CN102128865A - Method for detecting phenol compounds by using horseradish peroxidase-modified electrode - Google Patents
Method for detecting phenol compounds by using horseradish peroxidase-modified electrode Download PDFInfo
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- CN102128865A CN102128865A CN2010105614567A CN201010561456A CN102128865A CN 102128865 A CN102128865 A CN 102128865A CN 2010105614567 A CN2010105614567 A CN 2010105614567A CN 201010561456 A CN201010561456 A CN 201010561456A CN 102128865 A CN102128865 A CN 102128865A
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Abstract
The invention relates to a method for detecting phenol compounds by using an aluminum oxide nanoparticle/chitosan/horseradish peroxidase composite film-modified glassy carbon electrode and belongs to the technical field of electrochemical analysis detection. The key point of the method is to obtain the modified glassy carbon electrode which is equivalent to a current type biosensor by dispensing a certain amount of aluminum oxide nanoparticle/chitosan/horseradish peroxidase mixed solution on the surface of the glassy carbon electrode and use the aluminum oxide nanoparticle/chitosan/horseradish peroxidase composite film-modified glassy carbon electrode to quantitatively detect the phenol compounds. The method has the characteristics of quickness, sensitivity, accuracy, stability and the like.
Description
Technical field
The present invention relates to the complex film modified glass-carbon electrode of a kind of aluminium oxide nano particle/shitosan/horseradish peroxidase and measure the method for phenolic compound, belong to electrochemical analysis detection technique field.
Background technology
Phenolic compound is the big compounds of hydroxyl of ining succession on the aromatic hydrocarbon phenyl ring, and general formula is ArOH.Common phenol has phenol, catechol, p-dihydroxy-benzene etc.Phenolic compound can prepare series chemical products such as resin, dyestuff, pharmaceuticals, germifuge, explosive.But phenolic compound is bigger to environment and human beings'health harm, and therefore, phenolic compound is listed in " 129 kinds of priority pollutants blacklists " by American National Environmental Protection Agency.In recent years, the method for many survey phenol is developed, as ultraviolet spectrophotometry, vapor-phase chromatography, liquid phase chromatography and capillary electrophoresis etc.But the required instrument of these methods all compares expensive; operate more consuming time and complicated; be not suitable for on-the-spot the detection; and biosensor assay divides compounds to have characteristics such as simple to operate, that analysis speed is fast, detectability is low, and therefore development survey phenol biology sensor is significant for protection environment and human body health.
In surveying the phenol biology sensor, tyrosinase is a kind of enzyme commonly used, but the tyrosinase biology sensor can only be used for detecting the phenolic compound that has an empty ortho position at least.Equally, the biology sensor based on laccase only is fit to be used for measuring the phenolic compound that a free contraposition or a position are arranged.By comparison, the horseradish peroxidase biology sensor is all very sensitive for a large amount of phenolic compounds.Simultaneously, in surveying the process of phenol, the mechanism of the biology sensor that makes up based on horseradish peroxidase is different from tyrosinase and laccase biosensor.After the enzyme molecule was by dioxygen oxidation, tyrosinase and laccase were to be reduced by phenolic compound, and horseradish peroxidase is to pass through hydrogen-peroxide reduction.
Shitosan claims poly glucosamine, soluble chitin again, is the product of chitin behind the chemical treatment deacetylation, is a kind of natural cationic polymer, and is nontoxic.Shitosan has some rare physicochemical property, as high physical strength and water wettability, good film forming and biocompatibility.Therefore, shitosan is by the matrix of fixing as enzyme widely.
The fixing performance to biology sensor of enzyme plays important effect.Up to the present, horseradish peroxidase has been fixed on surfactant, on the various matrix such as polymkeric substance and inorganic material.In these matrix, inorganic material is owing to their regular texture, and characteristics such as good machinery, chemistry and thermal stability receive numerous researchers' fervent concern.Wherein, nano aluminium oxide also is the focus that people study always.In the present invention, use fixedly horseradish peroxidase of aluminium oxide nano particle, detailed research has been carried out in the performance and the application in phenolic compound is measured of prepared horseradish peroxidase biology sensor.
Summary of the invention
The objective of the invention is to utilize the complex film modified glass-carbon electrode of aluminium oxide nano particle/shitosan/horseradish peroxidase to make up and be equivalent to a kind of amperometric biosensor, be used for measuring the concentration of phenolic compound.
A kind of horseradish peroxidase modified electrode of the present invention is measured the method for phenolic compound, it is characterized in that having following process and step:
A. the pre-Liu Li of glass-carbon electrode: at first glass-carbon electrode is used 0.05mm Al
2O
3Burnishing powder and chamois leather polish, and throw to the light microscopic face, use distilled water, dilute nitric acid solution, absolute ethyl alcohol and redistilled water ultrasonic cleaning clean, stand-by then successively;
B. the preparation of the composite modified glass-carbon electrode of aluminium oxide nano particle/shitosan/horseradish peroxidase: at first take by weighing an amount of shitosan and be dissolved in the 0.1M acetum, and at room temperature ultrasonic 2h, obtain 0.2～0.6%(W/V, chitosan solution mg/ml); Then the appropriate amount of alumina nano particle is dispersed in above-mentioned 0.2～0.6%(W/V of 1ml, mg/ml) chitosan solution, and ultrasonic to even; In addition, with redistilled water preparation 6～10mg/ml horseradish peroxidase solution, this horseradish peroxidase solution is mixed with the above-mentioned volume ratio 1:1 that is dispersed with the chitosan solution of aluminium oxide nano particle, obtain aluminium oxide nano particle/shitosan/horseradish process enzyme mixed solution; This mixed solution of getting 4～8ml then drips and is applied to above-mentioned ready glass-carbon electrode surface, and dries in 4 ℃ refrigerator, places after a night stand-by;
C. to the electrochemical gaging of phenolic compound: utilize the above-mentioned complex film modified glass-carbon electrode of aluminium oxide nano particle/shitosan/horseradish peroxidase to be used as amperometric biosensor, phenolic compound is carried out electrochemical gaging, its assay method is as follows: utilize electrochemical workstation to adopt two electrode systems to test, be about to the complex film modified glass-carbon electrode of aluminium oxide nano particle/shitosan/horseradish peroxidase as working electrode, saturated calomel electrode is as contrast electrode, and the platinized platinum electrode is as auxiliary electrode; This three-electrode system is placed the 0.1M phosphate buffered solution of PH6.0 ,-1.0V to 1.0V cyclic voltammetry scan a few with activated electrode; Then with adding an amount of hydrogen peroxide in the 0.1M hydrochlorate buffer solution; Select electric current-time curve method, set certain application current potential, start-up routine, when the back of the body dry in the air electric current reach stable after, the usefulness microsyringe adds the p-dihydroxy-benzene sample in above-mentioned solution, write down corresponding current signal; In concentration 0.005mM～70mM scope, obtain the linear relationship of electric current and p-dihydroxy-benzene concentration, its linear equation is: I (mA)=0.533C (mM)+0.05, linearly dependent coefficient r=0.999, utilize this linear relationship curve and corresponding linear equation, can measure the concentration of p-dihydroxy-benzene liquor sample.
Relevant mechanism of the present invention or principle: the modified electrode among the present invention is equivalent to a kind of novel enzyme biologic sensor.Be fixed on the sensitive element primitive of the horseradish peroxidase on glass-carbon electrode surface among the present invention as biology sensor, by reaction produced and the signal the surveyed proportional relation of object between various physics, chemical signal transducer captured target thing and the sensitive element primitive, realize object is carried out quantitative measurement.In the present invention, the horseradish peroxidase that is fixed on the glass-carbon electrode surface is as the sensor element primitive, and electrode is as signal converter, thereby realizes the quantitative measurement to phenolic compound.Therefore, among the present invention, the complex film modified glass-carbon electrode of aluminium oxide nano particle/shitosan/horseradish peroxidase is equivalent to a kind of enzyme biologic sensor.
In the present invention, at first under horseradish peroxidase (going back ortho states) effect, hydrogen peroxide is reduced into water, and horseradish peroxidase is oxidized simultaneously; After the horseradish peroxidase of oxidation state and the phenolic compound effect king is become horseradish peroxidase (going back ortho states) and quinones substance or free radical; These quinones substances or free radical are in electrode surface generation reduction reaction, and its reduction current is directly proportional with phenolic compound concentration, thereby can the quantitative measurement phenolic compound.
Advantage of the present invention and characteristics are as described below: the glass-carbon electrode surface that the present invention utilizes the characteristics of the biocompatibility of characteristic such as the big specific surface area of aluminium oxide nano particle and shitosan to make that horseradish peroxidase is not only well fixing has kept good biologically active simultaneously.Simultaneously, the introducing of aluminium oxide nano particle has strengthened the catalytic activity of reaction.Again owing in solution, added the response current that an amount of hydrogen peroxide has increased reaction greatly.
Modified electrode among the present invention is equivalent to a kind of novel enzyme biologic sensor, is used for the mensuration to phenolic compound and actual sample, has characteristics such as quick, sensitive, accurate.Enzyme biologic sensor of the present invention has good stable and reappearance, and preparation is simple, quick.
Description of drawings
Fig. 1 is the cyclic voltammogram of p-dihydroxy-benzene solution (20mM) on shitosan/horseradish peroxidase modified electrode (a) and aluminium oxide nano particle/shitosan/horseradish peroxidating modified electrode (b) of same concentrations among the present invention;
Fig. 2 is the standard p-dihydroxy-benzene concentration that adds among the present invention and the linear relationship curve map of peak current.
