CN110018212A - A kind of rapid detection method of thiophanate-methyl pesticide and application - Google Patents
A kind of rapid detection method of thiophanate-methyl pesticide and application Download PDFInfo
- Publication number
- CN110018212A CN110018212A CN201910358743.9A CN201910358743A CN110018212A CN 110018212 A CN110018212 A CN 110018212A CN 201910358743 A CN201910358743 A CN 201910358743A CN 110018212 A CN110018212 A CN 110018212A
- Authority
- CN
- China
- Prior art keywords
- thiophanate
- methyl
- pesticide
- electrode
- detection method
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention belongs to the technical field of electroanalytical chemistry detection of pesticide, rapid detection method and the application of a kind of thiophanate-methyl pesticide are disclosed, with functional material 3- aminopropyl triethoxy silane (APTS) APTS and Ni3P is decorative material, and combines graphite material, prepares APTS-Ni3The composite modified carbon paste electrode of P/CPE, carries out detection thiophanate-methyl.The present invention can be used for the detection of thiophanate-methyl, and detectable concentration range is 4.0 × 10‑6~5.0 × 10‑ 4Mol/L, equation of linear regression are Ipa (μ A)=2.35+109.76C (mmol/L), R=0.9971, and detection is limited to 3.04 × 10‑7Mol/L (S/N=3)；Measuring method of the present invention is simple and efficient, detection range is wide, and detection limit is low, and strong antijamming capability a little, can be used for the quantitative analysis detection of thiophanate-methyl content.
Description
Technical field
The invention belongs to the fast of the technical field of electroanalytical chemistry detection of pesticide more particularly to a kind of thiophanate-methyl pesticide
Fast detection method and application.
Background technique
Currently, the immediate prior art:
Thiophanate-methyl category benzimidazole germicide is mainly used for the veterinary antibiotics, gray mold of cereal, leaf mold, white
The prevention and treatment of the fungal diseases such as powder disease, black spot, wilt disease, anthracnose and foodstuff preservation and seed treatment.Because it is with price
Cheaply, broad spectrum activity sterilization idiocratic efficiently, less toxic is widely used in agricultural production.However enter in animal body can for the drug
It is decreased obviously hemoglobin and erythrocyte number, leucocyte and blood platelet are destroyed, in enzymatic activity decline, liver and kidney
Poison can also make liver and kidney that random dna degradation occur, and cyclooxygenase-2 gene expression increases in hepatic tissue, marker of inflammation
Increasing proves it with genotoxicity.Due to the blindness of thiophanate-methyl pesticide, it is long-term, excessively use so that the drug exists
Accumulate and enter in soil and water in food, thus caused by environmental pollution, the problems such as pesticide is exceeded cause the wide of people
General concern.
Therefore establishing one kind, quickly and effectively analysis method has particularly important meaning.GB 2763-2016 provides methyl
The residual of thiophanate is defined as the residual summation of thiophanate-methyl and carbendazim, in terms of carbendazim, and methyl in veterinary antibiotics
The measurement of thiophanate, carbendazim and benomyl is based primarily upon ultraviolet spectrophotometry (GB/T 5009.188-2003) and efficient liquid
Phase chromatography (SN/T 0162-2011), wherein the detection of thiophanate-methyl and benomyl residue limits is in terms of carbendazim.This
Uncertainty, and GB 2763- are brought unavoidably for the judgement in carbendazim source in agricultural product and the assessment of agricultural product security risk
The residue limits that carbendazim in citrus is defined in 2016 are 5mg/kg, but not yet residual of the regulation thiophanate-methyl in citrus
Limitation.
In conclusion problem of the existing technology is:
National standard cannot exclude the interference of carbendazim and benomyl, and existing national standard can not judge carbendazim,
The specific source of benomyl, thiophanate-methyl.
The residual limitation disunity of agriculture of thiophanate-methyl in the citrus of prior art detection.
Solve the difficulty of above-mentioned technical problem:
Benomyl, carbendazim, the chemical structure of thiophanate-methyl are similar, and when detection interferes with each other
Solve the meaning of above-mentioned technical problem:
The detection method can exclude the interference of benomyl and carbendazim, only detect the content of thiophanate-methyl.In water, water
Metal ion, starch and excipient substance in fruit, in pesticide does not generate the detection of thiophanate-methyl dry under general concentration yet
It disturbs.This method belongs to Direct Electrochemistry detection, and pre-treatment is simple, quickly and effectively.
