CN113899805B - Electrochemical sensor for detecting thiabendazole and preparation method and application thereof - Google Patents
Electrochemical sensor for detecting thiabendazole and preparation method and application thereof Download PDFInfo
- Publication number
- CN113899805B CN113899805B CN202111062672.1A CN202111062672A CN113899805B CN 113899805 B CN113899805 B CN 113899805B CN 202111062672 A CN202111062672 A CN 202111062672A CN 113899805 B CN113899805 B CN 113899805B
- Authority
- CN
- China
- Prior art keywords
- mwcnts
- zif
- electrochemical sensor
- solution
- thiabendazole
- 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.)
- Active
Links
Images
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
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
-
- 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
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)
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The invention discloses an electrochemical sensor for detecting thiabendazole, and a preparation method and application thereof. The invention takes MWCNTs/ZIF-L modified glassy carbon electrode (MWCNTs/ZIF-L/GCE) as an electrochemical sensor, and carries out electrochemical detection on TBZ in an electrolyte solution. MWCNTs/ZIF-L/GCE showed excellent catalytic and detection sensitivity to TBZ. The electrochemical sensor constructed by the invention can realize the quantitative analysis of TBZ and can rapidly detect TBZ.
Description
Technical Field
The invention relates to the technical field of electrochemical sensors, in particular to an electrochemical sensor for quickly and efficiently detecting thiabendazole and a preparation method and application thereof.
Background
Thiabendazole (TBZ, 2- (thiazole-4-yl) benzimidazole) is also called thiabendazole, and is one of benzimidazole bactericides with wide application. Residues and accumulations in the environment and food pose serious risks to human health, such as liver problems, anemia, and thyroid disease. Therefore, the establishment of a sensitive and accurate rapid TBZ detection method is of great significance. The most commonly used qualitative and quantitative detection techniques for TBZ in food samples are high performance liquid chromatography, liquid chromatography-mass spectrometry, gas chromatography-mass spectrometry and electrochemical methods. Among them, the electrochemical method has the advantages of simplicity, sensitivity, low cost, etc., and is considered to be an effective method for detecting pesticide residues. The analytical performance of electrochemical methods depends mainly on the electrode material. At present, some nano materialsSuch as MWCNTs-COOH/MoS 2 、ZnFe 2 O 4 the/SWCNTs modified electrode has been applied to the determination of TBZ, but MWCNTs-COOH/MoS 2 And ZnFe 2 O 4 the/SWCNTs have the defects of low sensitivity and the like, and ZnFe 2 O 4 The SWCNTs can detect the thiabendazole and the carbendazim, have no specificity, and cannot detect accurately when the two substances are contained. Therefore, the search for novel electrode materials to construct a TBZ sensing platform with high performance is very necessary.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides an electrochemical sensor for quickly and efficiently detecting thiabendazole and a preparation method and application thereof. The invention adopts a solvent method to prepare a novel two-dimensional leafy ZIF-L (MWCNTs/ZIF-L) modified by multi-wall carbon nano-tubes, and the two-dimensional leafy ZIF-L is used as an electrode material of thiabendazole sensitive electrochemical sensing. MWCNTs/ZIF-L/GCE showed excellent catalytic and detection sensitivity to TBZ. The detection method has the advantages of simple operation, high response speed, high sensitivity and good stability, and makes the on-site and on-line rapid detection of thiabendazole possible.
The invention is realized by the following technical scheme:
in a first aspect of the invention, a preparation method of an electrochemical sensor for detecting thiabendazole is provided, which comprises the following steps:
(1) Adding Zn (NO) 3 ) 2 ·6H 2 Dispersing O and multi-walled carbon nanotubes into first ultrapure water to obtain a mixed dispersion liquid; dissolving 2-methylimidazole in second ultrapure water to obtain a 2-methylimidazole solution, adding the 2-methylimidazole solution into the mixed dispersion liquid under stirring, and continuing stirring; after stirring, washing the obtained product with third ultrapure water, centrifuging, collecting, and drying to obtain MWCNTs/ZIF-L;
(2) And (2) dispersing the MWCNTs/ZIF-L obtained in the step (1) in N, N-dimethylformamide to obtain an MWCNTs/ZIF-L solution, dripping the MWCNTs/ZIF-L solution on the surface of the glassy carbon electrode, and drying to obtain the MWCNTs/ZIF-L/GCE electrochemical sensor.
