CN-122016967-A - Working electrode for enhancing electrochemiluminescence performance based on catalyst, preparation method thereof and aptamer sensor for acetamiprid detection

CN122016967ACN 122016967 ACN122016967 ACN 122016967ACN-122016967-A

Abstract

The invention belongs to the technical field of analytical chemistry, and particularly relates to a working electrode for enhancing electrochemiluminescence performance based on a catalyst, a preparation method thereof and an aptamer sensor for acetamiprid detection, wherein the working electrode for enhancing electrochemiluminescence performance based on the catalyst is prepared by sequentially dripping activated europium-based MOF solution, cDNA1 solution, bovine serum albumin solution, target mixture and ZiF-67-cDNA2 solution on a glassy carbon electrode; the electrochemiluminescence signal intensity is synergistically improved through the nano-finite field effect and the redox mediation of ZIF-67, and an electrochemiluminescence enhancement strategy with ZIF-67 as a catalyst is provided, so that enrichment and reaction kinetics of active free radicals are remarkably promoted through the ternary synergistic effect of ZIF-67, europium-based MOF and tripropylamine during acetamiprid detection, sensitivity of a sensing system is improved, and a new technical support is provided for agricultural product safety monitoring.

Inventors

LIU SHUYUAN
WEI QIN
DONG XUE
WANG SHAN

Assignees

大理大学

Dates

Publication Date: 20260512
Application Date: 20260226

Claims (9)

1. A method for preparing a working electrode with enhanced electrochemiluminescence performance based on a catalyst, comprising the following steps: Dripping the activated europium-based MOF solution on the glassy carbon electrode, and drying at room temperature to obtain a glassy carbon electrode I; Wherein the activated europium-based MOF is obtained by activating a europium-based MOF material by adopting 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and N-hydroxysulfosuccinimide; dripping cDNA1 solution on a glassy carbon electrode I, wherein the cDNA1 is used for complementary pairing with the base of an acetamiprid aptamer, the nucleotide sequence of the cDNA1 is shown as SEQ ID No.1, the 5' end of the cDNA1 is modified by amino, and drying is carried out at room temperature to obtain a glassy carbon electrode II; dripping bovine serum albumin solution on the glassy carbon electrode II to seal a non-specific binding site on the glassy carbon electrode II, and drying at room temperature to obtain a glassy carbon electrode III; dropwise adding the target mixture on a glassy carbon electrode III, and drying at room temperature to obtain a glassy carbon electrode IV; dripping ZiF-67-cDNA2 solution on a glassy carbon electrode IV, and drying at room temperature to obtain a working electrode based on the catalyst for enhancing electrochemiluminescence performance; Wherein the ZiF-67-cDNA2 solution is obtained by mixing ZiF-67 with cDNA2 solution, centrifuging to obtain solid, and dispersing in PBS buffer solution, wherein cDNA2 is used for complementary pairing with cDNA1, the nucleotide sequence of cDNA2 is shown as SEQ ID No.2, and the 5' end of cDNA2 is modified by sulfhydryl.
2. The method for preparing the working electrode based on the catalyst for enhancing electrochemiluminescence performance according to claim 1, wherein the volume ratio of ZiF-67 mass to cDNA2 solution is 3 mg-5 mg, 1 mL-3 mL, and cDNA2 is 10 μm in cDNA2 solution.
3. The method for preparing the working electrode based on the catalyst for enhancing the electrochemiluminescence performance, according to claim 1, wherein the mass ratio of activated europium-based MOF, cDNA1 and ZiF-67-cDNA2 is 2 mg-5 mg, 5 mug-10 mug, 2 mg-5 mg.
4. The method for preparing the working electrode based on the catalyst for enhancing the electrochemiluminescence performance according to claim 1, wherein the volume ratio of the activated europium-based MOF solution to the bovine serum albumin solution is 8:3, the mass fraction of solute in the bovine serum albumin solution is 1% -2%, and the amount of europium-based MOF in the activated europium-based MOF solution is 2 mg/mL-5 mg/mL.
5. The method for preparing a catalyst-based working electrode with enhanced electrochemiluminescence properties according to claim 1, wherein the europium-based MOF material is prepared according to the following steps: EuCl 3 and tetra [4- (4' -carboxyphenyl) phenyl ] ethylene are dissolved in N, N-dimethylformamide together to obtain a mixture, then acetic acid is added into the mixture, and heating is carried out for 10-30 hours at 100-150 ℃ to obtain the europium-based MOF material; Wherein the mass ratio of EuCl 3 to tetra [4- (4' -carboxyphenyl) phenyl ] ethylene is 90-103:30-45.
6. The method for preparing the working electrode for enhancing electrochemiluminescence performance based on the catalyst according to claim 5, wherein the activation method is that europium-based MOF material, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and N-hydroxysulfosuccinimide are mixed together in PBS buffer solution and are oscillated for 2 hours.
7. A working electrode for enhancing electrochemiluminescence performance based on a catalyst, which is characterized by being prepared by the preparation method of any one of claims 1 to 6.
8. An aptamer sensor for acetamiprid detection, characterized in that it is prepared by using the working electrode for enhancing electrochemiluminescence performance based on a catalyst according to claim 7.
9. The aptamer sensor for acetamiprid detection according to claim 8, wherein the aptamer sensor for acetamiprid detection comprises a three-electrode system, an electrochemical workstation, and a chemiluminescent detector; A working electrode, a reference electrode and a counter electrode which are based on the catalyst for enhancing electrochemiluminescence performance are adopted to form a three-electrode system, the three-electrode system is connected with an electrochemical workstation, the electrochemical workstation is connected with a chemiluminescence detector, the high voltage of a photomultiplier is set to 800V, the cyclic voltammetry scanning potential range is set to 0V-1.5V, and the scanning rate is set to 0.15V/s; Taking PBS buffer solution with pH of 6.0-8.5 and tripropylamine as electrolyte, placing one end of a three-electrode system into the electrolyte, detecting the electrochemiluminescence signal intensities generated by different concentrations of acetamiprid standard solutions by an electrochemiluminescence method, and drawing a working curve of the relationship between the acetamiprid concentration and the electrochemiluminescence signal intensities; And (3) measuring the acetamiprid sample solution to be measured instead of the acetamiprid standard solution, and calculating the concentration of the acetamiprid in the acetamiprid sample solution to be measured according to the working curve and the obtained electrochemiluminescence signal intensity.

