University Of Connecticut | Biosensor for continuous monitoring of metabolites and proteins and methods of manufacture thereof |
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2011
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| JPH04253744A (en) * | 1991-02-04 | 1992-09-09 | Showa Denko Kk | Conductive polymeric material and its production |
| US20100116691A1 (en) * | 2008-11-07 | 2010-05-13 | University Of Connecticut | Biosensor for continuous monitoring of metabolites and proteins and methods of manufacture thereof |
Non-Patent Citations (4)
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103954660A (en) * | 2014-04-14 | 2014-07-30 | 华南理工大学 | Enzyme biosensor for detecting cholesterol as well as preparation method and application of biosensor |
| CN103954660B (en) * | 2014-04-14 | 2016-06-22 | 华南理工大学 | Enzyme biologic sensor of a kind of cholesterol detection and preparation method thereof and application |
| CN104034778A (en) * | 2014-06-18 | 2014-09-10 | 武汉工程大学 | Chitosan-ionic liquid-graphene-enzyme composite membrane modified electrode and preparation method thereof |
| CN104049016A (en) * | 2014-06-18 | 2014-09-17 | 武汉工程大学 | Graphene-polypyrrole-ion liquid-enzyme composite film modified electrode and preparation method thereof |
| CN105645523A (en) * | 2016-01-07 | 2016-06-08 | 西安建筑科技大学 | Method for preparing polypyrrole/chitosan composite electrode |
| CN105645523B (en) * | 2016-01-07 | 2018-05-11 | 西安建筑科技大学 | A kind of method for preparing polypyrrole/chitosan combination electrode |
| CN107033349A (en) * | 2017-03-30 | 2017-08-11 | 青岛科技大学 | A kind of preparation method and applications of polypyrrole/nano platinum particle composite |
| CN107033349B (en) * | 2017-03-30 | 2019-08-30 | 青岛科技大学 | A kind of preparation method and applications of polypyrrole/nano platinum particle composite material |
| WO2019218562A1 (en) * | 2018-05-17 | 2019-11-21 | 华南理工大学 | Glucose sensor electrode, preparation method therefor and use thereof |
| US11788984B2 (en) | 2018-05-17 | 2023-10-17 | South China University Of Technology | Glucose sensor electrode, preparation method therefor and use thereof |
| CN110411951A (en) * | 2019-08-13 | 2019-11-05 | 信阳师范学院 | A kind of preparation method of the Photoelectrochemistrbiosensor biosensor for the double Applications of Cardiac Markers of detection simultaneously |
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| CN102262114B (en) | 2013-06-19 |
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