Preferably, in step (1), the Zn (NO) is 3 ) 2 ·6H 2 The ratio of the addition amount of O, MWCNTs and the first ultrapure water is 0.744g:10mg:10mL; the ratio of the 2-MI to the adding amount of the second ultrapure water is 2.053g:90mL; the Zn (NO) 3 ) 2 ·6H 2 The molar ratio of O to 2-MI is 1:10.
preferably, in the step (1), the stirring temperature is 20-25 ℃, and the stirring time is 24 hours.
Preferably, in the step (1), the drying temperature is 60 ℃ and the drying time is 8-12 h.
Preferably, in the step (2), the concentration of the MWCNTs/ZIF-L solution is 1 mg/mL -1 。
Preferably, in the step (2), before the glassy carbon electrode is used, the glassy carbon electrode is polished to a mirror surface by using alumina powder with the particle size of 0.05 μm, and then the electrode is ultrasonically cleaned by using water, ethanol and water in sequence and dried in the air.
In a second aspect of the invention, the electrochemical sensor for detecting probenazole prepared by the preparation method is provided.
In a third aspect of the invention, the application of the electrochemical sensor in detecting thiabendazole is provided.
In a fourth aspect of the present invention, there is provided a method for detecting thiabendazole using the above electrochemical sensor, the method comprising: adding a thiabendazole-containing solution into an electrolyte solution, uniformly mixing to obtain a mixed test solution, connecting an electrochemical sensor to a test circuit, immersing the electrochemical sensor into the mixed test solution, detecting the oxidation peak current value of the electrochemical sensor by using a differential pulse stripping voltammetry method, establishing a standard curve according to the concentration of thiabendazole and the oxidation peak current value, and calculating the concentration of thiabendazole in the solution to be detected according to the standard curve.
Preferably, the electrolyte solution is 0.1M phosphate buffer at pH = 3.0.
Preferably, the detection range is 0.02. Mu.M-20.0. Mu.M, and the detection limit is 6.0nM.
The invention has the beneficial effects that:
1. the MWCNTs/ZIF-L prepared by the invention has excellent catalytic performance and electrical conductivity. The active center which is easy to be accessed by ZIF-L can accelerate the transfer rate of proton and electron, and enhance the interaction between the active center and TBZ, thereby improving the catalytic activity. And the MWCNTs are used as electronic leads, so that the conductivity of the material is improved. The MWCNTs/ZIF-L shows a synergistic catalytic effect, so that the electrochemical detection sensitivity can be greatly improved.
2. The method for detecting the concentration of probenazole by using the electrochemical sensor is simple to operate, high in response speed, high in sensitivity and good in stability, and enables on-site and on-line rapid detection of probenazole to be possible.
3. The electrochemical sensor prepared by the invention has the advantages of low cost, simple process and simple operation, can be successfully used for detecting probenazole, and has the advantages of high sensitivity (the lower limit of probenazole detection is 6.0 nM), strong anti-interference performance (K exists) + ,Na + ,Mg 2+ ,Cl - ,NO 3 - ,SO 4 2- Under the conditions of vitamin C, glucose, isoproturon and carbendazim, the current response of the probenazole has no obvious change), the stability is good, and the prepared MWCNTs/ZIF-L material modified electrode can be used for measuring the content of the probenazole in the environment.
