CN112098484A - Sensor for detecting acetamiprid based on electrochemical luminescence method, preparation method and application - Google Patents
Sensor for detecting acetamiprid based on electrochemical luminescence method, preparation method and application Download PDFInfo
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Abstract
The invention provides a method for detecting acetamiprid, and particularly belongs to the field of electrochemical luminescence detection. The operation flow comprises the following steps: (1) MoS2QDs-PATP @ PTCA and NH2-preparation of a composite of UiO-66; (2) preparing an electrochemiluminescence sensor; (3) the acetamiprid was detected by electrochemical luminescence. In which NH is used2‑UiO‑66‑pDNA/apt/MoS2The 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 10‑7mol/L～1.0×10‑18mol/L, minimum detection limit of 6.4X 10‑19mol/L. The method for detecting the acetamiprid has the advantages of low cost, high sensitivity, strong specificity and simple operation.
Description
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)2QDs-PATP), then MoS2QDs-PATP @ PTCA as a donor in energy resonance transfer, NH2-UiO-66 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 NH2-UiO-66-pDNA/apt/MoS2QDs-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 detect acetamipridThe shortcomings of the prior art provide a method for detecting by an electrochemical luminescence sensor. The invention is based on MoS2QDs-PATP @ PTCA and NH2The resonance energy transfer mechanism existing between-UiO-66 and the inhibition effect of acetamiprid on the mechanism thereof, as NH2-UiO-66-pDNA/apt/MoS2QDs-PATP @ PTCA/GCE is used as a working electrode, and an electrochemical luminescence analysis method for quantitatively detecting acetamiprid in an actual water sample is constructed. Due to MoS2Electrochemiluminescence emission spectra of QDs-PATP @ PTCA (Donor) and NH2The 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 has the advantages of high sensitivity, strong specificity, wide linear range, simple instrument and the like of electrochemical luminescence analysis, and has important practical significance for detecting the acetamiprid in the water sample.
The scheme adopted by the invention is to mix NH2-UiO-66-pDNA/apt/MoS2The 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)MoS2preparation of QDs-PATP @ PTCA composite:
mixing Na2MoO4·2H2O 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 added2MoO4·2H2The 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 MoS2QDs solutions. Dissolving 4-aminothiophenol (PATP) in ethanol solution, and injecting into MoS2Stirring in QDs solution for a period of time in the dark (4-aminothiophenol and Na)2MoO4·2H2The mass ratio of O is 1: 2). Washing with ethanol, centrifuging, separating, andthe MoS finally obtained is2QDs-PATP are 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 above2Stirring, centrifuging, washing and drying the QDs-PATP solution to obtain light red powder MoS2QDs-PATP@PTCA。
MoS2The mass ratio of QDs-PATP to PTCA is 1: 1-3: 1; preferably, the method comprises the following steps: adding MoS2The 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)NH2Preparation of UiO-66-pDNA:
a certain amount of ZrCl is added4And terephthalic acid were dissolved in N, N-Dimethylformamide (DMF), acetic acid was added after stirring uniformly, and then the solution 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 added2-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 NH2Oscillating 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 NH2-UiO-66-pDNA, and finally stored at 4 ℃ until use.
(3) Modified electrode NH2-UiO-66-pDNA/apt/MoS2Preparation 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 microsyringe2Dropping DMF solution of QDs-PATP @ PTCA on the surface of a clean glassy carbon electrode, and drying at room temperature to obtain MoS2The electrode is modified with QDs-PATP @ PTCA/GCE, followed by the aptamer (the aptamer is modified with a carboxyl group at the 5-terminus. the aptamer is orderedIn Biotechnology engineering (Shanghai) Inc., and the DNA sequence is: 5 '-COOH TGT AAT TTG TCT GCA GCG GTT CTT GAT CGC TGA CAC CAT ATT ATG AAG A-3'), NH2Dropwise addition of Tris-HCl solution of-UiO-66-pDNA to MoS2Surface of QDs-PATP @ PTCA/GCE to obtain NH2-UiO-66-pDNA/apt/MoS2QDs-PATP @ PTCA/GCE. Finally, NH is added2-UiO-66-pDNA/apt/MoS2And placing the QDs-PATP @ PTCA/GCE modified electrode in a refrigerator at 4 ℃ for 6h to obtain the ECL sensor.
