CN113960131A - Dual-signal electrochemical aptamer sensor and method for determining acetamiprid - Google Patents

Dual-signal electrochemical aptamer sensor and method for determining acetamiprid Download PDF

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CN113960131A
CN113960131A CN202111209320.4A CN202111209320A CN113960131A CN 113960131 A CN113960131 A CN 113960131A CN 202111209320 A CN202111209320 A CN 202111209320A CN 113960131 A CN113960131 A CN 113960131A
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mof
acetamiprid
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马东晓
颜梅
刘建辉
衣姜乐
夏方诠
田栋
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University of Jinan
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Abstract

The invention relates to the technical field of pesticide residue analysis and determination, in particular to a dual-signal sensor based on a porous Cu-MOF nano material and a method for determining acetamiprid by using the dual-signal sensor, which comprises the steps of preparing the dual-signal sensor, an operation method for determining the acetamiprid by using the sensor and the like; the sensor outputs two electrochemical signals, namely the electrochemical signal of the Cu-MOF and the self-generated current of the DNA, can detect the content of the acetamiprid, and has the advantages of simple and rapid construction process, high accuracy and good sensitivity.

Description

Dual-signal electrochemical aptamer sensor and method for determining acetamiprid
Technical Field
The invention relates to the technical field of pesticide residue analysis and determination, in particular to a dual-signal sensor based on a porous Cu-MOF nano material and a method for determining acetamiprid by using the dual-signal sensor, which comprises the steps of preparing the dual-signal sensor, an operation method for determining the acetamiprid by using the sensor and the like; the sensor outputs two electrochemical signals, namely the electrochemical signal of the Cu-MOF and the self-generated current of the DNA, can detect the content of the acetamiprid, and has the advantages of simple and rapid construction process, high accuracy and good sensitivity.
Background
With the frequent occurrence of pesticide pollution events of agricultural products, the quality safety problem of the agricultural products is paid high attention all over the world, so that the construction of an analysis method for quickly, accurately and highly sensitively detecting pesticide residues is particularly important. Electrochemical sensing is widely applied to various fields due to the advantages of quick response, high sensitivity, simple operation, low preparation cost and the like. In the traditional electrochemical aptamer sensor, an aptamer is used as a target substance capture molecule, and the electrochemical aptamer sensor has the advantages of good sensitivity, good selectivity and the like. It is known that the phosphate of DNA reacts with molybdate to generate phosphomolybdic heteropoly acid which generates an oxidation-reduction peak on the surface of an electrode. The sensor is constructed by utilizing the current signal generated by the DNA itself, and the current signal is used as a signal probe and captures a target object, so that the construction process of the sensor is simplified. However, most electrochemical sensors only contain a single response signal, and due to many factors, including the characteristics of the substrate electrode and the complex detection environment, the reproducibility is not ideal enough, and the single signal sensor has difficulty in meeting the requirements of a biosensor with high accuracy and accurate quantification. Therefore, in order to overcome the above problems, it is necessary to develop a sensor capable of generating a variety of signals, which are mutually verified, effectively avoid false positive or false negative results, and improve the stability and reliability of an electrochemical sensor.
Disclosure of Invention
The invention aims to overcome the defects in pesticide residue sensing analysis and construct a dual-signal electrochemical aptamer sensor which can be used for accurately and sensitively detecting pesticide residue acetamiprid. The invention aims to solve the technical problem that different electrochemical output signals can be generated by using functional materials and DNA chains in the same test, and the electrochemical output signals are verified and supported mutually, so that the acetamiprid detection method is used for detecting acetamiprid and improving the stability and reliability of the sensor.