Drawings
FIG. 1 is a scanning electron micrograph of ZIF-L (A) and MWCNTs/ZIF-L (B);
FIG. 2 is a plot of the cyclic voltammetric response of bare GCE (a), ZIF-L/GCE (b), MWCNTs/GCE (c) and the electrochemical sensor prepared in example 1 to 10.0 μ M thiabendazole;
FIG. 3 (A) is a graph of the differential pulse voltammetric response of the electrochemical sensor prepared in example 1 for detecting different concentrations of thiabendazole; the curves are from bottom to top: detecting the differential pulse voltammetry response curve of the thiabendazole solution with the concentration of 0.02 mu M,0.04 mu M,0.2 mu M,0.4 mu M,0.6 mu M,1.0 mu M,3.0 mu M,5.0 mu M,7.0 mu M,10.0 mu M and 20.0 mu M; and (B) is a standard curve graph.
FIG. 4 shows K at 100 times concentration under optimized conditions + ,Na + ,Mg 2+ ,Cl - ,NO 3 - ,SO 4 2- Interference of vitamin C, glucose, isoproturon and carbendazim at 50-fold concentrations on the oxidation peak current of 10.0 μ M thiabendazole.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
As mentioned in the background art, the porous structure of MOFs and its organic ligand can promote the enrichment of analyte, but its application in electrocatalysis is limited by the problems of poor stability and poor conductivity. Therefore, the design and synthesis of the MOFs material with high adsorption capacity to thiabendazole can meet the requirement of selective detection of thiabendazole, and the key for improving the sensitivity and selectivity of electrochemical detection is realized. Based on the electrochemical sensor, the invention provides the electrochemical sensor for rapidly, efficiently and sensitively detecting thiabendazole. A solvent method is adopted to prepare a novel two-dimensional leafy ZIF-L (MWCNTs/ZIF-L) modified by a multi-wall carbon nano tube. Directly taking MWCNTs/ZIF-L/GCE as an electrochemical sensor to measure thiabendazole in a solution taking phosphate as a supporting electrolyte.
The invention utilizes the porous structure of MOFs and the organic ligand thereof to promote the high-level enrichment of target molecules, and the metal center of MOFs serves as an active center for driving catalytic reaction. ZIF-8 constructed from zinc ions and 2-methylimidazole has excellent hydrothermal and chemical stability, but three-dimensional (3D) ZIF-8 is limited in proton or ion transport and access to active sites. The 2DMOF nanosheets have large specific surface area, thin thickness and abundant active sites, and the ultrathin MOF nanosheets can provide short ion and electron transfer pathways in the framework. Easy access to the active site of 2DMOF can enhance the interaction of target molecules with the active site in sensing applications, thereby improving the sensitivity of detection. However, it is noteworthy that pure MOFs have limited catalytic capacity. Therefore, the MWCNTs/ZIF-L/GCE electrochemical sensor prepared by the method has high catalytic performance and high sensitivity.
In order to make the technical solutions of the present application more clearly understood by those skilled in the art, the technical solutions of the present application will be described in detail below with reference to specific embodiments. If the experimental conditions not specified in the examples are specified, they are generally according to the conventional conditions or according to the conditions recommended by the reagents company; reagents, consumables, and the like used in the following examples are commercially available unless otherwise specified.
Example 1
Preparation of electrochemical sensor
1. 0.744gZn (NO) 3 ) 2 ·6H 2 O and 10mg MWCNTs were dispersed in 10mL of ultrapure water, and subjected to ultrasonic treatment for 30min (power: 100W, frequency: 40 kHz) to obtain a mixed dispersion. 2.053g 2-methylimidazole (2-MI) were dissolved in 90mL of ultrapure water, and the 2-methylimidazole solution was added to the solution containing Zn (NO) over 5min with stirring 3 ) 2 And (3) obtaining a mixed solution in the MWCNTs dispersion liquid. The mixed solution was stirred at 23 ℃ for 24 hours, washed 3 times with ultrapure water and centrifuged (8000rmp, 5min) to collect, and dried at 60 ℃ for 10 hours to obtain MWCNTs/ZIF-L.
