CN102565174A - Ionic liquid polyaniline modified electrode-electro chemical analysis system - Google Patents
Ionic liquid polyaniline modified electrode-electro chemical analysis system Download PDFInfo
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- CN102565174A CN102565174A CN2012100376699A CN201210037669A CN102565174A CN 102565174 A CN102565174 A CN 102565174A CN 2012100376699 A CN2012100376699 A CN 2012100376699A CN 201210037669 A CN201210037669 A CN 201210037669A CN 102565174 A CN102565174 A CN 102565174A
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Abstract
The invention relates to an electro chemical analysis system, in particular to the electro chemical analysis system for efficiently and selectively detecting Dopamine (DA), Ascorbic acid (AA) and Uric acid (UA) in a coexisting system of DA, AA and UA of human body serum by using an ionic liquid polyaniline modified electrode. Pure ionic liquid is used as supporting electrolyte, aniline is electrochemically polymerized by cyclic voltammetry, and the polyaniline modified electrode is used as a working electrode, so electrocatalytic oxidation and electrochemical differentiation of DA, AA and UA are realized. The system facilitates the activation of electrode surfaces, accelerates electron transferring, has high electrochemical activity on the electrocatalytic oxidation of substances, and improves the limit that a polyaniline film synthesized in an aqueous solution medium is only used under an acid condition, so the system can be used for directly detecting biological samples under neutral or slightly alkaline environments.
Description
Technical field
The present invention relates to a kind of electrochemical analysis system; Particularly relate to dopamine (dopamine (Dopamine in the ionic liquid polyaniline modified electrode efficient selective human body serum; DA), ascorbic acid (Ascorbic acid; AA) and the electrochemical analysis system of uric acid (Uric acid is in UA) the coexistence system).
Background technology
The Electrochemical Detection of three components is one of focus of research always in dopamine, ascorbic acid and the uric acid coexistence system. on general base electrode, electrochemical oxidation all can take place in three components, but spike potential is overlapped.Adopting chemically modified electrode is the effective way that realizes selective determination.Conducting polymer is a kind of new material with characteristics such as unique electrical conduction mechanism, discolourations, has broad application prospects at aspects such as chemically modified electrode, accumulator, electrochromic device, light emitting diode and immobilized enzymes.In numerous conducting polymers; Polyaniline is because have good inoxidizability and stability; And have unique doping behavior and excellent electrochemical reversibility, add that raw material is easy to get, synthetic method is simple, be considered to one of conducting polymer of tool using value.In the research of conducting polymer, electrochemical method is synthetic and the most frequently used method of research polyaniline film.Polyaniline modified electrode generally is (like H in the protonic acid aqueous solution medium
2SO
4, HCl solution), make through the electric polymerization reaction of aniline monomer.It is very responsive that to be its electrochemical activity change pH one big deficiency of kind electrode, only when strong acid condition (pH＜3.0), just have electroactive preferably, all can inactivation under neutrality or the alkali condition, limited to the application of this modified electrode in bioanalysis.In recent years along with the rise of Green Chemistry; Ionic liquid is as a kind of novel green solvent; Because of its unique advantage: fusing point is low, vapour pressure is little, dissolubility is good, viscosity is big, stability is high, electrochemical window is wide and ionic conductivity is good etc., has obtained widespread use in extraction, organic synthesis, catalysis, galvanochemistry and analytical chemistry field.As one type of novel non-aqueous media; Aspects such as electro-deposition, electropolymerization have been widely used in; Existing at present research shows that polyaniline film synthetic in anhydrous medium can improve its electrochemical activity, can in neutrality even slight alkali environment, remain unchanged to keep good electrochemical activity.Therefore, ionic liquid is the supporting electrolyte of one type of very promising polyaniline film electrochemical polymerization.
Summary of the invention
The present invention provides a kind of electrochemical analysis system of measuring ascorbic acid, dopamine and uric acid based on the ionic liquid polyaniline modified electrode; With ionic liquid as supporting electrolyte; Adopt cyclic voltammetry electrochemical polymerization aniline and obtain the polyaniline film modified electrode; This method with polyaniline modified electrode as working electrode; The employing cyclic voltammetry (Cyclic voltammetry, CV) (Differential pulse voltammetry DPV) measures ascorbic acid, dopamine and uric acid in neutrality even slight alkali environment simultaneously with the differential pulse voltammetry; Make three kinds of materials on this modified electrode, obtain the galvanochemistry separation, and efficient selective measured the dopamine in the human serum.
