CN109307695B - Preparation method and application of chlordimeform electrochemiluminescence sensor - Google Patents

Preparation method and application of chlordimeform electrochemiluminescence sensor Download PDF

Info

Publication number
CN109307695B
CN109307695B CN201811306537.5A CN201811306537A CN109307695B CN 109307695 B CN109307695 B CN 109307695B CN 201811306537 A CN201811306537 A CN 201811306537A CN 109307695 B CN109307695 B CN 109307695B
Authority
CN
China
Prior art keywords
chlordimeform
electrode
template
conin
nanoarray
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.)
Active
Application number
CN201811306537.5A
Other languages
Chinese (zh)
Other versions
CN109307695A (en
Inventor
张勇
程荣琦
杜斌
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of Jinan
Original Assignee
University of Jinan
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by University of Jinan filed Critical University of Jinan
Priority to CN201811306537.5A priority Critical patent/CN109307695B/en
Publication of CN109307695A publication Critical patent/CN109307695A/en
Application granted granted Critical
Publication of CN109307695B publication Critical patent/CN109307695B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • 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
    • 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
    • G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
    • G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
    • G01N27/3278—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction involving nanosized elements, e.g. nanogaps or nanoparticles

Abstract

The invention discloses a preparation method of an chlordimeform electrochemiluminescence sensor. Belongs to the technical field of novel nanometer functional materials and biosensing analysis. Firstly, a cobalt-nickel bimetallic nitride nanosheet array is prepared on a disposable throwable electrode, a polydopamine film and a molecular imprinting polymer which is coated with luminol in situ and takes chlordimeform as a template molecule are sequentially and directly prepared on the cobalt-nickel bimetallic nitride nanosheet array by utilizing the large specific surface area, the high adsorption activity to amino and the amino functional group of the polydopamine in an in-situ growth method, after the template molecule is eluted, the original position of the template molecule is changed into a cavity, namely the molecular imprinting polymer of the template molecule is eluted, and therefore, the chlordimeform electrochemiluminescence sensor is prepared.

