CN112098484B - Sensor for detecting acetamiprid based on electrochemical luminescence method, and preparation method and application thereof - Google Patents

Sensor for detecting acetamiprid based on electrochemical luminescence method, and preparation method and application thereof Download PDF

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CN112098484B
CN112098484B CN202010952583.3A CN202010952583A CN112098484B CN 112098484 B CN112098484 B CN 112098484B CN 202010952583 A CN202010952583 A CN 202010952583A CN 112098484 B CN112098484 B CN 112098484B
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acetamiprid
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CN112098484A (en
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陈智栋
李静娴
单学凌
蒋鼎
王文昌
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Changzhou University
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    • 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
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    • G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
    • 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
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    • 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
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    • G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage

Abstract

The invention provides a detection pyridineA method for preparing acetamiprid, which belongs to the field of electrochemical luminescence detection. The operation flow comprises the following steps: (1) MoS 2 QDs-PATP @ PTCA and NH 2 -UiO-66 composite preparation; (2) preparing an electrochemiluminescence sensor; (3) the acetamiprid is detected by an electrochemical luminescence method. In which NH is used 2 ‑UiO‑66‑pDNA/apt/MoS 2 The glass carbon electrode modified by QDs-PATP @ PTCA/GCE is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, and a platinum electrode is used as an auxiliary electrode to form a traditional three-electrode system. The detection range of the method is 1.0 multiplied by 10 ‑7 mol/L～1.0×10 ‑18 mol/L, minimum detection limit of 6.4X 10 ‑19 mol/L. The method for detecting the acetamiprid has the advantages of low cost, high sensitivity, strong specificity and simple operation.

Description

Sensor for detecting acetamiprid based on electrochemical luminescence method, preparation method and application
Technical Field
The invention relates to an electrochemiluminescence method for detecting acetamiprid, in particular to a method for fixing molybdenum sulfide quantum dots (MoS) on perylene tetracarboxylic acid (PTCA) 2 QDs-PATP), then MoS 2 QDs-PATP @ PTCA as a donor in energy resonance transfer, NH 2 -UiO-66 acts as a receptor in energy resonance transfer. Connecting donor and acceptor through two DNA chains (apt, pDNA), modifying on Glassy Carbon Electrode (GCE), using aptamer (apt) with specific recognition function as recognition element, then using NH 2 -UiO-66-pDNA/apt/MoS 2 QDs-PATP @ PTCA/GCE is a working electrode, and the electrochemical luminescence analysis method is used for quantitatively detecting acetamiprid in water.
Background
Acetamiprid is a novel nicotine pesticide, is widely used for pest control of agricultural products, has potential toxicity to nervous systems and reproductive systems of animals, and can affect the development of human neurons and threaten human health after long-term consumption of fruits and vegetables with residual acetamiprid. Therefore, the method has important significance in measuring the residual quantity of the acetamiprid in the vegetables.
At present, the main methods for detecting acetamiprid comprise high performance liquid chromatography, ultra high performance liquid chromatography-tandem mass spectrometry, DNA molecular probes, solid phase extraction-HPLC, electrocoagulation, gas chromatography and the like. However, these methods are complicated, time-consuming, costly and also have low sensitivity. Therefore, there is a need to establish a simple, fast and accurate method for detecting acetamiprid. Electrochemiluminescence (ECL) is an electrochemical analysis method, and has the advantages of high sensitivity, low background, easy control, short detection time and the like. It has both the advantages of electrochemical and chemiluminescence methods. The electrochemiluminescence does not need to introduce an external light source, and compared with a photoluminescence method, the electrochemiluminescence method can effectively avoid the interference of a background light source and improve the signal to noise ratio so as to improve the detection sensitivity. Resonance energy transfer is an emerging method of molecular spectroscopic analysis, specifically the transfer of electron excitation energy between appropriate pairs of energy donors and energy acceptors. The electrochemiluminescence-resonance energy transfer (ECL-RET) combines the advantages of the electrochemiluminescence and the resonance energy transfer (ECL-RET), and is a new field with development potential. The biosensor does not need an excitation light source, has low background noise, avoids the influence of scattered light, and is widely applied to the construction of biosensors.
