CN111551604A - Preparation method of flumorph molecular imprinting electrochemical sensor - Google Patents

Preparation method of flumorph molecular imprinting electrochemical sensor Download PDF

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Publication number
CN111551604A
CN111551604A CN202010627139.4A CN202010627139A CN111551604A CN 111551604 A CN111551604 A CN 111551604A CN 202010627139 A CN202010627139 A CN 202010627139A CN 111551604 A CN111551604 A CN 111551604A
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flumorph
electrochemical sensor
molecular imprinting
electrode
molecularly imprinted
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刘本志
陈天明
金建祥
崔立强
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Yancheng Institute of Technology
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Yancheng Institute of Technology
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
    • C08J2201/042—Elimination of an organic solid phase
    • C08J2201/0424—Elimination of an organic solid phase containing halogen, nitrogen, sulphur or phosphorus atoms

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Abstract

A method for preparing a flumorph molecular imprinting electrochemical sensor comprises the steps of using a processed screen printing carbon electrode as a substrate, modifying the screen printing carbon electrode by graphene, carrying out electropolymerization in an acidic sodium sulfate solution of 2-mercaptobenzimidazole and flumorph to form a molecular imprinting polymer, removing a template by using an isobutanol/acetic acid solution to obtain the molecular imprinting electrochemical sensor selectively responding to the flumorph, wherein the detection limit of the molecular imprinting electrochemical sensor prepared by the method to the flumorph is 2.3 × 10‑7mol/L, linear range 3.5 × 10‑6mol/L‑6.5×10‑5mol/L. The molecularly imprinted electrochemical sensor prepared by the method provided by the invention hasGood stability and selectivity, and simple and practical preparation method.

Description

Preparation method of flumorph molecular imprinting electrochemical sensor
Technical Field
The invention relates to the field of electrochemical sensors, in particular to a preparation method of a flumorph molecular imprinting electrochemical sensor.
Background
Flumorph (Flumorph) is the first novel bactericide with proprietary intellectual property rights in China and has been commercialized. Meanwhile, the morpholine agricultural bactericide is the first new pesticide variety obtained in the Chinese invention patent and the American invention patent, and is particularly effective to downy mildew and phytophthora bacteria. However, excessive residues in crops and pesticide application environments can cause pollution of water and soil in the environment and poison human and livestock. In addition, excessive uptake of flumorph in human body can cause a series of problems such as endocrine disturbance and the like, and has great influence on human health.
The traditional flumorph detection method comprises high performance liquid chromatography, high-speed counter-current chromatography, QuEChERS-HPLC method, QuEChERS-gas chromatography-mass spectrometry combination method, liquid chromatography-tandem mass spectrometry and the like, but the traditional methods have the characteristics of complex sample preparation, requirement of specific instrument operators, expensive equipment and the like. The fast, convenient and low-cost detection method of the flumorph has important significance.
The molecular imprinting technology is a technology for preparing a polymer having a recognition property for a template molecule. Molecularly Imprinted Polymers (MIPs) have the characteristics of specific identification, structural efficiency presetting, wide practicability and the like for the identification of template molecules. The molecularly imprinted polymer has the characteristics of good chemical stability, high selectivity, easy preparation and the like. The molecular imprinting electrochemical sensor combines the advantages of rapid detection and simple operation of the electrochemical sensor with a molecular imprinting technology, and can be used for selective detection of flumorph.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a simple preparation method of a flumorph molecular imprinting electrochemical sensor, which can be used for solving the problems of complex preparation process, poor stability and the like of the molecular imprinting electrochemical sensor.
The technical scheme is as follows: the invention adopts the following technical scheme.
The preparation method of the flumorph molecular imprinting electrochemical sensor is characterized in that a processed screen printing carbon electrode is used as a substrate, a graphene modified screen printing carbon electrode, an acidic sodium sulfate solution of 2-mercaptobenzimidazole and flumorph are used as electrolytes, and a molecular imprinting polymer is formed by polymerization through cyclic voltammetry, wherein the detection limit of the molecular imprinting electrochemical sensor prepared by the method to the flumorph is 2.3 × 10-7mol/L, linear range 3.5 × 10-6mol/L-6.5×10-5mol/L, the specific preparation method comprises the following stepsThe method comprises the following steps:
the method comprises the following steps: and (3) sequentially ultrasonically washing the screen printing carbon electrode by acetone, ethanol and deionized water for several minutes. Then the electrode is at K3Fe(CN)6And (5) performing medium scanning to obtain a reversible cyclic voltammetry peak, and proving that the electrode is well treated.
Step two: dispersing graphene into mixed acid solution (HNO)3: H2SO4Finishing carboxylation modification on the surface of graphene by refluxing in a ratio of 1: 3); then, filtering, washing and drying; ultrasonically dispersing the obtained product to obtain a suspension; and (3) dripping 2-10 mu L of suspension liquid on the surface of the treated screen printing carbon electrode to form a uniform dispersion layer, and naturally airing to obtain the graphene modified electrode.
Step three: dissolving 2-mercaptobenzimidazole and flumorph in an acid sodium sulfate solution, and uniformly mixing, wherein the molar ratio of the 2-mercaptobenzimidazole to the flumorph is 1:2-6: 2.
Step four: and taking the mixed solution in the third step as an electrolyte solution, then placing the graphene modified electrode in the mixed solution, performing electrochemical polymerization by adopting a cyclic voltammetry method to form a molecularly imprinted polymer, and eluting the flumorph by using an isobutanol/acetic acid solution to obtain the flumorph molecularly imprinted electrochemical sensor.
In the scheme, the pH value of the acidic sodium sulfate solution is 2-6.
The electrochemical polymerization method in the scheme is an electrodeposition method, the deposition potential is 0.5V-1.3V, and the deposition time is 60s-600 s.
In the scheme, the concentration of the isobutanol/acetic acid solution is 1:1-8: 1.
The flumorph molecular imprinting electrochemical sensor prepared by the method can be used for quantitative detection of flumorph in water.
Detailed Description
Example 1
Screen printing carbon electrode pretreatment
And (3) sequentially ultrasonically washing the screen printing carbon electrode by acetone, ethanol and deionized water for several minutes. Then the electrode is placed at K3Fe(CN)6Middle scan to obtain reversible cycleVoltammetry peak, which proves that the electrode is well treated.
Example 2
Graphene modified screen printing carbon electrode
Dispersing graphene into mixed acid solution (HNO)3: H2SO4Finishing carboxylation modification on the surface of graphene by refluxing in a ratio of 1: 3); then, filtering, washing and drying; ultrasonically dispersing the obtained product to obtain a suspension; and (3) dripping 2-10 mu L of suspension liquid on the surface of the treated screen printing carbon electrode to form a uniform dispersion layer, and naturally airing to obtain the graphene modified electrode.
Example 3
Preparing a polymerization solution
The method comprises the steps of taking flumorph as a template molecule and 2-mercaptobenzimidazole as a functional monomer, and fully dissolving the flumorph in an acidic sodium sulfate solution, wherein the molar ratio of the 2-mercaptobenzimidazole to the flumorph is 1:2-6: 2.
Example 4
Electrochemical polymerization
Placing the graphene-modified silk-screen printing carbon electrode in the prepared polymerization solution for electropolymerization, wherein the working electrode is the graphene-modified silk-screen printing carbon electrode, the reference electrode is an Ag/AgCl electrode, and the auxiliary electrode is a platinum wire electrode; the electrochemical polymerization method is an electrodeposition method, the deposition potential is 0.5V-1.3V, and the deposition time is 60s-600 s.
Example 5
And (3) placing the prepared polymer electrode in an isobutanol/acetic acid solution for eluting for 50min, then washing the eluted electrode with distilled water, and airing at room temperature for later use.
Example 6
Drawing of working curves
The concentration determination experiment of the flumorph is carried out by adopting square wave voltammetry. The start-stop potential of the square wave voltammetry is-0.3V-0.8V, the potential increment is 0.005V, the square wave frequency is 15Hz, the square wave amplitude is 0.1V, and the detection base solution is 5.0 mM K3[Fe(CN)6]And 0.1 MKCl. After each use, the electrode was immersed in an isobutanol/acetic acid solution, eluted with a magnetic stirrer for 30min to remove the template molecules adsorbed in the polymeric membrane, so thatThe standard curve is drawn according to the difference between the known concentration of the flumorph and the square wave volt-ampere peak current, and the detection limit is 2.3 × 10-7mol/L, linear range 3.5 × 10-6mol/L-6.5×10-5mol/L。

