CN110186910B - Double-inhibition electrochemiluminescence sensor and method for measuring glyphosate - Google Patents
Double-inhibition electrochemiluminescence sensor and method for measuring glyphosate Download PDFInfo
- Publication number
- CN110186910B CN110186910B CN201910402589.0A CN201910402589A CN110186910B CN 110186910 B CN110186910 B CN 110186910B CN 201910402589 A CN201910402589 A CN 201910402589A CN 110186910 B CN110186910 B CN 110186910B
- Authority
- CN
- China
- Prior art keywords
- luminol
- electrode
- rgo
- glyphosate
- sensor
- 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.)
- Expired - Fee Related
Links
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/76—Chemiluminescence; Bioluminescence
-
- 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
Abstract
The invention relates to the technical field of pesticide residue analysis and determination, in particular to a double-inhibition electrochemiluminescence sensor and a method for determining glyphosate by using the same, wherein the method comprises the steps of preparing the double-inhibition sensor, and an operation method for determining the glyphosate by using the sensor; the double-inhibition sensor utilizes enzymatic reaction and catalysis of copper complex peroxidase, and combines two signal conversion modes to generate a synergistic effect, so that the detection sensitivity of the sensor is effectively improved; the method is used for detecting the glyphosate, and has the advantages of small interference of coexisting substances, good selectivity and high sensitivity.
Description
Technical Field
The invention relates to the technical field of pesticide residue analysis and determination, in particular to a double-inhibition electrochemiluminescence sensor and a method for determining glyphosate by using the same, wherein the method comprises the steps of preparing the double-inhibition sensor, and an operation method for determining the glyphosate by using the sensor; the double inhibition sensor utilizes enzymatic reaction and copper complex peroxidase catalysis, and is a synergistic effect generated by the combination of two signal conversion modes; the enzymatic reaction is inhibited by the glyphosate, the catalytic action of peroxidase-like enzyme is inhibited, the glyphosate is measured with high sensitivity, the interference of coexisting substances is small, and the selectivity is good.
Background
The development of pesticide residue detection technology, especially rapid detection technology, can monitor pesticide residue in environment and food in time, and has important significance for protecting environment and ensuring health and safety of people. Glyphosate is a non-selective, biocidal herbicide that has attracted a great deal of attention as a widely used pesticide for its potential residual hazard. The existing chemical analysis method is a conventional analysis method, mainly depends on chemical properties of the glyphosate to perform chemical reaction with other substances, has relatively low accuracy and sensitivity, and is not suitable for glyphosate residue and trace analysis; although the chemiluminescence method has good sensitivity, the chemiluminescence method is mostly used for detecting and analyzing glyphosate technical, and the sensitivity is not particularly high for analyzing glyphosate residues in food and water; the spectrophotometry is simple and convenient to operate and rapid to analyze, but is easily interfered by other ions; especially substances with the wavelength similar to the maximum absorption wavelength, so the method is not much researched in the detection and analysis of the residual quantity of the glyphosate; the enzyme-linked immunosorbent assay has the characteristics of accuracy, specificity, stability, wide application range, high detection speed and low cost, but cross reaction is easy to occur to influence the detection sensitivity; the glyphosate detection technology also comprises infrared spectroscopy, nuclear magnetic resonance, molecular imprinting-chemiluminescence, chromatography and other combined technologies besides the methods described above. An enzyme biosensor is one of the research hotspots in the current pesticide residue rapid detection technology, however, at present, a few reports are reported for biosensors for detecting glyphosate, and a new biosensor, including an enzyme biosensor, an immunosensor and a DNA sensor, needs to be developed and researched urgently to adapt to the current urgent need.