Disclosure of Invention
The invention aims to provide a method for detecting an electrochemiluminescence sensor, aiming at the defects of the acetamiprid detection prior art. The invention is based on MoS 2 QDs-PATP @ PTCA and NH 2 The resonance energy transfer mechanism existing between-UiO-66 and the inhibition effect of acetamiprid on the mechanism thereof, as NH 2 -UiO-66-pDNA/apt/MoS 2 QDs-PATP @ PTCA/GCE are used as working electrodes, and an electrochemical luminescence analysis method for quantitatively detecting acetamiprid in an actual water sample is constructed. Due to MoS 2 Electrochemiluminescence emission spectra of QDs-PATP @ PTCA (Donor) and NH 2 The ultraviolet visible absorption spectrum of the-UiO-66 (receptor) has a larger overlapping area, so a resonance energy transfer mechanism exists between the ultraviolet visible absorption spectrum and the visible absorption spectrum, the fluorescence of the modified electrode is enhanced based on the inhibition effect of the acetamiprid on the mechanism, and the increased light intensity has a linear relation with the concentration of the acetamiprid. The invention not only has the advantages of high sensitivity, strong specificity, wide linear range, simple instrument and the like of electrochemical luminescence analysis, but also has important significance for detecting acetamiprid in water sampleThe practical significance of.
The scheme adopted by the invention is to mix NH 2 -UiO-66-pDNA/apt/MoS 2 The detection method comprises the following steps of forming a three-electrode system for detection by taking a QDs-PATP @ PTCA/GCE modified electrode as a working electrode, a platinum electrode as an auxiliary electrode and Ag/AgCl as a reference electrode, wherein the three-electrode system comprises the following specific steps:
(1)MoS 2 preparation of QDs-PATP @ PTCA composite:
mixing Na 2 MoO 4 ·2H 2 O was dissolved in a quantity of deionized water and adjusted to pH 6.5 with HCl. After sonication, cysteine and a certain amount of deionized water (Na) were added 2 MoO 4 ·2H 2 The mass ratio of O to cysteine was 1: 2). Transferring the mixture into a polytetrafluoroethylene autoclave, reacting for 36h at 200 ℃, naturally cooling to room temperature, centrifuging, taking supernatant, and storing at 4 ℃ to obtain MoS 2 QDs solutions. Dissolving 4-aminothiophenol (PATP) in ethanol solution, and injecting into MoS 2 Stirring in QDs solution for a period of time in the dark (4-aminothiophenol and Na) 2 MoO 4 ·2H 2 The mass ratio of O is 1: 2). Washing with ethanol, centrifuging, separating, and collecting the final MoS 2 QDs-PATP dispersed in ethanol.
Dissolving perylene tetracarboxylic dianhydride (PTCDA) in NaOH, stirring to obtain a yellow-green solution, then dripping HCl until complete precipitation, centrifuging, washing with deionized water for three times, and drying to obtain dark red powder, namely PTCA.
Adding MoS into PTCA prepared above 2 Stirring, centrifuging, washing and drying the QDs-PATP solution to obtain light red powder MoS 2 QDs-PATP@PTCA。
MoS 2 The mass ratio of QDs-PATP to PTCA is 1: 1-3: 1; preferably, the method comprises the following steps: adding MoS 2 The volume of the QDs-PATP solution was 15.0mL, the concentration was 1mg/mL, and the amount of PTCA added was 5.0 mg.
(2)NH 2 Preparation of UiO-66-pDNA:
a certain amount of ZrCl is added 4 Dissolving terephthalic acid in N, N-Dimethylformamide (DMF), stirring, adding acetic acid, and dissolvingThe liquid was transferred to a Teflon lined stainless steel autoclave. The autoclave was sealed and heated in an oven at 120 ℃ for 24h under autogenous pressure. After natural cooling, the resulting material was centrifuged and washed with anhydrous ethanol for four times to purify, and then NH was added 2 -UiO-66 product was dried.
pDNA (DNA sequence: 5 '-COOH GCG ATC AAG AAC CGC TGC AGA CAA ATT ACA-3') in Tris-HCl was added to a solution containing NH 2 Oscillating in a centrifugal tube of-UiO-66, centrifuging, dissolving the precipitate in Tris-HCl (pH7.5), performing ultrasonic treatment on the obtained colloidal solution, and oscillating at room temperature to obtain NH 2 -UiO-66-pDNA, and finally stored at 4 ℃ until use.