Description

Preparation method and application of chlordimeform electrochemiluminescence sensor
Technical Field
The invention relates to a preparation method and application of an electrochemiluminescence sensor. Belongs to the technical field of novel nanometer functional materials and biosensing analysis.
Background
Chlordimeform, also known as ampicillin, is a beta-lactam antibiotic, a semi-synthetic broad-spectrum penicillin, and can treat a variety of bacterial infections. Indications include respiratory infections, urinary tract infections, meningitis, salmonella infections, and endocarditis. Because of convenient use and low cost, the medicine is multi-purpose for treating infectious diseases caused by chicken sensitive bacteria, such as escherichia coli, salmonella, pasteurella, staphylococcus, streptococcus and the like. In 2017, 10 and 27, the list of carcinogens published by the international agency for research on cancer of the world health organization, ampicillin is on the list of 3 types of carcinogens. Therefore, the development of a method for quickly, highly selectively and sensitively detecting the chlordimeform is very important to public health and has wide market application prospect.
The electroanalytical chemical sensors include electrochemical sensors, electrochemiluminescence sensors, photoelectrochemical sensors and the like, and the sensors have high specificity selectivity, excellent stability, excellent reproducibility, wide detection range and bottom detection limit. The sensor has the advantages of simple preparation, convenient detection, high sensitivity, low cost and the like, and can be widely applied to the fields of chromatographic separation, membrane separation, solid-phase extraction, drug controlled release, chemical sensing and the like. Molecularly Imprinted Polymers (MIPs), also known as "plastic antibodies", are capable of specifically recognizing and selectively adsorbing a specific target molecule (i.e., template molecule). The molecular imprinting technology has many advantages, such as corrosion resistance of organic reagents, good stability, high temperature resistance and simple preparation. Thus, MIP electroanalytical chemical sensors (MIP-ECS) based on the combination of MIPs with electroanalytical chemical sensors have attracted a great deal of interest in the field of electroanalytical chemistry, particularly the detection of small molecule contaminants, over the last few years. However, in the preparation process of the traditional MIP-ECS, the defects of difficult elution of template molecules, difficult control of the thickness of the imprinted membrane, poor reproducibility and the like exist, and the application of the molecularly imprinted membrane in an electroanalytical chemical sensor is limited. The problems, especially the technical problems that the sensitivity of the electrochemical sensor is reduced due to the fact that the thickness of the molecularly imprinted membrane is not easy to control, and the stability and the reproducibility are reduced due to the fact that the molecularly imprinted membrane is easy to fall off from the surface of an electrode in the elution process, limit the application of MIP _ ECS, so that the research of a new molecularly imprinted polymer synthesis method, a new molecularly imprinted membrane electrode modification method and a method for combining the molecularly imprinted membrane and a substrate material for solving the preparation and application problems of MIP-ECS has important research significance and market value.
Disclosure of Invention
The invention aims to provide a preparation method of an chlordimeform electrochemiluminescence sensor, which has the advantages of strong specificity, simple preparation, convenient detection, high sensitivity and low cost. Based on the purpose, firstly, a cobalt-nickel bimetallic nitride nanosheet array is prepared on a disposable throwable electrode, a polydopamine film and a molecular imprinting polymer which is coated with luminol in situ and takes chlordimeform as template molecules are sequentially and directly prepared on the cobalt-nickel bimetallic nitride nanosheet array by utilizing the large specific surface area, the high adsorption activity to amino and the amino functional group of the polydopamine in an in-situ growth method, and after the template molecules are eluted, the original positions of the template molecules are changed into cavities, namely the molecular imprinting polymer of the template molecules is eluted, so that the chlordimeform electrochemiluminescence sensor is prepared. When the electrochemiluminescence sensor is used for detecting the chlordimeform, the chlordimeform electrochemiluminescence sensor is inserted into a solution to be detected, and the chlordimeform in the solution to be detected is adsorbed into a cavity of the NIP. The greater the concentration of chlordimeform in the solution to be tested, the more chlordimeform that is adsorbed into the cavities of the NIP. When the electrochemiluminescence detection is carried out, the current intensity passing through the electrode is reduced along with the increase of the chlordimeform adsorbed in the hole of the NIP, and the corresponding electrochemiluminescence signal is reduced along with the current intensity, so that the concentration of the chlordimeform in the solution to be detected can be qualitatively and quantitatively determined according to the reduction degree of the intensity of the electrochemiluminescence optical signal.
The technical scheme adopted by the invention is as follows:
1. a preparation method of an amidine insecticidal electrochemiluminescence sensor is provided, wherein the amidine insecticidal electrochemiluminescence sensor is obtained by in-situ growth of a template-free molecularly imprinted polymer NIP on a cobalt-nickel bimetallic nitride nanosheet array electrode CoNiN-nanoarray; the template-free molecularly imprinted polymer NIP is a molecularly imprinted polymer without template molecules; the molecularly imprinted polymer without the template molecule is obtained by eluting the template molecule from a MIP containing the template molecularly imprinted polymer; the MIP containing the template molecule engram polymer is the MIP containing the template molecule; the template molecule is chlordimeform;