Summary of the invention
In view of the problems of the existing technology, the present invention provides a kind of rapid detection method of thiophanate-methyl pesticide and
Using.
The invention is realized in this way a kind of rapid detection method of thiophanate-methyl pesticide, the thiophanate-methyl agriculture
The rapid detection method of medicine is with functional material 3- aminopropyl triethoxy silane and Ni3P is decorative material, and combines graphite material
Material, prepares APTS-Ni3The composite modified carbon paste electrode of P/CPE, carries out detection thiophanate-methyl.
Further, APTS-Ni is prepared3The method of the composite modified carbon paste electrode of P/CPE includes:
The first step pipettes 400 microlitres of APTS into mortar, 0.012 gram of Ni is added3It is stirred evenly after P, is then added 1.2
The grinding of gram graphite powder uniformly, adds after 400 microlitres of atoleines are ground 10 hours that be put into 4 DEG C of refrigerators spare；
Second step enters the mixture prepared in 3 millimeters of diameter of empty carbon paste electrode, obtains APTS-Ni3P/CPE
Composite modified carbon paste electrode.
Further, in second step, the mixture prepared enter squeezed out in sky carbon paste electrode it is a little after, the handle on pan paper
It is stand-by after electrode surface polishing.
Further, the rapid detection method of the thiophanate-methyl pesticide further comprises utilizing electrode A PTS-Ni3P/
The composite modified carbon paste electrode of CPE is working electrode, and saturated calomel electrode is reference electrode, and CHI115 platinum electrode is auxiliary electrode
It connects CHI660D electrochemical workstation and carries out the thiophanate-methyl evaluation of pesticides；
It specifically includes:
1) foundation of working curve:
Square wave voltammetry is selected to carry out the electrochemical quantitative measurement of thiophanate-methyl, frequency 20Hz, amplitude 50mv, potential increases
Measure 8mv；The pH of electrolyte Bo Ruisitan Robinson, Robert solution (B-R) is 1.8, and oxidation peak current (Ipa) and thiophanate-methyl are dense
Degree 4.0 × 10-6~5.0 × 10-4The linear relationship of mol/L, equation of linear regression are Ipa (μ A)=2.35+109.76C
(mmol/L), R=0.9971, detection are limited to 3.04 × 10-7Mol/L, (S/N)=3；
2) reproducibility, stability and anti-interference capability testing:
Same electrode runs parallel measurement 1 × 10-4The thiophanate-methyl standard solution of mol/L 10 times, the RSD of peak current are
2.7%；By APTS-Ni3The composite modified carbon paste electrode of P/CPE saves 2 weeks at 4 DEG C；
When relative error is less than ± 5%, 100 times of glucose, starch, sucrose, 300 times of K are utilized+、Mg2+、Zn2+、Ca2 +、Na+、Cl-、NO3-、SO42-And the carbendazim and benomyl of same concentration do not generate the amperometric determination of thiophanate-methyl
Interference.
Further, the rapid detection method of the thiophanate-methyl pesticide further comprises thiophanate-methyl pesticide concentration
Measurement:
1 gram of thiophanate-methyl, 70% pesticide distilled water constant volume is weighed into 100ml volumetric flask, supernatant is taken after filtering
1ml, with pouring into 10 milliliters of electrolysis cups after B-R solution constant volume, is measured the drug in 10ml colorimetric cylinder, repeats three
Secondary to obtain 4.63uA, bringing into the concentration for calculating thiophanate-methyl in the formula in step 1) is 0.02077mmol/L, is converted back
Namely 71.11% is gone, error 1.59% is as a result satisfactory.
Another object of the present invention is to provide a kind of rapid detection methods using the thiophanate-methyl pesticide in water
Application in the measurement of fruit thiophanate-methyl pesticide concentration, the application include:
It takes after blending into homogeneous paste with pulper after fruit weighing to be measured, takes 10ml distilled water constant volume to 100ml capacity
In bottle, take supernatant 1ml in 10ml colorimetric cylinder with pouring into 10 milliliters of electrolysis cups after B-R solution constant volume after filtering, square wave lies prostrate
Peace measurement, parameter are set as frequency 20Hz, amplitude 50mv, potential increment 8mv；It is measured, records oxidation peak current, bring public affairs into
Formulas I pa (μ A)=2.35+109.76C calculates concentration value.
