CN111595915A - Preparation method of diethylstilbestrol molecularly imprinted electrochemical sensor - Google Patents

Preparation method of diethylstilbestrol molecularly imprinted electrochemical sensor Download PDF

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Publication number
CN111595915A
CN111595915A CN202010626030.9A CN202010626030A CN111595915A CN 111595915 A CN111595915 A CN 111595915A CN 202010626030 A CN202010626030 A CN 202010626030A CN 111595915 A CN111595915 A CN 111595915A
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China
Prior art keywords
diethylstilbestrol
preparation
electrochemical sensor
electrode
molecularly imprinted
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CN202010626030.9A
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Chinese (zh)
Inventor
刘本志
肖波
崔立强
周飞
王群
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Jiangsu Yida Testing Technology Co ltd
Yancheng Institute of Technology
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Jiangsu Yida Testing Technology Co ltd
Yancheng Institute of Technology
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Priority to CN202010626030.9A priority Critical patent/CN111595915A/en
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y15/00—Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/44—Polyester-amides
    • 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
    • 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
    • C08J2201/0422—Elimination of an organic solid phase containing oxygen atoms, e.g. saccharose
    • 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
    • C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • C08J2377/12—Polyester-amides

Abstract

A preparation method of a diethylstilbestrol molecular imprinting electrochemical sensor is characterized in that a treated glassy carbon electrode is used as a substrate, a carbon nano tube is used for modifying the glassy carbon electrode, electropolymerization is carried out in phosphate buffer solution of an o-aminophenol and p-aminobenzoic acid double-function monomer and diethylstilbestrol to form a molecular imprinting polymer, and a template is removed by using an ethanol/acetic acid solution to obtain the diethylstilbestrol selective response molecular imprinting electrochemical sensor. Molecules prepared by this methodThe detection limit of the imprinted electrochemical sensor on diethylstilbestrol is 1.2 × 10‑7mol/L, linear range 3 × 10‑7mol/L‑6×10‑6mol/L. The molecularly imprinted electrochemical sensor prepared by the method provided by the invention has good stability and selectivity, and the preparation method is simple and practical.