2. the preparation method of the cobalt-nickel bimetallic nitride nanosheet array electrode CoNiN-nanoarray in the technical scheme 1 comprises the following preparation steps:
(1) carrying out ultrasonic cleaning treatment on the disposable throwable electrode by respectively using dilute hydrochloric acid, absolute ethyl alcohol and deionized water so as to remove an oxide layer and surface impurities of the disposable throwable electrode;
(2) weighing 1-3 mmol of Ni (NO)3)2And Co (NO)3)2And 3 to 9mmol of urea CO (NH)2)2Placing the mixture into a 50mL beaker, adding 30mL deionized water, stirring until the mixture is clear, and then transferring the mixture into a 50mL polytetrafluoroethylene reaction kettle;
(3) putting the disposable throwable electrode processed in the step (1) into the solution in the reaction kettle in the step (2), and reacting at the temperature of 100-130 ℃ for 9-12 hours to prepare a precursor electrode of the cobalt-nickel bimetal layered hydroxide nanosheet array;
(4) inserting the cobalt-nickel bimetal layered hydroxide nanosheet array precursor electrode obtained in the step (3) into ammonia water for 5-30 seconds, taking out, heating to 340-400 ℃ in an ammonia environment, keeping for 4-8 hours, continuing to naturally cool to room temperature in the ammonia environment, then inserting the electrode into phosphate buffer solution PBS containing dopamine and ammonium persulfate, reacting for 4-6 hours at the temperature of 20-40 ℃, taking out, and performing immersion washing for 2-4 times by using deionized water to prepare a cobalt-nickel bimetal nitride nanosheet array electrode CoNiN-nanoarray;
the disposable and disposable electrode is selected from one of the following electrodes: foam nickel, foam copper, pure nickel sheets, pure copper sheets, pure cobalt sheets, pure silicon sheets and conductive carbon cloth; said Ni (NO)3)2And Co (NO)3)2In a mixture of nickel and cobalt in a molar ratio of 1: 1;
in phosphate buffer solution PBS containing dopamine and ammonium persulfate: the concentration of dopamine is 2-5 mg/mL, the concentration of ammonium persulfate is 3-8 mg/mL, the concentration of phosphate buffer solution PBS is 0.1mol/L, and the pH value is 7.2-8.5;
3. the preparation method of the MIP containing the template molecularly imprinted polymer grown in situ by CoNiN-nanoarray in the technical scheme 1 comprises the following preparation steps:
(1) respectively weighing 0.25-0.45 mmol of template molecules and 3-5 mmol of 2-methacrylic acid MAA in an ampoule bottle, adding 8-15 mL of acetonitrile, and carrying out ultrasonic treatment for 30min until all the template molecules and the 2-methacrylic acid MAA are dissolved;
(2) adding 15-25 mmol of ethylene glycol dimethacrylate EDMA into the solution obtained in the step (1), and carrying out ultrasonic treatment for 30min until the mixture is uniformly mixed to obtain a precursor mixed solution;
(3) clamping the CoNiN-nanoarray prepared in the technical scheme 2 onto a rotary stirrer, inserting the CoNiN-nanoarray into the precursor mixed solution in the step (2), and adding N into the precursor mixed solution2Rotating and stirring at the speed of 5-200 r/s and the speed of 1-20 drops/s in the mixed solution at the temperature of 20-40 ℃ in the environment and water bathDropwise adding 1-3 mL of 1mmol/L luminol solution and 1mmol of azobisisobutyronitrile AIBN to initiate polymerization, and obtaining an in-situ grown MIP containing a template molecular imprinting polymer on CoNiN-nanoarray;
4. the preparation steps of the template-free molecularly imprinted polymer NIP for CoNiN-nanoarray in-situ growth in the technical scheme 1 are as follows: immersing the MIP which is obtained in the technical scheme 3 and grows in situ on the CoNiN-nanoarray and contains the template molecularly imprinted polymer into an eluant, eluting the template molecules for 5-20 min at room temperature, and then taking out to obtain the NIP without the template molecularly imprinted polymer; the eluent is a mixed solution of formic acid and methanol, wherein the volume ratio of the formic acid to the methanol is 9 (1-5);
5. the preparation steps of the chlordimeform electrochemiluminescence sensor in the technical scheme 1 are as follows: washing the template-free molecularly imprinted polymer NIP which grows on the CoNiN-nanoarray in situ prepared in the technical scheme 2-4 with deionized water for 2-4 times, and airing at room temperature to prepare the chlordimeform electrochemiluminescence sensor;
6. the technical scheme 1-5 is adopted to prepare the chlordimeform electrochemiluminescence sensor, and the sensor is applied to detection of the chlordimeform and comprises the following application steps:
(1) preparing a standard solution: preparing a group of chlordimeform standard solutions with different concentrations including blank standard samples;
(2) modification of a working electrode: taking the chlordimeform electrochemiluminescence sensor as a working electrode, inserting the chlordimeform electrochemiluminescence sensor into the chlordimeform standard solutions with different concentrations prepared in the step (1), hatching for 10min, taking out, and washing for 3 times by using deionized water;