Enzyme biosensors can be classified into single enzyme, double enzyme, and the like. The enzymes used for pesticide detection mainly include acetylcholinesterase, choline oxidase, organophosphorus hydrolase and the like. A two-enzyme biosensor couples acetylcholinesterase (AChE) to choline oxidase (ChOX). AChE hydrolyzes its natural substrate to choline and acetate, and since choline is not electrochemically active, ChOX is used to oxidize choline and consume oxygen to produce H2O2Determination of O consumed in solution by means of amperometric enzyme electrodes2Or H generated2O2The content of organophosphorus and carbamate pesticides is detected. Similar to the present invention is the method reported by Shihua Hou et al: adsorbing gold nanoparticles on a thiolated silica sol containing multi-walled carbon nanotubes and ChOX, and assembling AChE on a modified electrode layer by layer through diallyl dimethyl ammonium chloride (PDDA) to obtain the double-enzyme sensor. Benefit toAmperometric detection of H at + 0.65V2O2However, the two-enzyme system amperometric method is easily interfered by other coexisting electroactive substances because of the relatively high operating potential.
Disclosure of Invention
The invention aims to construct a double-inhibition electrochemiluminescence sensor capable of being used for detecting pesticide residue glyphosate with high sensitivity aiming at the defects in glyphosate analysis and detection research. The technical problem to be solved by the invention is based on enzymatic reactions and Cu2+The sensor has peroxidase-like catalytic action, exerts the synergistic effect of two signal conversion modes, constructs a double-inhibition electrochemiluminescence sensor, is used for detecting glyphosate, and effectively improves the detection sensitivity and selectivity of the sensor.
Technical scheme of the invention
The invention assembles acetylcholinesterase (AChE) and choline oxidase (ChOx) on the surface of an electrode to synthesize luminol-Au-L-cys-Cu with luminous performance and peroxidase-like effect2+The composite material is loaded on the surface of the electrode to construct a double-inhibition electrochemiluminescence sensor; AChE catalyzes the production of thiocholine (RSH) from acetylcholine chloride (ATCl), and RSH is catalyzed by ChOx to produce H2O2；H2O2The luminol co-reactant is used as a co-reactant of the luminol composite material, so that the luminol luminous intensity is improved; meanwhile, the luminol composite material plays a peroxidase-like role and catalyzes H2O2Generating superoxide radical O2 ·-So as to catalyze the generation of luminol excited state and greatly improve the luminous intensity of luminol; when glyphosate exists, inhibiting the activity of acetylcholinesterase on the surface of the modified electrode; meanwhile, the Cu on the surface of the electrode can be modified2+Generating more stable complex to separate from the surface of the electrode and inhibit the catalytic action of peroxidase; the double inhibition effect reduces the luminous intensity of a luminol composite material luminous system; and the larger the concentration of glyphosate is, the weaker the signal is; the double-inhibition electrochemiluminescence sensor has high sensitivity, good selectivity, no toxicity and no environmental pollution, and provides a feasible new method for detecting the pesticide residue glyphosate; the specific scheme is as follows:
1. a double-inhibition electrochemiluminescence sensor and a method for measuring glyphosate are disclosed, wherein a luminol composite material with luminescence property and peroxidase-like effect is synthesized and loaded on the surface of a double-enzyme electrode; the high-sensitivity detection of the glyphosate is realized by the inhibition of enzymatic reaction of the glyphosate and the catalytic action of peroxidase-like enzyme; the double-enzyme electrode is characterized in that acetylcholinesterase AChE and choline oxidase ChOx are loaded on the surface of a gold nanoparticle-graphene modified glassy carbon electrode Au-rGO/GCE; the luminol composite material is prepared from luminol, nanogold and L-cysteine-Cu2+luminol-Au-L-cys-Cu formed by complex composition2+A composite material;
2. the preparation method of the Au-rGO/GCE modified electrode comprises the following steps:
(1) preparing graphene oxide: dissolving 6.8 g of potassium permanganate in a mixed solution of 120.0 mL of concentrated sulfuric acid and 14.0 mL of phosphoric acid in a 500.0 mL three-neck flask, adding 1.0 g of graphite powder, uniformly mixing, and continuously stirring in a water bath at 50 ℃ for 12 hours; slowly adding 140.0 mL of ice water into the solution, oxidizing unreacted potassium permanganate with 30% hydrogen peroxide, observing a brown-yellow mixture, carrying out ultrasonic treatment for more than 1.5 h after the solution is cooled, carrying out centrifugal washing on the solution at 6000 rpm until the solution is neutral to obtain graphene oxide, and drying the Graphene Oxide (GO) at 60 ℃ to obtain solid graphene oxide;
(2) preparing graphene: diluting the prepared GO to 0.5 mg/mL, putting 20.0 mL into a three-neck flask, adding 300.0 mu L of ammonia water and 20.0 mu L of hydrazine hydrate under stirring, quickly stirring for more than 10 min, continuously stirring for 3.5 h in a water bath at 60 ℃ to form black suspension, and performing vacuum drying to obtain graphene rGO;
(3) preparing graphene-gold nanoparticles: by injecting 1.2 mL of 0.1mol/L ice sodium borohydride into 40 mL of a solution containing 0.25mmol/L sodium citrate dihydrate and 0.25mmol/L HAuCl under vigorous stirring4Aging for 6 hours in the aqueous solution of (1); adding 5 mL of synthesized rGO and 10.0 mL of prepared Au NPs into a three-neck flask, stirring for 12h, and centrifuging and washing; dispersing the obtained product into 5.0mL of solution after the final centrifugal washing to obtain a rGO-Au composite material for storage and standby;
(4) the glassy carbon electrode was coated with 0.3, 0.05 μm Al in this order on a chamois2O3 Polishing to obtain mirror surface, and washing off Al on the surface with ultrapure water2O3Sequentially performing ultrasonic treatment in ethanol and ultrapure water for 10s respectively, and airing at room temperature for later use;
(5) dripping 8.0 mu L of Au-rGO on the surface of GCE and airing at room temperature to obtain a rGO-Au/GCE modified electrode;
3. the luminol-Au-L-cys-Cu2+The preparation method of the composite material comprises the following steps:
(1) 1.0mL, 15mmol/L luminol and 5.0mL, 0.25mmol/L HAuCl4Mixing, and violently stirring for 12h at room temperature to obtain a luminol-Au NPs solution;
(2) add 100. mu.L of 6.0mmol/L L-Cys aqueous solution to 1.0mL luminol-Au NPs solution at room temperature and incubate at 4 ℃ for 5 h; adding Cu of 100.0 mu L and 6mmol/L2+Shaking the solution at room temperature for 5min to obtain luminol-Au-L-cys-Cu2+A composite material;
4. the preparation method of the double-inhibition electrochemiluminescence sensor comprises the following steps:
(1) dripping 2.0 mu L of acetylcholinesterase and 10 mu L of choline oxidase onto the surface of an Au-rGO modified glassy carbon electrode Au-rGO/GCE, and incubating overnight to obtain a modified electrode AChE-ChOx/Au-rGO/GCE;
(2) 8.0 mu L of luminol-Au-L-cys-Cu is dripped on the surface of the electrode2+The composite material is incubated for 2 hours at 4 ℃ by glutaraldehyde for crosslinking to prepare luminol-Au-Lcys-Cu2+/AChE-ChOx/Au-rGO/GCE；
After incubation in the above steps, lightly washing with PBS (pH 7.4) to remove the physical adsorption material;
5. the double-inhibition electrochemiluminescence sensor is used for detecting glyphosate by the following method:
(1) different concentrations of glyphosate are dripped on luminol-Au-cys-Cu2+the/AChE-ChOx/Au-rGO/GCE surface is incubated at 37 ℃ for 60min and washed by PBS buffer solution with pH 7.4;
(2) in a PBS (phosphate buffer solution) with the pH value of 7.4 and containing 0.1mol/L of acetylcholine chloride, taking the electrode as a working electrode, an Ag/AgCl electrode as a reference electrode and a platinum electrode as an auxiliary electrode, performing cyclic voltammetry scanning within a potential range of 0.0-0.7V, and recording the luminous intensity;
(3) detecting the light intensity of a series of glyphosate standard solutions with different concentrations after incubation, and drawing a working curve; simultaneously measuring the linear range and the detection limit of the sensor;
(4) and (3) replacing the glyphosate standard solution with the sample solution to be detected, recording the light intensity according to the methods of the steps (1) and (2), and calculating the content of chlorpyrifos in the sample to be detected according to a linear equation.