Description

Preparation method of diethylstilbestrol molecularly imprinted electrochemical sensor
Technical Field
The invention relates to the field of electrochemical sensors, in particular to a preparation method of a diethylstilbestrol molecular imprinting electrochemical sensor.
Background
The diethylstilbestrol is one of environmental estrogen compounds, can enter organisms to imitate, obstruct, interfere or change the action of the hormones of the organisms, cause the disorder of the endocrine system of the bodies, obstruct the transmission of the nervous system, reduce the immune function of the organisms, even cause the malformation and canceration of organs, and seriously threaten the health and the survival of human bodies. Therefore, the method has important practical significance for quickly and accurately detecting the diethylstilbestrol.
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 molecularly imprinted electrochemical sensor combines the advantages of rapid detection and simple operation of the electrochemical sensor with a molecularly imprinted technology, and can be used for selective detection of diethylstilbestrol.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a simple preparation method of a diethylstilbestrol molecularly imprinted electrochemical sensor, which can be used for solving the problems of complex preparation process, poor stability and the like of the molecularly imprinted electrochemical sensor.
The technical scheme is as follows: the invention adopts the following technical scheme.
The preparation method of the diethylstilbestrol molecular imprinting electrochemical sensor is characterized in that a treated glassy carbon electrode is used as a substrate, a carbon nanotube modified glassy carbon electrode is used, phosphate buffer solution of an o-aminophenol and p-aminobenzoic acid double-function monomer and diethylstilbestrol is used as electrolyte, and a molecular imprinting polymer is formed by polymerization through a cyclic voltammetry method, wherein the detection limit of the diethylstilbestrol detection limit of the prepared molecular imprinting electrochemical sensor to diethylstilbestrol is 1.2 × 10-7mol/L, linear range 3 × 10- 7mol/L-6×10-6mol/L, and the specific preparation method comprises the following steps:
the method comprises the following steps: the glassy carbon electrode was successively coated with 0.5 μm and 0.05 μm Al2O3The powder was polished on chamois leather and then ultrasonically washed in ethanol and deionized water, respectively, for several minutes. Then the electrode is at K3Fe(CN)6And (4) performing medium scanning to obtain a reversible cyclic voltammetry peak (the peak current ratio is 1:1, and the peak potential difference is less than 70 mV), thereby proving that the electrode is well treated.
Step two: dispersing carbon nanotubes into mixed acid solution (HNO)3: H2SO4Finishing the carboxylation modification on the surface of the carbon nano tube by refluxing in a ratio of 1: 3); the reflux temperature is 60-90 ℃, and the reflux time is 3-8 h; 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 glassy carbon electrode to form a uniform dispersion layer, and naturally airing to obtain the carbon nano tube modified electrode.
Step three: dissolving ortho-aminophenol, a p-aminobenzoic acid bifunctional monomer and diethylstilbestrol in a phosphate buffer solution, and uniformly mixing, wherein the molar ratio of the ortho-aminophenol to the p-aminobenzoic acid bifunctional monomer to the diethylstilbestrol is (1-5): 1-4): 1.
Step four: and (3) taking the mixed solution in the third step as an electrolyte solution, then placing the electrode modified by the carbon nano tube into the mixed solution, performing electrochemical polymerization by adopting a cyclic voltammetry method to form a molecularly imprinted polymer, and eluting diethylstilbestrol by using an ethanol/acetic acid solution to obtain the molecularly imprinted electrochemical sensor of diethylstilbestrol.
In the above scheme, the pH of the phosphate buffer solution is 3-7.
The electrochemical polymerization method in the scheme is cyclic voltammetry, and the voltage range is as follows: 0V to 0.9V, a scanning rate of 50mV/s to 100mV/s, and a scanning period of 10 circles to 30 circles.
In the scheme, the concentration of the ethanol/acetic acid solution is 2:1-6: 1.
The diethylstilbestrol molecularly imprinted electrochemical sensor prepared by the method can be used for quantitative detection of diethylstilbestrol in water.
Detailed Description
Example 1
Glassy carbon electrode pretreatment
The glassy carbon electrode was successively coated with 0.5 μm and 0.05 μm Al2O3The powder was polished on chamois leather and then ultrasonically washed in ethanol and deionized water, respectively, for several minutes. Then the electrode is placed at K3Fe(CN)6And (4) performing medium scanning to obtain a reversible cyclic voltammetry peak (the peak current ratio is 1:1, and the peak potential difference is less than 70 mV), thereby proving that the electrode is well treated.
Example 2
Carbon nanotube modified glassy carbon electrode
Dispersing carbon nanotubes into mixed acid solution (HNO)3: H2SO4Finishing the carboxylation modification on the surface of the carbon nano tube by refluxing in a ratio of 1: 3); the reflux temperature is 60-90 ℃, and the reflux time is 3-8 h; 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 glassy carbon electrode to form a uniform dispersion layer, and naturally airing to obtain the carbon nano tube modified electrode.
Example 3
Preparing a polymerization solution
Diethylstilbestrol is used as a template molecule, an o-aminophenol and p-aminobenzoic acid bifunctional monomer is used as a functional monomer, and the functional monomer is fully dissolved in a phosphate buffer solution, wherein the molar ratio of the o-aminophenol to the p-aminobenzoic acid bifunctional monomer to the diethylstilbestrol is (1-5): 1-4): 1.
Example 4
Electrochemical polymerization
Placing the glassy carbon electrode modified by the carbon nano tube in the prepared polymerization solution, and performing electropolymerization by adopting a three-electrode system, wherein the working electrode is the glassy carbon electrode modified by the carbon nano tube, the reference electrode is a saturated calomel electrode, and the auxiliary electrode is a platinum sheet electrode; voltage range: 0V to 0.9V, a scanning rate of 50mV/s to 100mV/s, and a scanning period of 10 circles to 30 circles.
Example 5
And (3) placing the prepared polymer electrode in an ethanol/acetic acid solution for eluting for 60min, then washing the eluted electrode with distilled water, and airing at room temperature for later use.
Example 6
Drawing of working curves
The square wave voltammetry is adopted to carry out the diethylstilbestrol concentration determination experiment. The start-stop potential of the square wave voltammetry is-0.4V-0.7V, 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 3.0 mM K3[Fe(CN)6]And 0.1M KCl, after each use, immersing the electrode in ethanol/acetic acid solution, eluting with a magnetic stirrer for 30min, removing template molecules adsorbed in the polymeric membrane for reuse, drawing a standard curve according to the difference between the known concentration of diethylstilbestrol and the square wave volt-ampere peak current, and the detection limit is 1.2 × 10-7mol/L, linear range 3 × 10-7mol/L-6×10-6mol/L。

