CN202770803U - Modified electrochemical electrode for thiacloprid detection - Google Patents
Modified electrochemical electrode for thiacloprid detection Download PDFInfo
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- CN202770803U CN202770803U CN 201220231240 CN201220231240U CN202770803U CN 202770803 U CN202770803 U CN 202770803U CN 201220231240 CN201220231240 CN 201220231240 CN 201220231240 U CN201220231240 U CN 201220231240U CN 202770803 U CN202770803 U CN 202770803U
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Abstract
The utility model discloses a modified electrochemical electrode for thiacloprid detection, which comprises a substrate electrode, a nanogold film deposited on an external surface of the substrate electrode, and a grapheme/ thiacloprid composite film modified on the external surface of the nanogold film. The modified electrochemical electrode disclosed by the utility model is extremely high in sensitivity and good in stability, and can quickly detect the thiacloprid on site.
Description
Technical field
The utility model belongs to be analyzed and the detection technique field, relates to a kind of pick-up unit of thiacloprid, relates in particular a kind of modification electrochemical electrode for detection of thiacloprid.
Background technology
Thiacloprid (Thiacloprid) is anabasine pesticide, and is very little to the toxicity of people and livestock because it has high efficiency to sucking pest and some chewing type insects, therefore is widely used in pesticide.Agricultural chemicals more and more receives national governments and the public's concern as one of important pollution source of environment and food.
The residues of pesticides of agricultural product exceed standard, and the farm chemical ingredients of thereupon taking in human body can work the mischief to unify liver, kidney of the mankind's central nervous system, causes vomiting, diarrhoea even dead serious consequence.And China exports big country as agricultural product, and some agricultural product of Chinese exports have had a strong impact on the foreign exchange earning of agricultural product and competitive power in the international market because persticide residue surpasses international standard, have caused very large economic loss.Therefore, searching thiacloprid fast and accurately determination techniques just seems more important, and the meaning of research is more great.
The assay method of using at present maximum thiacloprids mainly contains gas chromatography, high performance liquid chromatography, Liquid Chromatography/Mass Spectrometry etc.But these analytical approachs need large-sized analytic instrument, and process operation is loaded down with trivial details, can not realize Site Detection, are necessary to study more efficient, quick, the sensitive analysis test method of foundation and analytical equipment.And electrochemical detection method usually more can satisfy the requirement that quick, sensitive on-the site analysis detects.
Summary of the invention
The purpose of this utility model is to provide a kind of modification electrochemical electrode for the fast detecting thiacloprid, has lower detection limit and the wider range of linearity, can be used for the Electrochemical Detection thiacloprid.
The utility model adopts following technical scheme:
A kind of modification electrochemical electrode for the thiacloprid detection comprises basal electrode, it is characterized in that described basal electrode outside deposition one deck nano-gold film, and the nano-gold film outside surface is modified one layer graphene/thiacloprid complexes membrane.
The preferred glass-carbon electrode of described basal electrode.It is the glass-carbon electrode of 3 mm and surface finish polishing that described glass-carbon electrode is selected diameter usually.For example, selecting diameter in the specific embodiment is the glass-carbon electrode of 3 mm, respectively through the Al of 1.0 μ m and 0.3 μ m
2O
3Behind the powder liquid sanding and polishing, each ultrasonic 3 min in the second alcohol and water.
Described nano-gold film adopts cyclic voltammetry to be deposited on described basal electrode outside surface.
Described Graphene/thiacloprid complexes membrane adopts drop-coating to be modified at the nano-gold film outside surface.
A kind of concrete method for making of modification electrochemical electrode of the present utility model is: with glass-carbon electrode elder generation deposited gold nano particle, be about to electrode and place 100 mg/L HAuCl
4In the solution, potentiostatic scanning 60 s under-0.2 V electromotive force, deposition obtains nano-gold film; Then dripping the suspending liquid that is coated with 4 μ L Graphenes at electrode surface, is that the thiacloprid solution 2 μ L of 0.2 g/L drop on the electrode again with concentration, 37 ℃ of lower oven dry; Last under 37 ℃, be immersed in 30 min in 5% the BSA solution.
The non-specific avtive spot on described Graphene/thiacloprid complexes membrane surface can the bovine serum albumin sealing.
Modification electrochemical electrode of the present utility model is used for Electrochemical Detection, realize in the following manner the detection of thiacloprid: will modify good electrode immersion cumulative volume is the free thiacloprid that contains variable concentrations of 50 μ L, with the concentration of tiring be in the phosphate buffer solution of monoclonal antibody of thiacloprid of 1:6400, hatch 25 min at 37 ℃, rear in the K of 2 mmol/L with the phosphate buffer solution flushing
3Fe (CN)
6Carry out differential pulse voltammetry (DPV) scanning in the solution.
The experimental result demonstration, along with the increase of thiacloprid concentration (C) in Incubating Solution, the DPV peak current increases.The DPV peak current that is defined in the modified electrode of hatching in the Incubating Solution that only contains thiacloprid antibody is I
0, the DPV peak current of the modified electrode after hatching is I
X, and calculate Δ I=I
X-I
0,Mapping can obtain linearity curve to thiacloprid concentration (C) with Δ I.Thiacloprid concentration 10 ~ 5000 ng/mL in scope are directly proportional with Δ I, and slope is 0.00174, and linearly dependent coefficient is 0.98226.
The utility model has following beneficial effect: modification electrochemical electrode of the present utility model, surface deposition has the Graphene of nano-gold film and modification/thiacloprid complexes membrane, because Graphene has large specific surface area and can be good at promoting the electronics transmission of bio-electrical activity molecule, it is large that nanogold particle has specific surface area, the bioaffinity advantages of higher, therefore, electrochemical electrode of the present utility model can be at normal temperatures, stable and detect rapidly the concentration of residual thiacloprid, have lower detection limit (0.5 ng/mL) and the wider range of linearity (10 ~ 5000 ng/mL).
Description of drawings
Fig. 1 is the structural representation of modification electrochemical electrode of the present utility model;
Wherein: 1 is basal electrode (glass-carbon electrode), and 2 is nano-gold film, and 3 is Graphene/thiacloprid complexes membrane.
Fig. 2 is the profile schematic diagram of modification electrochemical electrode of the present utility model;
Wherein: 1 is basal electrode (glass-carbon electrode), and 2 is nano-gold film, and 3 is Graphene/thiacloprid complexes membrane.
To be modification electrochemical electrode of the present utility model containing the monoclonal antibody of thiacloprid that the concentration of tiring is 1:6400 and free thiacloprid (a) 5000 ng/mL of variable concentrations to Fig. 3, (b) 4000 ng/mL, (c) 3000 ng/mL, (d) 2000 ng/mL, (e) 1000 ng/mL, (f) 500 ng/mL, (g) 100 ng/mL, (h) 50 ng/mL, (h) hatch in the Incubating Solution of 10 ng/mL after, at the K of 2 mmol/L
3[Fe (CN)
6] PBS solution in the DPV curve map.
Fig. 4 is thiacloprid testing curve map.
Embodiment
Below in conjunction with accompanying drawing embodiment of the present utility model is elaborated, embodiment provides detailed embodiment and concrete operating process according to the technical solution of the utility model.But protection domain of the present utility model is not limited to following embodiment.
Referring to Fig. 1 and Fig. 2, a kind of nano-complex for the thiacloprid detection is modified electrochemical electrode 4, comprise that basal electrode-diameter is the glass-carbon electrode 1 of 3 mm and surface finish polishing, cyclic voltammetry is deposited on the nano-gold film 2 of glass-carbon electrode 1 outside surface and drop-coating and modifies Graphene in nano-gold film 2 outside surfaces/thiacloprid complexes membrane 3.
The method for making of described electrode may further comprise the steps:
1) glass-carbon electrode is processed: diameter is the Al that glass-carbon electrode 1 usefulness of 3 mm is used respectively 1.0 μ m and 0.3 μ m
2O
3Behind the powder emulsion sanding and polishing, each ultrasonic cleaning 3 min in the second alcohol and water respectively;
2) nm of gold deposition: the glass-carbon electrode 1 usefulness electrochemical method deposited gold nano particle after the cleaning, in the HAuCl of 100 mg/L
4In the solution, potentiostatic scanning 60 s under-0.2 V electromotive force, deposition obtains nano-gold film 2;
3) preparation of graphene suspension: accurately take by weighing 5 g Graphene samples in 2 ml water, ultrasonic dispersion l h makes graphene suspension;
4) electrode face finish: be that the thiacloprid solution of 0.2 mg/mL mixes with 4 uL graphene suspensions and 2 uL concentration, drip be applied to step 2) electrode surface that makes, 40 ℃ of lower oven dry 30 min modify and obtain Graphene/thiacloprid complexes membrane 3;
5) nonspecific avtive spot sealing: the electrode after the finishing is immersed in 30 min in 5% the BSA solution under 37 ℃, to seal remaining avtive spot, make described electrochemical electrode 4.
It is the free thiacloprid that contains variable concentrations of 50 μ L that the electrode that modification is good immerses cumulative volume, with the concentration of tiring be in the phosphate buffer solution of monoclonal antibody of thiacloprid of 1:6400, hatch 40 min at 37 ℃, rear in the K of 2 mmol/L with the phosphate buffer solution flushing
3Fe (CN)
6Carry out differential pulse voltammetry (DPV) scanning in the solution.The experimental result demonstration, along with the increase of thiacloprid concentration in Incubating Solution, the DPV peak current increases.
The drafting of working curve: under different thiacloprid concentration, nano-complex is modified the electrochemical electrode immersion and is contained K
3[Fe (CN)
6] the PBS damping fluid get DPV figure.Such as Fig. 3 and Fig. 4, along with the increase of thiacloprid concentration in Incubating Solution, the DPV peak current increases.That is to say, free thiacloprid concentration is higher, and the antibody that is fixed on the thiacloprid molecule combination on the electrode is fewer.The DPV peak current that is defined in the modified electrode of hatching in the Incubating Solution that only contains thiacloprid antibody is I
0, the DPV peak current of the modified electrode after hatching is I
X, and calculate Δ I=I
X-I
0, mapping can obtain linearity curve to thiacloprid concentration (C) with Δ I.Thiacloprid concentration 10-5000 ng/mL in scope is directly proportional with Δ I, and slope 0.00174, linearly dependent coefficient are 0.98226.Take greater than concentration corresponding to the current signal of 3 times of noise signals as minimum detectability, repeat that experiment drawing more than 5 times, the lowest detection of said method is limited to 0.5 ng/mL.
The mensuration of mark-on thiacloprid in the embodiment 3 tomato samples
1) processing of tomato sample: take by weighing 2 ± 0.0050 g tomato homogenate in the sample hose of 10 mL, add the thiacloprid titer, and 3 mL acetonitriles, potpourri sonic oscillation 30 min, centrifugal 10 min are transferred to supernatant in the nitrogen blowpipe under 2000 r/m.Extract blows under the condition concentration and evaporation under 50 ℃ of temperature at nitrogen, and the pH that concentrate adds 1 mL is used for electrochemical analysis after the dissolving of 7.4 phosphate buffer solutions.
2) mensuration of mark-on thiacloprid in the tomato actual sample: the different tomato extract solution samples of getting respectively equivalent, be made into Incubating Solution with thiacloprid antibody-solutions and phosphate buffer solution mixing, so that cumulative volume is 50 μ L, and thiacloprid monoclonal antibody bulk concentration all equates, enter in the Incubating Solution modifying good electrode, hatch 25 min at 37 ℃, rear in the K of 2 mmol/L with the phosphate buffer solution flushing
3Fe (CN)
6Carry out differential pulse voltammetry (DPV) scanning in the solution.The peak current of blank sample is I
0, the peak current I of other samples
X, and calculate △ I=I
X-I
0, look into working curve and obtain thiacloprid concentration, recovery result such as table 1.
Table 1 detects the recovery of the thiacloprid concentration in the mark-on tomato
| Thiacloprid addition (ng/mL) | Thiacloprid measured quantity (ng/mL) | The recovery (%) |
| 500.0 | 412.5，441.2，584.9 | 95.9 |
| 2000.0 | 1981.4，2182.6，1579.1 | 95.7 |
| 4000.0 | 3797.5，4579.0，3504.4 | 99.0 |
Claims (5)
1. one kind is used for the modification electrochemical electrode (4) that thiacloprid detects, comprise basal electrode (1), it is characterized in that, described basal electrode (1) outside deposition one deck nano-gold film (2), nano-gold film (2) outside surface is modified one layer graphene/thiacloprid complexes membrane (3).
2. modification electrochemical electrode according to claim 1 (4) is characterized in that, described basal electrode (1) is glass-carbon electrode.
3. modification electrochemical electrode according to claim 2 (4) is characterized in that, the diameter of described glass-carbon electrode is 3 mm and surface finish polishing.
4. modification electrochemical electrode according to claim 1 (4) is characterized in that, described nano-gold film (2) adopts cyclic voltammetry to be deposited on described basal electrode (1) outside surface.
5. modification electrochemical electrode according to claim 1 (4) is characterized in that, described Graphene/thiacloprid complexes membrane (3) adopts drop-coating to be modified at nano-gold film (2) outside surface.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201220231240 CN202770803U (en) | 2012-05-22 | 2012-05-22 | Modified electrochemical electrode for thiacloprid detection |
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| CN 201220231240 CN202770803U (en) | 2012-05-22 | 2012-05-22 | Modified electrochemical electrode for thiacloprid detection |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103454333A (en) * | 2013-09-06 | 2013-12-18 | 南京理工大学 | Electrochemical detection method for pesticide imidacloprid based on polypyrrole/reduced graphene oxide (PPy/RGO) modified glassy carbon electrode |
| CN106525949A (en) * | 2016-12-13 | 2017-03-22 | 南京师范大学 | Electrochemical detection method of organophosphorus pesticide |
-
2012
- 2012-05-22 CN CN 201220231240 patent/CN202770803U/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103454333A (en) * | 2013-09-06 | 2013-12-18 | 南京理工大学 | Electrochemical detection method for pesticide imidacloprid based on polypyrrole/reduced graphene oxide (PPy/RGO) modified glassy carbon electrode |
| CN106525949A (en) * | 2016-12-13 | 2017-03-22 | 南京师范大学 | Electrochemical detection method of organophosphorus pesticide |
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| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130306 Termination date: 20150522 |
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| EXPY | Termination of patent right or utility model |