(3) drawing a working curve: forming a three-electrode system by using a saturated calomel electrode as a reference electrode, a platinum wire electrode as a counter electrode and the modified working electrode in the step (2), and connecting the three-electrode system to electrochemiluminescence detection equipment; 15mL of phosphate buffer PBS followed by 1mL of 2mmol/L hydrogen peroxide (H) was added to the cell2O2) A solution; detecting electrochemiluminescence light by applying cyclic voltage to assembled working electrode by using double-order pulse voltammetrySignal strength; the intensity of the response light signal of the blank standard was recorded asA 0The intensity of the response light signal of standard solutions containing different concentrations of chlordimeform was recordedA iThe difference in response to the decrease in optical signal intensity is ΔA = A 0-A i，ΔAAnd the mass concentration of chlordimeform standard solutionCWith a linear relationship therebetween, plotting ΔA－CA working curve; the concentration of the phosphate buffer solution PBS is 10mmol/L, and the pH value is 7.4; the parameters of the double-order pulse voltammetry during detection are set as follows: the initial potential is 0V, the pulse potential is 0.9V, the pulse time is 0.1s, and the pulse period is 30 s;
(4) detecting the chlordimeform in the sample to be detected: replacing the standard solution of chlordimeform in step (1) with the sample to be detected, detecting according to the method in steps (2) and (3), and detecting according to the difference delta of the decrease of the intensity of the response optical signalAAnd working curve to obtain the content of the chlordimeform in the sample to be detected.
Advantageous results of the invention
(1) The chlordimeform electrochemiluminescence sensor is simple to prepare, convenient to operate, low in cost, applicable to portable detection and has market development prospect, and rapid, sensitive and high-selectivity detection of a sample is realized;
(2) according to the invention, the molecular imprinting polymer is grown in situ on the CoNiN-nanoarray electrode for the first time, on one hand, more and more uniform molecular imprinting polymers can be grown by utilizing the large specific surface area of the CoNiN-nanoarray electrode, and the CoNiN-nanoarray electrode has excellent electron transfer capacity, so that the detection sensitivity is greatly improved; on the other hand, CoNiN-nanoarray has electrocatalytic activity on hydrogen peroxide, and can realize stable and efficient reaction of a luminol-hydrogen peroxide electrochemiluminescence system without adding horseradish peroxidase, so that the prepared sensor does not need to consider the problem of inactivation of biological enzyme, the use and storage of the sensor can be more stable and the conditions are loose, the signal background is further reduced, the detection sensitivity is improved, and meanwhile, the detection cost is greatly reduced and the environmental pollution is reduced;
(3) according to the preparation method, the high adsorption activity of the nitride on amino and the large specific surface area of the nano array electrode are combined with dopamine, so that when dopamine is polymerized in situ on the surface of a cobalt-nickel bimetallic nitride nanosheet array, a sufficiently thin polydopamine film is formed and simultaneously the polydopamine film is uniformly covered on the cobalt-nickel bimetallic nitride nanosheet array, and further, a better polymerized molecularly imprinted polymer is laid; then, strong adsorption and connection effects of polydopamine on amino groups rich in the molecularly imprinted polymer are utilized, CoNiN-nanoarray is skillfully used as a stirrer, the mixture is immersed and stirred in the molecularly imprinted precursor mixed solution, and the molecularly imprinted polymer with the film thickness can be controlled by directly growing in situ on the surface of the CoNiN-nanoarray by controlling the stirring speed, the dropping speed of a polymerization reaction initiator and the polymerization reaction temperature, so that the CoNiN-nanoarray can firmly load the molecularly imprinted polymer and luminol on the one hand, and the stability and the reproducibility of the prepared electrochemical sensor are obviously improved; on the other hand, the film forming thickness of the molecularly imprinted polymer on the surface of the electrode can be effectively controlled, and the technical problem of poor reproducibility caused by the fact that the film forming thickness of the molecularly imprinted film on the surface of the electrode cannot be controlled is solved; in addition, the preparation method of the invention has important scientific significance and application value for effectively controlling the thickness of the formed film and quantitatively coating the luminol in situ, and fully improving the sensitivity and detection limit of the electrochemical sensor based on the molecular imprinting.
Detailed Description
EXAMPLE 1 preparation of CoNiN-nanoarray
(1) Carrying out ultrasonic cleaning treatment on the disposable throwable electrode by respectively using dilute hydrochloric acid, absolute ethyl alcohol and deionized water so as to remove an oxide layer and surface impurities of the disposable throwable electrode;
(2) weighing 1mmol Ni (NO)3)2And Co (NO)3)2And 3mmol of urea CO (NH)2)2Put it into a 50mL beaker, add 30mL deionized water, stir until clear, then transfer to a 50mL polytetrafluoroethylene reaction kettle；
(3) Putting the disposable throwable electrode processed in the step (1) into the solution in the reaction kettle in the step (2), and reacting at the temperature of 100 ℃ for 12 hours to prepare a cobalt-nickel bimetal layered hydroxide nanosheet array precursor electrode;
(4) inserting the cobalt-nickel bimetal layered hydroxide nanosheet array precursor electrode obtained in the step (3) into phosphate buffer solution PBS containing dopamine and ammonium persulfate, reacting for 4 hours at the temperature of 20 ℃, taking out and washing with deionized water for 2 times to prepare a cobalt-nickel bimetal nitride nanosheet array electrode CoNiN-nanoarray;
wherein the disposable throwable electrode is foamed nickel; said Ni (NO)3)2And Co (NO)3)2In a mixture of nickel and cobalt in a molar ratio of 1: 1; the concentration of dopamine is 2 mg/mL, the concentration of ammonium persulfate is 3 mg/mL, the concentration of phosphate buffer solution PBS is 0.1mol/L, and the pH value is 7.2.