2. Before electrode modification, the glassy carbon electrode is polished to a mirror surface by using 0.05 mu m alumina powder, and then the electrode is sequentially cleaned by using water, ethanol and water in an ultrasonic mode and dried in the air. Dispersing the MWCNTs/ZIF-L composite material in DMF at the concentration of 1 mg/mL -1 .5 mu of LMWCNTs/ZIF-L dispersion liquid is dripped on the surface of GCE, and MWCNTs/ZIF-L/GCE is obtained after drying (50 ℃,5 min).
As shown in FIG. 1A, the MWCNTs/ZIF-L prepared in example 1 has a leaf-like shape in Scanning Electron Microscope (SEM), a transverse dimension of 3.7. + -. 0.8. Mu.m, a width of 1.5. + -. 0.2. Mu.m, and a thickness of about 211nm. The MWCNTs/ZIF-L can shorten the transmission path of ions and electrons, promote the adsorption of thiabendazole on effective binding sites, and is favorable for promoting the oxidation of TBZ on a modified electrode. For MWCNTs/ZIF-L, as shown in FIG. 1 (B), MWCNTs are uniformly distributed on the surface of ZIF-L, while the microstructure of ZIF-L remains unchanged. The multi-walled carbon nanotube can be used as an electron beam to effectively improve the conductivity of the ZIF-L and improve the sensing performance.
Example 2
Detection of concentration of probenazole
Prepared in example 1 in phosphate buffer solutions (pH = 3.0) containing different concentrations of thiabendazole (0.02. Mu.M, 0.04. Mu.M, 0.2. Mu.M, 0.4. Mu.M, 0.6. Mu.M, 1.0. Mu.M, 3.0. Mu.M, 5.0. Mu.M, 7.0. Mu.M, 10.0. Mu.M, 20.0. Mu.M)The prepared electrochemical sensor is connected into a test circuit, the concentration of the probenazole is measured by using a differential pulse voltammetry, the concentration of the probenazole is taken as an abscissa (unit is mu M), the oxidation peak current value is taken as an ordinate (unit is mu A), and a standard curve is established: y =2.198+1.272x (R) 2 ＝0.997)。
As shown in FIG. 3, the modified electrode has good linear relation (R) to thiabendazole 2 = 0.997) and has a wide linear range (0.2 μ M-20.0 μ M) and a low detection limit (6.0 nM), sufficiently indicating that the sensing electrode is capable of successfully detecting thiabendazole at unknown concentrations.
Test example 1
The MWCNTs/GCE, ZIF-L/GCE and the sensors prepared in example 1 are respectively used for detecting the concentration of probenazole by using a differential pulse voltammetry method, the detection responsivity of different modified electrodes to probenazole is tested, and the result is shown in figure 2.
As can be seen from FIG. 2, the sensor prepared in example 1 can respond to very low probenazole compared with MWCNTs/GCE, ZIF-L/GCE and glassy carbon electrode (i.e. BareGCE), and the detection sensitivity of the sensor is better than that of the MWCNTs/GCE and ZIF-L/GCE electrodes.
Test example 2
The electrochemical sensor prepared in example 1 was examined for the specificity of detecting the concentration of thiabendazole: the change of the oxidation peak current of thiabendazole before and after the addition of interfering ions is inspected, and the specific result is shown in figure 4; as is clear from FIG. 4, K was added to 10.0. Mu.M thiabendazole solution at a concentration of 100 times the concentration of the resulting mixture + 、Na + 、Mg 2+ 、Cl - 、NO 3 - 、SO 4 2- And after 50 times of concentration of vitamin C, glucose, isoproturon and carbendazim, the oxidation peak current of thiabendazole has no obvious change (error range of +/-5.0 percent), thereby excluding the interference of some common ions.
Test example 3
The electrochemical sensor prepared in example 1 was examined for the accuracy of the concentration of thiabendazole: using a standard addition method, apple juice and orange juice were sampled, respectively, and diluted 100-fold with a phosphate buffer solution (0.1M, pH 3.0), and then different concentrations of thiabendazole solution were added, and the above solutions were subjected to detection analysis using the sensor prepared in example 1, and the results are shown in Table 1.