Description

Working electrode for enhancing electrochemiluminescence performance based on catalyst, preparation method thereof and aptamer sensor for acetamiprid detection Technical Field The invention belongs to the technical field of analytical chemistry, and particularly relates to a working electrode for enhancing electrochemiluminescence performance based on a catalyst, a preparation method thereof and an aptamer sensor for acetamiprid detection, wherein the working electrode for enhancing electrochemiluminescence performance based on the catalyst is a working electrode for enhancing electrochemiluminescence performance based on a multifunctional catalyst zeolite imidazole ester framework material (ZIF-67). Background Acetamiprid (ACETAMIPRID, ACE) is a widely used nicotinic insecticide, and is commonly used in agricultural production. However, its residues in the environment and agricultural products accumulate through the food chain, causing neurotoxicity, cellular injury, etc. to mammals, and even triggering inflammation and apoptosis. Therefore, development of the acetamiprid detection method with high sensitivity and high selectivity has important significance for guaranteeing food safety and human health. Electrochemiluminescence (ECL) technology has received considerable attention in the field of biosensing because of its low background noise, high sensitivity and fast response. However, the conventional ECL system often faces problems of low efficiency of generation of active intermediates and slow electron transfer rate, which limits further improvement of detection performance. Metal-organic framework (MOF) materials are widely used in sensing platform construction due to their controllable pore structure, high specific surface area and good chemical stability. Among them, europium-based MOF (ETM) has a rigid skeleton structure, which can effectively suppress non-radiative relaxation and enhance luminous efficiency, but its electron transfer ability under electrochemical excitation is insufficient. Disclosure of Invention Aiming at the defects of the prior art, the invention provides a working electrode for enhancing electrochemiluminescence performance based on a catalyst, a preparation method thereof and an aptamer sensor for acetamiprid detection, wherein the working electrode for enhancing electrochemiluminescence performance based on the catalyst is obtained by sequentially dripping activated europium-based MOF solution, cDNA1 solution, bovine serum albumin solution, target mixture and ZiF-67-cDNA2 solution on a glassy carbon electrode, and the electrochemiluminescence signal intensity is synergistically enhanced through the nano-finite field effect and redox mediation of ZIF-67, so that an electrochemiluminescence enhancement strategy using ZIF-67 as a catalyst is provided, and enrichment and reaction kinetics of active free radicals are obviously promoted through ternary synergistic effect of ZIF-67, europium-based MOF and tripropylamine during acetamiprid detection, thereby improving sensitivity of a sensing system and providing new technical support for agricultural product safety monitoring. The second purpose of the invention is to construct the aptamer sensor by adopting the working electrode based on the catalyst for enhancing the electrochemiluminescence property, the constructed aptamer sensor is applied to high-sensitivity and high-specificity detection of the trace acetamiprid, the rapid analysis within the concentration range of 0.1 pM-20 nM is realized, the detection limit is as low as 52fM, the high-sensitivity and accurate detection of the acetamiprid is realized, and the high-sensitivity and accurate detection of the acetamiprid is realized. Based on the technical purpose, the invention adopts the following technical scheme: The invention discloses a preparation method of a working electrode for enhancing electrochemiluminescence performance based on a catalyst, which comprises the following steps: S1, polishing a glassy carbon electrode by using polishing powder, cleaning by using deionized water, placing the glassy carbon electrode in 5mM potassium ferricyanide solution, and scanning at-0.2V-0.6V potential to ensure that the difference value of peak potential is less than 110mV so as to ensure that the surface of the glassy carbon electrode is clean, the activity is high and the electron transfer rate is high, thereby providing a reliable substrate for the follow-up accurate electrochemical measurement. S2, dripping 8 mu L of activated europium-based MOF solution with the concentration of 2mg/mL to 5mg/mL on the glassy carbon electrode, and drying at room temperature to obtain the glassy carbon electrode I, wherein the europium-based MOF is an electroluminescent material. Wherein the activated europium-based MOF is obtained by activating a europium-based MOF material with 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) and N-hydroxysulfosuccinimide (NHS). S3, 8