EXAMPLE 2 preparation of CoNiN-nanoarray
(1) Carrying out ultrasonic cleaning treatment on the disposable throwable electrode by respectively using dilute hydrochloric acid, absolute ethyl alcohol and deionized water so as to remove an oxide layer and surface impurities of the disposable throwable electrode;
(2) weighing 2mmol of Ni (NO)3)2And Co (NO)3)2And 6 mmol of urea CO (NH)2)2Placing the mixture into a 50mL beaker, adding 30mL deionized water, stirring until the mixture is clear, and then transferring the mixture into a 50mL polytetrafluoroethylene reaction kettle;
(3) putting the disposable throwable electrode processed in the step (1) into the solution in the reaction kettle in the step (2), and reacting for 11 hours at the temperature of 110 ℃ to prepare a cobalt-nickel bimetal layered hydroxide nanosheet array precursor electrode;
(4) inserting the cobalt-nickel bimetal layered hydroxide nanosheet array precursor electrode obtained in the step (3) into phosphate buffer solution PBS containing dopamine and ammonium persulfate, reacting for 5 hours at the temperature of 30 ℃, taking out and washing with deionized water for 3 times to prepare a cobalt-nickel bimetal nitride nanosheet array electrode CoNiN-nanoarray;
wherein the disposable throwable electrode is a pure copper sheet; said Ni (NO)3)2And Co (NO)3)2In a mixture of nickel and cobalt in a molar ratio of 1: 1; the concentration of dopamine is 3.5 mg/mL, the concentration of ammonium persulfate is 6.2 mg/mL, the concentration of phosphate buffer solution PBS is 0.1mol/L, and the pH value is 8.0.
EXAMPLE 3 preparation of CoNiN-nanoarray
(1) Carrying out ultrasonic cleaning treatment on the disposable throwable electrode by respectively using dilute hydrochloric acid, absolute ethyl alcohol and deionized water so as to remove an oxide layer and surface impurities of the disposable throwable electrode;
(2) weighing 3mmol Ni (NO)3)2And Co (NO)3)2And 9mmol of urea CO (NH)2)2Placing the mixture into a 50mL beaker, adding 30mL deionized water, stirring until the mixture is clear, and then transferring the mixture into a 50mL polytetrafluoroethylene reaction kettle;
(3) putting the disposable throwable electrode processed in the step (1) into the solution in the reaction kettle in the step (2), and reacting at the temperature of 130 ℃ for 9 hours to prepare a cobalt-nickel bimetal layered hydroxide nanosheet array precursor electrode;
(4) inserting the cobalt-nickel bimetal nitride nanosheet array precursor electrode obtained in the step (3) into phosphate buffer solution PBS containing dopamine and ammonium persulfate, reacting for 6 hours at the temperature of 40 ℃, taking out, and performing immersion washing for 4 times by using deionized water to prepare a cobalt-nickel bimetal layered hydroxide nanosheet array electrode CoNiN-nanoarray;
wherein the disposable throwable electrode is a conductive carbon cloth; said Ni (NO)3)2And Co (NO)3)2In a mixture of nickel and cobalt in a molar ratio of 1: 1; the concentration of dopamine is 5mg/mL, the concentration of ammonium persulfate is 8mg/mL, the concentration of phosphate buffer solution PBS is 0.1mol/L, and the pH value is 8.5.
Example 4 preparation of Imidacloprid electrochemiluminescence sensor
(1) Respectively weighing 0.25 mmol of template molecules and 3mmol of 2-methacrylic acid MAA in an ampoule bottle, adding 8 mL of acetonitrile, and performing ultrasonic treatment for 30min until all the template molecules and the 3mmol of 2-methacrylic acid MAA are dissolved;
(2) adding 15 mmol of ethylene glycol dimethacrylate EDMA into the solution obtained in the step (1), and carrying out ultrasonic treatment for 30min until the mixture is uniformly mixed to obtain a precursor mixed solution;
(3) CoNiN-nanoarray prepared in example 1 was clamped to a rotary stirrer and inserted into the precursor mixed solution in step (2) in N2Under the temperature of environment and water bath 20 ℃, stirring in a rotating way at the speed of 200 r/s, simultaneously dripping 1mL of 1mmol/L luminol solution and 1mmol of azobisisobutyronitrile AIBN into the mixed solution at the speed of 1 drop/s to initiate polymerization, and obtaining the in-situ grown MIP containing the template molecularly imprinted polymer on CoNiN-nanoarray;
(4) immersing the MIP which is obtained in the step (3) and grows in situ on the CoNiN-nanoarray and contains the molecular imprinting polymer of the template into an eluant, eluting the molecular of the template for 5 min at room temperature, and then taking out to obtain the NIP of the molecular imprinting polymer without the template; continuously washing with deionized water for 2 times, and air drying at room temperature to obtain chlordimeform electrochemiluminescence sensor;
the eluent is a mixed solution of formic acid and methanol, wherein the volume ratio of the formic acid to the methanol is 9: 1.
Example 5 preparation of Imidacloprid electrochemiluminescence sensor
(1) Respectively weighing 0.35mmol of template molecules and 4 mmol of 2-methacrylic acid MAA in an ampoule bottle, adding 12 mL of acetonitrile, and carrying out ultrasonic treatment for 30min until all the template molecules and the 2-methacrylic acid MAA are dissolved;
(2) adding 18 mmol of ethylene glycol dimethacrylate EDMA into the solution obtained in the step (1), and carrying out ultrasonic treatment for 30min until the mixture is uniformly mixed to obtain a precursor mixed solution;
(3) clamping the CoNiN-nanoarray prepared in the technical scheme 2 onto a rotary stirrer, inserting the CoNiN-nanoarray into the precursor mixed solution in the step (2), and adding N into the precursor mixed solution2Stirring with a rotary speed of 60 rpm at a temperature of 30 ℃ in an ambient and water bath while adding 10 drops/secSimultaneously dripping 2 mL of 1mmol/L luminol solution and 1mmol of azobisisobutyronitrile AIBN into the mixed solution to initiate polymerization, and obtaining the in-situ grown MIP containing the template molecular imprinting polymer on CoNiN-nanoarray;