The invention has the advantages of
(1) The invention synthesizes luminol-Au-Lcys-Cu2+The composite material is modified on the surface of the electrode, so that the defect that a traditional copper (II) -luminol-hydrogen peroxide solution system is easy to cause other interference is overcome, the reagent is saved, and the manufacturing cost of the sensor is reduced;
(2) prepared luminol-Au-L-cys-Cu2+The luminol luminescent material is compounded with the copper ion complex, so that the composite material has dual functions of luminescent performance and peroxidase-like;
(3) the double inhibition mechanism generates a synergistic effect, and effectively improves the detection sensitivity of the sensor;
(4) the double-inhibition electrochemiluminescence sensor improves the detection selectivity of glyphosate; the traditional double-enzyme sensor has poor selectivity of single inhibition, and the Ampere method of a double-enzyme system is easily interfered by other coexisting electroactive substances;
(5) the sensor has high sensitivity and good selectivity, and can realize simple, quick and high-sensitivity detection on the pesticide residue glyphosate; the linear range is 0.001-1.0 mu mol/L, and the detection limit is 0.3 nmol/L.
Description of the drawings:
FIG. 1 is a graph of potential versus intensity for different modified electrodes
Wherein, 1- -Lu-Au-Lcys modified glassy carbon electrode, 2- -Lu-Au-Lcys-Cu2+Modifying the glassy carbon electrode;
FIG. 2 is a graph of electrochemiluminescence intensity (A) and linear fit (B) for various concentrations of glyphosate
Wherein, 1-7 respectively represent the glyphosate concentration as follows: 0.001, 0.005, 0.01, 0.05, 0.1, 0.5, 1.0 μmol/L.
Detailed Description
For better understanding of the present invention, the technical solution of the present invention will be described in detail with specific examples, but the present invention is not limited thereto.
Example 1 preparation method of Au-rGO/GCE modified electrode
(1) Preparing graphene oxide: dissolving 6.8 g of potassium permanganate in a mixed solution of 120.0 mL of concentrated sulfuric acid and 14.0 mL of phosphoric acid in a 500.0 mL three-neck flask, adding 1.0 g of graphite powder, uniformly mixing, and continuously stirring in a water bath at 50 ℃ for 12 hours; slowly adding 140.0 mL of ice water into the solution, oxidizing unreacted potassium permanganate with 30% hydrogen peroxide, observing a brown-yellow mixture, carrying out ultrasonic treatment for more than 1.5 h after the solution is cooled, carrying out centrifugal washing on the solution at 6000 rpm until the solution is neutral to obtain graphene oxide, and drying the Graphene Oxide (GO) at 60 ℃ to obtain solid graphene oxide;
(2) preparing graphene: diluting the prepared GO to 0.5 mg/mL, putting 20.0 mL into a three-neck flask, adding 300.0 mu L of ammonia water and 20.0 mu L of hydrazine hydrate under stirring, quickly stirring for more than 10 min, continuously stirring for 3.5 h in a water bath at 60 ℃ to form black suspension, and performing vacuum drying to obtain graphene rGO;
(3) preparing graphene-gold nanoparticles: by injecting 1.2 mL of 0.1mol/L ice sodium borohydride into 40 mL of a solution containing 0.25mmol/L sodium citrate dihydrate and 0.25mmol/L HAuCl under vigorous stirring4Aging for 6 hours in the aqueous solution of (1); 5 mL of synthesized rGO and 10.0 mL of prepared Au NPs were added to a three-neck flask, stirred for 12h, and washed by centrifugation. Dispersing the obtained product into 5.0mL of solution after the final centrifugal washing to obtain a rGO-Au composite material for storage and standby;
(4) the glassy carbon electrode was coated with 0.3, 0.05 μm Al in this order on a chamois2O3 Polishing to obtain mirror surface, and washing off Al on the surface with ultrapure water2O3And is combined withSequentially performing ultrasonic treatment in ethanol and ultrapure water for 10s respectively, and airing at room temperature for later use;
(5) and dripping 8.0 mu L of Au-rGO on the surface of the GCE, and airing at room temperature to obtain the rGO-Au/GCE modified electrode.