(3) Modified electrode NH 2 -UiO-66-pDNA/apt/MoS 2 Preparation of QDs-PATP @ PTCA/GCE:
polishing glassy carbon electrode, sequentially performing ultrasonic treatment with nitric acid, anhydrous ethanol and deionized water, naturally drying, and transferring MoS with microsyringe 2 Dropping the DMF solution of QDs-PATP @ PTCA on the surface of a clean glassy carbon electrode, and drying at room temperature to obtain MoS 2 QDs-PATP @ PTCA/GCE modified electrode, followed by aptamer (aptamer modified with carboxyl group at 5-terminal. the aptamer was ordered from Biotechnology engineering (Shanghai) Co., Ltd., and has DNA sequence of 5 '-COOH TGT AAT TTG TCT GCA GCG GTT CTT GAT CGC TGA CAC CAT ATT ATG AAG A-3'), NH 2 Dropwise addition of Tris-HCl solution of-UiO-66-pDNA to MoS 2 Surface of QDs-PATP @ PTCA/GCE to obtain NH 2 -UiO-66-pDNA/apt/MoS 2 QDs-PATP @ PTCA/GCE. Finally, NH is added 2 -UiO-66-pDNA/apt/MoS 2 And placing the QDs-PATP @ PTCA/GCE modified electrode in a refrigerator at 4 ℃ for 6h to obtain the ECL sensor.
MoS 2 QDs-PATP @ PTCA solution, aptamer solution, NH 2 -volume ratio of the UiO-66 solution: 1:1 to 2. Preferably, the method comprises the following steps: MoS 2 The dripping amount of QDs-PATP @ PTCA is 2.0 mu L, and the concentration is 1.0 mg/mL; NH (NH) 2 The amount of dripping of the-UiO-66 was 2.0. mu.L, and the concentration was 2.0 mg/mL. The aptamer was dispensed in an amount of 2.0. mu.L at a concentration of 2.0. mu. mol/L.
The role of PTCA is to better immobilize MoS 2 QDs, and PATP actionsIs the modification of MoS by ligand exchange 2 QDs, which have a large number of amino groups on their surface, not only increase the light intensity of PTCA, but also allow the connection of MoS2QDs with more aptamers through amide bonds.
(4) Containing potassium persulfate (K) 2 S 2 O 8 ) Preparation of Phosphate (PB) buffer solution:
0.05mol/L K was prepared from a 0.1mol/L PB buffer solution at pH7.5 2 S 2 O 8 PB buffer solution of (1).
(5) Preparation of acetamiprid standard solutions with different concentrations
Accurately weighing a certain amount of acetamiprid, and preparing with deionized water to obtain a solution of 1.0 × 10 -6 Obtaining a series of acetamiprid standard solutions with different concentrations by mol/L solution, wherein the concentration range is 1.0 multiplied by 10 -7 mol/L～1.0×10 -18 mol/L。
(6) Drawing of standard curve
Modifying the electrode NH 2 -UiO-66-pDNA/apt/MoS 2 The method comprises the following steps of taking QDs-PATP @ PTCA/GCE as a working electrode, a platinum electrode as an auxiliary electrode and Ag/AgCl as a reference electrode to form a three-electrode system, placing the three-electrode system in a solution containing acetamiprid with a series of different concentrations to be soaked for 60min, carrying out cyclic voltammetry scanning on the solution at a photomultiplier high voltage of 800V and a sweeping speed of 0.1V/s within an electrochemical window range of-1.6-0V, recording a potential-luminous intensity curve (E-ECL), and establishing a linear relation between a luminous intensity difference value before and after the acetamiprid is added and a logarithmic value of the acetamiprid concentration to obtain a corresponding linear regression equation;
(6) sample detection
And (3) pre-treating the actual sample, testing according to the electrochemical luminescence test conditions same as those in the step (5), recording the luminescence intensity, and calculating the concentration of the acetamiprid in the sample to be tested by using the linear regression equation corresponding to the standard curve obtained in the step (5) to obtain the luminescence intensity.
Compared with the common electrochemical luminescence sensor, the electrochemical luminescence sensor for detecting the acetamiprid and the preparation method thereof have the following three remarkable advantages: MoS 2 Greatly improved QDs-PATPThe light intensity of PTCA is shown; NH (NH) 2 Loading the probe DNA with UiO-66, so that the signal of the sensor changes significantly; the acetamiprid is sensitively detected by utilizing the inhibition effect of the acetamiprid on a resonance energy transfer system.