(4) immersing the MIP which is obtained in the step (3) and grows in situ on the CoNiN-nanoarray and contains the molecular imprinting polymer of the template into an eluant, eluting the molecular of the template for 10min at room temperature, and then taking out to obtain the NIP of the molecular imprinting polymer without the template; continuously washing with deionized water for 3 times, and air drying at room temperature to obtain chlordimeform electrochemiluminescence sensor;
the eluent is a mixed solution of formic acid and methanol, wherein the volume ratio of the formic acid to the methanol is 9: 3.
Example 6 preparation of Imidacloprid electrochemiluminescence sensor
(1) Respectively weighing 0.45mmol of template molecules and 5mmol of 2-methacrylic acid MAA in an ampoule bottle, adding 15mL of acetonitrile, and carrying out ultrasonic treatment for 30min until all the template molecules and the 5mmol of 2-methacrylic acid MAA are dissolved;
(2) adding 25mmol of ethylene glycol dimethacrylate EDMA into the solution obtained in the step (1), and carrying out ultrasonic treatment for 30min until the mixture is uniformly mixed to obtain a precursor mixed solution;
(3) clamping the CoNiN-nanoarray prepared in the technical scheme 2 onto a rotary stirrer, inserting the CoNiN-nanoarray into the precursor mixed solution in the step (2), and adding N into the precursor mixed solution2Under the temperature of environment and water bath 40 ℃, rotationally stirring at the speed of 5 r/s, simultaneously dripping 3mL of 1mmol/L luminol solution and 1mmol of azobisisobutyronitrile AIBN into the mixed solution at the speed of 20 drops/s to initiate polymerization, and obtaining the in-situ grown MIP containing the template molecularly imprinted polymer on CoNiN-nanoarray;
(4) immersing the MIP which is obtained in the step (3) and grows in situ on the CoNiN-nanoarray and contains the molecular imprinting polymer of the template into an eluant, eluting the molecular of the template for 20min at room temperature, and then taking out to obtain the NIP of the molecular imprinting polymer without the template; continuously washing with deionized water for 4 times, and air drying at room temperature to obtain chlordimeform electrochemiluminescence sensor;
the eluent is a mixed solution of formic acid and methanol, wherein the volume ratio of the formic acid to the methanol is 9: 5.
Example 7 the electrochemiluminescence sensor for chlordimeform, prepared in examples 1 to 6, is applied to detection of chlordimeform, and includes the following steps:
(1) preparing a standard solution: preparing a group of chlordimeform standard solutions with different concentrations including blank standard samples;
(2) modification of a working electrode: taking the chlordimeform electrochemiluminescence sensor as a working electrode, inserting the chlordimeform electrochemiluminescence sensor into the chlordimeform standard solutions with different concentrations prepared in the step (1), hatching for 10min, taking out, and washing for 3 times by using deionized water;
(3) drawing a working curve: forming a three-electrode system by using a saturated calomel electrode as a reference electrode, a platinum wire electrode as a counter electrode and the modified working electrode in the step (2), and connecting the three-electrode system to electrochemiluminescence detection equipment; 15mL of phosphate buffer PBS followed by 1mL of 2mmol/L hydrogen peroxide (H) was added to the cell2O2) A solution; applying cyclic voltage to the assembled working electrode by using a double-order pulse voltammetry to detect the intensity of an optical signal of electrochemiluminescence; the intensity of the response light signal of the blank standard was recorded asA 0The intensity of the response light signal of standard solutions containing different concentrations of chlordimeform was recordedA iThe difference in response to the decrease in optical signal intensity is ΔA = A 0-A i，ΔAAnd the mass concentration of chlordimeform standard solutionCWith a linear relationship therebetween, plotting ΔA－CA working curve; the concentration of the phosphate buffer solution PBS is 10mmol/L, and the pH value is 7.4; the parameters of the double-order pulse voltammetry during detection are set as follows: the initial potential is 0V, the pulse potential is 0.9V, the pulse time is 0.1s, and the pulse period is 30 s;
(4) detecting the chlordimeform in the sample to be detected: replacing the standard solution of chlordimeform in step (1) with the sample to be detected, detecting according to the method in steps (2) and (3), and detecting according to the difference delta of the decrease of the intensity of the response optical signalAAnd working curve to obtain the content of chlordimeform in the sample to be detectedAmount of the compound (A).
Example 8 the electrochemiluminescence sensor for chlordimeform prepared in examples 1 to 6 was used for the detection of chlordimeform according to the detection procedure of example 7, and the linear range was 4.0 × 10-51000 mmol/L, detection limit is 2.0 nmol/L.
Example 9 detection of Imidacloprid in Water samples
Accurately transferring an environmental water sample, adding a chlordimeform standard solution with a certain mass concentration, taking the water sample without the chlordimeform as a blank, performing a standard addition recovery experiment, detecting by using the chlordimeform electrochemiluminescence sensor prepared in the embodiment 1-6 according to the steps of the embodiment 7, determining the recovery rate of the chlordimeform in the water sample, wherein the detection result is shown in a table 1:
TABLE 1 detection results of chlordimeform in water samples
Figure 701061DEST_PATH_IMAGE002
The detection results in table 1 show that the Relative Standard Deviation (RSD) of the results is less than 3.1%, the average recovery rate is 98.0-101.4%, and the method can be used for detecting the chlordimeform in the water sample, and is high in sensitivity, strong in specificity, and accurate and reliable in result.