In conclusion advantages of the present invention and good effect are as follows:
The present invention can be used for the detection of thiophanate-methyl, and detectable concentration range is 4.0 × 10-6~5.0 × 10-4Mol/L,
Equation of linear regression is Ipa (μ A)=2.35+109.76C (mmol/L), R=0.9971, and detection is limited to 3.04 × 10-7mol/L
(S/N=3).This method is to 100 times of glucose, starch, sucrose, 300 times of K+, Mg2+, Zn2+, Ca2+, Na+, Cl-, NO3-,
SO4 2-It does not have an impact.Benomyl and carbendazim are tested without response current simultaneously, therefore electrochemistry directly measures
Method is not only able to exclude the interference of carbendazim, benomyl, is conducive to the judgement of the residual pollution sources of agriculture, but also filled up in citrus
An unbounded quantity of blank of the residual detection of thiophanate-methyl agriculture, while also having that detection range is wide, detection limit is low, sample pre-treatments are simple
Feature.
Detailed description of the invention
Fig. 1 is provided in an embodiment of the present invention
Fig. 2 is APTS and Ni provided in an embodiment of the present invention3The cyclic voltammogram of P composite modified electrode.Compare naked carbon paste
Electrode, oxidation peak current increases 10 times, therefore the electrode has good electro-catalysis effect.
Fig. 3 is thiophanate-methyl concentration provided in an embodiment of the present invention and oxidation peak current linear relationship chart,
In figure: thiophanate-methyl concentration 4.0 × 10-6~5.0 × 10-4Mol/L, equation of linear regression be Ipa (μ A)=
2.35+109.76C (mmol/L), R=0.9971, detection are limited to 3.04 × 10-7Mol/L (S/N=3)
Fig. 4 be the electrode material provided in an embodiment of the present invention made, empty carbon paste electrode, saturated calomel electrode and
CHI115 platinum electrode pictorial diagram.
Fig. 5 is the peak current data of certain orange peel provided in an embodiment of the present invention measured, and being brought into linear equation can count
Calculate levels curve graph.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
National standard cannot exclude the interference of carbendazim and benomyl, and the prior art cannot to carbendazim pollution source into
Row determines.The prior art is that the residual limitation of thiophanate-methyl agriculture cannot provide standard foundation in citrus.
In order to solve the above technical problems, below with reference to scheme, the present invention will be described in detail.
The rapid detection method of thiophanate-methyl pesticide provided in an embodiment of the present invention, with functional material 3- aminopropyl three
Oxysilane (APTS) and Ni3P is decorative material, using common graphite as main material, prepares APTS-Ni3P/CPE is compound to be repaired
Decorations carbon paste electrode carrys out analysis detection thiophanate-methyl, and there is not been reported both at home and abroad for the electrochemical method, and this method can exclude
The interference of carbendazim and benomyl, to be conducive to the judgement in carbendazim source.
Functional material 3- aminopropyl triethoxy silane (APTS) can be used as the bridging agent of nano material, and being formed has spy
The nano material of different structure, and its good electric conductivity also makes it be applied to Electrochemical Detection.Transiting state metal phosphide
Ni3P because of it there is the good chemical properties such as improvement electronics transfer to be applied to fuel cell.The present invention by both
Material prepares modified carbon paste electrode as elctro-catalyst and carries out analysis detection to thiophanate-methyl.
In embodiments of the present invention, APTS-Ni is prepared3The method of the composite modified carbon paste electrode of P/CPE includes:
The first step pipettes 400 microlitres of APTS into mortar, 0.012 gram of Ni is added3It is stirred evenly after P, is then added 1.2
The grinding of gram graphite powder uniformly, adds after 400 microlitres of atoleines are ground 10 hours and is put into 4 DEG C of spare (experimental chemicals of refrigerator
It is purity assay, Ni3P provides for Dalian University of Technology).
Second step enters the mixture prepared in 3 millimeters of diameter of empty carbon paste electrode, obtains APTS-Ni3P/CPE
Composite modified carbon paste electrode.
In second step, the material prepared squeezed out in empty carbon paste electrode it is a little after electrode surface is polished on pan paper again
For use.
In embodiments of the present invention, as shown in Figure 1, the quick detection of thiophanate-methyl pesticide provided in an embodiment of the present invention
Method is including the use of electrode A PTS-Ni3The composite modified carbon paste electrode of P/CPE is working electrode, and saturated calomel electrode is reference electricity
Pole, CHI115 platinum electrode are that auxiliary electrode is connected to the progress thiophanate-methyl evaluation of pesticides of CHI660D electrochemical workstation；
It specifically includes:
The foundation of working curve: S101 selects square wave voltammetry to carry out the electrochemical quantitative measurement of thiophanate-methyl, frequency
20Hz, amplitude 50mv, potential increment 8mv；The pH of electrolyte Bo Ruisitan Robinson, Robert solution (B-R) is 1.8, oxidation peak current
(Ipa) and thiophanate-methyl is in concentration 4.0 × 10-6~5.0 × 10-4The linear relationship of mol/L, equation of linear regression are Ipa (μ
A)=2.35+109.76C (mmol/L), R=0.9971, detection are limited to 3.04 × 10-7Mol/L, (S/N)=3.
S102, reproducibility, stability and anti-interference capability testing: same electrode runs parallel measurement 1 × 10-4The methyl of mol/L
Thiophanate standard solution 10 times, the RSD of peak current is 2.7%；By APTS-Ni3The composite modified carbon paste electrode of P/CPE is at 4 DEG C
It saves 2 weeks；When relative error is less than ± 5%, 100 times of glucose, starch, sucrose, 300 times of K are utilized+、Mg2+、Zn2+、Ca2 +、Na+、Cl-、NO3-、SO42-And the carbendazim and benomyl of same concentration do not generate the amperometric determination of thiophanate-methyl
Interference.
In embodiments of the present invention, sample of the present invention reaches first support using the Weir of Weierda Chemical Co., Ltd., Zhejiang's production
Thiophanate-methyl 70%, pesticide product standard card number: QW34895-23.
The measurement of thiophanate-methyl pesticide concentration:
1 gram of thiophanate-methyl, 70% pesticide distilled water constant volume is weighed into 100ml volumetric flask, supernatant is taken after filtering
1ml, with pouring into 10 milliliters of electrolysis cups after B-R solution constant volume, is measured the drug in 10ml colorimetric cylinder, repeats three
Secondary to obtain 4.63uA, bringing into the concentration for calculating thiophanate-methyl in the formula in step 1) is 0.02077mmol/L, is converted back
Namely 71.11% is gone, error 1.59% is as a result satisfactory.
It is of the invention to provide a kind of rapid detection method using the thiophanate-methyl pesticide in fruit thiophanate-methyl
Application in pesticide concentration measurement, the application include:
It takes after blending into homogeneous paste with pulper after fruit weighing to be measured, takes 10ml distilled water constant volume to 100ml capacity
In bottle, take supernatant 1ml in 10ml colorimetric cylinder with pouring into 10 milliliters of electrolysis cups after B-R solution constant volume after filtering, square wave lies prostrate
Peace measurement, parameter are set as frequency 20Hz, amplitude 50mv, potential increment 8mv；It is measured, records oxidation peak current, bring public affairs into
Formulas I pa (μ A)=2.35+109.76C calculates concentration value.
The invention will be further described combined with specific embodiments below.
Embodiment 1:
Weigh 1 gram of pesticide distilled water constant volume takes supernatant 1ml in 10ml colorimetric into 100ml volumetric flask, after filtering
It is poured into 10 milliliters of electrolysis cups after Guan Zhongyong B-R solution constant volume, square wave voltammetric measuring, parameter is set as frequency 20Hz, amplitude
50mv, potential increment 8mv.It is measured, records oxidation peak current, bring formula Ipa (μ A)=2.35+109.76C (mmol/ into
L concentration value can) be calculated.
Embodiment 2:
After blending into homogeneous paste with pulper after taking fruit to be measured (such as citrus) to weigh, take 10 can be arrived with distilled water constant volume
Take supernatant 1ml in 10ml colorimetric cylinder with pouring into 10 milliliters of electrolysis cups after B-R solution constant volume in 100ml volumetric flask, after filtering
In, square wave voltammetric measuring, parameter is set as frequency 20Hz, amplitude 50mv, potential increment 8mv.It is measured, record oxidation peak electricity
Stream, concentration value can be calculated by bringing formula Ipa (μ A)=2.35+109.76C (mmol/L) into.