Concrete technical scheme of the present invention is following:
The present invention is a kind of ionic liquid polyaniline modified electrode-electrochemical analysis system; Utilize pure ionic liquid as supporting electrolyte; Utilize cyclic voltammetry electrochemical polymerization aniline; Utilize this polyaniline modified electrode as working electrode, realize the catalytic oxidation and the galvanochemistry differentiation of ascorbic acid, dopamine and uric acid.
Analytic system simple and fast of the present invention, favorable reproducibility, the polyaniline film of being modified evenly more helps the electrode surface activation than the level and smooth of conventional method, and the accelerated electron transmission shows better electrochemical activity to the catalytic oxidation of material.
PH value in the ionic liquid scalable polyaniline film microenvironment that the present invention mixes; Thereby can in neutrality even slight alkali environment, work; Electrochemical activity is high; Having improved polyaniline film synthetic in aqueous medium can only use this limitation under acid condition, can be used for directly detection under neutrality such as biological sample or the slight alkali environment.
The present invention has following advantage and effect:
The present invention utilize that the ionic liquid fusing point is low, vapour pressure is little, ionic conductivity and Heat stability is good, advantage such as electrochemical window is wide and viscosity is big; The polyaniline film that electropolymerization obtains in ion liquid medium is than more evenly level and smooth in general aqueous medium; More help the electrode surface activation; Accelerated electron transmits, and the catalytic oxidation of material is shown better electrochemical activity.
2. the present invention is based on the ionic liquid polyaniline modified electrode is working electrode; PH value in the ionic liquid scalable polyaniline film microenvironment of mixing; Thereby can in neutrality even slight alkali environment, work; And electrochemical activity is high, has improved that synthetic polyaniline film can only use this limitation in aqueous medium under acid condition, so can be used for directly detection under neutrality such as biological sample or the slight alkali environment.
Description of drawings
Fig. 1 is aniline electropolymerization CV figure in ionic liquid;
Fig. 2 is naked glass-carbon electrode and the CV figure of polyaniline modified electrode in pH=7 buffer solution;
Fig. 3 is that naked glass-carbon electrode and polyaniline modified electrode CV to AA in pH=7 buffer solution scheme;
Fig. 4 is that naked glass-carbon electrode and polyaniline modified electrode CV to DA in pH=7 buffer solution scheme;
Fig. 5 is that naked glass-carbon electrode and polyaniline modified electrode CV to UA in pH=7 buffer solution scheme;
Fig. 5 is polyaniline modified electrode CV figure to AA, DA and UA in pH=7.5 buffer solution;
Fig. 6 is polyaniline modified electrode DPV figure to AA, DA and UA in pH=7.5 buffer solution;
Fig. 7 be polyaniline modified electrode in pH=7.5 buffer solution to DA time-current-responsive figure;
Fig. 8 is a polyaniline modified electrode to DA time in the sample-current-responsive figure;
Be labeled as among Fig. 2:
The 1-ascorbic acid;
Be labeled as among Fig. 3:
The 2-dopamine;
Be labeled as among Fig. 4:
The 3-uric acid;
Be labeled as among Fig. 5:
The 1-ascorbic acid; The 2-dopamine; The 3-uric acid;
Be labeled as among Fig. 6:
The 1-ascorbic acid; The 2-dopamine; The 3-uric acid.
Specific embodiments
Do further bright specifically below in conjunction with Figure of description to the present invention:
Fig. 1 is for adopting the cyclic voltammogram of electrochemical polymerization aniline; The present invention is a supporting electrolyte with ionic liquid (1-butyl, 3-methyl imidazolium tetrafluoroborate), and aniline monomer concentration is 0.1M, and naked glass-carbon electrode is a working electrode, and naked glass-carbon electrode is used 0.3 μ m, α-Al of 0.05 μ m successively
2O
3Polishing, and successively clean 5min at absolute ethyl alcohol and deionized water for ultrasonic, subsequently at 0.1M H
2SO
4In, with 100mV.s
-1Sweep velocity between-0.5～1.2V, carry out cyclic voltammetry scan, stable up to CV figure, Ag/AgCl (saturated KCl solution) is a contrast electrode, platinum electrode is to electrode, in above-mentioned mixed solution with 50mV.s
-1Sweep velocity between-1.0～1.0V, circulate 30 weeks of volt scanning.Clean with deionized water after accomplishing, place air drying promptly to get the ionic liquid polyaniline modified electrode.