Claims (5)

1. The preparation method of the chlordimeform electrochemiluminescence sensor is characterized in that the chlordimeform electrochemiluminescence sensor is obtained by in-situ growth of a template-free molecularly imprinted polymer NIP on a cobalt-nickel bimetallic nitride nanosheet array electrode CoNiN-nanoarray; the template-free molecularly imprinted polymer NIP is a molecularly imprinted polymer without template molecules; the molecularly imprinted polymer without the template molecule is obtained by eluting the template molecule from a MIP containing the template molecularly imprinted polymer; the MIP containing the template molecule engram polymer is the MIP containing the template molecule; the template molecule is chlordimeform; the MIP containing the template molecular engram polymer is directly grown on CoNiN-nanoarray in situ, and the preparation method comprises the following preparation steps:
(1) respectively weighing 0.25-0.45 mmol of template molecules and 3-5 mmol of 2-methacrylic acid MAA in an ampoule bottle, adding 8-15 mL of acetonitrile, and carrying out ultrasonic treatment for 30min until all the template molecules and the 2-methacrylic acid MAA are dissolved;
(2) adding 15-25 mmol of ethylene glycol dimethacrylate EDMA into the solution obtained in the step (1), and carrying out ultrasonic treatment for 30min until the mixture is uniformly mixed to obtain a precursor mixed solution;
(3) clamping CoNiN-nanoarray on a rotary stirrer, and inserting the CoNiN-nanoarray into the precursor mixed solution in the step (2), wherein N is2And (2) rotationally stirring at the speed of 5-200 r/s at the temperature of 20-40 ℃ in an environment and a water bath, simultaneously dropwise adding 1-3 mL of 1mmol/L luminol solution and 1mmol of azobisisobutyronitrile AIBN into the mixed solution at the speed of 1-20 drops/s to initiate polymerization, and obtaining the in-situ grown MIP containing the template molecularly imprinted polymer on the CoNiN-nanoarray.
2. The method for preparing an acetamiprid electrochemiluminescence sensor as claimed in claim 1, wherein the method for preparing CoNiN-nanoarray comprises the following steps:
(1) carrying out ultrasonic cleaning treatment on the disposable throwable electrode by respectively using dilute hydrochloric acid, absolute ethyl alcohol and deionized water so as to remove an oxide layer and surface impurities of the disposable throwable electrode;
(2) weighing 1-3 mmol of Ni (NO)3)2And Co (NO)3)2And 3 to 9mmol of urea CO (NH)2)2Placing the mixture into a 50mL beaker, adding 30mL deionized water, stirring until the mixture is clear, and then transferring the mixture into a 50mL polytetrafluoroethylene reaction kettle;
(3) putting the disposable throwable electrode processed in the step (1) into the solution in the reaction kettle in the step (2), and reacting at the temperature of 100-130 ℃ for 9-12 hours to prepare a precursor electrode of the cobalt-nickel bimetal layered hydroxide nanosheet array;
(4) inserting the cobalt-nickel bimetal layered hydroxide nanosheet array precursor electrode obtained in the step (3) into ammonia water for 5-30 seconds, taking out, heating to 340-400 ℃ in an ammonia environment, keeping for 4-8 hours, continuing to naturally cool to room temperature in the ammonia environment, then inserting the electrode into phosphate buffer solution PBS containing dopamine and ammonium persulfate, reacting for 4-6 hours at the temperature of 20-40 ℃, taking out, and performing immersion washing for 2-4 times by using deionized water to prepare a cobalt-nickel bimetal nitride nanosheet array electrode CoNiN-nanoarray;
the disposable and disposable electrode is selected from one of the following electrodes: foam nickel, foam copper, pure nickel sheets, pure copper sheets, pure cobalt sheets, pure silicon sheets and conductive carbon cloth; said Ni (NO)3)2And Co (NO)3)2In a mixture of nickel and cobalt in a molar ratio of 1: 1;
in phosphate buffer solution PBS containing dopamine and ammonium persulfate: the concentration of dopamine is 2-5 mg/mL, the concentration of ammonium persulfate is 3-8 mg/mL, the concentration of phosphate buffer solution PBS is 0.1mol/L, and the pH value is 7.2-8.5.
3. The method for preparing an acetamiprid electrochemiluminescence sensor as claimed in claim 1, wherein the template-free molecularly imprinted polymer NIP is prepared by the steps of: immersing the obtained MIP which grows in situ on CoNiN-nanoarray and contains the template molecularly imprinted polymer in an eluant, eluting the template molecules for 5-20 min at room temperature, and then taking out to obtain the NIP without the template molecularly imprinted polymer; the eluent is a mixed solution of formic acid and methanol, wherein the volume ratio of the formic acid to the methanol is 9 (1-5).
4. The method of claim 1, wherein the chlordimeform electrochemiluminescence sensor is prepared by the steps of: and (3) washing the obtained template-free molecularly imprinted polymer NIP growing in situ on the CoNiN-nanoarray for 2-4 times by using deionized water, and airing at room temperature to obtain the chlordimeform electrochemiluminescence sensor.
5. The application of the chlordimeform electrochemiluminescence sensor prepared by the preparation method of any one of claims 1 to 4 in the detection of chlordimeform, wherein the detection steps are as follows:
(1) preparing a standard solution: preparing a group of chlordimeform standard solutions with different concentrations including blank standard samples;
(2) modification of a working electrode: taking the chlordimeform electrochemiluminescence sensor as a working electrode, inserting the chlordimeform electrochemiluminescence sensor into the chlordimeform standard solutions with different concentrations prepared in the step (1), hatching for 10min, taking out, and washing for 3 times by using deionized water;
(3) drawing a working curve: forming a three-electrode system by using a saturated calomel electrode as a reference electrode, a platinum wire electrode as a counter electrode and the modified working electrode in the step (2), and connecting the three-electrode system to electrochemiluminescence detection equipment; 15mL of phosphate buffer PBS followed by 1mL of 2mmol/L hydrogen peroxide (H) was added to the cell2O2) A solution; applying cyclic voltage to the assembled working electrode by using a double-order pulse voltammetry to detect the intensity of an optical signal of electrochemiluminescence; the intensity of the response light signal of the blank standard is recorded as A0The intensity of the response light signal of standard solutions containing different concentrations of chlordimeform is recorded as AiThe difference in response to the decrease in the optical signal intensity is Δ a ═ a0-AiThe mass concentration C of the standard chlordimeform solution is linearly related to the mass concentration A of the standard chlordimeform solution, and a working curve of delta A-C is drawn; the concentration of the phosphate buffer solution PBS is 10mmol/L, and the pH value is 7.4; the parameters of the double-order pulse voltammetry during detection are set as follows: the initial potential is 0V, the pulse potential is 0.9V, the pulse time is 0.1s, and the pulse period is 30 s;
(4) detecting the chlordimeform in the sample to be detected: and (3) replacing the standard solution of the chlordimeform in the step (1) with a sample to be detected, detecting according to the methods in the steps (2) and (3), and obtaining the content of the chlordimeform in the sample to be detected according to the difference delta A of the reduction of the intensity of the response optical signal and the working curve.
CN201811306537.5A 2018-11-05 2018-11-05 Preparation method and application of chlordimeform electrochemiluminescence sensor Active CN109307695B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811306537.5A CN109307695B (en) 2018-11-05 2018-11-05 Preparation method and application of chlordimeform electrochemiluminescence sensor