Example 2 luminol-Au-L-cys-Cu2+The preparation method of the composite material comprises the following steps:
(1) 1.0mL, 15mmol/L luminol and 5.0mL, 0.25mmol/L HAuCl4Mixing, and violently stirring for 12h at room temperature to obtain a luminol-Au NPs solution;
(2) add 100. mu.L of 6.0mmol/L L-Cys aqueous solution to 1.0mL luminol-Au NPs solution at room temperature and incubate at 4 ℃ for 5 h; adding Cu of 100.0 mu L and 6mmol/L2+Shaking the solution at room temperature for 5min to obtain luminol-Au-L-cys-Cu2+A composite material.
Example 3 method of preparation of a dual-inhibition electrochemiluminescence sensor:
(1) dripping 2.0 mu L of acetylcholinesterase and 10 mu L of choline oxidase onto the surface of an Au-rGO modified glassy carbon electrode Au-rGO/GCE, and incubating overnight to obtain a modified electrode AChE-ChOx/Au-rGO/GCE;
(2) 8.0 mu L of luminol-Au-L-cys-Cu is dripped on the surface of the electrode2+The composite material is incubated for 2 hours at 4 ℃ by glutaraldehyde for crosslinking to prepare luminol-Au-L-cys-Cu2+/AChE-ChOx/Au-rGO/GCE；
After incubation in each of the above steps, the material was gently washed with PBS pH 7.4 to remove the physisorbed material.
Example 4 method of detecting glyphosate with a double-inhibition electrochemiluminescence sensor:
(1) different concentrations of glyphosate are dripped on luminol-Au-L-cys-Cu2+the/AChE-ChOx/Au-rGO/GCE surface is incubated at 37 ℃ for 60min and washed by PBS buffer solution with pH 7.4;
(2) in a PBS (phosphate buffer solution) containing 0.1mol/L of acetylcholine chloride and having the pH value of 7.4, taking the electrode as a working electrode, an Ag/AgCl electrode as a reference electrode and a platinum electrode as an auxiliary electrode, performing cyclic voltammetry scanning in a 0-0.7V potential range by an MPI-B type multi-parameter chemiluminescence analysis test system, and recording the obtained light intensity;
(3) detecting the light intensity of a series of glyphosate standard solutions with different concentrations, and drawing a working curve; simultaneously measuring the linear range and the detection limit of the sensor; the result is shown in fig. 2, the electrochemiluminescence intensity decreases with the increase of the glyphosate concentration and is in negative correlation with the logarithm of the glyphosate concentration, the linear equation is I = -454 lgc +465, the correlation coefficient r =0.992, the linear range is 0.001-1.0 [ mu ] mol/L, and the detection limit is 0.3 nmol/L;
(4) and (3) replacing the glyphosate standard solution with the sample solution to be detected, recording the light intensity according to the methods of the steps (1) and (2), and calculating the glyphosate content in the sample to be detected according to a linear equation.