Fig. 2 is for adopting cyclic voltammetry; Use naked glass-carbon electrode and prepared ionic liquid polyaniline modified electrode as working electrode respectively; Ag/AgCl (saturated KCl solution) is a contrast electrode, and platinum electrode is to electrode, in the phosphate buffer solution of pH=7.0 to the catalytic oxidation cyclic voltammetric comparison diagram (wherein ascorbic acid concentrations is 100mg/kg) of ascorbic acid; Can find out that by comparison diagram the ionic liquid polyaniline modified electrode has fabulous catalytic oxidation effect to ascorbic acid.
Fig. 3 is for adopting cyclic voltammetry; Use naked glass-carbon electrode and prepared ionic liquid polyaniline modified electrode as working electrode respectively; Ag/AgCl (saturated KCl solution) is a contrast electrode, and platinum electrode is to electrode, in the phosphate buffer solution of pH=7.0 to the catalytic oxidation cyclic voltammetric comparison diagram (wherein dopamine concentration is 5mg/kg) of dopamine; Can find out that by comparison diagram the ionic liquid polyaniline modified electrode has fabulous catalytic oxidation effect to dopamine.
Fig. 4 is for adopting cyclic voltammetry; Use naked glass-carbon electrode and prepared ionic liquid polyaniline modified electrode as working electrode respectively; Ag/AgCl (saturated KCl solution) is a contrast electrode, and platinum electrode is to electrode, in the phosphate buffer solution of pH=7.0 to the catalytic oxidation cyclic voltammetric comparison diagram (wherein uric acid concentration is 100mg/kg) of uric acid; Can find out that by comparison diagram the ionic liquid polyaniline modified electrode has fabulous catalytic oxidation effect to uric acid.
Fig. 5 is for adopting cyclic voltammetry; As working electrode, Ag/AgCl (saturated KCl solution) is a contrast electrode with prepared ionic liquid polyaniline modified electrode, and platinum electrode is to electrode; (wherein ascorbic acid concentrations is 100mg/kg to the catalytic oxidation cyclic voltammogram of ascorbic acid, dopamine and uric acid in the phosphate buffer solution of pH=7.4; Dopamine concentration is 5mg/kg, and uric acid concentration is 100mg/kg), select the buffer solution of identical pH value for use with blood environment; Cyclic voltammetry can realize three's galvanochemistry differentiation basically, but effect is not very desirable.
Fig. 6 is for adopting the differential pulse voltammetry; With prepared ionic liquid polyaniline modified electrode as working electrode; Ag/AgCl (saturated KCl solution) is a contrast electrode, and platinum electrode is to electrode, and (wherein ascorbic acid concentrations is 100mg/kg to the catalytic oxidation differential pulse voltammogram of ascorbic acid, dopamine and uric acid in the phosphate buffer solution of pH=7.4; Dopamine concentration is 5mg/kg; Uric acid concentration is 100mg/kg), the differential pulse voltammetry can realize three's galvanochemistry differentiation fully, and should technology have the high response of selectivity to dopamine.
Fig. 7 is 0; .1V under the set potential and in the phosphate buffer solution of pH=7.4; The dopamine standard items that add 0.05mg/kg continuously, record ionic liquid polyaniline modified electrode is as the ampere response of working electrode to the dopamine catalytic oxidation, the electric current-time diagram of gained.
Fig. 8 is 0, the set potential of .1V down with the phosphate buffer solution of pH=7.4 in, add the blood serum sample behind the mark-on continuously, record ionic liquid polyaniline modified electrode responds the electric current-time diagram of gained as working electrode to the ampere of dopamine in the sample.
At last; It is also to be noted that what more than enumerate only is a specific embodiment of the present invention, obviously; The invention is not restricted to above embodiment; Many distortion can also be arranged, and all distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.