TABLE 1
As can be seen from Table 1, the accuracy of the detection is between 96.00% and 103.00%, and the relative standard deviation is lower than 5.0%, which shows that the sensor constructed by the invention is feasible for detecting and analyzing the practical sample of probenazole.
In conclusion, the electrochemical sensor disclosed by the invention not only can successfully detect probenazole, but also has the characteristics of high sensitivity, high detection speed, good stability and the like, and can be used for measuring the concentration of probenazole and the content of probenazole in apples or oranges; the preparation method of the electrochemical sensor has the advantages of low preparation cost, simple process and simple and easy operation.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (3)
1. An electrochemical sensor for detecting thiabendazole is characterized by being prepared by the following steps:
(1) Adding Zn (NO) 3 ) 2 ·6H 2 Dispersing O and multi-walled carbon nanotubes into first ultrapure water to obtain a mixed dispersion liquid; dissolving 2-methylimidazole in second ultrapure water to obtain a 2-methylimidazole solution, adding the 2-methylimidazole solution into the mixed dispersion liquid, and stirring; after stirring, washing the obtained product with third ultrapure water, centrifuging, collecting, and drying to obtain MWCNTs/ZIF-L; said Zn (NO) 3 ) 2 ·6H 2 The adding amount ratio of O, MWCNTs and first ultrapure water is 0.744g:10mg:10mL; the 2-methylimidazole and the secondThe adding amount ratio of the ultrapure water is 2.053g:90mL; the Zn (NO) 3 ) 2 ·6H 2 The molar ratio of O to 2-methylimidazole is 1:10; the stirring temperature is 20 to 25 ℃, and the stirring time is 24 hours; the drying temperature is 60 ℃, and the drying time is 8 to 12 hours;
(2) Dispersing the MWCNTs/ZIF-L obtained in the step (1) in N, N-dimethylformamide to obtain MWCNTs/ZIF-L solution, dripping the MWCNTs/ZIF-L solution on the surface of a glassy carbon electrode, and drying to obtain the MWCNTs/ZIF-L/GCE electrochemical sensor; the concentration of the MWCNTs/ZIF-L solution is 1 mg/mL -1 。
2. Use of an electrochemical sensor according to claim 1 for the detection of thiabendazole.
3. The method for detecting thiabendazole by using the electrochemical sensor according to claim 1, characterized in that a solution containing thiabendazole is added to an electrolyte solution, a mixed test solution is obtained after uniform mixing, the electrochemical sensor according to claim 1 is connected with a test circuit, then the electrochemical sensor is immersed in the mixed test solution, the oxidation peak current value of the electrochemical sensor is detected by using a differential pulse stripping voltammetry, a standard curve is established by using the concentration of thiabendazole and the oxidation peak current value, and the concentration of thiabendazole in the solution to be detected is calculated according to the standard curve;
the electrolyte solution is 0.1M phosphate buffer at pH = 3.0;
the detection range is 0.02 mu M-20.0 mu M, and the detection limit is 6.0nM.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111062672.1A CN113899805B (en) | 2021-09-10 | 2021-09-10 | Electrochemical sensor for detecting thiabendazole and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111062672.1A CN113899805B (en) | 2021-09-10 | 2021-09-10 | Electrochemical sensor for detecting thiabendazole and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113899805A CN113899805A (en) | 2022-01-07 |
| CN113899805B true CN113899805B (en) | 2022-10-11 |
Family
ID=79027959