Example 5 Cu2+Catalytic properties
To test Cu2+The catalytic performance of the composite material is tested, and the potential-light intensity of different modified electrodes is tested; as shown in FIG. 1, when Cu2+When present, the electrochemiluminescence intensity is enlarged by about 3 times, which shows that Cu2+Has excellent catalytic performance for improving the electrochemiluminescence intensity.
Example 6 optimization of the experimental conditions
(1) Volume ratio of double enzymes: when the volume ratio of the choline oxidase to the acetylcholinesterase is less than 5:1, the electrochemiluminescence intensity is increased along with the increase of the volume ratio of the double enzymes, and when the volume ratio of the double enzymes is more than 5:1, the change of the light intensity tends to be stable;
(2) selection of metal ions: experiment of Cu2+、Pb2+、Cd2+、Co2+、Hg2+、Ni2+The influence on the luminescence property of the system shows that only Cu is used2+Can generate a complex with cysteine to play a catalytic role, and the influence of other metal ions on the system can be ignored;
（3）Cu2+ influence of concentration: explore Cu2+The effect of concentration on the luminescence intensity; the results show that with Cu2+The concentration is increased, and the electrochemiluminescence intensity is gradually increased; when Cu2+When the concentration is more than 0.6 mmol/L, the luminous intensity is not changed any more;
(4) influence of the pH: the alkaline environment is favorable for luminol and H2O2While the luminous intensity decreases at a pH greater than 7.4 in order to maintain the activity of the biomaterial;
the optimal experimental conditions are as follows: the volume ratio of the choline oxidase to the acetylcholinesterase is 5:1, and Cu is2+The concentration was 0.6 mmol/L and the pH was 7.4.
Example 7 MoS2CdS nanosphere and MoS2Comparison of luminescence Properties of CdS nanosheets
In order to test the stability of the electrochemiluminescence sensor, the prepared sensor is placed at 4 ℃ for 10 days, and the measured light intensity after 10 days is 92.2% of the initial light intensity, which indicates that the sensor has good stability; in order to detect the nonspecific interference of other pesticides on glyphosate, the prepared sensor is used for carrying out interference tests on deltamethrin, acetamiprid, chlorpyrifos and carbendazim, and the result shows that the prepared sensor only generates sensitive response to the solution containing glyphosate, and other pesticides have small influence on light intensity; in addition, in order to detect the reproducibility of the sensor, the light intensity results of five modified electrodes are tested, and the relative standard deviation is 8.15%; the results show that the sensor has better stability, selectivity and reproducibility.
Claims (1)
1. The application of the double-inhibition electrochemiluminescence sensor in detecting glyphosate is characterized in that the preparation method of the double-inhibition electrochemiluminescence sensor is as follows:
(1) dripping 2.0 mu L of acetylcholinesterase and 10 mu L of choline oxidase onto the surface of an Au-rGO modified glassy carbon electrode Au-rGO/GCE, and incubating overnight to obtain a modified electrode AChE-ChOx/Au-rGO/GCE;
(2) 8.0 mu L of luminol-Au-L-cys-Cu is dripped on the surface of the electrode2+The composite material is incubated for 2 hours at 4 ℃ by glutaraldehyde for crosslinking to prepare luminol-Au-L-cys-Cu2+/AChE-ChOx/Au-rGO/GCE；
After incubation in the above steps, the incubation solution is washed gently by PBS buffer solution with pH 7.4, and the physical adsorption material is removed;
the preparation method of the Au-rGO/GCE comprises the following steps:
(1) the glassy carbon electrode was coated with 0.3, 0.05 μm Al in this order on a chamois2O3Polishing to obtain mirror surface, and washing off Al on the surface with ultrapure water2O3Sequentially performing ultrasonic treatment in ethanol and ultrapure water for 10s respectively, and airing at room temperature for later use;
(2) dripping 8.0 mu L of Au-rGO on the surface of GCE and airing at room temperature to obtain an Au-rGO/GCE modified electrode;
the luminol-Au-L-cys-Cu2+The preparation steps of the composite material are as follows:
(1) 1.0mL, 15mmol/L luminol and 5.0mL, 0.25mmol/L HAuCl4Mixing, and violently stirring for 12h at room temperature to obtain a luminol-Au NPs solution;
(2) add 100. mu.L of 6.0mmol/L L-Cys aqueous solution to 1.0mL luminol-Au NPs solution at room temperature and incubate at 4 ℃ for 5 h; adding Cu of 100.0 mu L and 6mmol/L2+Shaking the solution at room temperature for 5min to obtain luminol-Au-L-cys-Cu2+A composite material;
the glyphosate detection method comprises the following steps:
(1) different concentrations of glyphosate are dripped on luminol-Au-L-cys-Cu2+the/AChE-ChOx/Au-rGO/GCE surface is incubated at 37 ℃ for 60min and washed by PBS buffer solution with pH 7.4;
(2) in a PBS (phosphate buffer solution) containing 0.1mol/L of acetylcholine chloride and having the pH value of 7.4, taking the prepared sensor as a working electrode, an Ag/AgCl electrode as a reference electrode and a platinum electrode as an auxiliary electrode, performing cyclic voltammetry scanning within a potential range of 0.0-0.7V, and recording the luminous intensity.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910402589.0A CN110186910B (en) | 2019-05-15 | 2019-05-15 | Double-inhibition electrochemiluminescence sensor and method for measuring glyphosate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910402589.0A CN110186910B (en) | 2019-05-15 | 2019-05-15 | Double-inhibition electrochemiluminescence sensor and method for measuring glyphosate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110186910A CN110186910A (en) | 2019-08-30 |
| CN110186910B true CN110186910B (en) | 2021-11-12 |
Family
ID=67716332
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910402589.0A Expired - Fee Related CN110186910B (en) | 2019-05-15 | 2019-05-15 | Double-inhibition electrochemiluminescence sensor and method for measuring glyphosate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110186910B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021054917A2 (en) * | 2019-09-18 | 2021-03-25 | T.C. Erciyes Universitesi | A method and biosensor for determination and measurement of deltamethrin |
| CN111579548B (en) * | 2020-05-20 | 2022-03-18 | 重庆师范大学 | Luminol-gallium nano assembly and preparation method and application thereof |
| CN111443076B (en) * | 2020-06-01 | 2023-01-20 | 中国农业科学院农业质量标准与检测技术研究所 | Glyphosate detection system based on tyrosinase inhibition and SERS detection method |
| CN111948188A (en) * | 2020-09-23 | 2020-11-17 | 江南大学 | Method for measuring organic phosphorus |
| CN112175960B (en) * | 2020-10-12 | 2023-10-13 | 广东石油化工学院 | Modified glyphosate nucleic acid aptamer and application thereof |
| CN116593557B (en) * | 2023-05-17 | 2024-01-23 | 海南师范大学 | Electrochemical sensor prepared from molybdenum disulfide @ black phosphazene composite material and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106248748A (en) * | 2016-07-22 | 2016-12-21 | 云南省产品质量监督检验研究院 | A kind of acetylcholinesterasebiosensor biosensor and application thereof |
| CN107121484A (en) * | 2017-05-19 | 2017-09-01 | 济南大学 | A kind of electrochemical method of Sensitive Detection glyphosate |
| CN107247079A (en) * | 2017-07-19 | 2017-10-13 | 济南大学 | A kind of electrochemiluminescdetection detection method of easy glyphosate pesticide |
-
2019
- 2019-05-15 CN CN201910402589.0A patent/CN110186910B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106248748A (en) * | 2016-07-22 | 2016-12-21 | 云南省产品质量监督检验研究院 | A kind of acetylcholinesterasebiosensor biosensor and application thereof |
| CN107121484A (en) * | 2017-05-19 | 2017-09-01 | 济南大学 | A kind of electrochemical method of Sensitive Detection glyphosate |
| CN107247079A (en) * | 2017-07-19 | 2017-10-13 | 济南大学 | A kind of electrochemiluminescdetection detection method of easy glyphosate pesticide |
Non-Patent Citations (1)
| Title |
|---|
| 硅胶表面分子印迹聚合物及新型电化学发光生物传感器在农药残留分析中的应用;苗珊珊;《中国博士学位论文全文数据库 农业科技辑》;20171215(第12期);107-108页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110186910A (en) | 2019-08-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110186910B (en) | Double-inhibition electrochemiluminescence sensor and method for measuring glyphosate | |
| Xie et al. | A multifunctional hemin@ metal–organic framework and its application to construct an electrochemical aptasensor for thrombin detection | |
| Long et al. | Visual observation of the mercury-stimulated peroxidase mimetic activity of gold nanoparticles | |
| Hosseini et al. | Enhancement of the peroxidase-like activity of cerium-doped ferrite nanoparticles for colorimetric detection of H 2 O 2 and glucose | |
| Wu et al. | Amperometric glucose sensor based on catalytic reduction of dissolved oxygen at soluble carbon nanofiber | |
| Ricci et al. | Prussian Blue and enzyme bulk-modified screen-printed electrodes for hydrogen peroxide and glucose determination with improved storage and operational stability | |
| Lin et al. | An ECL biosensor for glucose based on carbon-nanotube/Nafion film modified glass carbon electrode | |
| Stasyuk et al. | Amperometric biosensors based on oxidases and PtRu nanoparticles as artificial peroxidase | |
| Zhang et al. | A novel nonenzymatic sensor based on LaNi0. 6Co0. 4O3 modified electrode for hydrogen peroxide and glucose | |
| Stege et al. | Determination of β-glucosidase activity in soils with a bioanalytical sensor modified with multiwalled carbon nanotubes | |
| Zhang et al. | Direct electrocatalytic oxidation of hydrogen peroxide based on nafion and microspheres MnO2 modified glass carbon electrode | |
| Zhang et al. | Bioinspired nanozyme enabling glucometer readout for portable monitoring of pesticide under resource-scarce environments | |
| Damos et al. | Iron (III) tetra-(N-methyl-4-pyridyl)-porphyrin as a biomimetic catalyst of horseradish peroxidase on the electrode surface: an amperometric sensor for phenolic compound determinations | |
| Jena et al. | Enzyme integrated silicate–Pt nanoparticle architecture: A versatile biosensing platform | |
| CN105891189B (en) | A kind of copper ion detection kit and its application | |
| CN109342529B (en) | Non-enzymatic glucose sensor and preparation method thereof | |
| CN113758983B (en) | Construction method of glucose biosensor based on glutathione assembly | |
| Kim et al. | Poly-γ-glutamic Acid/Chitosan hydrogel nanoparticles entrapping glucose oxidase and magnetic nanoparticles for glucose biosensing | |
| Kamyabi et al. | A highly sensitive ECL platform based on GOD and NiO nanoparticle decorated nickel foam for determination of glucose in serum samples | |
| Dai et al. | A highly performing electrochemiluminescent biosensor for glucose based on a polyelectrolyte-chitosan modified electrode | |
| Wu et al. | Biofunctional nanocomposite of carbon nanofiber with water-soluble porphyrin for highly sensitive ethanol biosensing | |
| Campanella et al. | A new tool for superoxide and nitric oxide radicals determination using suitable enzymatic sensors | |
| CN110186912B (en) | Electrochemiluminescence aptamer sensor based on thiocholine co-reaction accelerator and method for determining chlorpyrifos | |
| Liu et al. | Enhanced electron-transfer reactivity of horseradish peroxidase in phosphatidylcholine films and its catalysis to nitric oxide | |
| Gründig et al. | Electron mediator-modified electrode for the determination of glucose in fermentation media |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20211112 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |