CN103033548B - Fabrication method of ACHE biosensor based on composite nano-material - Google Patents
Fabrication method of ACHE biosensor based on composite nano-material Download PDFInfo
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- CN103033548B CN103033548B CN201210588922.XA CN201210588922A CN103033548B CN 103033548 B CN103033548 B CN 103033548B CN 201210588922 A CN201210588922 A CN 201210588922A CN 103033548 B CN103033548 B CN 103033548B
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Abstract
The invention relates to a fabrication method of an ACHE (Acetylcholine Esterase) biosensor based on a composite nano-material. The fabrication method is characterized in that the method comprises the steps of fabricating the multi-walled carbon-graphene-polydiene propyl dimethyl ammonium chloride composite nano-material, and further fabricating the ACHE biosensor based on the composite nano-material. Multi-walled carbon and graphene have unique physicochemical properties, but are insoluble in common solvents; and with the adoption of the method, the solubility of multi-walled carbon and graphene in a solution is improved obviously. The fabricated multi-walled carbon-graphene-polydiene propyl dimethyl ammonium chloride composite nano-material can improve a micro-environment of an electrode surface obviously and a current response of the electrode surface, serve as a carrier material to modify an electrode, and be used for fabricating the electrochemical biosensor with higher sensitivity. The electric current type ACHE sensor fabricated by the method is short in detection time, good in stability, high in sensitivity and good in regeneration capacity, and can be used for detecting organophosphorus pesticide in actual fruit and vegetable samples.
Description
Technical field
The invention provides a kind of acetylcholinesterasebiosensor biosensor preparation method based on composite nano materials, belong to biosensor technology field.
Background technology
Agricultural chemicals is used to the chemical-biological medicament prevented and treated agricultural pest and regulate crop growth.Agricultural chemicals has irreplaceable effect in world's agricultural production.But meanwhile, due to agricultural chemicals unreasonable use caused by pollution by pesticides and the hazard analysis and HACCP of generation be serious, Residual Pesticides in Farm Produce exceeds standard, the serious threat safe diet of the mankind.In order to the safety and health of Protection of consumer, improve the quality safety of agricultural products in China, enhance our international competitiveness, the quality security problem of agricultural product more and more receives publicity, and especially Pesticide Residues in Vegetables problem has become the focus of public attention.In order to stop underproof agricultural product to come into the market from source, the Chinese government starts the various detection techniques greatly developing agricultural chemicals, strengthens the Real-Time Monitoring to rapid test paper.The most kind of pesticide of producing due to China and use is Organophosphorus and carbamate pesticides class agricultural chemicals, so the emphasis of Detecting Pesticide is also on Organophosphorus and carbamate pesticides class agricultural chemicals.
At present, to the method for Detecting Pesticide mainly gas chromatography, liquid chromatography, thin-layer chromatography, high performance liquid chromatography and be combined with simple analytic approach.Although these method analysis precisions are high, quantitatively accurately, be also state specified standards detection method.But these methods need to carry out pre-treatment, complicated operation to analyzed sample mostly, time-consuming for a long time and somewhat expensive, need skilled professional and technical personnel, the requirement of field quick detection sample can not be met.The fast determining method of China's residues of pesticides is enzyme level test paper method and enzyme level spectrophotometric method (the residual fast detector of agriculture), can realize the field quick detection of organophosphorus pesticide and carbamate chemicals for agriculture, have good practicality.Quick measuring card is changed by the color of visual inspection card, therefore generally can only be used for the vegetable sample of observational measurement severe overweight.Enzyme level spectrophotometric method also has to be applied more widely, the domestic existing multiple pesticide residue rapid detector based on this principle.Spectrophotometric method carries out detecting based on the change of absorbance, but a large amount of pigments that vegetable and fruit contains can make a big impact to absorbance, cause the inaccurate of testing result.And it is low that said method exists the recovery, false retrieval, undetected ratio are higher, poor repeatability, are difficult to the requirement etc. meeting low-residual and quantitatively detect.