MoS2QDs-PATP @ PTCA solution, aptamer solution, NH2The volume ratio of the-UiO-66 solution is: 1:1 to 2. Preferably, the method comprises the following steps: MoS2The dripping amount of QDs-PATP @ PTCA is 2.0 mu L, and the concentration is 1.0 mg/mL; NH (NH)2The 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 MoS2QDs, while PATP acts to modify MoS through ligand exchange2QDs, 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)2S2O8) Preparation of Phosphate (PB) buffer solution:
0.05mol/L K was prepared from a 0.1mol/L PB buffer solution at pH7.52S2O8PB 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 × 10-6Obtaining a series of acetamiprid standard solutions with different concentrations by mol/L solution, wherein the concentration range is 1.0 multiplied by 10-7mol/L～1.0×10-18mol/L。
(6) Drawing of standard curve
Modifying the electrode NH2-UiO-66-pDNA/apt/MoS2QDs-PATP @ PTCA/GCE is used as a working electrode, a platinum electrode is used as an auxiliary electrode, Ag/AgCl is used as a reference electrode to form a three-electrode system, and the three-electrode system is arranged in the system containing one electrodeSoaking the acetamiprid solution with different concentrations for 60min, performing cyclic voltammetry scanning on the solution with a photomultiplier tube high voltage of 800V and a scanning 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 an acetamiprid concentration logarithmic value 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: MoS2QDs-PATP greatly improves the light intensity of PTCA; NH (NH)2Loading 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 easy to prepare. And the invention firstly proposes the MoS2QDs by exchange with PATP ligands give aminated MoS2QDs makes the quantum dot surface possess a large amount of amino to realize being connected with the adapter, and then better has built the bridge between donor and the acceptor, makes the detection range of sensor wider relatively, and 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), MoS2QDs-PATP(B)、MoS2QDs-PATP @ PTCA (C) and NH2Transmission electron micrograph of UiO-66 (D).
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
The invention is described in more detail below with reference to the following examples:
example (b):
(1)MoS2preparation of QDs-PATP @ PTCA composite:
0.25g of Na2MoO4·2H2O 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 solution and injected into 10mL of fluorescent molybdenum disulfide quantum dots (MoS)2QDs) solution, stirred under dark conditions for 6 h. Washing with ethanol, centrifuging, separating, and collecting the final MoS2QDs-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 added2Stirring for 6h in QDs-PATP solution, centrifuging, washing, and drying to obtain light red powder MoS2QDs-PATP@PTCA。
(2)NH2Preparation of UiO-66-pDNA:
0.1142g of ZrCl4(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 added2the-UiO-66 product was dried at 60 ℃.
100 μ LpDNA (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 (pH7.5) with 1mg of NH2Subjecting 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 NH2-UiO-66-pDNA, and finally stored at 4 ℃ until use.
(3) Modified electrode NH2-UiO-66-pDNA/apt/MoS2Preparation 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 microsyringe2Dropping DMF solution of QDs-PATP @ PTCA on the surface of a clean glassy carbon electrode, and drying at room temperature to obtain MoS2A QDs-PATP @ PTCA/GCE modified electrode; next, 2.0. mu.L of 2.0. mu. mol/L apt (the aptamer, which is ordered from Biotechnology (Shanghai) Co., Ltd., and has a carboxyl group modified at the 5-terminus, and a DNA sequence of 5 '-COOH TGT AAT TTG TCT GCA GCG GTT CTT GAT CGC TGA CAC CAT ATT ATG AAG A-3') was added dropwise to MoS2The surface of QDs-PATP @ PTCA/GCE is obtained to obtain apt/MoS2QDs-PATP @ PTCA/GCE; then 2.0. mu.L of 2.0mg/mL NH2(iii) dropwise addition of Tris-HCl solution of-UiO-66-pDNA to apt/MoS2QDs-PATP @ PTCA/GCE to obtain NH2-UiO-66-pDNA/apt/MoS2QDs-PATP @ PTCA/GCE modified electrode. Finally, NH is added2-UiO-66-pDNA/apt/MoS2And 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 NH2-UiO-66-pDNA/apt/MoS2QDs-PATP @ PTCA/GCE is used as a working electrode, a platinum electrode is used as an auxiliary electrode, Ag/AgCl is used as a reference electrode to form a three-electrode system, the three-electrode system is placed in the standard solution containing a series of acetamiprid with different concentrations to be soaked for 60min, and K with the concentration of 0.05mol/L is used2S2O8The luminescence intensity was measured using 0.1mol/L PB buffer solution (pH7.5) as a blank solution. The three-electrode system was placed at a range of acetamiprid concentrations(1.0×10-7mol/L、1.0×10-8mol/L、1.0×10-9mol/L、1.0×10-10mol/L、1.0×10-11mol/L、1.0×10-12mol/L、1.0×10-13mol/L、1.0×10-14mol/L、1.0×10-15、1.0×10-16mol/L、1.0×10- 17mol/L and 1.0X 10-18mol/L) contains 0.05mol/L of K2S2O8In 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:
△IECL19293.07+1046.65Log C (mol/L), correlation coefficient (R)2) Is 0.9991. The detection range of the linear regression equation is 1.0 multiplied by 10-7～1.0×10-18mol/L, minimum detection limit of 6.4X 10-19mol/L。
(3) Detection of samples
Taking a certain amount of treated wastewater (the treated wastewater contains K)+、Na+、Mg2+、Li+、Ca2+Plasma and acetamiprid) was added to a solution containing 0.05mol/L of K2S2O8The 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 MoS2The 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 using a microsyringe2Dropping DMF solution of QDs-PATP @ PTCA material on the surface of a clean glassy carbon electrode, and drying at room temperature to obtain MoS2The QDs-PATP @ PTCA/GCE modified electrode is used as a sensor.
Comparative example 2:
by NH2-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 microsyringe2dripping-UiO-66 on the surface of a clean glassy carbon electrode, and drying at room temperature to obtain NH2-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, so that it was not possible to selectively bind specifically the target molecule acetamiprid, and it was difficult to cause resonance energy transfer, so MoS alone was used2QDs-PATP @ PTCA or NH2the-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 NH2-UiO-66-pDNA/apt/MoS2QDs @ PTCA/GCE as the working electrode.
Comparative example 3 No modification of 4-aminothiophenol (PATP) and acetamiprid detection were difficult because MoS was not modified for 4-aminothiophenol (PATP)2The 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 of acetamiprid in water samples
NH as shown in Table 12-UiO-66-pDNA/apt/MoS2QDs-PATP @ PTCA as working electrode, parallel detecting sample for 3 times, relative standard deviation less than 5%, addingThe standard recovery rate ranges from 98% to 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 (9)
1. A sensor for detecting acetamiprid based on an electrochemical luminescence method is characterized in that: the sensor is NH2-UiO-66-pDNA/apt/MoS2QDs-PATP @ PTCA/GCE 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.
2. The method for preparing the sensor for detecting acetamiprid based on the electrochemiluminescence method according to claim 1, wherein the preparation steps comprise:
(1)MoS2preparing a QDs-PATP @ PTCA composite material;
(2)NH2-preparation of UiO-66-pDNA;
(3)NH2-UiO-66-pDNA/apt/MoS2preparation of QDs-PATP @ PTCA/GCE sensor:
MoS transfer with microsyringe2Dropping DMF solution of QDs-PATP @ PTCA on the surface of a clean glassy carbon electrode, and drying at room temperature to obtain MoS2QDs-PATP @ PTCA/GCE modified electrode, then apt, NH2Dropwise addition of Tris-HCl solution of-UiO-66-pDNA to MoS2Surface of QDs-PATP @ PTCA/GCE to obtain NH2-UiO-66-pDNA/apt/MoS2QDs-PATP @ PTCA/GCE; finally, NH is added2-UiO-66-pDNA/apt/MoS2And placing the QDs-PATP @ PTCA/GCE modified electrode in a low-temperature environment to obtain the ECL sensor.
3. The method for detecting acetamiprid based on electrochemiluminescence according to claim 2Characterized in that the MoS2The preparation method of the QDs-PATP @ PTCA composite material comprises the following steps:
mixing Na2MoO4·2H2Dissolving 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 MoS2Solutions of QDs; dissolving 4-aminothiophenol (PATP) in ethanol solution, and injecting into MoS2Stirring in QDs solution in dark for a certain time, washing with ethanol, centrifuging, separating, and collecting the final MoS2QDs-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 prepared PTCA into MoS2Stirring, centrifuging, washing and drying the QDs-PATP solution to obtain light red powder MoS2QDs-PATP@PTCA。
4. The method for preparing the sensor for detecting acetamiprid based on the electrochemiluminescence method as claimed in claim 2, wherein NH is2-UiO-66-pDNA was prepared as follows:
adding Tris-HCl solution of pDNA into solution containing NH2Centrifuging 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 NH2-UiO-66-pDNA。
5. 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'.
6. The method for detecting acetamiprid based on electrochemiluminescence method according to claim 3The preparation method is characterized by comprising the following steps: MoS2The mass ratio of QDs-PATP to PTCA is 1: 1-3: 1.
7. The sensor for detecting acetamiprid by the electrochemiluminescence method of any one of claims 1 to 5, wherein the detection step is as follows:
(1) containing potassium persulfate (K)2S2O8) Preparing a Phosphate (PB) buffer solution 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 × 10-6Preparing 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 10-7mol/L～1.0×10-18mol/L；
(3) Drawing of standard curve
Modifying the electrode NH2-UiO-66-pDNA/apt/MoS2QDs-PATP @ PTCA/GCE is used as a working electrode, a platinum electrode is used as an auxiliary electrode, Ag/AgCl is used as a reference electrode to form a three-electrode system, the three-electrode system is placed in the standard solution containing a series of acetamiprid with different concentrations for soaking for a certain time, and K is contained2S2O8The PBS is used 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).
8. The electrochemiluminescence method for detecting acetamiprid according to claim 7, wherein: the PB buffer solution contains 0.05mol/LK2S2O8Of PB buffer solutionThe pH value is 7.5, and the concentration is 0.1 mol/L;
modified electrode NH2-UiO-66-pDNA/apt/MoS2The soaking time of QDs-PATP @ PTCA/GCE in acetamiprid standard solutions with different concentrations is 60 min.
9. The electrochemiluminescence method for detecting acetamiprid according to claim 7, wherein: the lowest detection limit is 6.4 multiplied by 10-19mol/L。
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