Fig. 4 be the electrode material provided in an embodiment of the present invention made, empty carbon paste electrode, saturated calomel electrode and
CHI115 platinum electrode pictorial diagram.
Fig. 5 is the peak current data of certain orange peel provided in an embodiment of the present invention measured, and being brought into linear equation can count
Calculate levels curve graph.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (6)
1. a kind of rapid detection method of thiophanate-methyl pesticide, which is characterized in that the quick inspection of the thiophanate-methyl pesticide
Survey method is with functional material 3- aminopropyl triethoxy silane and Ni3P is decorative material, and combines graphite material, is prepared
APTS-Ni3The composite modified carbon paste electrode of P/CPE, carries out detection thiophanate-methyl.
2. the rapid detection method of thiophanate-methyl pesticide as described in claim 1, which is characterized in that preparation APTS-Ni3P/
The method of the composite modified carbon paste electrode of CPE includes:
The first step pipettes 400 microlitres of APTS into mortar, 0.012 gram of Ni is added3It is stirred evenly after P, 1.2 grams of graphite is then added
It is spare that powder grinding uniformly, after adding 400 microlitres of atoleines grindings 10 hours is put into 4 DEG C of refrigerators；
Second step enters the mixture prepared in 3 millimeters of diameter of empty carbon paste electrode, obtains APTS-Ni3P/CPE is compound to be repaired
Adorn carbon paste electrode.
3. the rapid detection method of thiophanate-methyl pesticide as claimed in claim 2, which is characterized in that in second step, preparation
Good mixture enters in sky carbon paste electrode after extrusion, stand-by after electrode surface is polished on pan paper.
4. the rapid detection method of thiophanate-methyl pesticide as described in claim 1, which is characterized in that the methyl sulfur bacterium
The rapid detection method of clever pesticide further comprises utilizing electrode A PTS-Ni3The composite modified carbon paste electrode of P/CPE is work electricity
Pole, saturated calomel electrode are reference electrode, and CHI115 platinum electrode is that auxiliary electrode carries out the thiophanate-methyl evaluation of pesticides；
It specifically includes:
1) foundation of working curve:
Square wave voltammetry is selected to carry out the electrochemical quantitative measurement of thiophanate-methyl, frequency 20Hz, amplitude 50mv, potential increment
8mv；The pH of electrolyte Bo Ruisitan Robinson, Robert solution (B-R) is 1.8, and oxidation peak current (Ipa) and thiophanate-methyl are in concentration
4.0×10-6~5.0 × 10-4The linear relationship of mol/L, equation of linear regression are Ipa (μ A)=2.35+109.76C (mmol/
L), R=0.9971, detection are limited to 3.04 × 10-7Mol/L, (S/N)=3；
2) reproducibility, stability and anti-interference capability testing:
Same electrode runs parallel measurement 1 × 10-4The thiophanate-methyl standard solution of mol/L 10 times, the RSD of peak current are 2.7%；It will
APTS-Ni3The composite modified carbon paste electrode of P/CPE saves 2 weeks at 4 DEG C；
When relative error is less than ± 5%, 100 times of glucose, starch, sucrose, 300 times of K are utilized+、Mg2+、Zn2+、Ca2+、Na+、Cl-、NO3-、SO42-And the carbendazim and benomyl of same concentration do not generate interference to the amperometric determination of thiophanate-methyl.
5. the rapid detection method of thiophanate-methyl pesticide as described in claim 1, which is characterized in that the methyl sulfur bacterium
The rapid detection method of clever pesticide further comprises:
The measurement of thiophanate-methyl pesticide concentration:
Weigh 1 gram of thiophanate-methyl, 70% pesticide distilled water constant volume taken into 100ml volumetric flask, after filtering supernatant 1ml in
With being poured into 10 milliliters of electrolysis cups after B-R solution constant volume in 10ml colorimetric cylinder, the drug is measured, is obtained in triplicate
4.63uA, bringing into the concentration for calculating thiophanate-methyl in the formula in step 1) is 0.02077mmol/L.