Claims (5)

1. A preparation method of a flumorph molecular imprinting electrochemical sensor is characterized in that the preparation method of the flumorph molecular imprinting electrochemical sensor is characterized in that a screen printing carbon electrode modified by graphene is used as a substrate, and electropolymerization is carried out in an acidic sodium sulfate solution of 2-mercaptobenzimidazole and flumorph to form a molecular imprinting polymer, and the detection limit of the prepared molecular imprinting electrochemical sensor to the flumorph is 2.3 × 10-7mol/L, linear range 3.5 × 10-6mol/L-6.5×10-5mol/L; the preparation method comprises the following steps: firstly, the silk-screen printing carbon electrode is respectively washed by ultrasound for several minutes in acetone, ethanol and deionized water in sequence, and then the electrode is placed in K3Fe(CN)6Performing intermediate scanning to obtain a reversible cyclic voltammetry peak, and proving that the electrode is well treated; then dropwise adding the dispersed graphene suspension onto a screen-printed carbon electrode to form a uniform dispersion layer, and naturally drying to obtain a graphene-modified electrode; dissolving 2-mercaptobenzimidazole and flumorph in an acid sodium sulfate solution, and uniformly mixing, wherein the molar ratio of the 2-mercaptobenzimidazole to the flumorph is 1:2-6: 2; and (III) taking the mixed solution as an electrolyte solution, placing the graphene modified electrode in the mixed solution, performing electrochemical polymerization by adopting a cyclic voltammetry method to form a molecularly imprinted polymer, and washing away fluorine morpholine template molecules by using an isobutanol/acetic acid solution to obtain the fluorine morpholine molecularly imprinted electrochemical sensor.
2. The method for preparing a flumorph molecularly imprinted electrochemical sensor according to claim 1, wherein the electrolyte solution is an acidic sodium sulfate solution with a pH of 2-6.
3. The method for preparing a flumorph molecularly imprinted electrochemical sensor according to claim 1, wherein the amount of graphene suspension dropped onto the screen printed carbon electrode in the method is 2 μ L-10 μ L.
4. The method for preparing a flumorph molecularly imprinted electrochemical sensor according to claim 1, wherein the electrochemical polymerization method in the preparation method is electrodeposition, the deposition potential is 0.5V-1.3V, and the deposition time is 60s-600 s.
5. The method for preparing a flumorph molecularly imprinted electrochemical sensor according to claim 1, wherein the concentration of isobutanol/acetic acid solution in the method is 1:1-8: 1.
CN202010627139.4A 2020-07-02 2020-07-02 Preparation method of flumorph molecular imprinting electrochemical sensor Pending CN111551604A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101644680A (en) * 2009-09-01 2010-02-10 济南大学 Molecular imprinting chemiluminescence sensor for detecting trace amount pesticide residue and application thereof
CN103866367A (en) * 2014-03-31 2014-06-18 福建师范大学 Preparation method and application of tri-(2, 3-dibromopropyl) isocyanurate sensor

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101644680A (en) * 2009-09-01 2010-02-10 济南大学 Molecular imprinting chemiluminescence sensor for detecting trace amount pesticide residue and application thereof
CN103866367A (en) * 2014-03-31 2014-06-18 福建师范大学 Preparation method and application of tri-(2, 3-dibromopropyl) isocyanurate sensor

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
HONGMEI ZHANG等: "Molecularly Imprinted Sensor based on o-phenylenediamine for Electrochemical Detection of Sulfamethoxazole", 《INT. J. ELECTROCHEM. SCI.》 *
李籽萱: "四种酰胺类农药分子印迹电化学传感器的制备及应用研究", 《中国优秀博硕士学位论文全文数据库(硕士) 工程科技Ⅰ辑》 *

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