CN103123331A - Preparation method of poly acriflavine-nickel composite modified electrode - Google Patents
Preparation method of poly acriflavine-nickel composite modified electrode Download PDFInfo
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- CN103123331A CN103123331A CN2012105701047A CN201210570104A CN103123331A CN 103123331 A CN103123331 A CN 103123331A CN 2012105701047 A CN2012105701047 A CN 2012105701047A CN 201210570104 A CN201210570104 A CN 201210570104A CN 103123331 A CN103123331 A CN 103123331A
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- acridine yellow
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Abstract
The invention discloses a preparation method of a poly acriflavine-nickel composite modified electrode. The preparation method disclosed by the invention comprises the following steps of: (1) activating an electrode; (2) preparing a poly acriflavine modified electrode: the steps of placing the activated electrode into an acriflavine phosphoric acid buffer solution with the pH value of 6 and the concentration of 1.0*10<-3>mol/>, and carrying out cyclic voltammetry polymerization for seven circles while electric potential ranges from minus 1.0V to 1.7V and a scanning speed is 100mV/s, so that the poly acriflavine modified electrode is obtained; and (3) preparing a poly acriflavine-nickel composite modified electrode, namely scanning the poly acriflavine modified electrode for 10 minutes in a nickel sulphate solution with the concentration of 0.1mol/L at a speed of 20mV/s while voltage ranges from minus 0.2V to 0.8V, so that the poly acriflavine-nickel composite modified electrode is obtained; and placing the poly acriflavine-nickel composite modified electrode into a phosphoric acid buffer solution with the pH of 6.0, and carrying out cyclic voltammetry scanning, so that an anodic peak appears at a voltage about 0.15V and electrochemical activity of the electrode is improved.
Description
Technical field
That the present invention relates to is the preparation method of a kind of poly-acridine yellow for determine uric acid-nickel composite modified electrode.
Background technology
Chemically modified electrode refer to by physics or chemical method the chemical group with certain function then on the conductive electrode surface, electrode surface is modified, cause certain microstructure at electrode surface, give electrode specific function.Can be divided into glass carbon modified electrode, graphitic carbon modified electrode, carbon paste modified electrode etc. according to the difference of electrode used therein material; Can be divided into absorbent-type modified electrode, covalent bond mould assembly modified electrode etc. according to the difference of the combination of dressing agent and electrode surface.Adopt cyclic voltammetry (Cyclic Voltammetry in experiment, CV), so-called cyclic voltammetry adopts the linear sweep experimental provision exactly, make electrode potential within the specific limits with constant pace of change scanning, usually adopt triangular wave potential scan signal, electrode current is called cyclic voltammogram with the curve map of potential change.The three-electrode system that experiment is adopted is comprised of working electrode, auxiliary electrode and contrast electrode, adopts the cyclic voltammetric method, can observe quickly on the one hand the wider interior electrode process that occurs of potential range, for electrode process study provides abundant information; Can infer reaction mechanism according to cyclic voltammetry curve again on the other hand.This method has become the normal experiment means that research material electrochemical properties extensively adopts.Differential pulse voltammetry (DPV) is to add a repetition pulse voltage signal on the linear potential of linear sweep voltammetry, and DPV has been owing to having reduced background current, thereby has higher detection sensitivity and lower detection limit.
Chemically modified electrode is highly sensitive, selectivity good, and is very active in the research in the fields such as biology sensor and environmental analysis. and at bare electrode finishing redox active film, can reduce the overpotential of electrode process, accelerate reaction rate, reduce the pollution on surface.Dyestuff conductive polymerized film modified electrode is because having the advantages such as good stability, selectivity are strong, and the irreversible electrochemical behavior that the polymer film of electrode surface can accelerate to produce on bare electrode has unique contribution aspect electrocatalysis.various azophenlyene, the phenothiazines organic dyestuff, good electrochemical activity is arranged self, its molecular structure mostly has a large heterocycle conjugated system, all with amino or the hydroxyl of electron donor, the electropolymerization of its electropolymerization process and amine or phenol is similar, the characteristics that namely have free radical polymerization, namely cause under a noble potential, form the dye molecule radical cation, the polymerization of free radical trigger monomer, carrying out along with scanning, polymkeric substance is in the continuous generation of electrode surface, showing as peak current on cyclic voltammogram constantly increases, thereby obtain the dye polymer modified electrode.After the dye molecule electropolymerization, original adsorptive power and chemical property have been changed.
Uric acid is one of final product of purine metabolism, is regarded as human body " rubbish ".The variation of its content in human body fluid, the situation that can fully reflect the functions such as human body metabolism, immunity. therefore, be necessary to formulate in routine analysis easy, method is determined it fast. the method for usually measuring UA has spectroscopic methodology, high performance liquid chromatography, electrochemical process etc., wherein electrochemical process has cheapness, fast and be convenient to the advantage such as Real-Time Monitoring, is used widely.
Have very high overpotential due to uric acid, and electrode is easily contaminated on common bare electrode, causes the reappearance measured very poor, these drawbacks limit the uric acid in the direct working sample of bare electrode.
Summary of the invention
Technical matters to be solved by this invention is that the preparation method of a kind of poly-acridine yellow-nickel composite modified electrode is provided for the deficiencies in the prior art.
Technical scheme of the present invention is as follows:
The preparation method of a kind of poly-acridine yellow-nickel composite modified electrode comprises the following steps:
(1) activation of electrode; With the Al of electrode at 0.03 μ m
2O
3Wear into minute surface on powder, use successively second alcohol and water ultrasonic cleaning 5min, obtain processing clean glass-carbon electrode standby; Then in the sulfuric acid solution of 0.5mol/L, the rate loop volt-ampere scanning 15min with 100mV/s under-1.0～1.6V current potential makes electrode activation;
(2) the poly-acridine yellow modified electrode of preparation: the electrode after activation is placed in 1.0 * 10 of pH=6
-3In mol/L acridine yellow phosphate buffer solution, cyclic voltammetric polymerase 17 circle in-1.0～1.7V potential range, sweep speed is 100mV/s, makes the poly-film modified electrode of acridine yellow;
(3) the poly-acridine yellow of preparation-nickel composite modified electrode: will gather the acridine yellow modified electrode in the nickel sulfate solution of 0.1mol/L in the scope of-0.2～0.8V with the rate scanning of 20mV/s 10 minutes, obtain poly-acridine yellow-nickel composite modified electrode; Poly-acridine yellow-nickel composite modified electrode is put into the phosphate buffer solution of pH=6.0, carry out cyclic voltammetry scanning, in 0.15V left and right appearance one oxidation peak, improved the electrochemical activity of electrode.
Preparation method of the present invention has the following advantages:
1, electrode preparation method is simple;
2, poly-acridine yellow coordinates with nickel ion, can give full play to advantage separately, and cooperative effect is obvious;
3, the thickness of film is easy to regulation and control:
4, the electrocatalysis characteristic of film modified electrod is easy to regulate by film thickness and doping ion;
5, modified electrode stable performance, the mensuration of electrode pair uric acid is cheap, quick.
Description of drawings
Fig. 1 is acridine yellow electropolymerization process cyclic voltammogram, c
(acridine yellow)=1.0 * 10
-3Mol/L sweep speed 100mV/spH=6.00;
Fig. 2 is the poly-acridine yellow-cyclic voltammogram of nickel composite modified electrode in phosphate buffer solution, sweep speed: 100mV/s:
Fig. 3 is the cyclic voltammogram of uric acid on bare electrode and poly-acridine yellow-nickel composite modified electrode; c
Uric acid=1.0 * 10
-3Mol/LpH=6.5 sweep speed: 100mV/s; A: poly-acridine yellow-nickel composite modified electrode; B: naked glass-carbon electrode;
Fig. 4 is the differential pulse voltammetry figure of variable concentrations uric acid on poly-acridine yellow-nickel composite modified electrode, and uric acid concentration is 1.0 * 10 from top to bottom
-3Mol/L, 1.0 * 10
-3Mol/L.8.0 * 10
-4Mol/L, 6.0 * 10
-4Mol/L, 5.0 * 10
-4Mol/L, 2.0 * 10
-4Mol/L, 1.0 * 10
-4Mol/L, 8.0 * 10
-5Mol/L, 5.0 * 10
-5Mol/L, 2.0 * 10
-5Mol/LpH=6.5
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.
The present invention is based on poly-acridine yellow and the formed composite membrane of nickel doping, have good electrochemical activity, and then affect the electrocatalysis characteristic of electrode.But when film was too thick, the thin-film electro resistive was large, reduced the electroactive of electrode.Therefore, obtaining best electroactive film is the key that preparation has the modified electrode of excellent properties.
The acridine yellow electrochemical polymerization is relevant with factors such as polymerization current potential, end liquid pH, polymerization times.Experimental result shows, the acridine yellow oxidizing potential is during lower than 0.8V, and the electrochemical polymerization reaction can not occur.The more different polymerization current potential upper limits (1.2,1.5,1.7V) find, along with the increase of the polymerization current potential upper limit, near 0.2V, oxidation peak current also constantly increases, and shows that poly-acridine yellow generates.Experimental selection polymerization current potential is-1.0～1.7V.Polymerization in the end of different pH values liquid, result show, acridine yellow in the PBS of pH=6.0 during polymerization, near 0.2V the oxidation peak current increase the most obvious, the modified electrode that makes electrochemical properties in liquid at the bottom of blank PBS is best, electrocatalysis characteristic is best.Polymerization time is longer, and the polymer film that acridine yellow forms at electrode surface will be thicker, if but polymer film is too thick, film resistance is increased, thereby affect electric conductivity and the electrocatalysis characteristic of electrode, and polymerization time is too short, the polymer film that can cause again polymerization to form is even not.The more different polymerization number of turns (5-10 circle), the experimental selection polymerization number of turns are 7 circles.
The preparation method that the present invention gathers acridine yellow-nickel composite modified electrode comprises the following steps:
(1) activation of glass-carbon electrode; With glass-carbon electrode at Al
2O
3Wear into minute surface on (0.03 μ m) powder, use successively second alcohol and water ultrasonic cleaning 5min, obtain processing clean glass-carbon electrode standby.Then in the sulfuric acid solution of 0.5mol/L, the rate loop volt-ampere scanning 15min with 100mV/s under-1.0～1.6V current potential makes electrode activation.
(2) the poly-acridine yellow modified electrode of preparation: the electrode after activation is placed in 1.0 * 10 of pH=6
-3In mol/L acridine yellow phosphate buffer solution, cyclic voltammetric polymerase 17 circle (Fig. 1) in-1.0～1.7V potential range, sweep speed is 100mV/s, makes the poly-film modified electrode of acridine yellow.
(3) the poly-acridine yellow of preparation-nickel composite modified electrode: will gather the acridine yellow modified electrode in the nickel sulfate solution of 0.1mol/L in the scope of-0.2～0.8V with the rate scanning of 20mV/s 10 minutes, obtain poly-acridine yellow-nickel composite modified electrode.To gather acridine yellow-nickel composite modified electrode and put into phosphate buffer solution (pH=6.0), carry out cyclic voltammetry scanning, in 0.15V left and right appearance one oxidation peak (Fig. 2), improve the electrochemical activity of electrode.
The mensuration of poly-acridine yellow-nickel composite modified electrode to uric acid:
With reference to figure 3, use respectively bare electrode and modified electrode 10
-3In the uric acid phosphate buffer solution of mol/L, in-0.2～0.8V potential range, carry out cyclic voltammetry scan, on poly-acridine yellow-nickel composite modified electrode, the oxidation peak current potential of uric acid is E
p.a=0.38V, the oxidation peak current potential on naked glass-carbon electrode is E
p.a=0.54V compares with naked glass-carbon electrode, and its oxidation peak current potential is negative moves 0.16V, and the redox peak current obviously increases, and has reduced the overpotential of the oxidizing process of uric acid.Illustrate that poly-acridine yellow-nickel modified electrode has accelerated uric acid and interelectrode electronics transfer rate, uric acid is had significant catalytic action, and peak current is along with in solution, the increase of uric acid being increased.
In order further to improve the sensitivity of this modified electrode, experiment adopts the differential pulse method to carrying out electro-chemical test in the variable concentrations uric acid.Poly-acridine yellow-nickel combination electrode is placed in the phosphate buffer solution of variable concentrations uric acid, in-0.2～0.8V potential range, records corresponding differential pulse method curve.Impulsive condition: the current potential increment is 0.005, and pulse height is 0.05V, and pulse width is 0.2s, and the recurrent interval is 0.1s, obtains differential pulse voltammetry figure (Fig. 4).Along with the continuous increase of uric acid concentration, peak current also constantly increases, and spike potential is constant.2.0 * 10
-5Mol/L～1.0 * 10
-3In the mol/L concentration range, the oxidation peak current of uric acid and concentration are good linear relationship, and equation of linear regression is i
p/ μ A=0.37375+0.00547c
Uric acid(r=0.99847), detect and be limited to 2.0 * 10
-6Mol/L.Thereby realize the mensuration to uric acid.
Should be understood that; for those of ordinary skills; can be improved according to the above description or conversion; for example; can be with gathering the film modified glass-carbon electrode determine uric acid of acridine yellow; the poly-film modified electro-conductive glass of acridine yellow (ITO) determination of electrode uric acid, and all these improve and conversion all should belong to the protection domain of claims of the present invention.
Claims (1)
1. the preparation method of poly-acridine yellow-nickel composite modified electrode, is characterized in that, comprises the following steps:
(1) activation of electrode; With the Al of electrode at 0.03 μ m
2O
3Wear into minute surface on powder, use successively second alcohol and water ultrasonic cleaning 5min, obtain processing clean glass-carbon electrode standby; Then in the sulfuric acid solution of 0.5mol/L, the rate loop volt-ampere scanning 15min with 100mV/s under-1.0～1.6V current potential makes electrode activation;
(2) the poly-acridine yellow modified electrode of preparation: the electrode after activation is placed in 1.0 * 10 of pH=6
-3In mol/L acridine yellow phosphate buffer solution, cyclic voltammetric polymerase 17 circle in-1.0～1.7V potential range, sweep speed is 100mV/s, makes the poly-film modified electrode of acridine yellow;
(3) the poly-acridine yellow of preparation-nickel composite modified electrode: will gather the acridine yellow modified electrode in the nickel sulfate solution of 0.1mol/L in the scope of-0.2～0.8V with the rate scanning of 20mV/s 10 minutes, obtain poly-acridine yellow-nickel composite modified electrode; Poly-acridine yellow-nickel composite modified electrode is put into the phosphate buffer solution of pH=6.0, carry out cyclic voltammetry scanning, in 0.15V left and right appearance one oxidation peak, improved the electrochemical activity of electrode.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109164154A (en) * | 2018-10-28 | 2019-01-08 | 桂林理工大学 | The preparation method and applications of poly- acridine orange modification ITO electrode |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005024408A1 (en) * | 2003-08-21 | 2005-03-17 | Colorado State University Research Foundation | Direct determination of carbohydrates, amino acids and antibiotics by microchip electrophoresis with pulsed amperometric detection |
| CN102507670A (en) * | 2011-09-30 | 2012-06-20 | 长沙三诺生物传感技术股份有限公司 | Electrochemical uric acid test strip and manufacturing method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005024408A1 (en) * | 2003-08-21 | 2005-03-17 | Colorado State University Research Foundation | Direct determination of carbohydrates, amino acids and antibiotics by microchip electrophoresis with pulsed amperometric detection |
| CN102507670A (en) * | 2011-09-30 | 2012-06-20 | 长沙三诺生物传感技术股份有限公司 | Electrochemical uric acid test strip and manufacturing method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109164154A (en) * | 2018-10-28 | 2019-01-08 | 桂林理工大学 | The preparation method and applications of poly- acridine orange modification ITO electrode |
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