6. a kind of rapid detection method using thiophanate-methyl pesticide described in claim 1 contains in fruit thiophanate-methyl pesticide
Measure the application on fixed, which is characterized in that the application includes:
It takes after blending into homogeneous paste with pulper after fruit weighing to be measured, takes 10ml distilled water constant volume into 100ml volumetric flask,
Take supernatant 1ml in 10ml colorimetric cylinder with pouring into 10 milliliters of electrolysis cups after B-R solution constant volume after filtering, square wave volt-ampere is surveyed
Fixed, parameter is set as frequency 20Hz, amplitude 50mv, potential increment 8mv；It is measured, records oxidation peak current, bring formula into
Ipa (μ A)=2.35+109.76 C calculates concentration value.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910358743.9A CN110018212A (en) | 2019-04-30 | 2019-04-30 | A kind of rapid detection method of thiophanate-methyl pesticide and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910358743.9A CN110018212A (en) | 2019-04-30 | 2019-04-30 | A kind of rapid detection method of thiophanate-methyl pesticide and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110018212A true CN110018212A (en) | 2019-07-16 |
Family
ID=67192925
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910358743.9A Pending CN110018212A (en) | 2019-04-30 | 2019-04-30 | A kind of rapid detection method of thiophanate-methyl pesticide and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110018212A (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105044183A (en) * | 2015-08-06 | 2015-11-11 | 石河子大学 | Method for detecting sodium equilin sulfate in pregnant mare's urine |
| CN105044193A (en) * | 2015-05-25 | 2015-11-11 | 遵义师范学院 | Disposable trace carbendazim silk-screen printing electrochemical sensor |
| CN106568815A (en) * | 2016-10-21 | 2017-04-19 | 西安建筑科技大学 | Cobalt nickel bimetal sulfide organophosphorus pesticide biosensor and preparation method thereof |
| CN107367536A (en) * | 2017-08-31 | 2017-11-21 | 常州市丰瑞电子有限公司 | A kind of preparation method of stable type carbon paste electrode |
| CN107422017A (en) * | 2017-08-01 | 2017-12-01 | 信阳师范学院 | A kind of chemically modified electrode of highly sensitive detection probenazole and preparation method thereof |
| CN107478699A (en) * | 2017-08-16 | 2017-12-15 | 太原理工大学 | A kind of preparation method and its usage of foam transition metal phosphide carried noble metal |
| CN108075127A (en) * | 2017-12-21 | 2018-05-25 | 浙江大学 | A kind of nickel phosphorus base sodium-ion battery anode material and its preparation method and application |
| CN108872353A (en) * | 2018-07-13 | 2018-11-23 | 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 | A kind of electrochemical method detecting parathion pesticide |
| CN109632923A (en) * | 2019-01-29 | 2019-04-16 | 高昕宇 | A method of parathion-methyl and carbendazim are detected simultaneously using differential pulse voltammetry |
-
2019
- 2019-04-30 CN CN201910358743.9A patent/CN110018212A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105044193A (en) * | 2015-05-25 | 2015-11-11 | 遵义师范学院 | Disposable trace carbendazim silk-screen printing electrochemical sensor |
| CN105044183A (en) * | 2015-08-06 | 2015-11-11 | 石河子大学 | Method for detecting sodium equilin sulfate in pregnant mare's urine |
| CN106568815A (en) * | 2016-10-21 | 2017-04-19 | 西安建筑科技大学 | Cobalt nickel bimetal sulfide organophosphorus pesticide biosensor and preparation method thereof |
| CN107422017A (en) * | 2017-08-01 | 2017-12-01 | 信阳师范学院 | A kind of chemically modified electrode of highly sensitive detection probenazole and preparation method thereof |
| CN107478699A (en) * | 2017-08-16 | 2017-12-15 | 太原理工大学 | A kind of preparation method and its usage of foam transition metal phosphide carried noble metal |
| CN107367536A (en) * | 2017-08-31 | 2017-11-21 | 常州市丰瑞电子有限公司 | A kind of preparation method of stable type carbon paste electrode |
| CN108075127A (en) * | 2017-12-21 | 2018-05-25 | 浙江大学 | A kind of nickel phosphorus base sodium-ion battery anode material and its preparation method and application |
| CN108872353A (en) * | 2018-07-13 | 2018-11-23 | 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 | A kind of electrochemical method detecting parathion pesticide |
| CN109632923A (en) * | 2019-01-29 | 2019-04-16 | 高昕宇 | A method of parathion-methyl and carbendazim are detected simultaneously using differential pulse voltammetry |
Non-Patent Citations (6)
| Title |
|---|
| REZA KARIMI SHERVEDANI 等: "Studies of the Hydrogen Evolution Reaction on Ni-P Electrodes", 《J. ELECTROCHEM. SOC.》 * |
| RONGJING CUI 等: "Phosphorus-doped helical carbon nanofibers as enhanced sensing platform for electrochemical detection of carbendazim", 《FOOD CHEMISTRY》 * |
| YU YA 等: "Electrochemical Determination of Carbendazim in Food Samples Using an Electrochemically Reduced Nitrogen-Doped Graphene Oxide-Modified Glassy Carbon Electrode", 《FOOD ANAL. METHODS》 * |
| 吴锐 等: "呋塞米在APTS 与石墨烯复合修饰碳糊电极上的电化学行为及电分析方法研究", 《分析测试学报》 * |
| 张瑞 等: "丹皮酚在APTS 与离子液体复合修饰碳糊电极上的电化学性质及电分析方法", 《分析测试学报》 * |
| 张超: "自组装磷化镍纳米片阵列电极的电催化析氢性能研究", 《材料导报》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yin et al. | Preparation and characteristic of cobalt phthalocyanine modified carbon paste electrode for bisphenol A detection | |
| Zare et al. | Electrochemical properties of a tetrabromo-p-benzoquinone modified carbon paste electrode. Application to the simultaneous determination of ascorbic acid, dopamine and uric acid | |
| Hu et al. | Selective determination of dopamine in the presence of high concentration of ascorbic acid using nano-Au self-assembly glassy carbon electrode | |
| Narang et al. | A non-enzymatic sensor for hydrogen peroxide based on polyaniline, multiwalled carbon nanotubes and gold nanoparticles modified Au electrode | |
| CN104198559B (en) | Electrochemica biological sensor and preparation method for detection of organic phosphorus pesticide | |
| CN103940883B (en) | Can quickly detect the preparation method of disposable microbial membrane sensor, application, device and the detection method of aqueous bio toxicity | |
| Ensafi et al. | Simultaneous determination of dopamine and uric acid by electrocatalytic oxidation on a carbon paste electrode using pyrogallol red as a mediator | |
| CN107941879A (en) | A kind of preparation method and applications of gold nanometer cage and myoglobins modified electrode | |
| D'Souza et al. | A multi-walled carbon nanotube/poly-2, 6-dichlorophenolindophenol film modified carbon paste electrode for the amperometric determination of l-tyrosine | |
| CN105021679A (en) | Silk-screen printing electrode sensor preparation method based on ionic liquid-multi-wall carbon nano-tube modification | |
| CN109270140A (en) | The preparation method and application of high dispersive graphene/Zn Base Metal organic framework composite material electrochemical sensor | |
| Luo et al. | Voltammetric determination of ferulic acid by didodecyldimethyl-ammonium bromide/Nafion composite film-modified carbon paste electrode | |
| CN106404863A (en) | Microelectrode biosensor used for in-vivo online detection of plant zeatin, and application of microelectrode biosensor | |
| Zhai et al. | Core-shell composite N-doped-Co-MOF@ polydopamine decorated with Ag nanoparticles for nonenzymatic glucose sensors | |
| CN109580741A (en) | It is a kind of to detect the modified electrode of dopamine, preparation method and applications | |
| CN104931554A (en) | Preparation method and application of sensor based on screen-printed carbon electrode | |
| CN108303456B (en) | Method for rapidly detecting pesticide residues on fruits and vegetables | |
| CN106248770A (en) | A kind of electrochemical method of quick detection fenifrothion pesticide residues | |
| CN103743804A (en) | Organic phosphorus electrochemical biosensor based on adsorption of nano particles | |
| Jimenez-Perez et al. | Non-enzymatic screen-printed sensor based on PtNPs@ polyazure A for the real-time tracking of the H2O2 secreted from living plant cells | |
| CN101576530B (en) | Method for measuring dopamine by utilizing graphite nano-sheet/Nafion composite film to modify electrode | |
| Jia et al. | Electrochemical behavior of metribuzin based on L-Norvaline modified electrode and its sensitive determination | |
| Hur et al. | Cell-based electrochemical cytosensor for rapid and sensitive evaluation of the anticancer effects of saponin on human malignant melanoma cells | |
| CN110018212A (en) | A kind of rapid detection method of thiophanate-methyl pesticide and application | |
| CN106770555B (en) | A kind of electrochemical sensor of quick measurement sunset yellow, preparation method and the application in measurement sunset yellow |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190716 |