The technical scheme of the invention is as follows: modifying nanogold by adopting a porous Cu-MOF nano material, loading an acetamiprid aptamer complementary chain, hybridizing cDNA (complementary deoxyribonucleic acid) and an aptamer on the surface of an electrode to form a double-chain structure, and constructing a double-signal electrochemical sensor; the Cu-MOF has large specific surface area and layered pores, can generate current by itself and generates an oxidation-reduction peak at the potential of 0.05V; the phosphate radical of the DNA can react with molybdate radical, and the generated phosphomolybdic heteropoly acid can generate an oxidation reduction peak at 0.23V; when the acetamiprid exists, the aptamer is combined with the acetamiprid, and the DNA double strand unwinds to enable the signal label to fall off; in the same system, signals are generated by Cu-MOF and DNA chains at the same time in an electrochemical mode, and mutual verification is carried out. The specific scheme is as follows:
1. a dual-signal electrochemical aptamer sensor based on a porous Cu-MOF nano material has two current output signals which are mutually verified: the porous Cu-MOF nano material is used for loading complementary strand cDNA of an acetamiprid aptamer and is used for loading and catalytically amplifying signals; the Cu-MOF generates electrochemical signals by itself to realize signal output; the DNA can react with sodium molybdate to generate an electrochemical signal to form double signal output;
2. the Cu-MOF is characterized in that the preparation method is as follows: 0.435 g of Cu (NO)3)2·3H2O, a mixture of 0.62 mL of acetic acid, 0.50 mL of trimethylamine, and 12 mL of ethanol was stirred at room temperature for 1 hour, and then H was added3BTC benzene tricarboxylic acid (0.210 g, 1.0 mmoL) was added to the solution and stirred for 2 hours to form a homogeneous solution; the mixture was transferred to an autoclave and heated at 85 ℃ for 24 hours. Centrifuging to recover solid, and washing with anhydrous ethanol for 3 times; finally, treating the product with ethanol at 65 ℃ for 12 hours, and drying to obtain Cu-MOF;
3. the construction method of the dual-signal electrochemical aptamer sensor comprises the following steps:
(1) remove 20. mu.L of HAuCl4(1% wt) and 2mL of NaBH 2 mM ice4Adding the solution into a Cu-MOF solution, continuously stirring for 1h, centrifuging and washing to obtain Au NPs/Cu-MOF, and dispersing the Au NPs/Cu-MOF into 2mL of absolute ethyl alcohol for storage and later use; the complementary strand (cDNA) of the acetamiprid aptamer strand was taken as a solution (50. mu.L, 10)-7 M) adding the solution into 500 mu L of the prepared Au NPs/Cu-MOF solution for overnight culture to prepare Cu-MOF @ AuNPs/cDNA;
(2) the processed glassy carbon electrode GCE is operated for 120 s under constant potential of-0.1V in 1% chloroauric acid solution to prepare an Au NPs/GCE modified electrode;
(3) 10 mu L of 10 was added dropwise to the modified electrode-7 Incubating an M acetamiprid aptamer Apt at 4 ℃ for 12 h to obtain Apt/Au NPs/GCE, and then sealing a non-specific site with MCH;
(4) dripping 10 mu L of Cu-MOF @ AuNPs/cDNA on the surface of an electrode, incubating for 1h at 37 ℃, and then washing with PBS buffer solution with pH of 7.8 to obtain Cu-MOF @ AuNPs/cDNA/Apt/Au NPs/GCE;
4. the dual-mode aptamer sensor is used for detecting acetamiprid and comprises the following steps:
(1) dripping acetamiprid pesticide with different concentrations on the surface of the constructed sensor, incubating for 1h at 37 ℃, and dripping 5 mu L10 mM Na2MoO4The reaction was carried out for 20 min, washed with PBS buffer at pH 7.8;
(2) taking the aptamer sensor as a working electrode, an Ag/AgCl electrode as a reference electrode and a platinum electrode as an auxiliary electrode; in 0.5M sulfuric acid solution, SWV scanning is carried out in a potential interval of-0.3-0.5V, and oxidation peak potential and current intensity are recorded.
The invention has the beneficial effects that:
1. the invention utilizes the characteristic of DNA self-generating current, not only serves as a target object capturing molecule, but also serves as a signal probe, simplifies the construction process of the sensor, has simple and convenient operation and saves time;
2. the Cu-MOF synthesized by the method has a high specific surface area and a controllable pore structure, so that active sites are increased, the adsorption capacity is improved, and the detection performance of a sensor is improved;
3. the double-signal action mechanism, mutual verification and mutual support between different signals, effectively avoids interference of other factors and improves the detection accuracy;
4. the sensor has high sensitivity and good accuracy, and can realize the rapid and efficient detection of the pesticide residue acetamiprid.
Description of the drawings:
FIG. 1 shows a SWV plot of acetamiprid at various concentrations
Wherein, 1 to 10-8, 2--10-9, 3--10-10, 4--10-11,5--10-12,6--10-13,7--10-14,8--0 M;
FIG. 2 shows the corresponding linear curves for the Cu-MOF probe (A) and the DNA signaling probe (B).
The specific implementation mode is as follows:
for better understanding of the present invention, the technical solution of the present invention will be described in detail with specific examples, but the present invention is not limited thereto.
Example 1 preparation of porous Cu-MOF:
0.435 g of Cu (NO)3)2·3H2O, a mixture of 0.62 mL of acetic acid, 0.50 mL of trimethylamine, and 12 mL of ethanol was stirred at room temperature for 1 hour, and then H was added3BTC benzene tricarboxylic acid (0.210 g, 1.0 mmoL) was added to the solution and stirred for 2 hours to form a homogeneous solution; the mixture was transferred to an autoclave and heated at 85 ℃ for 24 hours. Centrifuging to recover solid, and washing with anhydrous ethanol for 3 times; finally, the product was treated with ethanol at 65 ℃ for 12 hours and dried to obtain Cu-MOF.
Example 2 dual signal aptamer sensor preparation:
(1) remove 20. mu.L of HAuCl4(1% wt) and 2mL of NaBH 2 mM ice4Adding the solution into a Cu-MOF solution, continuously stirring for 1h, centrifuging and washing to obtain Au NPs/Cu-MOF, and dispersing the Au NPs/Cu-MOF into 2mL of absolute ethyl alcohol for storage and later use; the complementary strand (cDNA) of the acetamiprid aptamer strand was taken as a solution (50. mu.L, 10)-7 M) adding the solution into 500 mu L of the prepared Au NPs/Cu-MOF solution for overnight culture to prepare Cu-MOF @ AuNPs/cDNA;
(2) the processed glassy carbon electrode GCE is operated for 120 s under constant potential of-0.1V in 1% chloroauric acid solution to prepare an Au NPs/GCE modified electrode;
(3) 10 mu L of 10 was added dropwise to the modified electrode-7 Incubating an M acetamiprid aptamer Apt at 4 ℃ for 12 h to obtain Apt/Au NPs/GCE, and then sealing a non-specific site with MCH;
(4) and dripping 10 mu L of Cu-MOF @ AuNPs/cDNA on the surface of the electrode, incubating for 1h at 37 ℃, and washing by PBS buffer solution with pH 7.8 to obtain Cu-MOF @ AuNPs/cDNA/Apt/Au NPs/GCE.
Example 3 method of using dual signal aptamer sensor for detection of acetamiprid:
(1) dripping acetamiprid pesticide with different concentrations on the surface of the constructed sensor, incubating for 1h at 37 ℃, and dripping 5 mu L10 mM Na2MoO4The reaction was carried out for 20 min, washed with PBS buffer at pH 7.8;
(2) an aptamer sensor is taken as a working electrode, an Ag/AgCl electrode is taken as a reference electrode,the platinum electrode is an auxiliary electrode; in 0.5M sulfuric acid solution, SWV scanning is carried out in a potential interval of-0.3-0.5V, and oxidation peak potential and current intensity are recorded. And respectively drawing working curves, and simultaneously measuring the linear range and the detection limit of the sensor. The results show that the linear equation corresponding to the Cu-MOF signaling probe is DI =2.9915lgc+45.5551 (R2=0.9904), the linear range is 0.01 pM-0.01 μ M, and the detection limit is 3.33 fM; the linear equation for DNA as a signaling probe is DI =1.9028lgc+28.9768 (R2=0.9972), linear range of 0.01 pM ~ 0.01. mu.M, detection limit of 3.47 fM.
Example 4 optimization of aptamer sensor usage conditions
The invention optimizes the conditions of aptamer incubation temperature, incubation time and reaction time with sodium molybdate. The results show that the peak current increases and then decreases with incubation temperature, reaching a maximum at 37 ℃; when the incubation time of the aptamer is less than 60 minutes, the peak current increases along with the increase of the incubation time, and then the peak current tends to be stable along with the increase of the incubation time; the peak current gradually increases along with the increase of the reaction time of the sodium molybdate, the peak current reaches the maximum value at 20 min, and the peak current tends to be stable after 20 min, at the moment, the sodium molybdate has completely reacted. The optimal conditions are that the incubation temperature of the aptamer is 37 ℃, the incubation time is 60 min, and the reaction time with sodium molybdate is 20 min.

Claims (5)

1. A dual-signal electrochemical aptamer sensor based on porous Cu-MOF nano materials is characterized in that the sensor has two mutually verified current output signals: the porous Cu-MOF nano material is used for loading complementary strand cDNA of an acetamiprid aptamer and is used for loading and catalytically amplifying signals; the Cu-MOF generates electrochemical signals by itself to realize signal output; the DNA can react with sodium molybdate to generate an electrochemical signal, and a double-signal output is formed.
2. The Cu-MOF of claim 1, prepared by the following method: 0.435 g of Cu (NO)3)2·3H2O, 0.62 mL of acetic acid, 0.50 mL of trimethylamine, and 1After 2mL of the mixture of ethanol had been stirred at room temperature for 1 hour, H was added3BTC benzene tricarboxylic acid (0.210 g, 1.0 mmoL) was added to the solution and stirred for 2 hours to form a homogeneous solution; transferring the mixture into an autoclave, heating at 85 ℃ for 24 hours, centrifuging to recover the solid, and washing with absolute ethanol for 3 times; finally, the product was treated with ethanol at 65 ℃ for 12 hours and dried to obtain Cu-MOF.
3. The sensor of claim 1, prepared by the following method:
(1) remove 20. mu.L of HAuCl4(1% wt) and 2mL of NaBH 2 mM ice4Adding the solution into a Cu-MOF solution, continuously stirring for 1h, centrifuging and washing to obtain Au NPs/Cu-MOF, and dispersing the Au NPs/Cu-MOF into 2mL of absolute ethyl alcohol for storage and later use; the complementary strand (cDNA) of the acetamiprid aptamer strand was taken as a solution (50. mu.L, 10)-7 M) was added to 500. mu.L of the Au NPs/Cu-MOF solution prepared above and cultured overnight;
(2) the processed glassy carbon electrode GCE is operated for 120 s under constant potential of-0.1V in 1% chloroauric acid solution to prepare an Au NPs/GCE modified electrode;
(3) 10 mu L of 10 was added dropwise to the modified electrode-7 Incubating an M acetamiprid aptamer Apt at 4 ℃ for 12 h to obtain Apt/Au NPs/GCE, and then sealing a non-specific site with MCH;
(4) and dripping 10 mu L of Cu-MOF @ AuNPs/cDNA on the surface of the electrode, incubating for 1h at 37 ℃, and washing by PBS buffer solution with pH 7.8 to obtain Cu-MOF @ AuNPs/cDNA/Apt/Au NPs/GCE.
4. The dual signal aptamer sensor of claim 1 for use in detecting acetamiprid.
5. The dual-signal aptamer sensor of claim 1, for detecting acetamiprid, according to the following method:
(1) dripping acetamiprid pesticide with different concentrations on the surface of the constructed sensor, incubating for 1h at 37 ℃, and dripping 5 mu L10 mM Na2MoO4The reaction was carried out for 20 min, washed with PBS buffer at pH 7.8;
(2) taking the aptamer sensor as a working electrode, an Ag/AgCl electrode as a reference electrode and a platinum electrode as an auxiliary electrode; in 0.5M sulfuric acid solution, SWV scanning is carried out in a potential interval of-0.3-0.5V, and oxidation peak potential and current intensity are recorded.
CN202111209320.4A 2021-10-18 2021-10-18 Dual-signal electrochemical aptamer sensor and method for determining acetamiprid Pending CN113960131A (en)

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
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Application publication date: 20220121