The material provided by the invention is environment-friendly and is easy to prepare. And the invention firstly proposes the MoS 2 QDs are exchanged with PATP ligands to yield aminated MoS 2 QDs, make the quantum dot surface possess a large amount of amino to realize being connected with the adapter, and then better has set up the bridge between donor and the acceptor, make the detection range of sensor wider relatively, the detection limit is lower, and sensitivity is higher.
Drawings
FIG. 1 is a schematic flow chart of the preparation of the sensor and the detection of acetamiprid in the invention.
FIG. 2 is a standard curve of the difference of luminescence intensity before and after adding acetamiprid and the logarithm of the acetamiprid concentration.
FIG. 3 is PTCA (A), MoS 2 QDs-PATP(B)、MoS 2 QDs-PATP @ PTCA (C) and NH 2 Transmission electron micrograph of UiO-66 (D).
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The invention is described in further detail below with reference to examples:
example (b):
(1)MoS 2 preparation of QDs-PATP @ PTCA composite:
0.25g of Na 2 MoO 4 ·2H 2 O was dissolved in 20mL of water and adjusted to pH 6.5 with 0.1M HCl. After 10min of sonication, 0.5g cysteine and 40mL deionized water were added. Transferring the mixture into a 100mL polytetrafluoroethylene autoclave, reacting at 200 ℃ for 36h, naturally cooling to room temperature, centrifuging at 10000rpm for 20min, and taking and storing supernatant at 4 ℃. 125mg of 4-aminothiophenol (PATP) was dissolved in 10mL of ethanol and injected into 10mL of fluorescent molybdenum disulfide quantum dots (MoS) 2 QDs) solution, stirred under dark conditions for 6 h. Washing with ethanol, centrifuging, separating, and collecting the final MoS 2 QDs-PATP was dispersed in ethanol (1 mg/mL).
Dissolving 0.1g of perylene tetracarboxylic dianhydride (PTCDA) in 10mL of 0.1M NaOH, stirring for 2h at 80 ℃ to obtain a yellow-green solution, then dripping 1.0M HCl until complete precipitation, centrifuging, washing with deionized water for three times, and drying at 60 ℃ to obtain dark red powder, namely perylene tetracarboxylic dianhydride (PTCA).
5mg of PTCA prepared above was taken and 15mL of MoS was added 2 Stirring for 6h in QDs-PATP solution, centrifuging, washing, and drying to obtain light red powder MoS 2 QDs-PATP@PTCA。
(2)NH 2 Preparation of UiO-66-pDNA:
0.1142g of ZrCl 4 (0.2mmol) and 0.0888g of terephthalic acid (0.2mmol) were dissolved in 50mL of N, N-Dimethylformamide (DMF), and after stirring to homogeneity, 8.82mL of acetic acid was added, and the solution was transferred to a 100mL Teflon lined stainless steel autoclave. The autoclave was sealed and heated in an oven at 120 ℃ for 24h under autogenous pressure. After natural cooling, the resulting material was centrifuged and washed with anhydrous ethanol for four times to purify, and then NH was added 2 The product-UiO-66 was dried at 60 ℃.
100 μ L pDNA (pDNA ordered from Biotechnology engineering, Shanghai, Ltd.) and having a DNA sequence of 5 '-COOH GCG ATC AAG AAC CGC TGC AGA CAA ATT ACA-3') in Tris-HCl solution (pH7.5) was added to a solution containing 1mg NH 2 Subjecting to oscillatory reaction for 16h in a centrifugal tube of-UiO-66, centrifuging at 10000rpm for 10min, dissolving the precipitate in 100 μ L Tris-HCl (pH7.5), subjecting the obtained colloidal solution to ultrasonic treatment for 10min, and shaking at room temperature for 1h to obtain NH 2 -UiO-66-pDNA, and finally stored at 4 ℃ until use.