Embodiment
After now specific embodiments of the invention being described in.
Embodiment 1: comprise the preparation of modified electrode (biology sensor) and the mensuration of p-dihydroxy-benzene in the present embodiment, its detailed process is as follows:
(1) pre-service of glass-carbon electrode: at first with glass-carbon electrode with 0.05 mm Al
2O
3Burnishing powder and chamois leather polish, and are polished to minute surface, use distilled water, dilute nitric acid solution, absolute ethyl alcohol and redistilled water ultrasonic cleaning clean, stand-by then successively;
(2) preparation of a kind of aluminium oxide nano particle/shitosan/complex film modified electrode of horseradish peroxidase (biology sensor): take by weighing at first that an amount of shitosan is dissolved in the 0.1 M acetum and at room temperature ultrasonic 2 h obtain 0.2%-0.6% (w/v, mg/ml) chitosan solution, the appropriate amount of alumina nano particle is dispersed in 0.2%-0.6% (w/v, mg/ml) chitosan solution and ultrasonic of 1 mL to even.With redistilled water preparation 6-10 mg/mL horseradish peroxidase solution, this horseradish peroxidase solution and above-mentioned alumina solution mixed obtaining aluminium oxide nano particle/shitosan/horseradish peroxidase mixed solution with volume ratio 1:1.This mixes drop and is applied to the glass-carbon electrode surface of step a gained to get 4-8 uL, and dries in 4 ℃ refrigerator, places after a night stand-by; Finally make the complex film modified glass-carbon electrode of aluminium oxide nano particle/shitosan/horseradish peroxidase.
(3) mensuration of modified glassy carbon electrode p-dihydroxy-benzene, its assay method is as follows:
Utilize electrochemical workstation to adopt three-electrode system to measure, be about to the complex film modified glass-carbon electrode of aluminium oxide nano particle/shitosan/horseradish peroxidase as working electrode, saturated calomel electrode and platinized platinum electrode are respectively as contrast electrode, auxiliary electrode; The 0.1 M phosphate buffered solution current potential that this three-electrode system is placed pH 6.0 from-1.0 V to 1.0 V cyclic voltammetry scans a few with activated electrode; In 0.1 M phosphate buffered solution, add an amount of hydrogen peroxide then.Select electric current-time curve method, set certain application current potential, start-up routine, when background current reach stable after, the usefulness microsyringe adds the p-dihydroxy-benzene sample in above-mentioned solution, write down corresponding current signal; In concentration 0.005 mM-70 mM scope, obtain the linear relationship of electric current and p-dihydroxy-benzene concentration, its linear equation is:
I(mA)=0.533
C(mM)+0.05, its linearly dependent coefficient
r=0.999, utilize this linear relationship curve and corresponding linear equation, the concentration of available its mensuration p-dihydroxy-benzene liquor sample.
Determination test in the present embodiment the results are shown among Fig. 1 and Fig. 2.
Referring to Fig. 1, Fig. 1 is the cyclic voltammetry curve figure of the p-dihydroxy-benzene solution (20mM) of same concentrations in the present embodiment at shitosan/horseradish peroxidase modified electrode (a) and aluminium oxide nano particle/shitosan/horseradish peroxidase modified electrode.As can be seen from Figure, latter's (being b) has higher volt-ampere performance and shows, that is to say that electrode signal shows preferably.
Referring to Fig. 2, Fig. 2 is the standard p-dihydroxy-benzene concentration that adds in the present embodiment and the linear relationship curve map of peak current.And obtain linear equation thus::
I(mA)=0.533
C(mM)+0.05; Its linearly dependent coefficient r=0.999.