The object of invention is to provide one can overcome above-mentioned defect, and the preparation method of the acetylcholinesterasebiosensor biosensor of detection residues of pesticides simple to operate, the response time is short, cheap, highly sensitive.
Its technical scheme is: based on the acetylcholinesterasebiosensor biosensor preparation method of composite nano materials, it is characterized in that: the assembling process of acetylcholinesterasebiosensor biosensor is for dissolving many walls carbon (MWNTs) and Graphene (GR) diallyl dimethyl ammoniumchloride (PDDA), form PDDA-MWCNTs-GR compound, this compound is dripped and is coated onto on glass-carbon electrode (GCE), then drip and be coated with acetylcholinesterase (AChE), obtain AChE/PDDA-MWCNTs-GR/GCE sensor.
The described acetylcholinesterasebiosensor biosensor preparation method based on composite nano materials, it is characterized in that: the cleaning of glass-carbon electrode (d=3mm), the structure at acetylcholinesterase sensor sensing interface and process thereof characterize, the foundation of acetylcholinesterase working sensor curve, the detection of acetylcholinesterase sensor performance, acetylcholine ester enzyme sensor is to the detection of actual sample.
The described acetylcholinesterasebiosensor biosensor preparation method based on composite nano materials, it is characterized in that: the working curve of prepared current mode acetylcholine ester enzyme sensor is: the concentration of carbaryl pesticide when 0.5-50 ng/mL, I%=0.313c+20.228; The concentration of carbaryl pesticide when 50-3000 ng/mL, I%=0.0128c+36.185.Acetylcholinesterase sensor performance detects and comprises accuracy, stability, recyclability, and acetylcholine ester enzyme sensor is to the mensuration of the vegetable sample recovery.
Its preparation principle is: because carbamate chemicals for agriculture and acetylcholinesterase have higher specific binding, and therefore conventional acetylcholinesterase is as the molecular recognition elements detecting carbamate chemicals for agriculture.Acetylcholinesterasebiosensor biosensor is that acetylcholinesterase is fixed on electrode surface, and substrate for enzymatic activity acetylcholine hydrolyzation generates choline and acetic acid.Agricultural chemicals is structurally a bit similar with substrate acetyl choline, and it effectively can combine with the activated centre of acetylcholine, the activity of acetylcholine esterase inhibition.Choline is a kind of electroactive material, under certain potentials, oxidation reaction can occur, and can measure the concentration of residues of pesticides by the size of thiocholine oxidation peak in voltammetric scan process.Obtain the inhibiting rate of agricultural chemicals to enzyme by comparing with or without the change of enzymatic reaction current signal during agricultural chemicals, this inhibiting rate becomes corresponding relation with the concentration of agricultural chemicals, just can record the content of organophosphorus or carbamate chemicals for agriculture.
The present invention adopts many walls carbon-graphite alkene-diallyl dimethyl ammoniumchloride compound to modify glass-carbon electrode, compared with traditional method, because many walls carbon and Graphene have good electric conductivity, electrochemical stability and bio-compatibility, be widely used in biology sensor always, but theirs is poorly soluble, as all undesirable in the solubleness in shitosan, dimethyl formamide equal solvent at general reagent, by dissolving many walls carbon and Graphene by diallyl dimethyl ammoniumchloride, significantly improve their dissolubility.And by after many walls carbon and Graphene mixing, because mutual acting force, reduce polymerization when dissolving separately, settlement action, further promote their dissolubility.The enzyme sensor made after being modified with above-mentioned compound by glass-carbon electrode, the precision detecting agricultural chemicals is higher, wider, and detectability is lower, can realize object that is small-sized, convenient, that be applicable to Site Detection.Before adopting the current mode acetylcholinesterasebiosensor biosensor made of the present invention can gather at vegetables and fruits, going on the market, carry out the Fast Measurement of residues of pesticides, directly whether residues of pesticides are exceeded standard and quantitatively detect, for crop production safety and consumption provide the technical support of Detecting Pesticide.
For reaching above object, following technical scheme is taked to realize: based on the acetylcholinesterasebiosensor biosensor preparation method of composite nano materials, it is characterized in that: the cleaning of glass-carbon electrode before the preparation of (1) current mode acetylcholine ester enzyme sensor, activation and performance test, when the spike potential difference in test loop volt-ampere curve is at 80 below mV, and during as far as possible close to 64 mV, described glass-carbon electrode can use, otherwise return in cleaning step, until meet the requirements.(2) many walls carbon-graphite alkene-diallyl dimethyl ammoniumchloride compound is configured, the glass-carbon electrode cleaned up drips and is coated with this compound, naturally after drying under room temperature, clean up by phosphate buffered solution, drip and be coated with acetylcholinesterase, rinse well by phosphate buffered solution after 2h, the preparation of current mode acetylcholine ester enzyme sensor terminates, and puts in refrigerator and saves backup under 4 DEG C of conditions.
For reaching above object, following technical scheme is taked to realize: based on the acetylcholinesterasebiosensor biosensor preparation method of composite nano materials, it is characterized in that: (1) configures a series of sevin titer, carry out differential pulse voltammetry scanning, obtain inhibiting rate, obtain the working curve of the current mode acetylcholinesterasebiosensor biosensor of above-mentioned preparation, sensing range and detectability further; (2) electrode after being suppressed by agricultural chemicals immerses 12 min in pralidoxime solution, records the regenerability of acetylcholinesterasebiosensor biosensor; (3) degree of accuracy of acetylcholinesterasebiosensor biosensor and stability are evaluated; (4) actual fruits and vegetables sample is analyzed to the recovery and reappearance that draw this sensor.
The present invention is by preparation many walls carbon-graphite alkene-diallyl dimethyl ammoniumchloride compound, take full advantage of the physicochemical property of many walls carbon and Graphene uniqueness, comprise high specific surface area, excellent conductivity, high physical strength, good adsorptive power and excellent biocompatibility.Utilize diallyl dimethyl ammoniumchloride to dissolve many walls carbon-graphite alkene compound, effectively improve the two solubleness in the solution.And after many walls carbon and Graphene mixing, the interaction force between them reduces the two polymerization, settlement action, further increases their dissolubility.Many walls carbon-graphite alkene-diallyl dimethyl ammoniumchloride compound can improve the microenvironment of electrode surface, promote the transmission of electronics in electrochemical reaction, improve the current-responsive on electrode, therefore can be used as carrier material modified electrode, be used for preparing the electrochemica biological sensor of higher sensitivity; Reacted by the carboxyl in carboxylated many walls carbon and the amino in acetylcholinesterase, form amido link, acetylcholinesterase is fixed on electrode surface, improves the stability of biology sensor.
The described acetylcholinesterasebiosensor biosensor preparation technology based on composite nano materials is as follows: 7 μ L many walls carbon-graphite alkene-diallyl dimethyl ammoniumchloride compounds drip and are coated on the good glass-carbon electrode of pre-service by (1), after at room temperature drying, rinse the compound do not fixed by phosphate buffered solution, then carefully dry up with nitrogen; (2) get 5 μ L acetylcholine ester enzyme solutions to drip to be coated in and be above-mentionedly modified with on the electrode of composite membrane, 2 h are placed under normal temperature, then surface is rinsed by the phosphate buffered solution of PH=7.0, then dry up with nitrogen, acetylcholinesterasebiosensor biosensor completes, and saves backup under 4 DEG C of conditions.
Embodiment
Embodiment: the preparation of (1) many walls carbon-graphite alkene-diallyl dimethyl ammoniumchloride compound: first the potpourri (many walls carbon: Graphene=3:1) of 2 mg many walls carbon and Graphene being dissolved in 4 mL concentration is 0.25% containing ultrasonic dissolution 30 min in the diallyl dimethyl ammoniumchloride solution of 0.5M NaCl.Then above-mentioned solution is cleaned 3 times with deionized water centrifuging under 14000 rpm.Finally, become by above-mentioned solution preparation concentration to be the solution of 1 mg/mL, each use before ultrasonic 5 min, namely obtain many walls carbon-graphite alkene-diallyl dimethyl ammoniumchloride compound.(2) cleaning of glass-carbon electrode: before glass-carbon electrode is modified, first immerses " piranha " solution (H
2sO
4: 30% H
2o
2=3:1) in soak 15 min, next clean up with water, with 0.3 μm, the Al of 30 nm
2o
3slurry is polished to minute surface on chamois leather, puts into ultrasonic water bath and cleans, each 5 min, repeats secondary, then uses the HNO of 6 mol/L successively
3, absolute ethyl alcohol and deionized water ultrasonic cleaning, nitrogen carefully dries up; (3) activation of glass-carbon electrode: thoroughly after cleaning, electrode is at 0.5 mol/L H
2sO
4under scope 1.0V ~-1.0V, activation is scanned by cyclic voltammetry, till reaching stable cyclic voltammogram in solution.(4) test of the glass-carbon electrode that pre-service is good: containing 1 × 10 of 0.1 mol/L KCl
-3mol/L K
3fe (CN)
6carry out cyclic voltammetry scan in solution, sweep velocity 50 mV/s, sweep limit is-0.1 V ~ 0.6 V; When the spike potential difference in described cyclic voltammetry curve is at 80 below mV, and during as far as possible close to 64 mV, described glass-carbon electrode can use, otherwise will return in step (2), and pre-service glass-carbon electrode, until meet the requirements; (5) 7 μ L many walls carbon-graphite alkene-diallyl dimethyl ammoniumchloride compounds dripped be coated on the good glass-carbon electrode of pre-service, after at room temperature drying, with phosphate buffered solution rinse fixing on compound, then carefully dry up with nitrogen; (6) get 5 μ L acetylcholine ester enzyme solutions to drip to be coated in and be above-mentionedly modified with on the electrode of composite membrane, 2 h are placed under normal temperature, then surface is rinsed by the phosphate buffered solution of PH=7.0, then dry up with nitrogen, acetylcholinesterasebiosensor biosensor completes, and saves backup under 4 DEG C of conditions.(7) by the above-mentioned acetylcholine ester enzyme sensor prepared containing 1 mM chlorinated thio acetylcholine and carry out differential pulse voltammetry test with 50 mV/s sweep velocitys in the phosphate buffered solution of pH=7.0, potential window is 0.3 V ~ 1.0 V; (8) the sevin standard solution of 0.1 ng/mL-4000 ng/mL is configured, when agricultural chemicals is measured, above-mentioned acetylcholine ester enzyme sensor is immersed in 12 min in the pesticide standard solution of variable concentrations, then in containing the phosphate buffered solution of 1 mM chlorinated thio acetylcholine (ATCl), carry out differential pulse voltammetry scanning, inhibiting rate I can be tried to achieve by following formula:
I(%)=(i
P, control?i
P, exp)/i
P, control×100%
Wherein i
p, controland i
p, expbe respectively test electrode without agricultural chemicals suppression with after agricultural chemicals suppresses, peak current in chlorinated thio acetylcholine solution, according between pesticide concentration and inhibiting rate in certain linear relationship, make working curve diagram, obtain the linear relationship between pesticide concentration and inhibiting rate, and detectability.(9) accuracy of acetylcholinesterasebiosensor biosensor is studied by organizing deviation experiment between interior deviation and group.Same electrode carries out the coefficient of variation in five replication acquisition groups, is 4.7%; Carrying out mensuration with five electrodes through identical modification and obtain between-group variation coefficient, is 4.1%.When electrode, the used time is not kept in 4 DEG C of refrigerators, and obtain the stability of this sensor according to the change of 7 days and the response of 30 days after-currents, after 7 days, current-responsive value does not have significant change, reduces to 87% of primary current value after 30 days.(12) sensor after being suppressed by agricultural chemicals is immersed in 12 min in the pralidoxime iodide solution of 5.0 mM, rinse well by phosphate buffered solution, cyclic voltammetry scan is carried out in the phosphate buffered solution of 1 mM ATCl, to detect its power of regeneration, current-responsive value can return to 93% of primary current value.(13) vegetables thoroughly cleaned up and use washed with de-ionized water 3 times, certain density agricultural chemicals in sprinkling, after placing 24 h, by 10 mL acetone/0.1 M pH 7.0 phosphate buffered solution (1/9, v/v) be solvent supersonic process 15 min, and then carry out centrifugal treating (10 min, 10000 rpm), the supernatant obtained is used for detecting the recovery of actual sample, and its recovery can reach 92.3%-107%.
The method of this kind of current mode acetylcholinesterasebiosensor biosensor detection residues of pesticides is simple to operate, be convenient to grasp, and detection time is short, detectability is low, detect agricultural chemicals scope wide, good stability, highly sensitive, power of regeneration is good and have the higher recovery and reappearance to actual sample analysis, meets China's Fast Determination of Pesticide Residue technical development and internationalization requirement.
Claims (1)
1., based on the acetylcholinesterasebiosensor biosensor preparation method of composite nano materials, it is characterized in that, step is as follows:
1) preparation of many walls carbon-Graphene-diallyl dimethyl ammoniumchloride composite nano materials: first the potpourri of 2 mg many walls carbon and Graphene is mixed according to the ratio of many walls carbon with Graphene 3:1, be dissolved in 4 mL concentration be 0.25% containing 0.5M NaCl diallyl dimethyl ammoniumchloride solution in ultrasonic dissolution 30 min, then above-mentioned solution is cleaned 3 times with deionized water centrifuging under 14000 rpm, finally, concentration is become by above-mentioned solution preparation to be the solution of 1 mg/mL, ultrasonic 5 min before each use, namely many walls carbon-Graphene-diallyl dimethyl ammoniumchloride composite nano materials is obtained,
2) with many walls carbon-Graphene-diallyl dimethyl ammoniumchloride composite nano materials modified glassy carbon electrode, being dripped by 7 μ L many walls carbon-Graphene-diallyl dimethyl ammoniumchloride compounds is coated on the good glass-carbon electrode of pre-service, after at room temperature drying, rinse the compound do not fixed by phosphate buffered solution, then carefully dry up with nitrogen;
3) acetylcholinesterase is fixed on the glass-carbon electrode modified with above-mentioned composite nano materials, get 5 μ L acetylcholine ester enzyme solutions to drip to be coated in and be above-mentionedly modified with on the electrode of composite membrane, 2 h are placed under normal temperature, then surface is rinsed by the phosphate buffered solution of pH 7.0, then dry up with nitrogen, acetylcholinesterasebiosensor biosensor completes, and saves backup under 4 DEG C of conditions.
2. the acetylcholinesterasebiosensor biosensor preparation method based on composite nano materials as described in claim 1, it is characterized in that: the structure at acetylcholinesterase sensor sensing interface and process thereof characterize, the foundation of acetylcholinesterase working sensor curve, the detection of acetylcholinesterase sensor performance, acetylcholine ester enzyme sensor is to the detection of actual fruits and vegetables sample, the working curve of prepared current mode acetylcholine ester enzyme sensor is: when sevin concentration is 0.5 to 50 ng/mL, its linear equation is I%=0.313c+20.228; When concentration is 50 to 3000 ng/mL, its linear equation is I%=0.0128c+36.185, the prepared detection of current mode acetylcholine ester enzyme sensor to carbaryl pesticide is limited to 0.23 ng/mL, the Performance Detection of acetylcholine ester enzyme sensor comprises accuracy, stability and power of regeneration, and acetylcholine ester enzyme sensor is to the mensuration of actual fruits and vegetables sample recovery rate.
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