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811306537.5A CN109307695B (en) 2018-11-05 2018-11-05 Preparation method and application of chlordimeform electrochemiluminescence sensor

Publications (2)

Publication Number Publication Date
CN109307695A CN109307695A (en) 2019-02-05
CN109307695B true CN109307695B (en) 2021-02-19

Family

ID=65222961

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811306537.5A Active CN109307695B (en) 2018-11-05 2018-11-05 Preparation method and application of chlordimeform electrochemiluminescence sensor

Country Status (1)

Country Link
CN (1) CN109307695B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113092453A (en) * 2021-04-13 2021-07-09 中国热带农业科学院分析测试中心 Dipterex electrochemiluminescence molecularly imprinted sensor, and preparation method and application thereof
CN114199867B (en) * 2022-02-21 2022-04-19 广东江门中医药职业学院 Method for detecting chlordimeform in aquatic product

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2003279807A1 (en) * 2002-10-03 2004-04-23 The Board Of Trustees Of The University Of Arkansas Nanocrystals in ligand boxes exhibiting enhanced chemical, photochemical, and thermal stability, and methods of making the same
CN1494086B (en) * 2002-10-30 2010-06-16 哈娄利公司 Bimetal oxide-nitride-oxide bit line array addressing, reading, sequencing method and apparatus
CN101644680B (en) * 2009-09-01 2012-03-14 济南大学 Molecular imprinting chemiluminescence sensor for detecting trace amount pesticide residue and application thereof
CN104833767B (en) * 2015-06-02 2015-12-09 青岛大学 A kind of GR/WS 2-AuNPs-WS 2the preparation method of complex molecule trace sensor and application thereof

Also Published As

Publication number Publication date
CN109307695A (en) 2019-02-05

Similar Documents

Publication Publication Date Title
CN109342516B (en) Preparation method and application of sulfonamide molecule electrochemical sensor
CN109254049B (en) Preparation method and application of ampicillin sensor
CN109254052B (en) Preparation method and application of electrochemical luminescence sensor for organophosphorus pesticide
CN109307696B (en) Preparation method and application of molecular imprinting sensing electrode for detecting organochlorine pesticide
CN109781815B (en) Preparation method of olaquindox molecularly imprinted membrane electrochemical sensor
CN109307695B (en) Preparation method and application of chlordimeform electrochemiluminescence sensor
CN109254053B (en) Preparation method and application of environmental estrogen electrochemical analysis sensor
CN105738452B (en) Method and device for detecting ammonia nitrogen by using all-solid-state ammonia nitrogen sensor
CN109254056B (en) Preparation method and application of tetracyclic antibiotic electrochemiluminescence sensor
CN109254059B (en) Preparation method and application of tetracyclic antibiotic molecularly imprinted electrochemical sensor
CN109254048B (en) Preparation method and application of nitrofuran antibiotic sensor based on cobalt-nickel oxide
CN109254062B (en) Preparation method and application of macrolide antibiotic molecularly imprinted electrochemical sensor
CN109254046B (en) Nitrofuran antibiotic sensor and preparation method thereof
CN109254058B (en) Preparation method and application of organophosphorus pesticide sensor based on nickel nitride array
CN109307698B (en) Preparation method and application of iron-cobalt nitride sensing electrode for detecting organochlorine pesticide
CN109254060B (en) Clenbuterol electrochemical sensing electrode and preparation method thereof
CN109254054B (en) Preparation method and application of chlordimeform sensor based on cobalt-based nitride nano array
CN109254044B (en) Preparation method and application of macrolide antibiotic sensor based on FeN
CN109254050B (en) Clenbuterol electrochemiluminescence sensor and preparation method thereof
CN109254055B (en) Preparation method and application of ampicillin electrochemiluminescence sensor
CN109254057B (en) Preparation method and application of pyrethroid insecticide electrochemical sensing electrode
CN109254061B (en) Preparation method and application of sulfonamide molecule electrochemiluminescence sensor
CN109307697B (en) Preparation method and application of electrochemiluminescence sensing electrode for detecting praziquantel
CN109254045B (en) Cobalt-based nitride sensor for detecting praziquantel and preparation method thereof
CN109254051B (en) Preparation method and application of environmental estrogen electrochemiluminescence sensor

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