CN106370708B - A kind of electrochemical sensor and its detection method of organophosphorus pesticide residual quantity detection - Google Patents
A kind of electrochemical sensor and its detection method of organophosphorus pesticide residual quantity detection Download PDFInfo
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Abstract
The invention discloses the electrochemical sensors and its detection method of a kind of detection of organophosphorus pesticide residual quantity.The electrochemical sensor surface modification has nanogold particle, and sulfydryl second acephatemet amide molecule self assembly is connected to a nanometer gold surface by Au S keys.Using acetylcholinesterase the principle of strong combination can occur with organophosphorus insecticide for the present invention, provide it is a kind of without enzymatic reaction, detection time is short, the electrochemical detection method of can be used for organophosphor individually detection and total amount detection.
Description
Technical field
The invention belongs to food safety detections and analysis technical field, are related to one kind and can be used for organophosphorus pesticide residual quantity inspection
The electrochemical test sensors and its detection method of survey.
Background technology
China is populous nation, a large agricultural country, and the agricultural output imported and exported every year occupies first place in the world, organophosphorus pesticide
Have the characteristics that insecticidal spectrum is wider, desinsection mode is diversified, wide in variety, drug effect is high, degradable, the residence time is short, with strong points,
It has become in order to which China's use scope is most wide, the maximum insecticides of usage amount, huge economic benefit is brought to China.But
On the other hand, also huge harm is brought to food security, ecosystem etc..According to several organophosphorus poisonings reported recently
Event, organic phosphorus pesticide poisoning event, which occurs, for Zhong County causes 3 people dead, and 11 people are admitted to hospital；The thimet that Qingdao occurs severely exceeds
Malicious leek event causes 11 people to be poisoned；5.23 organophosphor event of Wuhan causes multidigit patient acute poisoning occur；The first of Jiangmen city
Amine phosphorus acute poisoning event；During 18 students in Qimen County, Anhui Province middle school are due to eating the green vegetables containing organophosphorus pesticide
Poison.Organic phosphorus pesticide poisoning event frequently occurs in recent years, brings serious social influence, and country uses organophosphorus pesticide
Supervision and require it is increasingly strict.
Country all defines its maximum residue limit (MRL) to each pesticide, this is inspection and quarantine department judgement agriculture at different levels
The whether qualified most basic standard of product, however " cocktail " method is widely present during Pesticide use, i.e., make simultaneously
The pesticide similar in a variety of effects reaches same purpose.This method can not only reach preferable practical function, but also can be with
It avoids making its content be judged to substandard product more than MRL using a kind of single pesticide.But the similar a variety of agricultures of effect
Although each is not all exceeded for medicine, its total amount is likely to be exceeded, from the point of view of the impact effect to human body and environment, still
So have and centainly endangers and need to draw attention.
The harmfulness of organophosphorus insecticide is mainly since organophosphor is easy and the acetylcholinesterase (AChE) in human body
Activated centre combine, inhibit the catalytic activity of AChE, lose catalysis acetylcholine (Ach) hydrolyze ability, to make choline
Assemble in human body, cause the disorder of Nerve conduction, a series of poisoning symptoms occurs.If had there are a variety of in crops
The Phosphorus pesticide of machine, although the content of each of which is below the MRL values of national regulation, since the inhibiting effect to AChE is
It can sum it up, therefore still suffer from the danger for causing poisoning.
Method currently used for organophosphorus residue detection mainly has gas chromatography-mass spectrometry, liquid phase chromatogram-mass spectrometry combination
Usage, high performance liquid chromatography and enzyme inhibition etc..Chromatography alanysis method needs large-sized analytic instrument, process operation numerous
It is trivial, it can not achieve Site Detection；Then since instrument miniaturization, detection time be short etc., advantages quickly detect enzyme inhibition in organophosphor
Field occupies a tiny space.However, since used enzyme source is various, selectivity and activity are all big variant, to practical
The repeatability and reliability of detection bring detrimental effect.
Invention content
The purpose of the present invention is to provide a kind of electrochemical test sensors of organophosphorus pesticide residual quantity.The sensing
Device can be used for independent detection and the total amount detection of organophosphorus pesticide residual quantity.
Another object of the present invention is to provide a kind of electrochemical methods of organophosphorus pesticide residual quantity detection.The detection
Method is quickly, efficient, 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 sensor of organophosphorus pesticide residual quantity detection, including basal electrode, which is characterized in that the electricity
The basal electrode surface deposition of chemical sensor has nanogold particle, sulfydryl second methylamine phosphamide to be modified in substrate electricity by Au-S
On the nanogold particle of pole surface deposition.
Preferably, the basal electrode is glass-carbon electrode.
The electrochemical sensor is prepared with the following method：It first will be by polishing, polishing and the substrate being cleaned by ultrasonic
Electrode immerses in chlorauric acid solution, uses potentiostatic method by gold chloride electrochemical reduction for nanogold particle, and be deposited on substrate
Electrode surface；Again by sulfydryl second methylamine phosphamide (TMA) solution drop coating on basal electrode surface, dry, pass through self assembly sulfydryl
Second methylamine phosphamide is modified with Au-S keys on the nanogold particle deposited to electrode surface；Finally received with the closing of sulfydryls hexanol solution
The residual activity site on rice gold particle surface.
Sulfydryl second methylamine phosphamide (TMA) structure is shown below,
It is prepared using following methods in the embodiment of the present invention：By N-bromosuccinimide (NHS) and 1- (3- dimethylaminos
Propyl) -3- ethyl-carbodiimide hydrochlorides (EDC) are dissolved in phosphate buffer solution (PBS) and are stirred at room temperature, it is then added to sulfydryl second
It is stirred in acid solution, finally adds in the hydrochloric acid solution of acephatemet and be stirred to react；Solid is precipitated after revolving solvent, obtains institute
The TMA stated.
A kind of electrochemical detection method of organophosphorus pesticide residual quantity, includes the following steps：
(1) preparation of electrochemical sensor：
First the glass-carbon electrode by polishing, polishing and ultrasonic cleaning is immersed in chlorauric acid solution, with constant potential electrochemistry
Gold chloride is reduced to nanogold particle by reduction method, and is deposited on glassy carbon electrode surface, uses PBS buffer solutions cleaning glass carbon electricity
It simultaneously dries pole；Again by sulfydryl second methylamine phosphamide (TMA) solution drop coating in glassy carbon electrode surface, dry；Finally use sulfydryls hexanol
Solution closes the residual activity site on glassy carbon electrode surface nanogold particle surface；Electrochemical sensor is made；
(2) preparation of standard solution：
The PBS bufferings for preparing one group of organophosphorus pesticide sample containing different known concentrations including blank standard specimen are molten
Liquid is standard solution, wherein the acetylcholinesterase (AChE) containing same concentrations；
(3) foundation of working curve：
The electrochemical test sensors prepared in step (1) are immersed respectively in the standard solution prepared in step (2) and are incubated
It educates, rinses electrochemical test sensors with PBS buffer solutions after incubation, then the electrochemical test sensors after flushing are placed in and are contained
There is K3[Fe(CN)6] PBS buffer solutions in carry out square wave voltammetry (SWV) scan, recording responses electric current；The sound of blank standard specimen
Induced current is I0, the response current containing organophosphor standard sample is Ix, the value added Δ I of response current is equal to IxWith I0Difference
Absolute value；The concentration C of organophosphorus pesticide in the Δ I and standard solution is depicted as Δ I-C working curves, is returned using linear
Method is returned to obtain Δ I-C equations of linear regression；
(4) detection of organophosphorus pesticide residual quantity：
It is molten that sample to be tested is formulated as the bufferings of the PBS containing the acetylcholinesterase (AChE) with step (2) same concentrations
Liquid to the electrochemical sensor be incubated and square wave voltammetry (SWV) scans, note according to the identical method with step (3)
Record response current；The value added Δ I of electric current and Δ I-C equations of linear regression according to response, it is residual to be calculated organic phosphorus compound
Allowance.
The organophosphorus pesticide residual quantity electrochemical detection method can also examine the total amount of organophosphorus residue amount
It surveys, further comprises the steps：
(5) organophosphorus pesticide total amount detects：
The different organophosphors obtained in step (3) are detected into corresponding Δ I-C equations of linear regression and advance fitting (to step
(3) slope of the corresponding Δ I-C equations of linear regression of different organophosphors obtained in, intercept distinguish averaged), had
The working curve of machine phosphorus residual quantity total amount detection；Sample to be tested is formulated as containing the acetylcholine with step (2) same concentrations
The PBS buffer solutions of esterase (AChE) carry out incubation and side according to the identical method with step (3) to the electrochemical sensor
Wave voltammetry (SWV) scans, recording responses electric current；Work between the value added of electric current and organophosphorus residue total amount according to response
Organophosphorus pesticide total amount is calculated in curve.
The organophosphorus pesticide includes but not limited to Entex, metrifonate, DDVP, chlopyrifos, parathion, diazine
Phosphorus, acephatemet, pirimiphos-methyl, Rogor, phoxim and flolimat.
The present invention is based on the principles that strong interaction 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 residue
Detection.The electrochemical sensor and its detection method of the present invention, it is short without enzymatic reaction, detection time, it can be used for organophosphor
Individually detection and total amount detection.
Electrochemical sensor of the present invention and detection method can be used for plant-derived food such as veterinary antibiotics, and
The independent detection and total amount detection of organophosphorus residue amount in environment.
A kind of detection when electrochemical sensor provided by the invention individually detects organophosphorus pesticide is limited to 0.19~
0.77ng/mL, the range of linearity are 1~1500ng/mL；When being detected for variety classes organophosphorus pesticide total amount, the range of linearity exists
Within the scope of 50~1000ng/mL, the relative error of total amount testing result is less than 10%.
Advantageous effect：The original of strong combination can occur using acetylcholinesterase with organophosphorus insecticide for the present invention
Reason, provide it is a kind of without enzymatic reaction, detection time is short, can be used for organophosphor individually detection and total amount detection electrochemistry pass
Sensor and its detection method.Electrochemical sensor of the present invention is prepared using chemical modification method, greatly strengthens sensor
Stability and repeatability so that working curve when variety classes organophosphorus pesticide individually detects is very close, thus reduces
The error brought when total amount detection working curve fitting, improves the reliability and accuracy of total amount testing result；Meanwhile this hair
It is bright with other using the method that quickly detects of enzyme inhibition progress organophosphor the difference is that electrochemical sensing provided by the invention
Without carrying out enzymatic reaction detection time is greatly saved, while also avoiding because using separate sources in device and detection method
Enzyme caused by testing result poor repeatability the problem of.
With reference to specific embodiment, the present invention will be described in detail.Protection scope of the present invention is not with specific implementation
Mode is limited, but is defined in the claims.
Description of the drawings
Fig. 1 be sulfydryl second methylamine phosphamide (TMA) hydrogen nuclear magnetic resonance spectrum (1H-NMR)。
Fig. 2 a)-Fig. 2 d) be followed successively by electrochemical sensor Entex, metrifonate, DDVP and chlopyrifos are carried out respectively it is single
The SWV curve graphs solely detected, wherein concentration is followed successively by 0ng/mL, 1ng/mL, 10ng/mL, 50ng/ from top to bottom in every width figure
ML, 100ng/mL, 200ng/mL, 400ng/mL, 600ng/mL, 800ng/mL, 1200ng/mL and 1500ng/mL.
Fig. 3 a)-Fig. 3 d) be followed successively by electrochemical sensor respectively to parathion, diazinon, acephatemet and pirimiphos-methyl into
The SWV curve graphs that row individually detects；In wherein every width figure from top to bottom 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.
Fig. 4 a)-Fig. 4 c) is followed successively by electrochemical sensor and individually detected to Rogor, phoxim and flolimat respectively
SWV curve graphs；In wherein every width figure from top to bottom 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.
Fig. 5 is the Δ I-C working curves individually detected to Entex.
Specific implementation mode
Technical solutions according to the invention are further described in detail below by specific embodiment, but it is necessary to
It points out that following embodiment is served only for the description to invention content, does not constitute limiting the scope of the invention.
The preparation of 1 organophosphorus pesticide residual quantity electrochemical test sensors of embodiment
(1) preparation of sulfydryl second methylamine phosphamide (TMA)
Acephatemet (0.1g) is dissolved in 10mL hydrochloric acid (0.1mol/L), 1h is stirred under condition of ice bath, prepares acephatemet
Hydrochloric acid solution；By N-bromosuccinimide (NHS, 0.542g) and 1- (3- dimethylamino-propyls) -3- ethyl carbodiimides
Hydrochloride (EDC, 0.254g), which is dissolved in during phosphate-buffered is dissolved in, to be stirred at room temperature 3 hours, is slow added into thioacetic acid and (is used
Sodium bicarbonate solution adjusts PH to neutrality) in solution, continues stirring 2 hours, gained reactant is added to the hydrochloric acid of acephatemet
Continue in solution after stirring 10 hours at room temperature, rotary evaporation goes out most of solvent at room temperature, and a large amount of white solids are precipitated.Decompression
It filters, is washed with a small amount of ice water, TMA is made.Its hydrogen nuclear magnetic resonance spectrum (1H-NMR) see Fig. 1.
(2) preparation of sensor：By the glass-carbon electrode of a diameter of 3mm successively with a diameter of 0.3 μm and 0.05 μm of Al2O3
Polishing powder is polishing to minute surface, uses absolute ethyl alcohol-distilled water, distilled water to be cleaned by ultrasonic 5min successively, then clean with distilled water flushing；
The glass-carbon electrode handled well is immersed in chlorauric acid solution (mass percent concentration 1%), with constant potential (- 0.2V) electrification
Learn deposition nanogold (duration 60s)；Above-mentioned electrode is rinsed well with PBS buffer solutions, by sulfydryl second first after drying
Amine phosphinylidyne amine aqueous solution (10 μ L, 0.1mol/L) drop coating on the electrode, is placed in 37 DEG C of vacuum drying chambers and dries；By covalent modification
30min is incubated in the sulfydryls hexanol aqueous solution (mass percent concentration 1%) that electrode after TMA is placed in, to close nanometer
The residual activity site of gold surface finally uses PBS buffer solutions that electrode washing is totally spare.
The independent detection of 2 organophosphor standard sample of embodiment
The present embodiment respectively individually detects organophosphor standard sample, and organophosphorus pesticide sample is selected from Entex, enemy
Hundred worms, DDVP, chlopyrifos, parathion, diazinon, acephatemet, pirimiphos-methyl, Rogor, phoxim and flolimat.
By the electrochemical sensor prepared in embodiment 1 immerse respectively organic phosphorus 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
It is incubated in the PBS buffer solutions (AchE for wherein containing a concentration of 10 μ g/mL) of 1500ng/mL, with PBS buffer solutions
It rinses well and is placed on containing K3[Fe(CN)6] PBS buffer solutions in carry out square wave voltammetry (SWV) scan, recording responses electricity
Stream；The response current of blank standard specimen is I0, the response current containing organophosphor standard specimen is Ix, the value added Δ I of response current is equal to
IxWith I0Difference；The concentration C of organophosphor in Δ I and Incubating Solution is depicted as Δ I-C working curves, is obtained using linear regression method
To Δ I-C equations of linear regression.
Sample to be tested to the electrochemical sensor be incubated under similarity condition using same procedure and SWV is swept
It retouches, recording responses electric current；The value added Δ I of response current is substituted into Δ I-C equations of linear regression, you can obtain in sample to be tested
The residual quantity of corresponding organophosphor.
Attached drawing 2a) -2d), Fig. 3 a) -3d), Fig. 4 a) -4c) be followed successively by Entex, metrifonate, DDVP, chlopyrifos, to sulphur
The SWV curves that phosphorus, diazinon, acephatemet, pirimiphos-methyl, Rogor, phoxim and flolimat individually detect.Attached drawing 5 is pair
The Δ I-C working curves that Entex individually detects.Δ I-C equations of linear regression that above-mentioned organophosphor individually detects, linear correlation
Coefficient (R), the range of linearity and minimum detection limit are shown in Table 1.
The 1 independent testing result of organophosphorus residue amount of table
The mark-on detection of DDVP in 3 apple of embodiment
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,
DDVP standard solution is added, 50mL water and 100mL acetone is then added, extraction 3min is rubbed with pulverizer.It is taken after filtering
100mL filtrates are placed in separatory funnel, and 15g sodium chloride is added, is stood after acutely vibrating 3min, and 50mL bis- is used after solution layering
Chloromethanes aqueous phase extracted merges acetone and dichloromethane extract.Wherein moisture is dried and removed with anhydrous sodium sulfate, revolving is dense
It is reduced to about 2mL, is dried up remaining liq with nitrogen, is eventually adding 10mL ethanol-water solutions (V：V=1：1), concussion is extremely dissolved,
Low temperature shading preserves for use.
The blank sample for being added without DDVP and 3 mark-ons that different DDVP concentration are added are prepared according to the method described above
Sample (standard addition method), and incubation and SWV scannings, 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 and concentration C of the corresponding response current of the DDVP obtained in embodiment 2
I-C equations of linear regression obtain the residual quantity of DDVP.The detection rate of recovery the results are shown in Table 2.
The mark-on testing result of DDVP in 2 apple of table
The mark-on detection of metrifonate 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,
Metrifonate standard solution is added, 50mL water and 100mL acetone is then added, extraction 3min is rubbed with pulverizer.It is taken after filtering
100mL filtrates are placed in separatory funnel, and 15g sodium chloride is added, is stood after acutely vibrating 3min, and 50mL bis- is used after solution layering
Chloromethanes aqueous phase extracted merges acetone and dichloromethane extract.Wherein moisture is dried and removed with anhydrous sodium sulfate, revolving is dense
It is reduced to about 2mL, is dried up remaining liq with nitrogen, is eventually adding 10mL ethanol-water solutions (V：V=1：1), concussion is extremely dissolved,
Low temperature shading preserves for use.
The blank sample for being added without metrifonate and 3 mark-ons that different metrifonate concentration are added are prepared according to the method described above
Sample (standard addition method), and incubation and SWV scannings, note are carried out to the electrochemical sensor in method described in embodiment 2
Record response current；According to the value added Δ I of the corresponding response current of the metrifonate obtained in embodiment 2 and metrifonate concentration C it
Between Δ I-C equations of linear regression, obtain the residual quantity of metrifonate.The detection rate of recovery the results are shown in Table 3.
The mark-on testing result of metrifonate in 3 green vegetables of table
The total amount of 5 organophosphor standard sample of embodiment detects
(1) foundation of organophosphor total amount detection linear equation：It is individually detected by a kind of ten organophosphor of gained in embodiment 2
Working curve it is found that the expression formula of working curve is very close when different organophosphor individually detects, wherein the average value of slope be-
0.022458, relative standard deviation 8.44%；The average value of intercept is -6.188, therefore by organophosphorus pesticide total amount and sound
The linear equation model of detection between the value added Δ I of induced current is Δ I=-0.022458C-6.188；
(2) the total amount detection of organophosphor standard sample：By chlopyrifos：DDVP：Phoxim：Parathion presses different mol ratio
Mixing is dissolved in PBS buffer solutions, is configured to a series of different sample to be tested of total concentrations.With method described in embodiment 2 into
Row is incubated and SWV scannings, recording responses electric current；The value added Δ I of response current is substituted into the linear equation being fitted in step (1)
In, obtain organophosphor total amount measured value.The comparison of measured value and add value is shown in Table 4 and table 5.
4 organophosphorus pesticide total amount of table detects (chlopyrifos：DDVP：Phoxim：Parathion molar ratio=1：1：1：1)
| Add concentration (ng/mL) | 800 | 600 | 400 | 300 | 200 | 100 | 50 | 1 |
| Detectable concentration (ng/mL) | 822.27 | 577.82 | 385.90 | 316.21 | 196.22 | 106.7 | 54.13 | 10.91 |
| The rate of recovery (%) | 102.8 | 96.3 | 96.4 | 105.4 | 98.1 | 106.7 | 108.3 | 1090 |
| Relative error (%) | +2.8 | -3.7 | -3.5 | +5.4 | -1.9 | +6.7 | +8.3 | +990 |
5 organophosphor total amount of table detects (chlopyrifos：DDVP：Phoxim：Parathion molar ratio=1：2：3：4)
| Add concentration (ng/mL) | 1000 | 800 | 600 | 400 | 200 | 100 | 50 | 1 |
| Detectable concentration (ng/mL) | 986.2 | 814.8 | 631.8 | 418.5 | 195.1 | 94.4 | 53.9 | 8.54 |
| The rate of recovery (%) | 98.6 | 101.9 | 105.3 | 104.6 | 97.5 | 94.4 | 107.8 | 854 |
| Relative error (%) | -1.4 | +1.9 | +5.3 | +4.6 | -2.5 | -5.6 | +7.8 | +854 |
Claims (7)
1. a kind of electrochemical sensor of organophosphorus pesticide residual quantity detection, including substrate glass-carbon electrode, which is characterized in that described
The basal electrode surface deposition of electrochemical sensor has nanogold particle, sulfydryl second methylamine phosphamide to be modified in institute by Au-S keys
The nanogold particle surface stated；The structure of the sulfydryl second methylamine phosphamide is shown below,
2. a kind of electrochemical sensor of organophosphorus pesticide residual quantity detection according to claim 1, which is characterized in that institute
Electrochemical sensor is stated to prepare with the following method：It first will be by polishing, polishing and the glass-carbon electrode immersion chlorine being cleaned by ultrasonic
In auric acid solution, use potentiostatic method by gold chloride electrochemical reduction for nanogold particle, and be deposited on basal electrode surface；Again
By sulfydryl second acephatemet amide solution drop coating on basal electrode surface, dry, by self assembly by sulfydryl second methylamine phosphamide with
On the nanogold particle that the modification of Au-S keys is deposited to electrode surface；Finally use sulfydryls hexanol solution closing nanogold particle surface
Residual activity site.
3. a kind of electrochemical sensor of organophosphorus pesticide residual quantity detection according to claim 1 or 2, feature exist
In the sulfydryl second methylamine phosphamide is prepared using following methods：By N-bromosuccinimide and 1- (3- dimethylaminos third
Base) -3- ethyl-carbodiimide hydrochlorides are dissolved in phosphate buffer solution and are stirred at room temperature, be then added in mercaptoacetic acid solution and stir
It mixes, finally adds in the hydrochloric acid solution of acephatemet and be stirred to react；Solid is precipitated after revolving solvent, obtains the sulfydryl second first
Amine phosphamide.
4. a kind of electrochemical detection method of organophosphorus pesticide residual quantity, which is characterized in that the detection method includes following step
Suddenly：
(1) preparation of electrochemical sensor：
First the glass-carbon electrode by polishing, polishing and ultrasonic cleaning is immersed in chlorauric acid solution, with constant potential electrochemical reduction
Gold chloride is reduced to nanogold particle by method, and is deposited on glassy carbon electrode surface, and glass carbon is cleaned using phosphate buffer solution (PBS)
Electrode simultaneously dries；Again by sulfydryl second acephatemet amide solution drop coating in glassy carbon electrode surface, dry；Finally use sulfydryls hexanol solution
The residual activity site on glassy carbon electrode surface nanogold particle surface is closed, electrochemical sensor is made；
(2) preparation of standard solution：
The PBS buffer solutions for preparing one group of organophosphorus pesticide sample containing different known concentrations including blank standard specimen are
Standard solution, wherein the acetylcholinesterase containing same concentrations；
(3) foundation of working curve：
The electrochemical test sensors prepared in step (1) are immersed respectively in the standard solution prepared in step (2) and are incubated, are incubated
Electrochemical test sensors are rinsed with PBS buffer solutions after educating, then the electrochemical test sensors after flushing are placed in containing K3
[Fe(CN)6] PBS buffer solutions in carry out square wave voltammetry scanning, recording responses electric current；The response current of blank standard specimen is
I0, the response current containing organophosphorus pesticide standard sample is Ix, the value added Δ I of response current is equal to IxWith I0Difference it is exhausted
To value；The concentration C of organophosphorus pesticide in the Δ I and standard solution is depicted as Δ I-C working curves, using linear regression method
Obtain Δ I-C equations of linear regression；
(4) detection of organophosphorus pesticide residual quantity：
Sample to be tested is formulated as the PBS buffer solutions containing the acetylcholinesterase with step (2) same concentrations, according to step
Suddenly (3) identical method to the electrochemical sensor be incubated and square wave voltammetry scans, recording responses electric current；According to sound
The value added Δ I and Δ I-C equations of linear regression of induced current, are calculated organic phosphorus compound residual quantity.
5. the electrochemical detection method of organophosphorus pesticide residual quantity according to claim 4, which is characterized in that further include with
Lower step：
(5) organophosphorus pesticide total amount detects：
The corresponding Δ I-C equations of linear regression of the different detection of organic phosphorus pesticide obtained in step (3) are fitted, are had
The working curve of machine phosphorus insecticide residual quantity total amount detection；Sample to be tested is formulated as containing the acetyl with step (2) same concentrations
The PBS buffer solutions of cholinesterase carry out incubation and square wave according to the identical method with step (3) to the electrochemical sensor
Voltammetry scans, recording responses electric current；Linear regression side between the value added of electric current and organophosphorus residue total amount according to response
Organophosphorus pesticide total amount is calculated in journey.
6. the electrochemical detection method of organophosphorus pesticide residual quantity according to claim 5, which is characterized in that the fitting
Afterwards organophosphorus pesticide residual quantity total amount detection working curve slope and intercept be respectively obtained in step (3) it is Bu Tong organic
Slope average value, the intercept average value of the corresponding Δ I-C equations of linear regression of phosphorus pesticide.
7. the electrochemical detection method of organophosphorus pesticide residual quantity according to claim 4 or 5, which is characterized in that described
Organophosphorus pesticide be selected from Entex, metrifonate, DDVP, chlopyrifos, parathion, diazinon, acephatemet, pirimiphos-methyl,
It is one or more in Rogor, phoxim and flolimat.
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| CN108872353B (en) * | 2018-07-13 | 2020-04-14 | 广西壮族自治区农业科学院农产品质量安全与检测技术研究所 | Electrochemical method for detecting parathion pesticide |
| CN114088685A (en) * | 2021-11-22 | 2022-02-25 | 生态环境部华南环境科学研究所 | Method for rapidly detecting pesticide residues in water body |
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| CN101892043A (en) * | 2010-03-18 | 2010-11-24 | 华中师范大学 | Method for preparing gold nano particles and application of particles in detection of cyhalothrin |
| CN102221529A (en) * | 2011-03-31 | 2011-10-19 | 吉林大学 | Method for rapidly detecting residuals of organophosphorus pesticides in vegetables by utilizing Au nano-particle colorimetric method |
| CN102608187A (en) * | 2012-03-30 | 2012-07-25 | 山东理工大学 | Preparation method of hollow gold nanometer particle-modified acetylcholinesterase biosensor |
| CN103063842A (en) * | 2013-01-04 | 2013-04-24 | 山东理工大学 | Preparation method of immunosensor for detecting Carbofuran pesticide residues |
| BR102013020075A2 (en) * | 2013-08-07 | 2015-08-11 | Univ Estadual Do Ct Oeste | Electrochemical determination process of the methyl thiophanate pesticide employing abnt 304 stainless steel electrode with modified surface with gold nanoparticles |
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| US20120270205A1 (en) * | 2011-04-19 | 2012-10-25 | Patel Sanjay V | High-flux chemical sensors |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101892043A (en) * | 2010-03-18 | 2010-11-24 | 华中师范大学 | Method for preparing gold nano particles and application of particles in detection of cyhalothrin |
| CN102221529A (en) * | 2011-03-31 | 2011-10-19 | 吉林大学 | Method for rapidly detecting residuals of organophosphorus pesticides in vegetables by utilizing Au nano-particle colorimetric method |
| CN102608187A (en) * | 2012-03-30 | 2012-07-25 | 山东理工大学 | Preparation method of hollow gold nanometer particle-modified acetylcholinesterase biosensor |
| CN103063842A (en) * | 2013-01-04 | 2013-04-24 | 山东理工大学 | Preparation method of immunosensor for detecting Carbofuran pesticide residues |
| BR102013020075A2 (en) * | 2013-08-07 | 2015-08-11 | Univ Estadual Do Ct Oeste | Electrochemical determination process of the methyl thiophanate pesticide employing abnt 304 stainless steel electrode with modified surface with gold nanoparticles |
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