Claims (3)
1. ionic liquid polyaniline modified electrode-electrochemical analysis system; It is characterized in that; Utilize pure ionic liquid as supporting electrolyte; Utilize cyclic voltammetry electrochemical polymerization aniline, utilize this polyaniline modified electrode, realize the catalytic oxidation and the galvanochemistry differentiation of ascorbic acid, dopamine and uric acid as working electrode.
2. ionic liquid polyaniline modified electrode-electrochemical analysis system according to claim 1; It is characterized in that described analytic system simple and fast, favorable reproducibility; The polyaniline film of being modified is evenly more level and smooth than conventional method; More help the electrode surface activation, the accelerated electron transmission shows better electrochemical activity to the catalytic oxidation of material.
3. ionic liquid polyaniline modified electrode-electrochemical analysis system according to claim 1; It is characterized in that; PH value in the ionic liquid scalable polyaniline film microenvironment of mixing, thus can in neutrality even slight alkali environment, work, and electrochemical activity is high; Having improved polyaniline film synthetic in aqueous medium can only use this limitation under acid condition, can be used for directly detection under neutrality such as biological sample or the slight alkali environment.
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Cited By (7)
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| CN102967645A (en) * | 2012-11-26 | 2013-03-13 | 济南大学 | Multi-channel electrode sensor for detecting ovarian cancer markers |
| CN103227331A (en) * | 2013-03-29 | 2013-07-31 | 扬州大学 | Polyaniline-based pH sensitive anode intelligent switch and application thereof |
| CN103789809A (en) * | 2014-01-16 | 2014-05-14 | 南京理工大学 | Method for enhancing electrochemical activity of polyaniline film in neutral medium |
| CN106680354A (en) * | 2016-12-09 | 2017-05-17 | 菏泽学院 | Electrochemical method for determining methyl parahydroxybenzoats |
| CN107192752A (en) * | 2017-08-01 | 2017-09-22 | 信阳师范学院 | A kind of chemically modified electrode for being used for highly sensitive detection nonyl phenol and preparation method thereof |
| CN111474223A (en) * | 2020-04-22 | 2020-07-31 | 中国药科大学 | Electrochemical sensor for simultaneously detecting uric acid, ascorbic acid and dopamine, and preparation method and application thereof |
| CN114674888A (en) * | 2022-02-28 | 2022-06-28 | 宁夏医科大学 | Controllable polymer film modified electrode, preparation method thereof and luteolin detection method |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102967645A (en) * | 2012-11-26 | 2013-03-13 | 济南大学 | Multi-channel electrode sensor for detecting ovarian cancer markers |
| CN103227331A (en) * | 2013-03-29 | 2013-07-31 | 扬州大学 | Polyaniline-based pH sensitive anode intelligent switch and application thereof |
| CN103789809A (en) * | 2014-01-16 | 2014-05-14 | 南京理工大学 | Method for enhancing electrochemical activity of polyaniline film in neutral medium |
| CN103789809B (en) * | 2014-01-16 | 2016-01-13 | 南京理工大学 | A kind of method strengthening polyaniline film electrochemical activity in neutral medium |
| CN106680354A (en) * | 2016-12-09 | 2017-05-17 | 菏泽学院 | Electrochemical method for determining methyl parahydroxybenzoats |
| CN106680354B (en) * | 2016-12-09 | 2019-02-01 | 菏泽学院 | A kind of electrochemical method measuring methyl p-hydroxybenzoate |
| CN107192752A (en) * | 2017-08-01 | 2017-09-22 | 信阳师范学院 | A kind of chemically modified electrode for being used for highly sensitive detection nonyl phenol and preparation method thereof |
| CN107192752B (en) * | 2017-08-01 | 2019-07-05 | 信阳师范学院 | A kind of chemically modified electrode and preparation method thereof for highly sensitive detection nonyl phenol |
| CN111474223A (en) * | 2020-04-22 | 2020-07-31 | 中国药科大学 | Electrochemical sensor for simultaneously detecting uric acid, ascorbic acid and dopamine, and preparation method and application thereof |
| CN114674888A (en) * | 2022-02-28 | 2022-06-28 | 宁夏医科大学 | Controllable polymer film modified electrode, preparation method thereof and luteolin detection method |
| CN114674888B (en) * | 2022-02-28 | 2023-11-21 | 宁夏医科大学 | Controllable polymer film modified electrode, preparation method thereof and luteolin detection method |
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Application publication date: 20120711 |