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111062672.1A Active CN113899805B (en) | 2021-09-10 | 2021-09-10 | Electrochemical sensor for detecting thiabendazole and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113899805B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114384133B (en) * | 2022-01-14 | 2022-11-04 | 山东农业大学 | Electrochemical sensor for detecting heavy metal lead ions in soil solution and construction method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| UA83032U (en) * | 2013-02-21 | 2013-08-27 | Государственное Высшее Учебное Заведение "Украинский Государственный Химико-Технологический Университет" | Method for quantitative determination of food admixture thiabendazole (e-233) in substance and food products |
| CN103472122A (en) * | 2013-09-18 | 2013-12-25 | 遵义师范学院 | Electrochemical sensor detection method for rapidly detecting trace carbendazim pesticide |
| CN106770551A (en) * | 2016-12-07 | 2017-05-31 | 信阳师范学院 | A kind of electrochemical sensor of quick measure carbendazim, preparation method and the application in carbendazim is determined |
| CN107037097A (en) * | 2017-04-20 | 2017-08-11 | 信阳师范学院 | Multi-walled carbon nanotube/poly- L histidine composite modified glassy carbon electrodes and preparation method thereof |
| CN107144612A (en) * | 2017-04-20 | 2017-09-08 | 信阳师范学院 | Carbendazim detection method |
| RO133103A2 (en) * | 2017-08-09 | 2019-02-28 | Institutul Naţional De Cercetare-Dezvoltare Pentru Inginerie Electrică Icpe-Ca | Process for preparing carbonic nanoparticles for carbendazim detection |
| CN112051312A (en) * | 2020-07-31 | 2020-12-08 | 江西农业大学 | Electrochemical sensing detection method for paraquat in food and modified electrode thereof |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106279033B (en) * | 2016-08-05 | 2019-01-04 | 安徽建筑大学 | Sheet intersects ZIF-L and preparation method thereof |
| CN107422017B (en) * | 2017-08-01 | 2019-06-04 | 信阳师范学院 | A kind of chemically modified electrode and preparation method thereof of highly sensitive detection probenazole |
| US10495592B1 (en) * | 2017-08-29 | 2019-12-03 | The United States Of America As Represented By The Secretary Of The Army | Use of metal-organic frameworks and metal oxides for sensing chemicals using electrical impedance spectroscopy |
| RO133207B1 (en) * | 2017-08-30 | 2022-01-28 | Institutul Naţional De Cercetare-Dezvoltare Pentru Inginerie Electrică Icpe-Ca | Carbonic sensor for carbendazim detection |
| CN109521071B (en) * | 2018-12-18 | 2020-09-11 | 江西农业大学 | Electrochemical sensing detection method for benzimidazole pesticide thiabendazole |
| CN110412096B (en) * | 2019-07-29 | 2021-09-10 | 青岛科技大学 | Preparation method and detection application of reduced graphene oxide @ ZIF-8 composite membrane modified electrode |
| CN111239214B (en) * | 2020-03-25 | 2021-05-25 | 吉林大学 | Three-electrode type Pb (II) and Cu (II) electrochemical sensor, preparation method and application thereof |
| CN113092554A (en) * | 2021-03-10 | 2021-07-09 | 李荣毓 | Preparation method and application of sensing electrode for glucose detection |
-
2021
- 2021-09-10 CN CN202111062672.1A patent/CN113899805B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| UA83032U (en) * | 2013-02-21 | 2013-08-27 | Государственное Высшее Учебное Заведение "Украинский Государственный Химико-Технологический Университет" | Method for quantitative determination of food admixture thiabendazole (e-233) in substance and food products |
| CN103472122A (en) * | 2013-09-18 | 2013-12-25 | 遵义师范学院 | Electrochemical sensor detection method for rapidly detecting trace carbendazim pesticide |
| CN106770551A (en) * | 2016-12-07 | 2017-05-31 | 信阳师范学院 | A kind of electrochemical sensor of quick measure carbendazim, preparation method and the application in carbendazim is determined |
| CN107037097A (en) * | 2017-04-20 | 2017-08-11 | 信阳师范学院 | Multi-walled carbon nanotube/poly- L histidine composite modified glassy carbon electrodes and preparation method thereof |
| CN107144612A (en) * | 2017-04-20 | 2017-09-08 | 信阳师范学院 | Carbendazim detection method |
| RO133103A2 (en) * | 2017-08-09 | 2019-02-28 | Institutul Naţional De Cercetare-Dezvoltare Pentru Inginerie Electrică Icpe-Ca | Process for preparing carbonic nanoparticles for carbendazim detection |
