CN103743804A - Organic phosphorus electrochemical biosensor based on adsorption of nano particles - Google Patents
Organic phosphorus electrochemical biosensor based on adsorption of nano particles Download PDFInfo
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Abstract
The invention particularly relates to an electrochemical biosensor capable of directly detecting an organic phosphorus pesticide in a water phase. The sensor comprises a glassy carbon electrode, a nano gold particle layer and a ZrO2 nano particle layer. A production method of the sensor comprises the following steps of firstly electro-plating a layer of nano gold particles on the surface of the glassy carbon electrode, and then electro-plating a layer of zirconium dioxide nano particles on the nano gold particles. After the produced sensor fully adsorbs in a prepared organic phosphorus solution, and quantitative detection of the organic phosphorus is realized through the dissolution peak current detected by an electrochemical workstation. The sensor takes full advantage of special performances of the nano gold particles and the ZrO2 nano particles in structure, is low in production cost, high in sensitivity, wide in linear detection range, good in reproducibility, small in nonspecific adsorption, and simple and fast in detection process, and has great application potential in food safety monitoring field.
Description
Technical field
The present invention is specifically related to a kind of organophosphorus electrochemica biological sensor preparation method for aqueous environment organophosphorus pesticide fast detecting, belongs to technical field of analysis and detection.
Background technology
Due to people's unreasonable or overdose use chemical pesticide in crop pest control process, cause part Practice for Pesticide Residue in Agricultural Products amount higher, not only affect health, also destroyed agroecological environment.
Traditional organophosphorus pesticide analytical approach has vapor-phase chromatography, thin-layered chromatography, high performance liquid chromatography and various spectrum coupling technique, selectivity, sensitivity and the accuracy of these methods are relatively high, but need expensive instrument and equipment, sample-pretreating method complexity, required analytical cycle is long, uses and gets up to have certain limitation.
Electrochemical sensor method detects organophosphorus and has simply, quick, low cost and the advantage such as be easy to carry, and do not need expensive instrument and equipment, can make up the deficiency of traditional detection method.In agricultural chemicals various in style, organophosphorus insecticide is water-soluble the strongest.Organophosphorus electrochemica biological sensing technology is as a kind of novel Fast Detection Technique, the organophosphorus in can direct-detection water, and agricultural product can detect by organic phosphorus sensor through simple process.The agricultural product of drinking after brewing for tealeaves etc., the residues of pesticides content in millet paste directly threatens the health of human body, the residues of organophosphate pesticides content by organic phosphorus sensor in can direct-detection millet paste; The solution of the agricultural product such as vegetables, fruit after soaking also can be directly used in detection, can the simple and quick residues of organophosphate pesticides contents level that judges vegetables.
Compared with traditional analysis technology, that organic phosphorus sensor fast detection method has is simple, quick, sensitive, low cost and the advantage such as be easy to carry.About the document that utilizes cholinesterase and organophosphor hydrolytic enzyme to detect organophosphorus, have been reported both at home and abroad
[1-4], but organophosphorus sensing technology based on enzyme is because cost is high, the easy inactivation of enzyme molecule, is difficult for the shortcomings such as regeneration, should use certain limitation.In recent years, the development of organophosphorus electrochemical sensor has obtained new progress, nano particle is as a kind of conventional nano material, has that preparation method is simple, surface is easy to the premium properties such as modifications, obtained applying comparatively widely in the structure of organic phosphorus sensor.The surface effect of nano particle and adsorption ability, meanwhile, the specific form feature that nano particle has can be accelerated the transfer of electronics, can improve the stability of electrode, accelerates electrode response speed, and improves sensitivity and the selectivity of sensor.Some researchers have reported that, by direct electro-deposition one deck ZrO on gold electrode
2nano particle, utilizes ZrO
2the strong adsorptive power of nano particle to organophosphorus insecticide, makes the electrochemica biological sensor that can be used for detecting residues of organophosphate pesticides in millet paste
[5].This method has overcome the shortcomings such as enzyme sensor is unstable, the easy inactivation of enzyme molecule, and electrode detection speed is fast, and easy and simple to handle, serviceable life is longer, can be directly used in the fast detecting of residues of organophosphate pesticides in solution.But, consider that gold electrode is expensive, for reducing sensor manufacturing cost, and further improve the reactivity worth of electrode, expand the considerations such as monitoring objective thing scope, wait further research to improve the Practical Performance of sensor.
