阅读说明：本技术 一种己烯雌酚分子印迹电化学传感器的制备方法 (Preparation method of diethylstilbestrol molecularly imprinted electrochemical sensor ) 是由 刘本志 肖波 崔立强 周飞 王群 于 2020-07-02 设计创作，主要内容包括：一种己烯雌酚分子印迹电化学传感器的制备方法,是以处理过的玻碳电极作为基底,采用碳纳米管修饰玻碳电极,在邻氨基苯酚与对氨基苯甲酸双功能单体和己烯雌酚的磷酸盐缓冲溶液中电聚合形成分子印迹聚合物制得,并用乙醇/乙酸溶液去除模板,得到对己烯雌酚选择性响应的分子印迹电化学传感器。这种方法制备出的分子印迹电化学传感器对己烯雌酚的检出限为1.2×10<Sup>-7 </Sup>mol/L,线性范围为3×10<Sup>-7</Sup>mol/L-6×10<Sup>-6</Sup> mol/L。本发明中提供的方法制备出的分子印迹电化学传感器具有良好的稳定性和选择性,而且制备方法简单实用。(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 ‑7 mol/L, linear range 3 × 10 ‑7 mol/L‑6×10 ‑6 mol/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.)

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.

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^{- 7}mol/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