CN103926282B - A kind of detection method of the hydrogen peroxide preparing enzyme sensor - Google Patents
A kind of detection method of the hydrogen peroxide preparing enzyme sensor Download PDFInfo
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Abstract
A kind of detection method of the hydrogen peroxide preparing enzyme sensor, the method utilizes the horseradish peroxidase high catalytic performance to hydrogen peroxide, the toluidine blue graphene complex signal amplification to electrode catalyst hydrogen peroxide, the characteristics such as the excellent electric conductivity of Graphene and bigger serface, using horseradish peroxidase modified electrode as working electrode, reference electrode is Ag/AgCl electrode, and auxiliary electrode is platinum electrode, composition three-electrode system, it is achieved the highly sensitive detection to hydrogen peroxide；The graphenic surface that described method is supported on the non-covalent functionalization of organic dyestuff by electropolymerization enzyme prepares enzyme sensor.The graphenic surface that the present invention is supported on the non-covalent functionalization of organic dyestuff by electropolymerization enzyme prepares enzyme sensor, owing to the Graphene of functionalization has good chemical property, is introduced in enzyme sensor the performance considerably improving enzyme sensor.The present invention is applicable to enzyme sensor and measures hydrogen peroxide.
Description
Technical field
The present invention relates to the detection method of a kind of hydrogen peroxide preparing enzyme sensor, especially relate to the detection method of a kind of peroxide preparing enzyme sensor based on Graphene-organic dyestuff-horseradish peroxidase electropolymerization, the invention belongs to bio-sensing and technical field of electroanalytical chemistry detection.
Background technology
Graphene is the two-dimentional carbonaceous new material neatly arranged by hexagonal lattice by carbon atom, there is the characteristics such as big specific surface area, high electric conductivity, preferable mechanical stability and good biocompatibility so that it is there is well application in electrochemical biosensor field.But owing to the strong π-π effect between the lamella of Graphene makes its dispersibility in the solution be severely impacted, it is easy to aggregate and precipitate, limit its application in electrochemica biological sensor, it is therefore necessary to Graphene is carried out covalent functionalization or non-covalent functionalization to its modification to realize Graphene dispersion in the solution.Covalent functionalization can destroy the original architectural feature of Graphene so that it is intrinsic performance is influenced to different extents.Rather than covalent functionalization can preferably keep the proper property of Graphene, receives extensive concern the most in recent years.
Thionine, toluidine blue and methylene blue etc. can be as the organic dye molecule non-covalent modification Graphenes of oxidoreduction electron mediator, on the one hand can promote Graphene dispersion in the solution, on the other hand electrocatalysis characteristic excellent to specific surface area big for Graphene, high electric conductivity, good biocompatibility and electron mediator and quick electron transmission performance be combined and can develop highly sensitive electrochemical sensor.
In electrochemica biological sensor, enzyme sensor is the most representational, has that selectivity is good, fast response time and a highly sensitive advantage.Fixation techniques for enzyme is core prepared by enzyme sensor, and the method such as multiple method such as absorption, covalent cross-linking, sol-gel, layer assembly and electropolymerization has been used for enzyme immobilizatio.Electropolymerization has simple and film strong interference immunity the advantage of method and is widely used in enzyme sensor field.Pyrroles, aniline, organic dyestuff thionine and toluidine blue have been used for Electropolymerizatioimmobilization immobilization enzyme in enzyme sensor.
So far, the non-covalent functionalization graphene of organic dye molecule electron mediator has no report for the research of enzyme biologic sensor, and the present invention builds Hydrogen Peroxide Biosensor by electropolymerization organic dyestuff immobilized HRP on the graphene modified basic electrode of the non-covalent functionalization of organic dyestuff electron mediator.The method is loaded with organic dye electron mediator and horseradish peroxidase at graphenic surface, and on the one hand the high conductivity of Graphene is conducive to the most effectively transmission of electronics thus improves the sensitivity of enzyme electrode；On the other hand the Graphene of high surface area can load the amount of electron mediator and HRP relatively greatly, this sensitivity being conducive to improving enzyme electrode further.
Summary of the invention
It is an object of the invention to, the sensitivity for the enzyme electrode method of detection hydrogen peroxide at present is relatively low, it is provided that a kind of electropolymerization based on Graphene-organic dyestuff-horseradish peroxidase prepares the method for the detection hydrogen peroxide of enzyme sensor；Electrode surface at the non-covalent functionalization graphene of organic dyestuff, it is prepared for the biosensor detection for hydrogen peroxide, a kind of method setting up new electrochemical method based on horseradish peroxidase detection hydrogen peroxide by electropolymerization method immobilized HRP.
Realization the technical scheme is that, the inventive method utilizes the horseradish peroxidase high catalytic performance to hydrogen peroxide, toluidine blue-the graphene complex signal amplification to electrode catalyst hydrogen peroxide, the characteristics such as the excellent electric conductivity of Graphene and bigger serface, using horseradish peroxidase modified electrode as working electrode, reference electrode is Ag/AgCl electrode, and auxiliary electrode is platinum electrode, composition three-electrode system, it is achieved the highly sensitive detection to hydrogen peroxide；The graphenic surface that the present invention is supported on the non-covalent functionalization of organic dyestuff by electropolymerization enzyme prepares enzyme sensor.
The present invention proposes the detection method of a kind of hydrogen peroxide preparing enzyme sensor, and described method step is as follows:
(1) with graphite powder as raw material, Hummers is passed through
Oxidizing process prepares graphene oxide, is reduced by hydrazine, prepares Graphene.
(2) by Graphene and the organic dyestuff (toluidine blue of 0.2～1.0 mmol/L of 0.5～2.0 mmol/L, thionine, Nile blue) mixing, ultrasonic 10～24 h, prepare Graphene-organic dyestuff complex, wash with water after Li Xin, by Graphene-organic dyestuff complex use water dialysis 12～24 h, remove unreacted organic dyestuff.
(3) Graphene-organic dyestuff complex taking 5～20 μ l drips uniformly in clean glassy carbon electrode surface, naturally dries, rinse well with deionized water under room temperature, obtains Graphene-organic dyestuff modified electrode.
(3) Graphene-organic dyestuff modified electrode is placed in the solution of horseradish peroxidase of the organic dyestuff containing 0.2～1.0 mmol/L and 1.0～4.0 mg/mL, 5～50 circles are scanned in-0.7～0.8 V cyclic voltammetry, sweep speed 50～200 mV/s, obtaining electropolymerization organic dyestuff/horseradish peroxidase/Graphene-organic dyestuff modified electrode, this enzyme modified electrode is target enzyme sensor.
It is 5.0 × 10 that enzyme sensor of the present invention measures the range of linearity of hydrogen peroxide-7～1.4 × 10-5
Mol/L, sensitivity is 0.0392 A. L/mol.Utilizing same glass-carbon electrode to prepare five times, measure its response current to hydrogen peroxide, its relative standard deviation is 1.3%, utilizes same modified electrode to H2O2The relative standard deviation that ten times measure is 3.4%, illustrates that this electrode has good repeatability.This sensor is placed in the environment of 4 DEG C investigates its stability, after surrounding, still retains more than the 85% of response current value, shows that this electrode has good stability.
The invention has the beneficial effects as follows, the graphenic surface that the present invention is supported on the non-covalent functionalization of organic dyestuff by electropolymerization enzyme prepares enzyme sensor, owing to the Graphene of functionalization has good chemical property, it is introduced in enzyme sensor the performance considerably improving enzyme sensor.
The present invention is applicable to enzyme sensor and measures hydrogen peroxide.
Accompanying drawing explanation
Fig. 1 be in the present invention enzyme sensor 0.2
Mol/L PBS(pH 7.0) cyclic voltammogram, (a) does not adds hydrogen peroxide, and (b) adds the hydrogen peroxide of 1.0 mol/L；
Fig. 2 is the different modifying electrode chronoa mperometric plot to the hydrogen peroxide of dropping 0.50 mol/L continuously, (a) electropolymerization toluidine blue modified electrode, (b) electropolymerization toluidine blue/Graphene-toluidine blue modified electrode, (c) electropolymerization toluidine blue/horseradish peroxidase/graphene modified electrode, (d) electropolymerization toluidine blue/horseradish peroxidase/Graphene-toluidine blue modified electrode；
Fig. 3 is the enzyme sensor chronoa mperometric plot to hydrogen peroxide；
Fig. 4 is the response current calibration curve to concentration of hydrogen peroxide of enzyme sensor.
Detailed description of the invention
Below by specific embodiment, the present invention is described in detail, and following example contribute to those skilled in the art and are further appreciated by the present invention, but are never limited in protection scope of the present invention.
Embodiment 1
Sensor is prepared based on Graphene-organic dyestuff-horseradish peroxidase electropolymerization.
(1) with graphite powder as raw material, prepare graphene oxide by Hummers oxidizing process, reduced by hydrazine, prepare Graphene.
(2) by Graphene and the organic dyestuff Nile blue mixing of 1.0 mmol/L, ultrasonic 10 h of 1.5 mmol/L, preparing Graphene-Nile blue complex, wash with water after being centrifuged, dialyse 24 h by Graphene-Nile blue complex water, removes unreacted Nile blue.
(3) Graphene-Nile blue complex taking 10 μ l drips uniformly in clean glassy carbon electrode surface, naturally dries, rinse well with deionized water under room temperature, obtains Graphene-Nile blue modified electrode.
(4) Graphene-Nile blue modified electrode is placed in the Nile blue containing 1.0 mmol/L and 2.0
In the solution of the horseradish peroxidase of mg/mL, scanning 5 circles, sweep speed 50 mV/s in-0.7～0.8 V cyclic voltammetry, obtain electropolymerization Nile blue/horseradish peroxidase/Graphene-Nile blue modified electrode, this enzyme modified electrode is target enzyme sensor.
Embodiment 2
Sensor is prepared based on Graphene-organic dyestuff-horseradish peroxidase electropolymerization.
(1) with graphite powder as raw material, prepare graphene oxide by Hummers oxidizing process, reduced by hydrazine, prepare Graphene.
(2) by Graphene and the organic dyestuff toluidine blue mixing of 1.0 mmol/L of 1.5 mmol/L, ultrasonic 10 h, prepare Graphene-toluidine blue complex, wash with water after being centrifuged, dialyse 24 h by Graphene toluidine blue complex water, removes unreacted toluidine blue.
(3) Graphene-toluidine blue complex taking 10 μ l drips uniformly in clean glassy carbon electrode surface, naturally dries, rinse well with deionized water under room temperature, obtains Graphene-toluidine blue modified electrode.
(4) Graphene-toluidine blue modified electrode is placed in the toluidine blue containing 1.0 mmol/L and 2.0
In the solution of the horseradish peroxidase of mg/mL, 5 circles are scanned in-0.7～0.8 V cyclic voltammetry, sweep speed 50 mV/s, obtains electropolymerization toluidine blue/horseradish peroxidase/Graphene-toluidine blue modified electrode, and this enzyme modified electrode is target enzyme sensor.
Embodiment 3
Sensor is prepared based on Graphene-organic dyestuff-horseradish peroxidase electropolymerization.
(1) with graphite powder as raw material, prepare graphene oxide by Hummers oxidizing process, reduced by hydrazine, prepare Graphene.
(2) by Graphene and the organic dyestuff toluidine blue mixing of 0.5 mmol/L of 1.0 mmol/L, ultrasonic 12 h, prepare Graphene-toluidine blue complex, wash with water after being centrifuged, dialyse 24 h by Graphene toluidine blue complex water, removes unreacted toluidine blue.
(3) Graphene-toluidine blue complex taking 5 μ l drips uniformly in clean glassy carbon electrode surface, naturally dries, rinse well with deionized water under room temperature, obtains Graphene-toluidine blue modified electrode.
(4) Graphene-toluidine blue modified electrode is placed in the toluidine blue containing 0.5 mmol/L and 3.0
In the solution of the horseradish peroxidase of mg/mL, 20 circles are scanned in-0.7～0.8 V cyclic voltammetry, sweep speed 100 mV/s, obtains electropolymerization toluidine blue/horseradish peroxidase/Graphene-toluidine blue modified electrode, and this enzyme modified electrode is target enzyme sensor.
Embodiment 4
The enzyme sensor that embodiment 3 obtains is used for electro-chemical test:
(1) cyclic voltammetry of enzyme sensor.
Being working electrode by enzyme modified electrode, reference electrode is Ag/AgCl electrode, and auxiliary electrode is platinum electrode；End liquid is 0.2
Mol/L PBS(pH 7.0) and added the hydrogen peroxide of 1.0 mol/L；Scanning speed is 0.1 V/s.Cyclic voltammogram is shown in Fig. 1, as seen from Figure 1, after adding hydrogen peroxide, the peak current of the reduction peak of toluidine blue increases, the peak current of oxidation peak reduces, illustrating that enzyme modified electrode creates catalysis reduction to hydrogen peroxide, catalytic current is mainly produced by horseradish peroxidase enzyme catalytic reduction hydrogen peroxide.
(2) comparison of different modifying electrode catalyst reduction hydrogen peroxide.Use chronoamperometry, it is working electrode by electropolymerization toluidine blue modified electrode, electropolymerization toluidine blue/Graphene-toluidine blue modified electrode, electropolymerization toluidine blue/horseradish peroxidase/graphene modified electrode and electropolymerization toluidine blue/horseradish peroxidase/Graphene-toluidine blue modified electrode respectively, reference 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-0.30
V, under magnetic stirring, is continuously added to the hydrogen peroxide of 0.50 mol/L, and measurement result is shown in Fig. 2.As it is clear from fig. 2 that electropolymerization toluidine blue/horseradish peroxidase/Graphene-toluidine blue modified electrode is optimal to the catalytic effect of hydrogen peroxide, toluidine blue-graphene complex has signal amplification to electrode catalyst hydrogen peroxide.
(3) chrono-amperometric of hydrogen peroxide is tested by enzyme sensor.Being working electrode by enzyme modified electrode, reference 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-0.30 V, under magnetic stirring, drips the hydrogen peroxide of 0.50 mol/L continuously, and measurement result is shown in Fig. 3.The range of linearity measuring hydrogen peroxide is 5 × 10– 7
Mol/L～3.22 × 10– 4Mol/L, sensitivity is 0.0392 A. L/mol.This sensor is placed in the environment of 4 DEG C, after surrounding, still retains more than the 85% of response current value.
Claims (3)
1. the detection method of the hydrogen peroxide preparing enzyme sensor, it is characterised in that described method utilizes
The horseradish peroxidase high catalytic performance to hydrogen peroxide, toluidine blue-graphene complex is to electrode catalyst
The signal amplification of hydrogen peroxide, the characteristic such as the excellent electric conductivity of Graphene and bigger serface, by peppery
Root peroxide enzyme modified electrode is as working electrode, and reference electrode is Ag/AgCl electrode, and auxiliary electrode is
Platinum electrode, forms three-electrode system, it is achieved the highly sensitive detection to hydrogen peroxide；Described method passes through voltolisation
The graphenic surface that conjunction is supported on the non-covalent functionalization of toluidine blue enzyme prepares enzyme sensor；
Concretely comprising the following steps of described method:
(1) with graphite powder as raw material, prepare graphene oxide by Hummers oxidizing process, pass through hydrazine
Reduction, prepares Graphene；
(2) Graphene of 0.5～2.0mmol/L and the toluidine blue of 0.2～1.0mmol/L are mixed,
Ultrasonic 10～24h, prepare Graphene-toluidine blue complex, wash with water, by Graphene-toluene after being centrifuged
Amine indigo plant complex use water dialysis 12～24h, removes unreacted toluidine blue；
(3) Graphene-toluidine blue complex taking 5～20 μ l drips uniformly at clean glass-carbon electrode table
Face, dries under room temperature naturally, rinses well with deionized water, obtains Graphene-toluidine blue modified electrode；
(4) Graphene-toluidine blue modified electrode is placed in the solution of toluidine blue and horseradish peroxidase
In, it is circulated voltammetry scanning, obtains electropolymerization toluidine blue/horseradish peroxidase/Graphene-toluidines
Blue modified electrode, this enzyme modified electrode is target enzyme sensor.
The detection method of a kind of hydrogen peroxide preparing enzyme sensor the most according to claim 1, its
Being characterised by, described cyclic voltammetry scanning voltage is-0.7～0.8V；Cyclic voltammetry scanning 5～50 circle,
Sweep speed 50～200mV/s.
The detection method of a kind of hydrogen peroxide preparing enzyme sensor the most according to claim 1, its
Being characterised by, described toluidine blue solution concentration is 0.2～1.0mmol/L；The solution of horseradish peroxidase
Concentration is 1.0～4.0mg/Ml.
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| CN105261761B (en) * | 2015-09-07 | 2017-08-25 | 华南理工大学 | A kind of biological fuel cell enzyme modification anode and preparation and application based on graphene |
| CN105866221B (en) * | 2016-01-29 | 2018-09-07 | 辽宁师范大学 | The electrochemical sensor of reduced hemoglobin can be catalyzed |
| CN107180706A (en) * | 2017-06-14 | 2017-09-19 | 福州大学 | The preparation method and application of dyefunctionalized grapheme/polyaniline composite material |
| CN109374704B (en) * | 2018-11-01 | 2020-07-07 | 华东交通大学 | Thrombin detection method based on metal ion coordination-molecular imprinting sensor |
| CN111007126A (en) * | 2019-12-16 | 2020-04-14 | 浙江清华柔性电子技术研究院 | Flexible sensor electrode preparation method, flexible sensor electrode and flexible sensor |
| CN112285181A (en) * | 2020-10-23 | 2021-01-29 | 徐州工业职业技术学院 | Preparation method of enzyme sensor for realizing hydrogen peroxide detection |
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| CN101349667A (en) * | 2007-07-16 | 2009-01-21 | 中国科学院化学研究所 | Electrochemical detection device of physiological active substance and special-purpose electrochemical sensor preparation method thereof |
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Non-Patent Citations (2)
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