List of references:
[1]?ALBAREDA?S?M，MERKOCI?A，ALEGRET?S.?Automated?detection?of?chlorpyrifosandits?metabolites?by?a?continuous?flow?system?based?enzyme?sensor[J].?Anal?Chim?Acta,?2001,?442:?35-44.
[2]?SUPRUN?E,?EVTUGYN?G,?BUDNIKOV?H,?et?al.Electrochemical?biosensors–principles?and?applications[J].Anal.?Bioanal.?Chem.,?2005,?383:?597-604.
[3] Liu Li, An Yumin, Sergei V. Dzyadevych, the inhibition research [J] of et.al. BuCh lipase electromotive force type biosensor assay DDVP residues of pesticides. Guizhou environmental protection science and technology, 2006,12 (2): 32-35.
[4]?JOSIANE?C,?SERGIO?A?S?M.?A?review?of?electrolyte?and?electrode?materials?for?high?temperature?electrochemical?CO
2?and?SO
2?gas?sensors[J].Sens.Actuators.?B,?2008,?129:?96-97.
[5] Liu Shujuan, Tan Zhengchu, Zhong Xinggang etc. the organophosphorus in the electrochemica biological sensor fast detecting millet paste based on nano particle absorption. food science and technology, 2012:37 (1): 283-287.
Summary of the invention
Technical matters to be solved by this invention is: for the deficiencies in the prior art, provide a kind of simple structure, highly sensitive, detect linear wide ranges, reproducibility is good, non-specific adsorption is little, testing process preparation and the detection method of organic phosphorus sensor fast.
The present invention, by glass-carbon electrode finishing one deck nanogold particle, then, at nanogold particle substrates one deck zirconium dioxide nanoparticles, makes a kind of organophosphorus electrochemica biological sensor, can be directly used in the detection of the organophosphorus pesticide in water.
This sensor comprises glass-carbon electrode, nanogold particle layer and ZrO
2nanoparticle layers.
Described glass-carbon electrode surface electrical is depositing nanogold particle layer.
Described nanogold particle layer surface electrical depositing ZrO
2nano particle.
Described ZrO
2particle has very strong suction-operated to the phosphate group of organophosphorus pesticide.After the sensor of making is fully adsorbed in ready organophosphorus solution, the stripping peak current detecting by electrochemical workstation is realized the quantitative detection (Fig. 1) of organophosphorus.
The detailed process of this sensor production and detection:
At the glass-carbon electrode surface electrical depositing nano gold grain cleaning, be specially: glass-carbon electrode is used the A1 of 0.3 μ m and 0.05 μ m successively
2o
3powder is polished to minute surface, and then each ultrasonic cleaning 4 min in 95% ethanol and distilled water successively take out and rinse and dry up with nitrogen with intermediate water.Electrode after cleaning is placed in to 4 mmol/L gold chloride (HAuCl
4) in solution, with 0.1 mol/L KNO
3for supporting electrolyte, utilize CHI760b electrochemical workstation electro-deposition nanogold particle, electrochemical reaction cell is three-electrode system, the glass-carbon electrode cleaning is working electrode, saturated calomel electrode is contrast electrode, and platinum electrode is to electrode, at constant potential-1.0 V electro-deposition 150 s, take out subsequently that electrode 95% ethanol and deionized water are cleaned and dry up with nitrogen, at glass-carbon electrode substrates one deck nanogold particle.Nanogold particle layer has not only increased the specific surface area of glass-carbon electrode effectively, and can effectively improve the response performance of electrode.
At described nanogold particle layer surface electrical deposition ZrO
2nano particle, is specially: the glass-carbon electrode of electro-deposition nanogold particle layer is rinsed well with 95% second alcohol and water successively, and dried up with nitrogen.At the ZrOCl that contains 3.0 mM
2﹒ 8H
2in the KCl solution of O and 0.3 M, take the glass-carbon electrode of modified nm of gold as working electrode, saturated calomel electrode is contrast electrode, platinum electrode is to electrode, utilize 12 circulations of sweep velocity scanning with 25 mV/s between-1.1 ~+0.6 V of CHI760b electrochemical workstation, after having scanned, electrode is taken out with deionized water and clean and dry up with nitrogen, in nanogold particle surface electrical, deposited one deck ZrO
2nano particle.
Above ZrO
2particle layer/nanogold particle layer/glass-carbon electrode is organic phosphorus sensor, after the sensor of making is fully adsorbed in ready organophosphorus solution, then by the concentration of organophosphorus in the large I calculating of the stripping peak current solution detecting.The detection of stripping peak current realizes by CHI760b electrochemical workstation equally, this sensor is done in the 0.1 M KCl solution of pH 7.0 to SWV scanning (square wave frequency 25 Hz, current potential increment is 4 mV), at scanning current potential, 0.093 V has a SWV stripping peak, it is carried out to baseline correction processing with Sigmaplot software, draw corresponding Stripping Voltammetry figure, the organophosphates of electrode adsorption is more, corresponding stripping peak is just larger, realizes the quantitative detection of organophosphorus in solution according to the large I of measured stripping peak current.
Within the scope of finite concentration, organophosphorus concentration and sensor SWV stripping peak current are linear.Take the organophosphorus concentration of standard solution of the concentration known that configures as horizontal ordinate, corresponding square wave stripping voltammetry peak current is that ordinate is figure, can draw the working curve of sensor.When carrying out actual sample detection, according to the size that records stripping peak current in organophosphorus solution to be measured, by inquiry the sensor working curve, can calculate the concentration of organophosphorus in solution to be measured.
The sensor completing after one-time detection is proceeded repeatedly to SWV scanning, can make the complete wash-out of organophosphorus of absorption, then electrode cleans with the gentle liquid that rushes of deionized water, can carry out mensuration next time.
Compared with prior art, the invention has the advantages that:
The present invention takes full advantage of the property of nano particle, and has expanded the scope that detects object, has improved sensor detection sensitivity.With Direct precipitation ZrO in gold electrode surfaces
2the organic phosphorus sensor of making is compared, and this sensor improves more than 1 times the detection sensitivity of organophosphorus solution, and the linear expanded range of detection of sensor is more than 60%.
The nanogold particle of glass-carbon electrode finishing of the present invention has Polyhedral Particles shape structure, and they are evenly distributed on glass-carbon electrode surface, has increased widely the specific surface area of electrode, makes electrode surface can deposit ZrO
2the site of nano particle is multiplied.The less ZrO of one deck diameter depositing in golden nanometer particle surface electrical subsequently
2nano particle has increased the surface area of electrode equally.Like this, in electrode specific surface area, after twice amplification, sensor is further strengthened the suction-operated of organophosphorus, and the current-responsive of sensor becomes sensitiveer.
Organic phosphorus sensor building process of the present invention inorganic material used is cheap, has overcome the shortcomings such as enzyme sensor is unstable, the easy inactivation of enzyme molecule, has reduced the construction cost of sensor.The reappearance of sensor and good stability, reproducibility is good, and non-specific absorption is little, can be directly used in the fast detecting of residues of organophosphate pesticides in solution, in food safety monitoring field, has larger application potential.
Accompanying drawing explanation
Fig. 1 sensor arrangement and detection principle schematic.
Embodiment
Embodiment 1:
Glass-carbon electrode is used the A1 of 0.3 μ m and 0.05 μ m successively
2o
3powder is polished to minute surface, and then each ultrasonic cleaning 4 min in 95% ethanol and distilled water successively take out and rinse and dry up with nitrogen with intermediate water.Electrode after cleaning is placed in to 4 mmol/L chlorauric acid solutions, with 0.1 mol/L KNO
3for supporting electrolyte, utilize CHI760b electrochemical workstation electro-deposition nanogold particle, electrochemical reaction cell is three-electrode system, glass-carbon electrode is working electrode, saturated calomel electrode is contrast electrode, platinum electrode is to electrode, at constant potential-1.0 V electro-deposition 150 s, at glass-carbon electrode substrates one deck nanogold particle.
The glass-carbon electrode of depositing nano gold is rinsed well with 95% second alcohol and water successively, and dried up with nitrogen, continue to utilize CHI760b electrochemical workstation electro-deposition ZrO
2nano particle.Three-electrode system is put into the ZrOCl of 3.0 mM
2﹒ 8H
2in the KCl solution of O and 0.3 M, between-1.1 ~+0.6 V, with 12 circulations of sweep velocity scanning of 25 mV/s, take out with deionized water and clean and dry up with nitrogen, in nanogold particle surface electrical, deposited one deck ZrO
2nano particle.Above ZrO
2particle layer/nm of gold/glass-carbon electrode is organic phosphorus sensor.
Above organic phosphorus sensor can be directly used in the detection of parathion in water.Sensor is immersed in ready parathion solution, and gentle agitation 5 min carry out, after the absorption of parathion, on CHI760b electrochemical workstation, carrying out the Electrochemical Detection of stripping peak current.First, take the parathion concentration of standard solution of the concentration known that configures as horizontal ordinate, corresponding square wave stripping voltammetry peak current is that ordinate is figure, draws the working curve of sensor to parathion.Sensor SWV stripping peak current and organophosphorus concentration are linear within the scope of 5-900 μ g/L, and its regression equation is: y=0.2475x+1.160, and linearly dependent coefficient r is 0.9963, sensor is limited to 1 μ g/L to detecting of parathion.Sensor is detected unknown parathion solution, according to typical curve, calculate parathion concentration.
Complete after one-time detection, sensor is proceeded repeatedly to SWV scanning, make the complete wash-out of parathion of absorption.Under the electrochemical parameter identical with working curve, the electrode completing after detection is carried out to continuous several times SWV scanning, along with the increase of scanning times, SWV stripping peak is more and more less, after continuous ten scanning, the parathion adsorbing on electrode is almost all dissolved, and electrode cleans with the gentle liquid that rushes of deionized water, can carry out mensuration next time.
In order to investigate the possibility of practical application, with this sensor, detected 5 different testing samples and added the recovery after parathion solution.First as stated above ready parathion sample is carried out to concentration determination, then in each sample, add the parathion solution of known quantity, in kind the sample after adding is measured again, the testing result obtaining is in Table 1, the average recovery rate obtaining, between 95.29% to 106.93%, shows that test findings is comparatively accurate.
table 1 adds recovery test
Detect 5 different parathion concentration solution with the parathion sensor that makes, and the result that testing result and vapor-phase chromatography obtain is compared, testing result conforms to substantially in Table the measurement result of 2, two kinds of methods.
the concentration of parathion in the aqueous sample that table 2 records respectively by sensor method and high resolution gas chromatography method
By the parathion sensor making, under the same conditions to parathion solution (concentration is 100 ng/mL) replication 6 times, relative standard deviation is 4.62%; 5 parathion sensors with batch preparation are measured under the same conditions, and relative standard deviation is 5.33%, illustrates that reappearance is good.The organic phosphorus sensor preparing is immersed in the phosphate buffer of pH 7.0 and is placed in 4 ℃ of refrigerators and preserve, response performance to parathion after determination sensor placement, result shows, sensor is placed sensor after 15 days the response of parathion is not obviously changed, and places 90% left and right that 30 days rear electrodes still can keep original response.
The current-responsive of experiment parathion solution (100 μ g/L) under the inorganic ions such as sulfate ion, phosphate anion and nitrate ion exist to sensor is investigated, and under this class ion exists, the current-responsive of sensor is without significant change; When experiment also exists organochlorine and pyrethrin pesticide, the current-responsive of sensor is investigated, this pesticide residue to the current-responsive of sensor also without obviously interference.Result shows that the specificity of sensor is better, can be directly used in the detection of parathion in solution.
Embodiment 2:
The method same with case 1 deposits one deck nanogold particle in glass-carbon electrode surface electrical, then, at nanogold particle substrates one deck zirconium dioxide nanoparticles, makes ZrO
2the organophosphorus electrochemica biological sensor of particle layer/nm of gold/glass-carbon electrode structure.
Above organic phosphorus sensor can be directly used in the detection of paraoxon in water.Above-mentioned organic phosphorus sensor is immersed in paraoxon solution, after gentle agitation 5 min adsorb, on CHI760b electrochemical workstation, carries out the Electrochemical Detection of stripping peak current.The first paraoxon concentration of standard solution take concentration known is as horizontal ordinate, and corresponding square wave stripping voltammetry peak current is that ordinate is figure, draws the working curve of sensor to paraoxon.Sensor SWV stripping peak current and paraoxon concentration are linear within the scope of 5-1000 μ g/L, and its regression equation is: y=0.2426x+1.205, and linearly dependent coefficient r is 0.9916, sensor is limited to 1 μ g/L to detecting of paraoxon.Sensor is detected unknown paraoxon solution, according to typical curve, calculate the concentration of paraoxon.
Complete after one-time detection, sensor is proceeded repeatedly to SWV scanning, make the complete wash-out of paraoxon of absorption.After continuous ten scanning, the paraoxon adsorbing on electrode is almost all dissolved, and electrode cleans with the gentle liquid that rushes of deionized water, can carry out mensuration next time.
With this sensor, detect 5 different testing samples and added the recovery after paraoxon solution.First as stated above ready paraoxon sample is carried out to concentration determination, then in each sample, add the paraoxon solution of known quantity, in kind the sample after adding is measured again, the testing result obtaining is in Table 3, the average recovery rate obtaining, between 95.98% to 104.11%, shows that test findings is comparatively accurate.
table 3 adds recovery test
Detect 5 different paraoxon concentration solution with the paraoxon sensor that makes, and the result that testing result and vapor-phase chromatography obtain is compared, the testing result obtaining conforms to substantially in Table the measurement result of 4, two kinds of methods.
the concentration of paraoxon in the aqueous sample that table 4 records respectively by sensor method and high resolution gas chromatography method
By the paraoxon sensor making, under the same conditions to paraoxon solution (concentration is 100 ng/mL) replication 6 times, relative standard deviation is 4.68%; 5 paraoxon sensors with batch preparation are measured under the same conditions, and relative standard deviation is 5.02%, illustrates that reappearance is good.The paraoxon sensor preparing is immersed in the phosphate buffer of pH 7.0 and is placed in 4 ℃ of refrigerators and preserve, response performance to paraoxon after determination sensor placement, result shows, sensor is placed sensor after 15 days the response of paraoxon is not obviously changed, and places 90% left and right that 30 days rear electrodes still can keep original response.
The current-responsive of experiment paraoxon solution (100 μ g/L) under the existence such as sulfate ion, phosphate anion, nitrate ion and organochlorine and pyrethrin pesticide to sensor is investigated, under this class ion exists, the current-responsive of sensor is without significant change, and result shows that the specificity of sensor is better.
Claims (2)
1. the organophosphorus electrochemica biological sensor based on nano particle absorption, comprises glass-carbon electrode, nanogold particle layer and ZrO
2nanoparticle layers, is characterized in that,
Described glass-carbon electrode surface electrical is depositing nanogold particle layer;
Described nanogold particle layer surface electrical depositing ZrO
2nano particle;
The stripping peak current that this sensor detects by electrochemical workstation is realized the quantitative detection of organophosphorus, with Direct precipitation ZrO in gold electrode surfaces
2the organic phosphorus sensor of making is compared, and this sensor improves more than 1 times the detection sensitivity of organophosphorus solution, the linear expanded range 60% of detection of sensor.
2. a kind of organophosphorus electrochemica biological sensor based on nano particle absorption according to claim 1, is characterized in that, this sensor production process is: (1) glass-carbon electrode is used the A1 of 0.3 μ m and 0.05 μ m successively
2o
3powder is polished to minute surface, and then each ultrasonic cleaning 4 min in absolute ethyl alcohol and distilled water successively take out and rinse and dry up with nitrogen with intermediate water, the electrode after cleaning are placed in to 4 mmol/L chlorauric acid solutions, with 0.1 mol/L KNO
3for supporting electrolyte, electrochemical reaction cell is three-electrode system, the glass-carbon electrode cleaning is working electrode, saturated calomel electrode is contrast electrode, platinum electrode is to electrode, utilize CHI760b electrochemical workstation at constant potential-1.0 V electro-deposition 150 s, in glass-carbon electrode finishing one deck nanogold particle;
(2) glass-carbon electrode of electro-deposition nanogold particle layer is rinsed well with 95% second alcohol and water successively, and dried up with nitrogen, at the ZrOCl that contains 3.0 mM
2﹒ 8H
2in the KCl solution of O and 0.3 M, take the glass-carbon electrode of modified nm of gold as working electrode, saturated calomel electrode is contrast electrode, platinum electrode is to electrode, utilize 12 circulations of sweep velocity scanning with 25 mV/s between-1.1 ~+0.6 V of CHI760b electrochemical workstation, at nanogold particle surface electrical deposition one deck ZrO
2nano particle.
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| CN104132980A (en) * | 2014-07-25 | 2014-11-05 | 哈尔滨工业大学 | Method for preparing nano-zirconia electrode having organophosphate pesticide sorption effect by electrochemical deposition and use of nano-zirconia electrode |
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| CN104777201A (en) * | 2015-04-16 | 2015-07-15 | 湖北民族学院 | Method for preparing electrochemical sensor for detecting parathion |
| CN107643332A (en) * | 2017-10-16 | 2018-01-30 | 浙江省农业科学院 | A kind of golden combination electrode and its preparation method and application |
| CN107907580A (en) * | 2017-11-10 | 2018-04-13 | 云南中烟工业有限责任公司 | The electrochemical transistor sensor of organophosphorus pesticide and its detection method to organophosphorus pesticide |
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| CN104132979A (en) * | 2014-07-25 | 2014-11-05 | 哈尔滨工业大学 | Method for preparing nano-zirconia electrode having organophosphate pesticide sorption effect by electrochemical deposition and use of nano-zirconia electrode |
| CN104777201A (en) * | 2015-04-16 | 2015-07-15 | 湖北民族学院 | Method for preparing electrochemical sensor for detecting parathion |
| CN104777201B (en) * | 2015-04-16 | 2017-07-11 | 湖北民族学院 | A kind of preparation method for the electrochemical sensor for detecting parathion |
| CN107643332A (en) * | 2017-10-16 | 2018-01-30 | 浙江省农业科学院 | A kind of golden combination electrode and its preparation method and application |
| CN107643332B (en) * | 2017-10-16 | 2019-08-09 | 浙江省农业科学院 | A kind of gold combination electrode and its preparation method and application |
| CN107907580A (en) * | 2017-11-10 | 2018-04-13 | 云南中烟工业有限责任公司 | The electrochemical transistor sensor of organophosphorus pesticide and its detection method to organophosphorus pesticide |
| CN107907580B (en) * | 2017-11-10 | 2020-04-21 | 云南中烟工业有限责任公司 | Electrochemical transistor sensor for organophosphorus pesticide and detection method for organophosphorus pesticide |
| CN108649254A (en) * | 2018-05-16 | 2018-10-12 | 天津大学 | Excitation formula flexible skin electrochemical energy device and its application method |
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Application publication date: 20140423 |