CN103954666A - Preparation method for enzyme sensor and method for determining hydrogen peroxide - Google Patents
Preparation method for enzyme sensor and method for determining hydrogen peroxide Download PDFInfo
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- CN103954666A CN103954666A CN201410212146.2A CN201410212146A CN103954666A CN 103954666 A CN103954666 A CN 103954666A CN 201410212146 A CN201410212146 A CN 201410212146A CN 103954666 A CN103954666 A CN 103954666A
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Abstract
The invention relates to a preparation method for an enzyme sensor and a method for determining hydrogen peroxide. According to the method, a high catalytic performance of horse radish peroxidase to hydrogen peroxide is used and a signal enhancement effect of a carbon nano tube is utilized. According to the method, the enzyme sensor is prepared by loading hydrotalcite-enzyme on the surface of a carbon nano tube modified basic electrode through electrolytic deposition; a simple electrolytic deposition method is used for preparing hydrotalcite and fixing the horse radish peroxidase on the surface of an electrode so that the enzyme is tightly loaded on the surface of the electrode; the fixation of the enzyme and direct electron transmission of the enzyme are easy to realize.
Description
Technical field
The present invention relates to enzyme sensor and Electroanalytical Chemistry detection technique field, relate in particular to a kind of preparation method and the mensuration thereof of hydrotalcite as the enzyme sensor of carrier mensuration hydrogen peroxide of take.
Background technology
The hydrotalcite lamellar compound that to be a class consist of the tradable negative ion of positively charged metal hydroxides and layer and interlayer filling.Due to the feature such as hydrotalcite has strong adsorbability, specific surface area is large, biocompatibility is good and ion-exchange performance is good, get more and more people's extensive concerning in recent years always, and be applied in enzyme sensor as in the carrier of immobilised enzymes and chemically modified electrode as dressing agent.But because the weak inductive of hydrotalcite is unfavorable for the electronics transmission of hydrotalcite modified electrode, reduced the chemical property of electrode material, limited its greatly developing in electrochemical field.Recently, the nano material that golden nanometer particle, carbon nano-tube and Graphene etc. have a satisfactory electrical conductivity is incorporated into and in hydrotalcite modified electrode, improves its chemical property.As preparing golden nanometer particle-hydrotalcite composite nano materials by coprecipitation method, Wang etc. builds the modified electrode of measuring methyl alcohol, synergy due to golden nanometer particle and hydrotalcite, the peak current of this electrode catalyst Oxidation of Methanol is much larger than peak current (the Wang Y. of hydrotalcite modified electrode, Zhang D., Tang M., Xu S., Li M.
electrochimica Acta,
2010, 55:4045-4049.).
Since carbon nano-tube self-discovery, with its unique structure, galvanochemistry and mechanical property, receive much concern, because its diameter is little, high surface energy and Atomic coordinate are not enough, to making, the Surface atomic mobility of carbon nano-tube is very high, and electronics transferance very easily occurs, due to its unique structure, making it have large specific surface area and good biocompatibility, is good electrochemical nano material.
Hydrogen peroxide is a kind of important chemical products, also participates in the enzymatic reaction of peroxidase simultaneously, and it has great importance in the quantitative measurement in biology, environmental protection, food, medicine and the field such as industrial.With respect to traditional hydrogen peroxide determination method as methods such as UV-VIS spectrophotometry, chemiluminescence and fluorescence, electrochemical sensor method based on enzyme electrode, highly sensitive because of it, fast response time, the feature that selectivity is good, the parent who is subject to numerous researchers looks at.As Chen etc. is fixed on glass-carbon electrode surface by drop-coating by horseradish peroxidase and nickel aluminum hydrotalcite, the enzyme sensor of formation determination hydrogen peroxide (Chen X., Fu C., Wang Y., Yang W., Evans D.G., Biosensors and Bioelectronics, 2008,24:356-361), but due to the shortcoming in the method for immobilised enzymes, make enzyme be easy to come off, be subject to the impact of environment large, limited its application.
At present, the carrier that the hydrotalcite of take is immobilised enzymes is prepared hydrogen peroxide sersor and for detection of the report of hydrogen peroxide, be all first to pass through coprecipitation or hydro-thermal method synthetic hydrotalcite, then adopt drop-coating or layer assembly legal system for hydrogen peroxide sersor.Said method is loaded down with trivial details, complicated time-consuming, patent of the present invention is fixed on horseradish peroxidase in hydrotalcite supports, to prepare hydrogen peroxide sersor by simple electrodeposition process, by simple electrodeposition process, prepare hydrotalcite and horseradish peroxidase is fixed on to electrode surface makes enzyme load on closely electrode surface, be conducive to the immobilization of enzyme and the direct electron transfer of enzyme; In addition, patent of the present invention is incorporated into basic electrode surface by carbon nano-tube, improves the electric conductivity of hydrotalcite modified electrode and improves the performance of enzyme sensor.
Summary of the invention
The object of the invention is, for take at present the shortcoming of poorly conductive of complicated, the loaded down with trivial details and hydrotalcite modified electrode of method that hydrotalcite prepares hydrogen peroxide sersor as carrier, having prepared on carbon nano tube modified basic electrode surface by a simple step electrodeposition process, take hydrogen peroxide sersor that hydrotalcite is carrier for detection of hydrogen peroxide.
Realizing technical scheme of the present invention is, the present invention by the method that drip to be coated with first by carbon nano tube modified in electrode surface, then by a step electrodeposition process, hydrotalcite and horseradish peroxidase are fixed on to carbon nano tube modified electrode surface, utilize the direct electron transfer of horseradish peroxidase to the catalytic reduction of hydrogen peroxide and enzyme, set up a kind of method of new mensuration hydrogen peroxide.
The present invention be take hydrotalcite and is prepared the preparation method of enzyme sensor as carrier, and described method step is as follows:
(1) with micro syringe, get 0.3～2.0 scattered mg/mL carbon nano tube suspension of 2～15 μ l and drip uniformly on clean glass-carbon electrode surface, at room temperature naturally dry, with deionized water, rinse well, obtain carbon nano tube modified electrode.
(2) first preparation is containing the electrodeposit liquid of cobalt nitrate 15～25 mmol/L, aluminium nitrate 5～10 mmol/L, potassium nitrate 0.1～0.5 mol/L and horseradish peroxidase 0.3～1.5 mg/mL, then carbon nano tube modified electrode is placed in to electrodeposit liquid and carries out potentiostatic electrodeposition under-0.6～-1.2 V, time is 10～80s, after finishing, deposition rinses well with deionized water, obtain hydrotalcite-horseradish peroxidase/carbon nano tube modified electrode, this horseradish peroxidase modified electrode is the enzyme sensor of measuring hydrogen peroxide.
Hydrotalcite is take in the present invention, and as carrier is prepared enzyme sensor, to detect the method for hydrogen peroxide as follows:
The present invention utilizes horseradish peroxidase to the direct electron transfer between the catalytic reduction of hydrogen peroxide and enzyme and electrode, using aforementioned horseradish peroxidase modified electrode as working electrode, contrast electrode is Ag/AgCl electrode, auxiliary electrode is platinum electrode, form three-electrode system, can realize the detection to hydrogen peroxide.
The range of linearity that this sensor is measured hydrogen peroxide is 2.5 * 10
-6～7.85 * 10
-4mol/L, detects and is limited to 1.6 * 10
-6mol/L, sensitivity is 0.00881 AL/mol.With 5 modified electrodes with a collection of preparation to 0.25mmol/L H
2o
2measure, its relative standard deviation is 3.2%.Adopt same modified electrode to carry out 5 times to hydrogen peroxide and detect, its relative standard deviation to hydrogen peroxide response is 2.1%.Enzyme modified electrode is at 0.25mmol/L H
2o
2the environment that is placed in 4 ℃ is investigated its stability, after surrounding, still retains 83% of response current value.Show that this electrode has good reappearance and stability.
The invention has the beneficial effects as follows, the present invention utilizes the bigger serface of carbon nano-tube, good electric conductivity and biocompatibility, on carbon nano tube modified basic electrode surface, horseradish peroxidase is loaded on hydrotalcite, to have realized the Direct Electrochemistry of enzyme and for measuring hydrogen peroxide by a step electrodeposition process.
Accompanying drawing explanation
Fig. 1 is enzyme modified electrode in the present invention cyclic voltammogram in 0.2 mol/L PBS (pH 7.0), (a) does not add hydrogen peroxide, (b) adds 125 μ mol/L hydrogen peroxide;
Fig. 2 is the cyclic voltammetry curve of different modifying electrode in the present invention, (a) hydrotalcite modified electrode, (b) hydrotalcite/carbon nano tube modified electrode, (c) horseradish peroxidase/carbon nano tube modified electrode, (d) hydrotalcite-horseradish peroxidase/carbon nano tube modified electrode;
Fig. 3 is the chronoa mperometric plot of enzyme modified electrode to hydrogen peroxide;
The calibration curve of the current-responsive of Fig. 4 enzyme modified electrode to concentration of hydrogen peroxide.
Embodiment
Below by specific embodiment, the present invention is described in detail, and following examples contribute to those skilled in the art further to understand the present invention, but never limit the scope of the invention.
Embodiment 1
The hydrotalcite of take is prepared enzyme sensor as carrier.
(1) with micro syringe, get 0.5 scattered mg/mL carbon nano tube suspension of 3 μ l and drip uniformly on clean glass-carbon electrode surface, at room temperature naturally dry, with deionized water, rinse well, obtain carbon nano tube modified electrode.
(2) first preparation is containing the electrodeposit liquid of cobalt nitrate 15 mmol/L, aluminium nitrate 5 mmol/L, potassium nitrate 0.1 mol/L and horseradish peroxidase 0.3 mg/mL, then carbon nano tube modified electrode is placed in to electrodeposit liquid and under-0.6 V, carries out potentiostatic electrodeposition, time is 80s, after finishing, deposition rinses well with deionized water, obtain hydrotalcite-horseradish peroxidase/carbon nano tube modified electrode, this horseradish peroxidase modified electrode is the enzyme sensor of measuring hydrogen peroxide.
Embodiment 2
The hydrotalcite of take is prepared enzyme sensor as carrier.
(1) with micro syringe, get 0.5 scattered mg/mL carbon nano tube suspension of 5 μ l and drip uniformly on clean glass-carbon electrode surface, at room temperature naturally dry, with deionized water, rinse well, obtain carbon nano tube modified electrode.
(2) first preparation is containing the electrodeposit liquid of cobalt nitrate 21 mmol/L, aluminium nitrate 7 mmol/L, potassium nitrate 0.2 mol/L and horseradish peroxidase 0.5 mg/mL, then carbon nano tube modified electrode is placed in to electrodeposit liquid and under-0.8 V, carries out potentiostatic electrodeposition, time is 70s, after finishing, deposition rinses well with deionized water, obtain hydrotalcite-horseradish peroxidase/carbon nano tube modified electrode, this horseradish peroxidase modified electrode is the enzyme sensor of measuring hydrogen peroxide.
Embodiment 3
The hydrotalcite of take is prepared enzyme sensor as carrier.
1) with micro syringe, get 1.0 scattered mg/mL carbon nano tube suspension of 5 μ l and drip uniformly on clean glass-carbon electrode surface, at room temperature naturally dry, with deionized water, rinse well, obtain carbon nano tube modified electrode.
(2) first preparation is containing the electrodeposit liquid of cobalt nitrate 22.5 mmol/L, aluminium nitrate 7.5 mmol/L, potassium nitrate 0.3 mol/L and horseradish peroxidase 1.0 mg/mL, then carbon nano tube modified electrode is placed in to electrodeposit liquid and under-0.9 V, carries out potentiostatic electrodeposition, time is 30s, after finishing, deposition rinses well with deionized water, obtain hydrotalcite-horseradish peroxidase/carbon nano tube modified electrode, this horseradish peroxidase modified electrode is the enzyme sensor of measuring hydrogen peroxide.
Embodiment 4
Electro-chemical test.
The enzyme modified electrode that embodiment 3 is obtained carries out electro-chemical test:
(1) cyclic voltammetry of enzyme modified electrode.
Enzyme modified electrode is as working electrode, and contrast electrode is Ag/AgCl electrode, and auxiliary electrode is platinum electrode; End liquid is 0.2 mol/L PBS (pH 7.0) and the hydrogen peroxide that has added 125 μ mol/L; Sweep velocity is 0.1 V/s.Cyclic voltammogram is shown in Fig. 1, as seen from Figure 1, adds after hydrogen peroxide, the peak current of reduction peak increases, the peak current of oxidation peak reduces, and illustrates that enzyme modified electrode has produced catalytic reduction to hydrogen peroxide, and catalytic current is that the horseradish peroxidase enzyme catalytic reduction hydrogen peroxide in enzyme electrode produces.
(2) cyclic voltammetric of different modifying electrode characterizes.
By hydrotalcite modified electrode, hydrotalcite/carbon nano tube modified electrode, horseradish peroxidase/carbon nano tube modified electrode and hydrotalcite-horseradish peroxidase/carbon nano tube modified electrode, be working electrode respectively, contrast electrode is Ag/AgCl electrode, and auxiliary electrode is platinum electrode; End liquid is 0.2 mol/L PBS (pH 7.0), and potential range is 0.4 ~-0.8 V, sweeps speed for 100m V/s; Cyclic voltammetry the results are shown in Figure 2.As can be seen from the figure, directly electro-deposition the modified electrode of hydrotalcite (curve is a) not have obvious redox peak to occur at this potential region; And there is a pair of less redox peak in hydrotalcite/carbon nano tube modified electrode (curve b), this be at electrode face finish one deck carbon nano-tube and the peak that occurs, now due to the effect of carbon nano-tube, makes its charged electrical rheology large; Horseradish peroxidase/carbon nano tube modified electrode (curve c) is after carbon nano tube surface has dripped one deck horseradish peroxidase,-0.097V and-there is a pair of obvious reversible redox peak in 0.293V, this is the reversible peak that Fe (II)/Fe (III) redox of horseradish peroxidase in PBS solution produces, but the method that makes horseradish peroxidase be fixed on carbon nano tube surface by drop-coating easily comes off when carrying out Electrochemical Detection, can cause the poor stability of experiment; Fixedly horseradish peroxidase is surperficial in carbon nano tube modified electrode by electro-deposition hydrotalcite method for hydrotalcite-horseradish peroxidase/carbon nano tube modified electrode (curve d), make the redox peak current of enzyme become larger, and also guaranteed the stability of experiment.
(3) the timing testing current of enzyme modified electrode
By hydrotalcite-horseradish peroxidase/carbon nano tube modified electrode, be working electrode, contrast electrode is Ag/AgCl electrode, and auxiliary electrode is platinum electrode; End liquid is 0.2 mol/L PBS (pH 7.0); Measuring current potential is-0.3 V, under magnetic agitation, drips continuously certain density hydrogen peroxide, and measurement result is shown in Fig. 3, Fig. 4.The range of linearity of measuring hydrogen peroxide is 2.5 * 10
-6～7.85 * 10
-4mol/L, detects and is limited to 1.6 * 10
-6mol/L, sensitivity is 0.00881 AL/mol.The relative standard deviation that replicate determination is 5 times is 2.1%, and the response current of measuring hydrogen peroxide after surrounding remains on more than 83%.
Claims (4)
1. a preparation method for enzyme sensor, is characterized in that, the concrete steps of described method are:
(1) with micro syringe, get 0.3～2.0 scattered mg/mL carbon nano tube suspension of 2～15 μ l and drip uniformly on clean glass-carbon electrode surface, at room temperature naturally dry, with deionized water, rinse well, obtain carbon nano tube modified electrode;
(2) first preparation is containing the electrodeposit liquid of cobalt nitrate 15～25 mmol/L, aluminium nitrate 5～10 mmol/L, potassium nitrate 0.1～0.5 mol/L and horseradish peroxidase 0.3～1.5 mg/mL, then carbon nano tube modified electrode is placed in to electrodeposit liquid and carries out potentiostatic electrodeposition under-0.6～-1.2 V, time is 10～80s, after finishing, deposition rinses well with deionized water, obtain hydrotalcite-horseradish peroxidase/carbon nano tube modified electrode, this horseradish peroxidase modified electrode is the enzyme sensor of measuring hydrogen peroxide.
2. the preparation method of a kind of enzyme sensor according to claim 1, it is characterized in that, described electrodeposit liquid is for containing cobalt nitrate 15～25 mmol/L, aluminium nitrate 5～10 mmol/L, potassium nitrate 0.1～0.5 mol/L and horseradish peroxidase 0.3～1.5 mg/mL.
3. the preparation method of a kind of enzyme sensor according to claim 1, is characterized in that, described electrodeposition condition is to carry out potentiostatic electrodeposition under-0.6～-1.2 V, and the time is 10～80s.
4. take enzyme sensor that hydrotalcite is carrier and detect the method for hydrogen peroxide for one kind, it is characterized in that, described method is utilized the catalytic performance of horseradish peroxidase to hydrogen peroxide, the signal humidification of carbon nano-tube, the characteristics such as the direct electron transfer of horseradish peroxidase, using horseradish peroxidase modified electrode as working electrode, contrast electrode is Ag/AgCl electrode, auxiliary electrode is platinum electrode, forms three-electrode system, realizes the Sensitive Detection to hydrogen peroxide.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109030599A (en) * | 2018-07-17 | 2018-12-18 | 华东交通大学 | A kind of preparation method of glucose oxidase sensor and its detection to glucose |
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| CN102141536A (en) * | 2010-12-10 | 2011-08-03 | 北京化工大学 | Composite material electrode based on carbon nano tubes as well as preparation method and application thereof |
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| CN102141536A (en) * | 2010-12-10 | 2011-08-03 | 北京化工大学 | Composite material electrode based on carbon nano tubes as well as preparation method and application thereof |
Non-Patent Citations (4)
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| ERIKA SCAVETTA, BARBARA BALLARIN, CLAUDIO CORTICELLI等: "An insight into the electrochemical behavior of Co/Al layered double hydroxide thin films prepared by electrodeposition", 《JOURNAL OF POWER SOURCES》 * |
| FENGNA XI, LIJUN LIU, ZHICHUN CHEN, XIANFU LIN: "One-step construction of reagentless biosensor based on chitosan-carbon nanotubes-nile blue-horseradish peroxidase biocomposite formed by electrodeposition", 《TALANTA》 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109030599A (en) * | 2018-07-17 | 2018-12-18 | 华东交通大学 | A kind of preparation method of glucose oxidase sensor and its detection to glucose |
| CN109030599B (en) * | 2018-07-17 | 2020-08-21 | 华东交通大学 | Preparation method of glucose oxidase sensor and detection of glucose by glucose oxidase sensor |
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