| CN112051312A (en) * | 2020-07-31 | 2020-12-08 | 江西农业大学 | Electrochemical sensing detection method for paraquat in food and modified electrode thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113899805A (en) | 2022-01-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liao et al. | Development of a new electrochemical sensor for determination of Hg (II) based on Bis (indolyl) methane/Mesoporous carbon nanofiber/Nafion/glassy carbon electrode | |
| CN112394095B (en) | Electrochemical sensor for selectively detecting nitrite ions and preparation method and application thereof | |
| Zhu et al. | A miniature and low-cost electrochemical system for sensitive determination of rhodamine B | |
| Zhang et al. | An ultrasensitive label-free immunoassay for C-reactive protein detection in human serum based on electron transfer | |
| Chen et al. | Sensitive analytical detection of nitrite using an electrochemical sensor with STAB-functionalized Nb2C@ MWCNTs for signal amplification | |
| CN104569097A (en) | Preparation method of copper nanowire graphene composite-modified electrode, as well as applications thereof | |
| Zhao et al. | Application of a carbon nanotube modified electrode in anodic stripping voltammetry for determination of trace amounts of 6-benzylaminopurine | |
| CN113189188B (en) | Preparation method and application of Au NPs@WP5/BiOBr composite material | |
| Zhang et al. | Sensitive electrochemical determination of rhodamine B based on a silica-pillared zirconium phosphate/nafion composite modified glassy carbon electrode | |
| CN111751421B (en) | Electrochemical sensor for detecting lead ions | |
| Gong et al. | Microperoxidase-11/metal–organic framework/macroporous carbon for detecting hydrogen peroxide | |
| Xiong et al. | Detection of di (2-ethylhexyl) phthalate through graphene–β-cyclodextrin composites by electrochemical impedance spectroscopy | |
| CN105973956B (en) | Detect the complex film modified acetylene black electrode of graphene-cuprous oxide and detection method of vanillic aldehyde in food | |
| Wang et al. | Conductive metal-organic frameworks for amperometric sensing of paracetamol | |
| CN101750442B (en) | Monodispersive bimetal Au/Pt nano-particle modified electrode for detecting mercury in water and preparation method thereof | |
| CN113899805B (en) | Electrochemical sensor for detecting thiabendazole and preparation method and application thereof | |
| CN109406599A (en) | A kind of preparation and application of the novel Electrochemical enzyme biosensor based on MOFs composite material | |
| Xiong et al. | Gold nanoparticle functionalized nanopipette sensors for electrochemical paraquat detection | |
| Jaworska et al. | Optimizing Carbon Nanotubes Dispersing Agents from the Point of View of Ion‐selective Membrane Based Sensors Performance–Introducing Carboxymethylcellulose as Dispersing Agent for Carbon Nanotubes Based Solid Contacts | |
| He et al. | Square wave anodic stripping voltammetric determination of lead (II) using a glassy carbon electrode modified with a lead ionophore and multiwalled carbon nanotubes | |
| Li et al. | Enhanced electrochemiluminescence of luminol at the gold nanoparticle/carbon nanotube/electropolymerised molecular imprinting composite membrane interface for selective recognition of triazophos | |
| Zhang et al. | A novel self-assembly voltammetric sensor for malachite green based on ethylenediamine and graphene oxide | |
| Chen et al. | Electrochemical Probe of the Reduced Graphene Oxide Modified by Bare Gold Nanoparticles Functionalized Zr (IV)‐based Metal‐organic Framework for Detecting Nitrite | |
| Liu et al. | Determination of cadmium (II) using glassy carbon electrodes modified with cupferron, ß-naphthol, and multiwalled carbon nanotubes | |
| Lin et al. | Sensitive and fast analysis of terbutaline sulfate in food using a modified electrode based on a MoS 2/AuNPs nanocomposite |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |