CN106525949B - A kind of electrochemical detection method of organophosphorus pesticide - Google Patents
A kind of electrochemical detection method of organophosphorus pesticide Download PDFInfo
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Abstract
The invention discloses a kind of electrochemical detection methods of organophosphorus pesticide.The detection method are as follows: graphene-chitosan-parathion compound modification electrochemical sensor is prepared first, then with K3[Fe(CN)6] it is probe, the principle of strong combination can occur with organophosphorus pesticide based on acetylcholinesterase, carry out differential pulse voltammetry (DPV) scanning, recording responses electric current, by the analysis and derivation of related data, the concentration of corresponding organophosphorus pesticide in sample to be tested can be obtained.Detection method provided by the invention limits between 0.012~0.23ng/mL the detection of organophosphorus pesticide, and the range of linearity is 1~1500ng/mL.The present invention is with following the utility model has the advantages that compared with other carry out methods that organophosphorus pesticide quickly detects using enzyme inhibition, detection method provided by the invention is without carrying out enzymatic reaction, therefore detection time is greatly saved, while also avoids because of the problem of using testing result poor repeatability caused by the enzyme of separate sources.
Description
Technical field
The invention belongs to food safety detections and technical field of analytical chemistry, are related to a kind of electrochemistry inspection of organophosphorus pesticide
Survey method particularly relates to a kind of detection side based on acetylcholinesterase and organophosphorus pesticide with strong combination
Method.
Background technique
China is a large agricultural country, and the agricultural output imported and exported every year occupies first place in the world.Organophosphorus pesticide is because having product
The features such as kind more, drug effect height, desinsection spectrum width, it has been increasingly becoming that China is most widely used, the maximum insecticides of usage amount.It is organic
Phosphorus pesticide also brings huge harm to food safety, ecosystem etc. while bringing great economic benefit to China.
In recent years, organophosphorus pesticide acute poisoning event takes place frequently, such organic phosphorus pesticide poisoning event consequence is serious, makes a very bad impression,
Therefore, the national supervision used organophosphorus pesticide in recent years and requirement are increasingly stringent.
The detection method of organophosphorus pesticide mainly includes gas chromatography-mass spectrometry, liquid chromatograph mass spectrography at present
Method, high performance liquid chromatography and enzyme inhibition etc..Chromatography alanysis method needs large-sized analytic instrument, and process is cumbersome,
It can not achieve on-site test, a kind of ten kinds of organophosphorus pesticide sides of Magneto separate-gas chromatographic detection disclosed in 103901129 A of CN
Method, used detection method are exactly chromatography alanysis method；Enzyme inhibition is then since instrument miniaturization, detection time are short etc.
Advantage occupies a tiny space in organic phosphorus field of fast detection, and 103421880 B of CN discloses a kind of detection of organic phosphorus pesticide side
Method, what is used is exactly typical enzyme inhibition.However, due to used enzyme source multiplicity, catalytic selectivity and catalysis
It is active big variant, detrimental effect is brought to actually detected repeatability and reliability.
Summary of the invention
The present invention designs sensor using molecule simulation method, and analog study chitosan first is to parathion
Modification and acetylcholinesterase and organophosphorus pesticide recognition mechanism, discovery parathion and chitosan are with very strong
Intermolecular force is conducive to modify；Using the combination of acetylcholinesterase and organophosphorus pesticide small molecule, analyze
The key effect group of machine phosphorus small molecule and site find that the small molecule modified on chitosan orientation completely can be by acetylcholine
Esterase identification, is suitable for the development of such sensor.Based on this, the present invention provides one kind to be not necessarily to enzymatic reaction, detection time
The electrochemical detection method of short, detectable Determination of Organophosphorus Pesticide.
The purpose of the present invention is to provide a kind of electrochemical detection method of organophosphorus pesticide, the detection method quickly,
Efficiently, high sensitivity, stability are good.
To achieve the above object, the technical solution adopted in the present invention is as follows:
A kind of electrochemical detection method of organophosphorus pesticide, comprising the following steps:
1) preparation of electrochemical sensor: by graphene-chitosan-parathion compound drop coating in clean glass-carbon electrode
Surface is made organic phosphorus pesticide multi-residue and detects electrochemical sensor；
2) preparation of Incubating Solution: the phosphate buffer solution for containing organophosphorus pesticide and acetylcholinesterase (AChE) is prepared
(PBS), Incubating Solution is called in the following text；
3) foundation of working curve: electrochemical sensor described in step 1) is immersed in the step 2) Incubating Solution and is incubated
It educates, is rinsed well with phosphate buffer solution, in K3[Fe(CN)6] differential pulse voltammetry (DPV) scanning is carried out in solution, record is rung
Answer electric current；The response current of blank standard specimen is I0, the response current containing organophosphorus pesticide standard specimen is Ix, the increase of response current
It is worth Δ I and is equal to IxWith I0Difference；The concentration C of organophosphorus pesticide in the Δ I and Incubating Solution is depicted as Δ I-C working curve,
Δ I-C equation of linear regression is obtained using linear regression method；
4) measurement of organophosphorus pesticide: sample to be tested is formulated as containing the acetylcholinesterase with step 2) same concentrations
Incubating Solution, according to method identical with step 3) to the electrochemical sensor described in step 1) carry out be incubated for and differential pulse volt
Peace scanning, recording responses electric current；The value added Δ I of electric current and Δ I-C equation of linear regression according to response obtain corresponding organic phosphorus
The content of pesticide.
Preferably, the organophosphorus pesticide is parathion, phoxim, chlopyrifos, DDVP, acephatemet, methylpyrimidine
One of phosphorus, Rogor, flolimat, diazinon, Entex, metrifonate.
Preferably, organophosphorus pesticide concentration is followed successively by 0ng/mL, 1ng/mL, 10ng/mL, 50ng/ in the Incubating Solution
ML, 100ng/mL, 200ng/mL, 400ng/mL, 600ng/mL, 800ng/mL, 1200ng/mL and 1500ng/mL, wherein containing
Having concentration is the acetylcholinesterase (AChE) of 10 μ g/mL.
Preferably, 10mg graphene the preparation method of the graphene-chitosan-parathion compound: is added to 4mL
Mass concentration is in the chitosan solution of 1g/L, and revolving speed 5000rpm ultrasonic disperse 30min, it is dense to be then added 2mL mass at room temperature
Degree is the parathion solution of 0.2g/L, continues ultrasound 30min, is placed in 4 DEG C of refrigerators and stores.
Preferably, the preparation method of the electrochemical sensor: the glass-carbon electrode Al for being 3mm by diameter2O3Polishing powder is beaten
It is milled to mirror surface, and is successively cleaned by ultrasonic 5min with ethyl alcohol, distilled water, then clean with distilled water flushing；6 μ L graphenes-shell is gathered
Sugar-parathion compound drop coating is placed in 37 DEG C of vacuum ovens and dries in the glassy carbon electrode surface cleaned up；Then by glass
Carbon electrode is placed in the bovine serum albumen solution that mass percent concentration is 0.05% and is incubated for 30min, poly- to close graphene-shell
The active site of sugared surface residual；Electrode surface finally is rinsed with the phosphate buffer solution that pH is 7.4, the electrochemistry is made and passes
Sensor.
Preferably, the electrochemical sensor includes substrate glass-carbon electrode, and modification is in the graphene-of glassy carbon electrode surface
Chitosan-parathion complexes membrane.
Detection method provided by the invention limits the linear model between 0.012~0.23ng/mL to the detection of organophosphorus pesticide
It encloses for 1~1500ng/mL.
The present invention is based on the principles that strong combination occurs for acetylcholinesterase (AchE) and organophosphorus pesticide, are tied
It closes on the electrochemical sensor, to change the electrochemical response signal of electrochemical sensor, realizes organophosphorus pesticide
Detection.
The present invention is with following the utility model has the advantages that carrying out the side that organophosphorus pesticide quickly detects using enzyme inhibition with other
Method is compared, and without carrying out enzymatic reaction detection time is greatly saved, while also avoiding in detection method provided by the invention
Because of the problem of testing result poor repeatability caused by the enzyme using separate sources.
Detailed description of the invention
Fig. 1 is graphene-chitosan-parathion compound ultraviolet-visible absorption spectroscopy figure.
Fig. 2 is the DPV curve graph that electrochemical sensor detects parathion.
Fig. 3 is the DPV curve graph that electrochemical sensor detects phoxim.
Fig. 4 is the DPV curve graph that electrochemical sensor detects chlopyrifos.
Fig. 5 is the DPV curve graph that electrochemical sensor detects DDVP.
Fig. 6 is the DPV curve graph that electrochemical sensor detects acephatemet.
Fig. 7 is the DPV curve graph that electrochemical sensor detects pirimiphos-methyl.
Fig. 8 is the DPV curve graph that electrochemical sensor detects Rogor.
Fig. 9 is the DPV curve graph that electrochemical sensor detects flolimat.
Figure 10 is the DPV curve graph that electrochemical sensor para-diazines phosphorus is detected.
Figure 11 is the DPV curve graph that electrochemical sensor detects Entex.
Figure 12 is the DPV curve graph that electrochemical sensor detects metrifonate.
Figure 13 is the Δ I-C working curve of parathion detection.
Specific embodiment
Technical solutions according to the invention are further described in detail below by specific embodiment combination attached drawing.
The preparation of 1 detection of organic phosphorus pesticide electrochemical sensor of embodiment
(1) graphene-chitosan-parathion compound preparation
Graphene (10mg) is added in 4mL chitosan solution (mass concentration 1g/L), at room temperature ultrasonic disperse
Then 2mL parathion solution (mass concentration 0.2g/L) is added in 30min (revolving speed 5000rpm), continues ultrasound 30min, sets
It is stored in 4 DEG C of refrigerators stand-by.
Graphene-chitosan-parathion compound ultraviolet-visible absorption spectroscopy is as shown in Figure 1.Graphene-chitosan point
The maximum absorption band of dispersion liquid is 262nm, and the maximum absorption band of parathion is 272nm, graphene-chitosan-parathion compound
Maximum absorption band be 267nm, between graphene-chitosan and parathion, it is right to show to have formed graphene-chitosan-
Sulphur phosphorus compound.
(2) glass-carbon electrode (diameter 3mm) preparation of electrochemical sensor: is used into Al2O3Polishing powder is polishing to mirror surface, and
Successively it is cleaned by ultrasonic 5min with ethyl alcohol, distilled water, then clean with distilled water flushing；Graphene-the shell prepared in embodiment 1 is gathered
Sugar-parathion compound (6 μ L) drop coating is placed in 37 DEG C of vacuum ovens and dries in the glassy carbon electrode surface cleaned up；So
Glass-carbon electrode is placed in bovine serum albumen solution (mass percent concentration 0.05%) afterwards and is incubated for 30min, to close graphite
Alkene-chitosan surface residual active site；Electrode surface finally is rinsed with phosphate buffer solution (pH 7.4), is made described
Electrochemical sensor.
Electrochemical sensor obtained includes substrate glass-carbon electrode, and modification is poly- in graphene-shell of glassy carbon electrode surface
Sugar-parathion complexes membrane.
The detection of 2 organophosphorus pesticide standard sample of embodiment
The present embodiment respectively detects organophosphorus pesticide standard sample, and organophosphorus pesticide sample is selected from parathion, pungent
Sulphur phosphorus, chlopyrifos, DDVP, acephatemet, pirimiphos-methyl, Rogor, flolimat, diazinon, Entex and metrifonate.
The electrochemical sensor prepared in embodiment 1 is immersed into organophosphorus pesticide concentration respectively and is followed successively by 0ng/mL, 1ng/
ML, 10ng/mL, 50ng/mL, 100ng/mL, 200ng/mL, 400ng/mL, 600ng/mL, 800ng/mL, 1200ng/mL and
It is incubated in the Incubating Solution (AchE for being wherein 10 μ g/mL containing concentration) of 1500ng/mL, is rinsed with phosphate buffer solution
Completely, in K3[Fe(CN)6] differential pulse voltammetry (DPV) scanning, recording responses electric current are carried out in solution；The response of blank standard specimen
Electric current is I0, the response current containing organic phosphorus standard specimen is Ix, the value added Δ I of response current is equal to IxWith I0Difference；By institute
It states concentration C organic phosphorus in Δ I and Incubating Solution and is depicted as Δ I-C working curve, Δ I-C is obtained using linear regression method and is linearly returned
Return equation.
Sample to be tested be incubated for the electrochemical sensor under similarity condition using same procedure and DPV is swept
It retouches, recording responses electric current；The value added Δ I of response current is substituted into Δ I-C equation of linear regression, can be obtained in sample to be tested
The concentration of corresponding organophosphorus pesticide.
Fig. 2~Figure 12 is followed successively by parathion, phoxim, chlopyrifos, DDVP, acephatemet, pirimiphos-methyl, Rogor, oxygen
The DPV curve for changing Rogor, diazinon, Entex and metrifonate, wherein concentration is followed successively by curve from top to bottom in every width figure
1500ng/mL、1200ng/mL、800ng/mL、600ng/mL、400ng/mL、200ng/mL、100ng/mL、50ng/mL、
10ng/mL, 1ng/mL and 0ng/mL.
Figure 13 is the Δ I-C working curve of parathion detection, and the range of linearity is 1~1500ng/mL, wherein linear regression
Equation Δ I=12.62071+0.00902C, linearly dependent coefficient R=0.99393.
The Δ I-C equation of linear regression of above-mentioned detection of organic phosphorus pesticide, linearly dependent coefficient (R), the range of linearity and minimum
Detection limit is shown in Table 1.
1 organophosphorus residue amount of table individually detects
The mark-on of 3 apple Chlorpyrifos of embodiment detects
The apple sample (three parts of parallel samples, every part of quality are 50 ± 0.005g) cleaned up is weighed to be put into beaker,
Chlopyrifos standard solution is added, 50mL water and 100mL acetone is then added, is rubbed with pulverizer and extracts 3min.It is taken after filtering
100mL filtrate is placed in separatory funnel, and 15g sodium chloride is added, stands after acutely vibrating 3min, uses 50mL bis- after solution layering
Chloromethanes aqueous phase extracted merges acetone and dichloromethane extract.Wherein moisture is dried and removed with anhydrous sodium sulfate, is rotated dense
It is reduced to about 2mL, is dried up remaining liq with nitrogen, is eventually adding 10mL ethanol-water solution (V:V=1:1), concussion to dissolution,
Low temperature shading saves stand-by.
The mark-on of the blank sample for being added without chlopyrifos and the different chlopyrifos concentration of 3 additions is prepared according to the method described above
Sample (standard addition method), and incubation and DPV scanning, note are carried out to the electrochemical sensor in method described in embodiment 2
Record response current；According to the Δ between the value added Δ I of the corresponding response current of chlopyrifos obtained in embodiment 2 and concentration C
The concentration of chlopyrifos is calculated in I-C equation of linear regression.The detection rate of recovery the results are shown in Table 2.
The mark-on testing result of 2 apple Chlorpyrifos of table
The mark-on detection of DDVP in 4 green vegetables of embodiment
The green vegetables sample (three parts of parallel samples, every part of quality are 50 ± 0.005g) cleaned up is weighed to be put into beaker,
DDVP standard solution is added, 50mL water and 100mL acetone is then added, is rubbed with pulverizer and extracts 3min.It is taken after filtering
100mL filtrate is placed in separatory funnel, and 15g sodium chloride is added, stands after acutely vibrating 3min, uses 50mL bis- after solution layering
Chloromethanes aqueous phase extracted merges acetone and dichloromethane extract.Wherein moisture is dried and removed with anhydrous sodium sulfate, is rotated dense
It is reduced to about 2mL, is dried up remaining liq with nitrogen, is eventually adding 10mL ethanol-water solution (V:V=1:1), concussion to dissolution,
Low temperature shading saves stand-by.
The mark-on of the blank sample for being added without DDVP and the different DDVP concentration of 3 additions is prepared according to the method described above
Sample (standard addition method), and incubation and DPV scanning, note are carried out to the electrochemical sensor in method described in embodiment 2
Record response current；According to the Δ between the value added Δ I of the corresponding response current of DDVP obtained in embodiment 2 and concentration C
The concentration of DDVP is calculated in I-C equation of linear regression.The detection rate of recovery the results are shown in Table 3.
The mark-on testing result of DDVP in 3 green vegetables of table
Claims (6)
1. a kind of electrochemical detection method of organophosphorus pesticide, comprising the following steps:
1) preparation of electrochemical sensor: by graphene-chitosan-parathion compound drop coating in clean glass-carbon electrode table
Electrochemical sensor is made in face；
2) preparation of Incubating Solution: the phosphate buffer solution containing organophosphorus pesticide and acetylcholinesterase is prepared, calls Incubating Solution in the following text；
3) foundation of working curve: electrochemical sensor described in step 1) being immersed in the step 2) Incubating Solution and is incubated for, with
Phosphate buffer solution is rinsed well, in K3[Fe(CN)6] differential pulse voltammetry scanning, recording responses electric current are carried out in solution；Blank
The response current of standard specimen is I0, the response current containing organophosphorus pesticide standard specimen is Ix, the value added Δ I of response current is equal to Ix
With I0Difference；The concentration C of organophosphorus pesticide in the Δ I and Incubating Solution is depicted as Δ I-C working curve, is returned using linear
Method is returned to obtain Δ I-C equation of linear regression；
4) sample to be tested the measurement of organophosphorus pesticide: is formulated as incubating containing the acetylcholinesterase with step 2) same concentrations
Liquid is educated, the electrochemical sensor described in step 1) be incubated for according to method identical with step 3) and differential pulse voltammetry is swept
It retouches, recording responses electric current；The value added Δ I of electric current and Δ I-C equation of linear regression according to response, obtain corresponding organophosphorus pesticide
Content.
2. a kind of electrochemical detection method of organophosphorus pesticide according to claim 1, it is characterised in that: described is organic
Phosphorus pesticide be parathion, phoxim, chlopyrifos, DDVP, acephatemet, pirimiphos-methyl, Rogor, flolimat, diazinon, times
One of sulphur phosphorus, metrifonate.
3. a kind of electrochemical detection method of organophosphorus pesticide according to claim 1, it is characterised in that: the incubation
In liquid organophosphorus pesticide concentration be followed successively by 0ng/mL, 1ng/mL, 10ng/mL, 50ng/mL, 100ng/mL, 200ng/mL,
400ng/mL, 600ng/mL, 800ng/mL, 1200ng/mL and 1500ng/mL, wherein the acetyl for being 10 μ g/mL containing concentration
Cholinesterase.
4. a kind of electrochemical detection method of organophosphorus pesticide according to claim 1, it is characterised in that: the graphite
Alkene-chitosan-parathion compound preparation method is that 10mg graphene is added to the chitosan that 4mL mass concentration is 1g/L
In solution, revolving speed 5000rpm ultrasonic disperse 30min, it is molten to be then added the parathion that 2mL mass concentration is 0.2g/L at room temperature
Liquid continues ultrasound 30min, is placed in 4 DEG C of refrigerators and stores.
5. a kind of electrochemical detection method of organophosphorus pesticide according to claim 1, it is characterised in that: the electrification
The preparation method for learning sensor is the glass-carbon electrode Al for being 3mm by diameter2O3Polishing powder is polishing to mirror surface, and successively with ethyl alcohol,
Distilled water is cleaned by ultrasonic 5min, then clean with distilled water flushing；By 6 μ L graphene-chitosan-parathion compound drop coatings clear
The glassy carbon electrode surface of wash clean is placed in 37 DEG C of vacuum ovens and dries；Then it is dense glass-carbon electrode to be placed in mass percent
Degree is is incubated for 30min in 0.05% bovine serum albumen solution, to close graphene-chitosan surface residual active site；
Electrode surface finally is rinsed with the phosphate buffer solution that pH is 7.4, the electrochemical sensor is made.
6. a kind of electrochemical detection method of organophosphorus pesticide according to claim 1, it is characterised in that: the electrochemistry
Sensor includes substrate glass-carbon electrode, and modification is in graphene-chitosan-parathion complexes membrane of glassy carbon electrode surface.
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| CN110031521B (en) * | 2019-05-15 | 2021-07-27 | 贵州大学 | Preparation of acetylcholinesterase biosensor and application of acetylcholinesterase biosensor in detection of organophosphorus |
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