Claims (1)
1. a horseradish peroxidase modified electrode is measured the method for phenolic compound, it is characterized in that having following process and step:
A. the pre-service of glass-carbon electrode: at first glass-carbon electrode is used 0.05mm Al
2O
3Burnishing powder and chamois leather polish, and throw to the light microscopic face, use distilled water, dilute nitric acid solution, absolute ethyl alcohol and redistilled water ultrasonic cleaning clean, stand-by then successively;
B. the preparation of the composite modified glass-carbon electrode of aluminium oxide nano particle/shitosan/horseradish peroxidase: at first take by weighing an amount of shitosan and be dissolved in the 0.1M acetum, and at room temperature ultrasonic 2h, obtain 0.2～0.6%(W/V, chitosan solution mg/ml); Then the appropriate amount of alumina nano particle is dispersed in above-mentioned 0.2～0.6%(W/V of 1ml, mg/ml) chitosan solution, and ultrasonic to even; In addition, with redistilled water preparation 6～10mg/ml horseradish peroxidase solution, this horseradish peroxidase solution is mixed with the above-mentioned volume ratio 1:1 that is dispersed with the chitosan solution of aluminium oxide nano particle, obtain aluminium oxide nano particle/shitosan/horseradish process enzyme mixed solution; This mixed solution of getting 4～8ml then drips and is applied to above-mentioned ready glass-carbon electrode surface, and dries in 4 ℃ refrigerator, places after a night stand-by;
C. to the electrochemical gaging of phenolic compound: utilize the above-mentioned complex film modified glass-carbon electrode of aluminium oxide nano particle/shitosan/horseradish peroxidase to be used as amperometric biosensor, phenolic compound is carried out electrochemical gaging, its assay method is as follows: utilize electrochemical workstation to adopt two electrode systems to test, be about to the complex film modified glass-carbon electrode of aluminium oxide nano particle/shitosan/horseradish peroxidase as working electrode, saturated calomel electrode is as contrast electrode, and the platinized platinum electrode is as auxiliary electrode; This three-electrode system is placed the 0.1M phosphate buffered solution of PH6.0 ,-1.0V to 1.0V cyclic voltammetry scan a few with activated electrode; Then with adding an amount of hydrogen peroxide in the 0.1M hydrochlorate buffer solution; Select electric current-time curve method, set certain application current potential, start-up routine, when the back of the body dry in the air electric current reach stable after, the usefulness microsyringe adds the p-dihydroxy-benzene sample in above-mentioned solution, write down corresponding current signal; In concentration 0.005mM～70mM scope, obtain the linear relationship of electric current and p-dihydroxy-benzene concentration, its linear equation is: I (mA)=0.533C (mM)+0.05, linearly dependent coefficient r=0.999, utilize this linear relationship curve and corresponding linear equation, can measure the concentration of p-dihydroxy-benzene liquor sample.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102654475A (en) * | 2012-03-23 | 2012-09-05 | 上海大学 | Bioelectrochemical sensor used for detecting hydrogen peroxide and manufacturing method thereof |
| CN103645316A (en) * | 2013-12-25 | 2014-03-19 | 扬州大学 | Streptavidin functionalized semiconductor nano material-based tumor marker electrochemical immunosensor and preparation method thereof |
| CN108845008A (en) * | 2018-05-04 | 2018-11-20 | 杭州电子科技大学 | A kind of phenol sensor of direct electron transfer type and its preparation method and application |
| CN110823967A (en) * | 2019-10-30 | 2020-02-21 | 广州钰芯传感科技有限公司 | Chitosan-copper compound modified electrode for hydrogen peroxide detection and preparation method thereof |
| CN113999879A (en) * | 2022-01-04 | 2022-02-01 | 中国科学院天津工业生物技术研究所 | Method for catalytic oxidation of aromatic hydrocarbon and derivative thereof by peroxidase |
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| CN101029886A (en) * | 2007-03-29 | 2007-09-05 | 上海大学 | Method for determining nitrobenzyl phenol three isomer simultaneouslly |
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Non-Patent Citations (6)
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| 《J Solid State Electrochem》 20100616 Xiaojuan Liu. et al "Hydrogen peroxide biosensor based on the immobilization of horseradish peroxidase on gamma-Al2O3 nanoparticles/chitosan film-modified electrode" 第447-453页 1 第15卷, 第3期 * |
| 《分析化学研究报告》 20020630 陈海明等 "辣根过氧化物酶反应的化学动力学分析" 第654-657页 1 第30卷, 第6期 * |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102654475A (en) * | 2012-03-23 | 2012-09-05 | 上海大学 | Bioelectrochemical sensor used for detecting hydrogen peroxide and manufacturing method thereof |
| CN103645316A (en) * | 2013-12-25 | 2014-03-19 | 扬州大学 | Streptavidin functionalized semiconductor nano material-based tumor marker electrochemical immunosensor and preparation method thereof |
| CN108845008A (en) * | 2018-05-04 | 2018-11-20 | 杭州电子科技大学 | A kind of phenol sensor of direct electron transfer type and its preparation method and application |
| CN108845008B (en) * | 2018-05-04 | 2020-12-29 | 杭州电子科技大学 | Direct electron transfer type phenol sensor and preparation method and application thereof |
| CN110823967A (en) * | 2019-10-30 | 2020-02-21 | 广州钰芯传感科技有限公司 | Chitosan-copper compound modified electrode for hydrogen peroxide detection and preparation method thereof |
| CN113999879A (en) * | 2022-01-04 | 2022-02-01 | 中国科学院天津工业生物技术研究所 | Method for catalytic oxidation of aromatic hydrocarbon and derivative thereof by peroxidase |
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Application publication date: 20110720 |