CN102636537A - Enzyme-free methyl parathion detection sensor, and preparation and application methods thereof - Google Patents
Enzyme-free methyl parathion detection sensor, and preparation and application methods thereof Download PDFInfo
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Abstract
The invention discloses an enzyme-free methyl parathion detection sensor, and preparation and application methods thereof. The sensor comprises a three-electrode system, wherein a graphene/carbon nanotube/chitosan deposition modified glassy carbon electrode is used as a working electrode, a platinum sheet is used as a counter electrode, and a calomel electrode is used as a reference electrode. In the detection process, by using the graphene/carbon nanotube/chitosan deposition modified glassy carbon electrode as the working electrode, the platinum sheet as the counter electrode and the calomel electrode as the reference electrode, an electrochemical work station is utilized to determine the content of methyl parathion. The enzyme-free methyl parathion detection sensor disclosed by the invention has the advantages of short preparation time and environment friendliness, is simple to operate, and can be recycled; and the low detection limit is 0.8ng/L. The invention also has the advantages of short sample detection time and simple treatment.
Description
Technical field:
The present invention relates to a kind of no enzyme parathion-methyl detecting sensor of easy, quick, environmental protection and the method and the method for application of one of which step prepared by electrodeposition.
Background technology:
Organophosphorus insecticide has the drug effect height, and consumption is few, and controlling object is many, is prone to advantages such as decomposition at occurring in nature, and it is used widely in China's agricultural production.Wherein, parathion-methyl (MP) once was used in the control of insect of agricultural crops such as grain, cotton in a large number as the Phosphorus pesticide of a kind of broad spectrum activity High-Efficient Organic, acaricide in worldwide scope.But parathion-methyl has hypertoxicity to people and animals, can get in the animal body through esophagus, respiratory tract and skin to cause poisoning.Although China has forbidden its production and use at present; The report of methyl parathion poisoning incident happens occasionally; Therefore; Realization is easy, quick to parathion-methyl, high-sensitivity detection is for the pollution level of parathion-methyl in the testing environment, and it is significant to study its bio-toxicity mechanism.At present; The analytical approach that detects organophosphorus insecticide mainly contains vapor-phase chromatography, liquid phase chromatography, enzyme inhibition method, immunoassay etc.; But these methods need expensive instrument and equipment, complicated sample processing procedure, consuming time, all are unfavorable for realizing, fast detection easy to parathion-methyl.The present invention utilizes the no enzyme parathion-methyl detecting sensor of step electrodeposition process preparation, and realizes simple, convenient, the highly sensitive detection of parathion-methyl.
Summary of the invention:
The purpose of this invention is to provide a kind of no enzyme parathion-methyl detecting sensor of easy, quick, environmental protection and the method and the method for application of one of which step prepared by electrodeposition.
A kind of no enzyme parathion-methyl detecting sensor comprises: Graphene, CNT and shitosan deposition modified glassy carbon are working electrode, and platinized platinum is to electrode, and mercurous chloride electrode is the three-electrode system of contrast electrode.
The preparation method of described Graphene, CNT and shitosan deposition modified glassy carbon is following:
After 5mg～20mg graphite oxide and 5mg～the 20mg CNT mixes, join in the chitosan solution of 5mL～20mL 0.2wt%; Sonic oscillation 3h～4h obtains graphene oxide-CNT-chitosan solution;
Graphene oxide-CNT-chitosan solution is being working electrode with the glass-carbon electrode; Platinized platinum is to electrode; Mercurous chloride electrode is in the three-electrode system of contrast electrode, carries out the potentiostatic method electro-deposition, obtains Graphene, CNT and shitosan deposition modified glassy carbon.
Described potentiostatic method electrodeposition condition is: sedimentation potential-0.5V～-1.5V, sedimentation time 300s～500s.
Described glass-carbon electrode is the process pre-service before carrying out the potentiostatic method electro-deposition:
Glass-carbon electrode before the electro-deposition in advance on chamois leather the pasty liquid with 0.3 μ m and 0.05 μ m alumina powder be polished to " minute surface ", respectively clean 5min～10min with ethanol, ultrapure water ultrasound wave respectively after rinsing well with deionized water.
With pretreated glass-carbon electrode through carrying out the potentiostatic method electro-deposition after the following process again: be 3～7 in the pH value, concentration is in the phosphate buffer of 0.05mol/L～0.20mol/L; In-0.6V～+ the 0.6V scanning voltage under; With 0.05V/s～0.2V/s sweep velocity scanning 2～8 circles; In the cyclic voltammogram that obtains, the potential difference (PD) at a pair of redox peak is at 60mV～90mV;
The potentiostatic method electro-deposition is carried out under magnetic agitation speed 200rpm～500rpm condition.
The preparation method of above-mentioned no enzyme parathion-methyl detecting sensor:
As working electrode, the platinized platinum conduct is to electrode with Graphene, CNT and shitosan deposition modified glassy carbon, and mercurous chloride electrode constitutes three-electrode system as contrast electrode; The preparation method of described Graphene, CNT and shitosan deposition modified glassy carbon is following:
(1) after 5mg～20mg graphite oxide and 5mg～the 20mg CNT mixes, joins in the chitosan solution of 5mL～20mL 0.2wt%; Sonic oscillation 3h～4h obtains graphene oxide-CNT-chitosan solution, and is subsequent use;
(2) glass-carbon electrode is polished to " minute surface " with the pasty liquid of 0.3 μ m and 0.05 μ m alumina powder on chamois leather, respectively cleans 5min～10min with ethanol, ultrapure water ultrasound wave respectively after rinsing well with deionized water; Then with glass-carbon electrode be 3～7 in the pH value, concentration is in the phosphate buffer of 0.05mol/L～0.20mol/L; In-0.6V～+ the 0.6V scanning voltage under; With 0.05V/s～0.2V/s sweep velocity scanning 2～8 circles; In the cyclic voltammogram that obtains, the potential difference (PD) at a pair of redox peak is at 60mV～90mV;
(3) under magnetic agitation speed 200rpm～500rpm condition; Graphene oxide-CNT-chitosan solution that step (1) obtains is a working electrode handling the glass-carbon electrode that obtains with step (2); Platinized platinum is to electrode, and mercurous chloride electrode is in the three-electrode system of contrast electrode, uses electrochemical workstation to carry out the potentiostatic method electro-deposition; Mode of deposition is: sedimentation potential-0.5V～-1.5V, sedimentation time 300s～500s; Graphene, CNT and shitosan on the glass-carbon electrode surface, are obtained Graphene, CNT and shitosan deposition modified glassy carbon by a step electro-deposition.
The method of application of above-mentioned no enzyme parathion-methyl detecting sensor:
Prepare the parathion-methyl sample solution with phosphate buffer, described Graphene, CNT and shitosan deposition modified glassy carbon are soaked wherein, parathion-methyl is fully adsorbed; After this, be working electrode with Graphene, CNT and shitosan deposition modified glassy carbon again, platinized platinum is to electrode, mercurous chloride electrode is under the three-electrode system of contrast electrode, uses electrochemical workstation; Adopt square wave volt-ampere working method, the parathion-methyl of various criterion concentration is detected, the production standard working curve, thus realize mensuration to parathion-methyl.
In the above-mentioned method of application: use that the pH value is 3～7, concentration is the phosphate buffer preparation normal concentration of the 0.05mol/L～0.20mol/L parathion-methyl sample solution as 2ng/mL, 8ng/mL, 17ng/mL, 50ng/mL, 80ng/mL, 100ng/mL, 120ng/mL, 150ng/mL, 180ng/mL, 200ng/mL; Graphene, CNT and shitosan deposition modified glassy carbon are soaked wherein 150s～300s, parathion-methyl is fully adsorbed.
Also can be earlier in the above-mentioned method of application phosphate buffer that 4mL～20mL, pH value are 3～7, concentration is 0.05mol/L～0.20mol/L be mixed with the parathion-methyl of 4 μ g～20 μ g, preparation concentration is 1 μ g/mL parathion-methyl sample solution; Graphene, CNT and shitosan deposition modified glassy carbon are soaked wherein 150s～300s, parathion-methyl is fully adsorbed; Use again that the pH value is 3～7, concentration as the phosphate buffer of 0.05mol/L～0.20mol/L with the above-mentioned 1 μ g/mL parathion-methyl sample solution dilution for preparing; The preparation normal concentration is to be used for behind the parathion-methyl standard solution of 2ng/mL, 8ng/mL, 17ng/mL, 50ng/mL, 80ng/mL, 100ng/mL, 120ng/mL, 150ng/mL, 180ng/mL, 200ng/mL measuring the production standard working curve.
During detection, under magnetic agitation speed 150rpm～400rpm condition, carry out.Testing conditions is: scanning voltage scope-0.4V～+ 0.2V, stepped voltage 3mV～6mV, amplitude 10mV～30mV, frequency 20Hz～30Hz.
The principle of the invention is following:
Utilize electrochemical analysis method that methyl sulphur phosphorus is detected, reason is that methyl sulphur phosphorus can produce tangible redox peak (as shown in Figure 2) on cyclic voltammetry curve.The nitro that its irreversible reduction peak belongs on the methyl sulphur phosphorus is reduced to azanol (shown in 1); A pair of reversible redox peak belongs to the bielectron transfer process (suc as formula 2, formula 3 shown in) of azanol.The parathion-methyl that adds variable concentrations can cause square wave volt-ampere collection of illustrative plates superiors electric current change (as shown in Figure 3).Interfering ion detects the influence little (as shown in table 1) of parathion-methyl to this method.
The influence that the possible chaff interference of table 1 detects parathion-methyl
| Chaff interference | Current ratio |
| Nitrophenol | 0.93 |
| Nitrobenzene | 1.08 |
| Trinitro-toluene | 0.99 |
| PO 4 3- | 0.85 |
| SO 4 2- | 1.14 |
| NO 3 - | 0.91 |
Through this method, we have realized easy, quick, high-sensitivity detection to parathion-methyl.Through this method, the preparation time of no enzyme parathion-methyl detecting sensor is short, and is easy and simple to handle, and the recyclable recycling of this sensor, environmental protection, and its detectability is low to moderate 0.8ng/L; Simultaneously, the sample detection time is short, processing is simple.To sum up, explain that the inventive method is that a kind of no enzyme of easy, quick, environmental protection is to methyl sulphur phosphorus detecting sensor novel preparation method.
Synthetic graphene-carbon nano tube-the chitosan structure of this method is stablized, the detection signal favorable reproducibility, and chemical property is outstanding; CNT struts graphene film, improves its specific surface area effectively, thereby helps realizing the absorption of compound substance to parathion-methyl, improves the sensitivity of sensor.
Description of drawings:
Fig. 1: A, Graphene-shitosan scanning electron microscope; B, graphene-carbon nano tube-shitosan scanning electron microscope;
Fig. 2 is that methyl sulphur phosphorus produces tangible redox peak figure on cyclic voltammetry curve;
Fig. 3 causes the square wave volt-ampere collection of illustrative plates superiors electric current figure that changes for the parathion-methyl of variable concentrations.
Embodiment:
Further specify the present invention below in conjunction with embodiment, and unrestricted the present invention.
Utilize the inventive method inventor to realize easy, quick, high-sensitivity detection to middle parathion-methyl in the soil of Xiang River somewhere.
1, the extraction of parathion-methyl: 1g takes from Xiang River somewhere soil and 5mL normal hexane mixing 2.5 hours under ultrasound condition in the soil; Use the 80kDa dialysis membrane to filter, remove post precipitation, use N
2Residue normal hexane content was 0.1mL～0.5mL during air-blowing was done and extremely filtrated, and the sample after must concentrating is to be detected.
2, the detection of parathion-methyl in the soil:
After 5mg graphite oxide and 5mg CNT mix, join in the chitosan solution of 10mL 0.2wt%; Sonic oscillation 3h obtains graphene oxide-CNT-chitosan solution;
Glass-carbon electrode is polished to " minute surface " with the pasty liquid of 0.3 μ m and 0.05 μ m alumina powder on chamois leather, respectively clean 10min with ethanol, ultrapure water ultrasound wave respectively after rinsing well with deionized water; With glass-carbon electrode be 5.2 in the pH value, concentration is in the phosphate buffer of 0.1mol/L; In-0.6V～+ the 0.6V scanning voltage under; With 0.05V/s sweep velocity scanning 4 circles, in the cyclic voltammogram that obtains, the potential difference (PD) at a pair of redox peak is at 60mV～90mV; Under the magnetic agitation speed 300rpm condition; The former glass-carbon electrode of handling of stating of graphene oxide-CNT-chitosan solution is a working electrode; Platinized platinum is to electrode, and mercurous chloride electrode is in the three-electrode system of contrast electrode, uses electrochemical workstation to carry out the potentiostatic method electro-deposition; Mode of deposition is: sedimentation potential-1.0V, sedimentation time 400s; Graphene oxide, CNT and shitosan on the glass-carbon electrode surface, are obtained Graphene, CNT and shitosan deposition modified glassy carbon by a step electro-deposition.
The phosphate buffer that 5mL, pH value are 5.2, concentration is 0.10mol/L is mixed with the parathion-methyl of 5 μ g, and preparation concentration is 1 μ g/mL parathion-methyl sample solution; Graphene, CNT and shitosan deposition modified glassy carbon are soaked wherein 180s, parathion-methyl is fully adsorbed; Use that the pH value is 5.2, concentration is diluted 500 times, 125 times, 59 times, 20 times, 12.5 times, 10 times, 8.5 times, 6.5 times, 5.5 times, 5 times as the phosphate buffer of 0.10mol/L respectively with the above-mentioned 1 μ g/mL parathion-methyl sample solution for preparing, the preparation normal concentration is to be used for measuring behind the parathion-methyl standard solution of 2ng/mL, 8ng/mL, 17ng/mL, 50ng/mL, 80ng/mL, 100ng/mL, 120ng/mL, 150ng/mL, 180ng/mL, 200ng/mL.After this, be working electrode with Graphene, CNT and shitosan deposition modified glassy carbon again, platinized platinum is to electrode, mercurous chloride electrode is under the three-electrode system of contrast electrode, uses electrochemical workstation; Adopt square wave volt-ampere working method,, under magnetic agitation speed 300rpm condition, detect the parathion-methyl of various criterion concentration, the production standard working curve, thus realize mensuration to parathion-methyl; Testing conditions is: scanning voltage scope-0.4V～+ 0.2V, stepped voltage 5mV, amplitude 20mV, frequency 25Hz.Parathion-methyl concentration is evaluated as 9ng/L in the soil.The 8.7ng/L as a result that its result and inductivity coupled plasma mass spectrometry are measured does not have significant difference.
Claims (10)
1. a no enzyme parathion-methyl detecting sensor is characterized in that, comprising: Graphene, CNT and shitosan deposition modified glassy carbon are working electrode, and platinized platinum is to electrode, and mercurous chloride electrode is the three-electrode system of contrast electrode.
2. no enzyme parathion-methyl detecting sensor according to claim 1 is characterized in that, the preparation method of described Graphene, CNT and shitosan deposition modified glassy carbon is following:
After 5mg～20mg graphite oxide and 5mg～the 20mg CNT mixes, join in the chitosan solution of 5mL～20mL 0.2wt%; Sonic oscillation 3h～4h obtains graphene oxide-CNT-chitosan solution;
Graphene oxide-CNT-chitosan solution is being working electrode with the glass-carbon electrode; Platinized platinum is to electrode; Mercurous chloride electrode is in the three-electrode system of contrast electrode, carries out the potentiostatic method electro-deposition, obtains Graphene, CNT and shitosan deposition modified glassy carbon.
3. no enzyme parathion-methyl detecting sensor according to claim 2 is characterized in that the potentiostatic method electrodeposition condition is: sedimentation potential-0.5V～-1.5V, sedimentation time 300s～500s.
4. no enzyme parathion-methyl detecting sensor according to claim 2 is characterized in that, glass-carbon electrode is the process pre-service before carrying out the potentiostatic method electro-deposition:
Glass-carbon electrode before the electro-deposition in advance on chamois leather the pasty liquid with 0.3 μ m and 0.05 μ m alumina powder be polished to " minute surface ", respectively clean 5min～10min with ethanol, ultrapure water ultrasound wave respectively after rinsing well with deionized water.
5. no enzyme parathion-methyl detecting sensor according to claim 4; It is characterized in that; With pretreated glass-carbon electrode through carrying out the potentiostatic method electro-deposition after the following process again: be 3～7 in pH value, concentration is in the phosphate buffer of 0.05mol/L～0.20mol/L, in-0.6V～+ the 0.6V scanning voltage under, enclose with 0.05V/s～0.2V/s sweep velocity scanning 2～8; In the cyclic voltammogram that obtains, the potential difference (PD) at a pair of redox peak is at 60mV～90mV;
The potentiostatic method electro-deposition is carried out under magnetic agitation speed 200rpm～500rpm condition.
6. the preparation method of each described no enzyme parathion-methyl detecting sensor of claim 1-5; It is characterized in that; Graphene, CNT and shitosan are deposited modified glassy carbon as working electrode; The platinized platinum conduct is to electrode, and mercurous chloride electrode constitutes three-electrode system as contrast electrode; The preparation method of described Graphene, CNT and shitosan deposition modified glassy carbon is following:
(1) after 5mg～20mg graphite oxide and 5mg～the 20mg CNT mixes, joins in the chitosan solution of 5mL～20mL 0.2wt%; Sonic oscillation 3h～4h obtains graphene oxide-CNT-chitosan solution, and is subsequent use;
(2) glass-carbon electrode is polished to " minute surface " with the pasty liquid of 0.3 μ m and 0.05 μ m alumina powder on chamois leather, respectively cleans 5min～10min with ethanol, ultrapure water ultrasound wave respectively after rinsing well with deionized water; Then with glass-carbon electrode be 3～7 in the pH value, concentration is in the phosphate buffer of 0.05mol/L～0.20mol/L; In-0.6V～+ the 0.6V scanning voltage under; With 0.05V/s～0.2V/s sweep velocity scanning 2～8 circles; In the cyclic voltammogram that obtains, the potential difference (PD) at a pair of redox peak is at 60mV～90mV;
(3) under magnetic agitation speed 200rpm～500rpm condition; Graphene oxide-CNT-chitosan solution that step (1) obtains is a working electrode handling the glass-carbon electrode that obtains with step (2); Platinized platinum is to electrode, and mercurous chloride electrode is in the three-electrode system of contrast electrode, uses electrochemical workstation to carry out the potentiostatic method electro-deposition; Mode of deposition is: sedimentation potential-0.5V～-1.5V, sedimentation time 300s～500s; Graphene, CNT and shitosan on the glass-carbon electrode surface, are obtained Graphene, CNT and shitosan deposition modified glassy carbon by a step electro-deposition.
7. the method for application of each described no enzyme parathion-methyl detecting sensor of claim 1-5 is characterized in that,
Prepare the parathion-methyl sample solution with phosphate buffer, described Graphene, CNT and shitosan deposition modified glassy carbon are soaked wherein, parathion-methyl is fully adsorbed; After this, be working electrode with Graphene, CNT and shitosan deposition modified glassy carbon again, platinized platinum is to electrode, mercurous chloride electrode is under the three-electrode system of contrast electrode, uses electrochemical workstation; Adopt square wave volt-ampere working method, the parathion-methyl of various criterion concentration is detected, the production standard working curve, thus realize mensuration to parathion-methyl.
8. method of application according to claim 7 is characterized in that,
Use that the pH value is 3～7, concentration is the phosphate buffer preparation normal concentration of the 0.05mol/L～0.20mol/L parathion-methyl sample solution as 2ng/mL, 8ng/mL, 17ng/mL, 50ng/mL, 80ng/mL, 100ng/mL, 120ng/mL, 150ng/mL, 180ng/mL, 200ng/mL; Graphene, CNT and shitosan deposition modified glassy carbon are soaked wherein 150s～300s, parathion-methyl is fully adsorbed.
9. method of application according to claim 7 is characterized in that,
During detection, under magnetic agitation speed 150rpm～400rpm condition, carry out.
10. method of application according to claim 7 is characterized in that,
Testing conditions is: scanning voltage scope-0.4V～+ 0.2V, stepped voltage 3mV～6mV, amplitude 10mV～30mV, frequency 20Hz～30Hz.
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