(3) Modified electrode NH 2 -UiO-66-pDNA/apt/MoS 2 Preparation of QDs-PATP @ PTCA/GCE:
polishing glassy carbon electrode, sequentially performing ultrasonic treatment with nitric acid, anhydrous ethanol and deionized water, naturally drying, transferring 2.0 μ L of 1.0mg/mL MoS with microsyringe 2 Dropping the DMF solution of QDs-PATP @ PTCA on the surface of a clean glassy carbon electrode, and drying at room temperature to obtain MoS 2 A QDs-PATP @ PTCA/GCE modified electrode; next, 2.0. mu.L of 2.0. mu. mol/L apt (the aptamer was ordered from Biotechnology (Shanghai) Inc., aptamer)The 5-end is modified with carboxyl, and the DNA sequence is as follows: 5 '-COOH TGT AAT TTG TCT GCA GCG GTT CTT GAT CGC TGA CAC CAT ATT ATG AAG A-3') was added dropwise to MoS 2 The surface of QDs-PATP @ PTCA/GCE is obtained to obtain apt/MoS 2 QDs-PATP @ PTCA/GCE; then 2.0. mu.L of 2.0mg/mL NH 2 (iii) dropwise addition of Tris-HCl solution of-UiO-66-pDNA to apt/MoS 2 QDs-PATP @ PTCA/GCE to obtain NH 2 -UiO-66-pDNA/apt/MoS 2 QDs-PATP @ PTCA/GCE modified electrode. Finally, NH is added 2 -UiO-66-pDNA/apt/MoS 2 And placing the QDs-PATP @ PTCA/GCE modified electrode in a refrigerator at 4 ℃ for 6h to obtain the ECL sensor.
(4) Drawing of standard curve
Modifying the electrode NH 2 -UiO-66-pDNA/apt/MoS 2 Forming a three-electrode system by using QDs-PATP @ PTCA/GCE as a working electrode, a platinum electrode as an auxiliary electrode and Ag/AgCl as a reference electrode, soaking the three-electrode system in the standard solution containing acetamiprid with different concentrations for 60min, and soaking the standard solution containing acetamiprid with the concentration of 0.05mol/L 2 S 2 O 8 The luminescence intensity was measured as a blank solution using 0.1mol/L PB buffer solution (pH 7.5). The three-electrode system was placed in a series of acetamiprid concentrations (1.0X 10) -7 mol/L、1.0×10 -8 mol/L、1.0×10 -9 mol/L、1.0×10 -10 mol/L、1.0×10 -11 mol/L、1.0×10 -12 mol/L、1.0×10 -13 mol/L、1.0×10 -14 mol/L、1.0×10 -15 、1.0×10 -16 mol/L、1.0×10 - 17 mol/L and 1.0X 10 -18 mol/L) contains 0.05mol/L of K 2 S 2 O 8 In the 0.1mol/L PB buffer solution with the pH of 7.5, in the electrochemical window range of-1.6-0V, the photomultiplier tube has the high voltage of 800V, the amplification factor is 2, the sweep rate is 0.1V/s, cyclic voltammetry scanning is carried out, a potential-luminescence intensity curve (E-ECL) is recorded, a linear relation between the luminescence intensity difference before and after the acetamiprid is added and the logarithmic value of the acetamiprid concentration is established, and a corresponding linear regression equation is obtained as follows:
△I ECL 19293.07+1046.65Log C (mol/L), correlation coefficient (R) 2 ) Is 0.9991. The detection range of the linear regression equation is 1.0 × 10 -7 ～1.0×10 -18 mol/L, minimum detection limit of 6.4X 10 -19 mol/L。
(3) Detection of samples
Taking a certain amount of treated wastewater (the treated wastewater contains K) + 、Na + 、Mg 2+ 、Li + 、Ca 2+ Plasma and acetamiprid) was added to a solution containing 0.05mol/L of K 2 S 2 O 8 The pH of the sample solution (2) is 0.1mol/L PB, and the concentration of the acetamiprid in the sample to be detected is calculated according to the linear regression equation corresponding to the step (2) by using the buffer solution for electrochemical luminescence detection, and the results are listed in Table 1.
Comparative example 1:
in MoS 2 The QDs-PATP @ PTCA/GCE modified electrode is used as a sensor.
Polishing the glassy carbon electrode, respectively performing ultrasonic treatment on the polished glassy carbon electrode by using nitric acid, absolute ethyl alcohol and deionized water in sequence, and naturally drying the polished glassy carbon electrode for later use. 2.0. mu.L of 1.0mg/mL MoS was pipetted with a microsyringe 2 Dropping DMF solution of QDs-PATP @ PTCA material on the surface of a clean glassy carbon electrode, and drying at room temperature to obtain MoS 2 The QDs-PATP @ PTCA/GCE modified electrode is used as a sensor.
Comparative example 2:
by NH 2 -UiO-66/GCE modified electrode as sensor
Polishing the glassy carbon electrode, respectively performing ultrasonic treatment on the polished glassy carbon electrode by using nitric acid, absolute ethyl alcohol and deionized water in sequence, and naturally drying the polished glassy carbon electrode for later use. 2.0. mu.L of 2.0mg/mL NH was pipetted using a microsyringe 2 dripping-UiO-66 on the surface of a clean glassy carbon electrode, and drying at room temperature to obtain NH 2 -UiO-66/GCE modified electrode as working electrode for electrochemiluminescence test.
The modified electrodes prepared in comparative examples 1 and 2 were working electrodes, and the detection was performed by the same method as in example 1, but no aptamer was present, and thus it was not possible to bind specifically the target molecule acetamiprid, and it was difficult to cause resonance energy transfer, and MoS alone was used 2 QDs-PATP @ PTCA or NH 2 the-UiO-66 modified glassy carbon electrode cannot detect acetamiprid.
Comparative example 3
Comparative example 3 is different from example 1 in that: wherein 4-aminothiophenol (PATP) is not added to obtain NH 2 -UiO-66-pDNA/apt/MoS 2 QDs @ PTCA/GCE as the working electrode.
Comparative example 3 No modification of 4-aminothiophenol (PATP) and acetamiprid detection were difficult because 4-aminothiophenol (PATP), MoS was not modified 2 The surface of QDs has no amino group, so that the QDs cannot be well connected with a carboxyl aptamer, the connection between a donor and a receptor is further influenced, and when acetamiprid is detected, the acetamiprid cannot pull the aptamer from a sensor, so that resonance energy transfer cannot be inhibited, and the acetamiprid cannot be quantitatively detected.
TABLE 1 determination results of acetamiprid in water samples
Figure BDA0002677517350000081
NH as shown in Table 1 2 -UiO-66-pDNA/apt/MoS 2 The QDs-PATP @ PTCA is used as a working electrode, a sample is parallelly detected for 3 times, the relative standard deviation is less than 5%, and the range of the standard recovery rate is 98-102%. The method is feasible and high in sensitivity when used for detecting the acetamiprid in the wastewater.
The above embodiments are only used for illustrating the present invention, and are not meant to be limiting, and those skilled in the relevant art can make various changes without departing from the scope of the present invention, and therefore all technical solutions formed by equivalent substitutions or equivalent modifications belong to the protection scope of the present invention.

Claims (8)

1. A sensor for detecting acetamiprid based on an electrochemical luminescence method is characterized in that: the sensor is NH 2 -UiO-66-pDNA/apt/MoS 2 QDs-PATP @ PTCA/GCE, which is used as a working electrode for an electrochemiluminescence test, a platinum electrode is used as an auxiliary electrode, Ag/AgCl is used as a reference electrode, and a three-electrode system is formed to detect acetamiprid by an electrochemiluminescence method;
NH 2 -UiO-66-pDNA/apt/MoS 2 MoS in QDs-PATP @ PTCA/GCE sensor 2 The preparation method of the QDs-PATP @ PTCA composite material comprises the following steps:
mixing Na 2 MoO 4 •2H 2 Dissolving O in deionized water, adjusting pH to 6.5 with HCl, performing ultrasonic treatment, adding cysteine and deionized water, transferring the mixture into a high-pressure kettle for reaction, naturally cooling to room temperature, centrifuging, collecting supernatant, and storing at low temperature to obtain MoS 2 Solutions of QDs; dissolving 4-aminothiophenol in ethanol solution, and injecting into MoS 2 Stirring in QDs solution in dark for a certain time, washing with ethanol, centrifuging, separating, and collecting the final MoS 2 QDs-PATP dispersed in ethanol;
dissolving perylene tetracarboxylic dianhydride in NaOH, stirring to obtain a yellow-green solution, then dripping HCl until complete precipitation, centrifuging, washing with deionized water for three times, and drying to obtain dark red powder, namely PTCA;
adding prepared PTCA into MoS 2 Stirring, centrifuging, washing and drying the QDs-PATP solution to obtain light red powder MoS 2 QDs-PATP@PTCA。
2. The method for preparing the sensor for detecting acetamiprid based on the electrochemiluminescence method, according to claim 1, is characterized in that the preparation steps comprise:
（1）MoS 2 preparing a QDs-PATP @ PTCA composite material;
（2）NH 2 -preparation of UiO-66-pDNA;
（3）NH 2 -UiO-66-pDNA/apt/MoS 2 preparation of QDs-PATP @ PTCA/GCE sensor:
MoS transfer with microsyringe 2 Dropping the DMF solution of QDs-PATP @ PTCA on the surface of a clean glassy carbon electrode, and drying at room temperature to obtain MoS 2 QDs-PATP @ PTCA/GCE modified electrode, then apt, NH 2 Dropwise addition of Tris-HCl solution of-UiO-66-pDNA to MoS 2 Surface of QDs-PATP @ PTCA/GCE to obtain NH 2 -UiO-66-pDNA/apt/MoS 2 QDs-PATP @ PTCA/GCE; finally, NH is added 2 -UiO-66-pDNA/apt/MoS 2 QDs-PATP @ PTCA/GCE modified electrodeAnd placing the mixture in a low-temperature environment to obtain the ECL sensor.
3. The method for preparing the sensor for detecting acetamiprid based on the electrochemiluminescence method as claimed in claim 2, wherein NH is 2 -UiO-66-pDNA was prepared as follows:
adding Tris-HCl solution of pDNA into solution containing NH 2 Centrifuging the centrifugal tube of-UiO-66 after oscillation reaction, taking precipitate to dissolve in Tris-HCl, carrying out ultrasonic treatment on the obtained colloidal solution, and oscillating the colloidal solution at room temperature to obtain NH 2 -UiO-66-pDNA。
4. The method for preparing the sensor for detecting acetamiprid based on the electrochemical luminescence method according to claim 2, is characterized in that: the DNA sequence of the apt aptamer is: 5 '-COOH TGT AAT TTG TCT GCA GCG GTT CTT GAT CGC TGA CAC CAT ATT ATG AAG A-3'.
5. The method for preparing the sensor for detecting acetamiprid based on the electrochemical luminescence method according to claim 1, wherein: MoS 2 The mass ratio of QDs-PATP to PTCA is 1: 1-3: 1.
6. Use of a sensor according to claim 1 or a sensor prepared according to any one of claims 2 to 5 for the electrochemiluminescence detection of acetamiprid,
(1) preparing a phosphate buffer solution containing potassium persulfate to be used as a blank solution;
(2) preparing standard solutions containing acetamiprid with different concentrations:
accurately weighing a certain amount of acetamiprid, and preparing with deionized water to obtain a solution of 1.0 × 10 -6 Preparing a series of acetamiprid standard solutions with different concentrations by mol/L solution, wherein the concentration range of the acetamiprid standard solution is 1.0 multiplied by 10 -7 mol/L~1.0×10 -18 mol/L；
(3) Drawing of standard curve
Will modify the electrode NH 2 -UiO-66-pDNA/apt/MoS 2 QDs-PATP @ PTCA/GCE as working electrode, platinum electrodeUsing Ag/AgCl as an auxiliary electrode and a reference electrode to form a three-electrode system, placing the three-electrode system in the standard solution containing acetamiprid with a series of different concentrations, soaking for a certain time, and using the standard solution containing K 2 S 2 O 8 The PBS as a blank solution to detect the luminous intensity; in the electrochemical window range of-1.6-0V, the photomultiplier has a high voltage of 800V, the amplification number is 2, the sweep rate is 0.1V/s, cyclic voltammetry scanning is carried out, a potential-luminescence intensity curve (E-ECL) is recorded, a linear relation between a luminescence intensity difference value before and after the acetamiprid is added and an acetamiprid concentration logarithm value is established, and a corresponding linear regression equation is obtained;
(4) actual sample detection
And (4) carrying out pretreatment and then adjusting the pH value in the actual sample detection, and calculating according to the linear regression equation in the step (3).
7. Use according to claim 6, characterized in that: the phosphate buffer solution contains 0.05mol/LK 2 S 2 O 8 The pH of the PB buffer solution is 7.5, and the concentration of the PB buffer solution is 0.1 mol/L;
modified electrode NH 2 -UiO-66-pDNA/apt/MoS 2 The soaking time of QDs-PATP @ PTCA/GCE in acetamiprid standard solutions with different concentrations is 60 min.
8. Use according to claim 7, characterized in that: the lowest detection limit is 6.4 multiplied by 10 -19 mol/L。
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