Claims (5)

1. A preparation method of a diethylstilbestrol molecular imprinting electrochemical sensor is characterized in that the preparation method of the diethylstilbestrol molecular imprinting electrochemical sensor is characterized in that a glassy carbon electrode modified by a carbon nano tube is used as a substrate, and the glassy carbon electrode is prepared by electropolymerization in phosphate buffer solution of an o-aminophenol, a p-aminobenzoic acid bifunctional monomer and diethylstilbestrol to form a molecular imprinting polymer, wherein the detection limit of the diethylstilbestrol detection electrochemical sensor prepared by the method is 1.2 × 10-7mol/L, linear range 3 × 10-7mol/L-6×10-6mol/L; the preparation method comprises the following steps: firstly, using 0.5 mu m Al and 0.05 mu m Al for a glassy carbon electrode in sequence2O3Polishing the powder on chamois leather, ultrasonic washing in alcohol and deionized water for several min, and putting electrode in K3Fe(CN)6Middle scanning to obtain reversible cyclic voltammetry peaks (the peak current ratio is 1:1, and the peak potential difference is less than 70 mV), which proves that the electrode is well treated; then dripping the dispersed carbon nano tube suspension liquid on a glassy carbon electrode to form a uniform dispersion layer, and naturally airing to obtain a carbon nano tube modified electrode; (II) dissolving the o-aminophenol and p-aminobenzoic acid double-function monomer and the diethylstilbestrol in phosphate bufferMixing in the solution uniformly, wherein the molar ratio of the o-aminophenol to the p-aminobenzoic acid bifunctional monomer to the diethylstilbestrol is (1-5) to (1-4) to 1; and (III) taking the mixed solution as an electrolyte solution, placing the electrode modified by the carbon nano tube in the mixed solution, performing electrochemical polymerization by adopting a cyclic voltammetry method to form a molecularly imprinted polymer, and washing away diethylstilbestrol template molecules by using an ethanol/acetic acid solution to obtain the diethylstilbestrol molecularly imprinted electrochemical sensor.
2. The method for preparing the diethylstilbestrol molecular imprinting electrochemical sensor according to claim 1, wherein an electrolyte solution in the preparation method is a phosphate buffer solution, and the pH value is 3-7.
3. The preparation method of the diethylstilbestrol molecularly imprinted electrochemical sensor according to claim 1, wherein the amount of the carbon nanotube suspension dropped onto the glassy carbon electrode in the preparation method is 2 μ L to 10 μ L.
4. The preparation method of the diethylstilbestrol molecularly imprinted electrochemical sensor according to claim 1, wherein the electrochemical polymerization method in the preparation method is cyclic voltammetry, and the voltage range is as follows: 0V to 0.9V, a scanning rate of 50mV/s to 100mV/s, and a scanning period of 10 circles to 30 circles.
5. The preparation method of the diethylstilbestrol molecularly imprinted electrochemical sensor according to claim 1, wherein the concentration of the ethanol/acetic acid solution in the preparation method is 2:1-6: 1.
CN202010626030.9A 2020-07-02 2020-07-02 Preparation method of diethylstilbestrol molecularly imprinted electrochemical sensor Pending CN111595915A (en)

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