CN115785462B - Zr-PTC luminophor material, electrochemical luminescence sensor, and preparation method and application thereof - Google Patents
Zr-PTC luminophor material, electrochemical luminescence sensor, and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of electrochemical detection, in particular to a Zr-PTC luminophor material, an electrochemical luminescence sensor, a preparation method and application thereof. The Zr-PTC luminophor material is zirconium-based MOF material, and is a solid substance obtained by heating and reacting a mixture of perylene tetracarboxylic acid potassium and zirconium salt solution in an autoclave. The electrochemical luminescence sensor comprises a Zr-PTC luminophor material which is used as a donor and is modified on the surface of an electrode, an aptamer apt with carboxyl which is modified on the surface of the Zr-PTC luminophor material, GSH-Au NCs which is used as an acceptor and is modified on the surface of the electrode, wherein the Zr-PTC and the GSH-Au NCs are connected through an aptamer complementary strand cDNA and form a plasmon resonance mechanism. The sensor has the advantages of high detection sensitivity, high detection speed, strong specificity, wide linear range and convenient use.
Description
Technical Field
The invention belongs to the technical field of electrochemical detection, and relates to a Zr-PTC luminophor material, an electrochemical luminescence sensor, a preparation method and application thereof. In particular to a Zr-PTC modified electrode which is taken as a luminous body and a donor of plasma resonance, and a glutathione stabilized Au nano-cluster (GSH-Au NCs) which is taken as an acceptor in energy resonance transfer. The electrochemical luminescence analysis method comprises the steps of connecting a donor and an acceptor through two DNA chains (apt and cDNA), jointly modifying the two DNA chains on an electrode, taking an aptamer (apt) with a specific recognition function as a recognition element, and quantitatively detecting endocrine disruptors in water environment by taking the electrochemical luminescence sensor as a working electrode.
Background
Acetamiprid is a novel nicotine pesticide, which is widely used for preventing and controlling rice, vegetables, fruit trees and tea, and killing aphids, plant hoppers, thrips and part of lepidoptera pests. It has potential toxicity to the nervous system and reproductive system of animals, can influence the development of human neurons, forms a threat to human health, and is an environmental endocrine disrupter. Acetamiprid is easy to enrich in soil and water environment, so that the detection of trace endocrine disrupters in an environmental water sample has important significance.
Disclosure of Invention
In order to further improve the detection sensitivity of substances, the invention provides a luminous zirconium-based MOF material (Zr-PTC) with high ECL emission intensity and an electrochemical luminescence sensor with high sensitivity, which can be used for detecting environmental endocrine disruptors (such as acetamiprid). Based on a plasma resonance mechanism existing between the Zr-PTC and the GSH-Au NCs, quantitative detection of environmental endocrine disruptors is realized. The sensor has the advantages of high detection sensitivity, high detection speed, convenient use and wide detection range.
The technical aim of the invention is realized by the following technical scheme:
a Zr-PTC luminophor material is a zirconium-based MOF material, which is a solid substance obtained by heating and reacting a mixture of perylene tetracarboxylic acid potassium and zirconium salt solution in an autoclave.
Further, the heating reaction temperature is 80-150 ℃, K 4 The molar ratio of PTC to zirconium salt is 1:1-4.
An electrochemical luminescence sensor comprises the Zr-PTC luminophor material which is used as a donor and is modified on the surface of an electrode, an aptamer apt which is modified on the surface of the Zr-PTC luminophor material, GSH-Au NCs which is used as an acceptor and is modified on the surface of the electrode, wherein the Zr-PTC and the GSH-Au NCs are connected through an aptamer complementary strand cDNA and form a plasmon resonance mechanism.
The invention also provides a preparation method of the electrochemical luminescence sensor, which comprises the following steps: polishing the electrode, sequentially respectively carrying out ultrasonic treatment on the electrode, the absolute ethyl alcohol and the deionized water, and naturally airing the electrode for later use; transferring the ethanol solution of Zr-PTC to the surface of the electrode, and drying at room temperature to obtain a Zr-PTC modified electrode; dripping an aptamer apt on the surface of a Zr-PTC modified electrode, and then dripping GSH-Au NCs-cDNA dispersion liquid to obtain the electrochemical luminescence sensor;
GSH-Au NCs-cDNA dispersion was prepared by the following method: and fully mixing the aptamer complementary strand cDNA activated by EDC and NHS solution with GSH-Au NCs.
Further, the preparation method of the luminophor Zr-PTC comprises the following operation steps:
s1, perylene tetracarboxylic dianhydride (PTCDA) and KOH are dissolved in deionized water to obtain a yellowish green solution, and the solution is heated and stirred in a water bath to obtain a compound;
s2, precipitating the mixture obtained in the step S1 by ethanol, centrifuging and drying to obtain yellow powdery solid, namely perylene tetracarboxylic acid potassium K 4 PTC；
S3, K is taken 4 The PTC is dripped into a zirconium salt (preferably, zirconium chloride, zirconium nitrate or zirconium acetate) solution, and the mixture is obtained by stirring and mixing uniformly.
S4, transferring the mixture of the S3 into a polytetrafluoroethylene-lined high-pressure reaction kettle, reacting for 10-14 h at 90-120 ℃, centrifugally washing the obtained product with deionized water and ethanol, and drying to obtain a red solid, namely Zr-PTC.
The invention utilizes a plasma resonance mechanism existing between Zr-PTC and GSH-Au NCs to construct an electrochemiluminescence analysis method which can be used for quantitatively detecting endocrine disruptors (especially trace) in an environmental water sample. Since there is a large overlap area between the electrochemiluminescence emission spectrum of Zr-PTC (donor) and the uv-vis absorption spectrum of GSH-Au NCs (acceptor), there is a plasmon resonance mechanism between the two, and the concentration of added endocrine disruptors has a linear relationship with the increased light intensity. The sensitivity of electrochemiluminescence analysis is greatly improved, the specificity is enhanced, and the linear range is widened by local surface plasmon resonance.
Further, the preparation method of GSH-Au NCs-cDNA comprises the following operation steps:
A1. an amount of HAuCl 4 Mixing the solution with Glutathione (GSH) solution in deionized water;
A2. the mixed solution of A1 is stirred gently, heated in water bath overnight, and the dark yellow solution with orange fluorescence is obtained, namely GSH-Au NCs;
A3. and (3) dripping a certain amount of cDNA into EDC and NHS solution, mixing the cDNA with GSH-Au NCs after shaking at a constant speed, and obtaining the GSH-Au NCs-cDNA after shaking for a period of time.
Further, the drop-coating amount of Zr-PTC is 5.0 mu L, and the concentration is 1.0mg/mL; the amount of apo applied was 2.5. Mu.L and the concentration was 1.0. Mu. Mol/L.
Further, the amount of cDNA in GSH-Au NCs-cDNA was 5. Mu.L, and the concentration was 0.5. Mu. Mol/L. apt has carboxyl groups and Zr in luminophores 4+ Is a strong coordination bond of (a); GSH on GSH-Au NCs is provided with amino, and cDNA is combined with the GSH through an amide bond to obtain GSH-Au NCs-cDNA.
The third object of the invention is to provide an electrochemiluminescence method for detecting acetamiprid, wherein the electrochemiluminescence sensor is used as a working electrode for 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 for electrochemiluminescence detection of acetamiprid.
As the preferable technical scheme, the method comprises the following specific steps:
B1. preparing phosphate buffer solution containing potassium persulfate;
B2. preparation of acetamiprid standard solutions with different concentrations:
acetamiprid is prepared into 1.0X10 by using absolute ethyl alcohol -5 Diluting the mol/L solution into a series of acetamiprid standard solutions with different concentrations, wherein the concentration range is 1.0X10 -14 mol/L～1.0×10 -5 mol/L；
B3. Drawing a standard curve:
the electrochemical luminescence sensor is used as a working electrode, a platinum electrode is used as an auxiliary electrode, and Ag/AgCl is used as a reference electrode to form a three-electrode system. And placing the three-electrode system in phosphate buffer solution containing potassium persulfate as a blank solution, and carrying out cyclic voltammetry scanning to detect the luminous intensity within an electrochemical window range of-1.6-0V at a high voltage of 800V and a scanning speed of 0.1V/s of the photomultiplier. And B2, soaking the working electrode in a series of acetamiprid standard solutions with different concentrations prepared in the step B for a certain time, taking out the working electrode, flushing the surface of the electrode, continuously testing the luminous intensity of the working electrode in a phosphate buffer solution containing potassium persulfate under the same test conditions, recording a time-luminous intensity curve, and establishing a linear relation between the luminous intensity difference before and after acetamiprid is added and the acetamiprid concentration logarithmic value to obtain a corresponding linear regression equation.
B4. And (3) detecting acetamiprid to-be-detected liquid: and detecting the luminous intensity of the acetamiprid to-be-detected liquid by referring to the B3 three-electrode system and the cyclic voltammetry scanning condition, and calculating the acetamiprid concentration in the acetamiprid to-be-detected liquid based on the linear regression equation.
Analysis by the test result of the step B3, the acetamiprid concentration is 1.0x10 -14 mol/L～1.0×10 -7 The mol/L has good linear relation. The minimum detection limit is 1.96×10 -15 mol/L。
In summary, the invention also has the following beneficial effects:
the invention discloses a novel electrochemiluminescence luminophor material, a preparation method and an application method of a working electrode for detecting acetamiprid by using an electrochemiluminescence method. The luminophor Zr-PTC provided by the invention has excellent electrochemiluminescence performance, and contains 0.05mol/L K 2 S 2 O 8 In the 0.1mol/L silver phosphate buffer solution with pH of 7.4, the photomultiplier is set to 800V, and the photomultiplier is scanned at-1.6-0V by cyclic voltammetry, so that the luminous intensity can reach about twenty thousands. The electrode is assembled based on a plasma resonance mechanism existing between the Zr-PTC and the GSH-Au NCs, so that the ECL strength can be greatly amplified.
Drawings
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate the invention and together with the embodiments of the invention, serve to explain the invention. In the drawings:
FIG. 1 is a schematic flow chart and mechanism diagram of the preparation of the sensor and detection of acetamiprid in the present invention;
FIG. 2 is a linear graph of luminescence intensity after addition of acetamiprid at different concentrations, a-h: 1.0X10 -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；
FIG. 3 is a standard curve of the difference in luminescence intensity before and after addition of acetamiprid and the log acetamiprid concentration.
FIG. 4 is a graph of the difference in scale (K 4 PTC：ZrCl 4 (mol)) synthesis of ECL spectra of Zr-PTC, a to f:1:1;1:2;1:4;1:10;1:20;1:40.
FIG. 5 is a graph of the difference in scale (K 4 PTC：ZrCl 4 (mol)) SEM images of synthetic Zr-PTC, a to F:1:1;1:2;1:4;1:10;1:20;1:40.
FIG. 6 is an ECL spectrum of a different material modified electrode.
Detailed Description
In order to further illustrate the technical means and effects adopted by the invention to achieve the preset aim, the invention is further illustrated by taking acetamiprid detection as an example, and the specific embodiments, the characteristics and the effects thereof are described in detail below. The present invention is not limited to the following embodiments, and those skilled in the art can implement the present invention in various other embodiments according to the present invention, or simply change or modify the design structure and thought of the present invention, which fall within the protection scope of the present invention. It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other. In the present invention, the electrode material may be any one of those in the art, such as ITO, FTO, and glassy carbon, and the following examples are given by way of example.
Examples: a preparation and application method of a novel electrochemiluminescence material for detecting acetamiprid based on plasma resonance.
(1) A preparation method of a novel electrochemiluminescence material Zr-PTC comprises the following steps:
s1, 1mmol of perylene tetracarboxylic dianhydride (PTCDA) and 5mmol of KOH are dissolved in 4mL of deionized water, and a yellowish green solution is obtained. Heating and stirring in a water bath at 55 ℃ for 12 hours to obtain a compound;
s2, precipitating the mixture obtained in the step S1 with 30mL of ethanol, centrifuging for 15min at 10000rpm by using a centrifuge, and drying for 12h at 60 ℃ to obtain yellow powdery solid which is K 4 PTC；
S3, 0.05mmol K 4 PTC was added to 0.2mmol ZrCl 4 In 15mL of the prepared solution (K 4 PTC and ZrCl 4 The molar ratio of (2) is 1:4), and stirring for 30min and uniformly mixing.
S4, transferring the mixture obtained in the step S3 into a polytetrafluoroethylene-lined high-pressure reaction kettle, heating at 100 ℃ for 12 hours, respectively centrifugally washing the product with deionized water and ethanol for 15 minutes at 10000rpm for three times, and drying at 60 ℃ for 12 hours to obtain red solid, namely Zr-PTC.
(2) The preparation method of the Zr-PTC (1:4)/GCE modified electrode comprises the following steps:
polishing the glassy carbon electrode, sequentially respectively carrying out ultrasonic treatment by using nitric acid, absolute ethyl alcohol and deionized water, naturally airing for standby, transferring 1mg/mL of Zr-PTC ethanol solution to the surface of the glassy carbon electrode by using a microsyringe, baking the glassy carbon electrode by using an infrared lamp until the modification amount is 5.0 mu L, and obtaining the Zr-PTC/GCE modified electrode.
Taking a modified electrode Zr-PTC/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; and placing the three-electrode system in a solution containing 0.05mol/L K 2 S 2 O 8 Luminescence intensity was measured in 0.1mol/L PBS buffer at ph=7.4; and (3) in the electrochemical window range of-1.6-0V, the photomultiplier is subjected to high-voltage 800V and scanning speed of 0.1V/s, cyclic voltammetry scanning is carried out, and a T-ECL curve is recorded.
(3) The preparation method of GSH-Au NCs-cDNA comprises the following steps:
A1. 0.50mL of freshly prepared HAuCl at 20mmol/L 4 The solution was mixed with 0.15mL 100mmol/L Glutathione (GSH) solution in 4.35mL deionized water;
A2. the mixed solution of A1 is stirred gently at 500rpm, heated to 70 ℃ in water bath and kept for 24 hours, and the dark yellow solution with orange fluorescence is obtained, namely GSH-Au NCs;
A3. 60 mu L of 1 mu mol/L cDNA is dripped into 9 mu L of EDC and NHS solution, and is mixed with 60 mu L of GSH-Au NCs after shaking at a constant speed, and the GSH-Au NCs-cDNA is obtained after shaking for 2 hours.
(4) The preparation method of the modified electrode GSH-Au NCs-cDNA/apt/Zr-PTC/GCE comprises the following steps:
polishing a glassy carbon electrode, sequentially respectively carrying out ultrasonic treatment by using nitric acid, absolute ethyl alcohol and deionized water, naturally airing for standby, transferring an ethanol solution of Zr-PTC to the surface of the glassy carbon electrode by using a microsyringe, and baking under an infrared lamp to obtain a Zr-PTC/GCE modified electrode; and dripping apt and GSH-Au NCs-cDNA activated by EDC.NHS on the surface of the Zr-PTC/GCE electrode to obtain the GSH-Au NCs-cDNA/apt/Zr-PTC/GCE.
(4) An application method of a working electrode for detecting acetamiprid by an electrochemiluminescence method comprises the following steps:
B1. preparing phosphate buffer solution containing potassium persulfate;
B2. preparation of acetamiprid standard solutions with different concentrations:
acetamiprid is prepared into 1.0X10 by using absolute ethyl alcohol -5 Diluting the mol/L solution into a series of acetamiprid standard solutions with different concentrations, wherein the concentration range is 1.0X10 -14 mol/L～1.0×10 -5 mol/L；
B3. Drawing a standard curve:
the modified electrode GSH-Au NCs-cDNA/apt/Zr-PTC/GCE is used as a working electrode, a platinum electrode is used as an auxiliary electrode, and Ag/AgCl is used as a reference electrode to form a three-electrode system. The three-electrode system was placed in a system containing 0.05mol/L K 2 S 2 O 8 The pH=7.4 of 0.1mol/L PBS is used as a blank solution, the high pressure 800V of the photomultiplier tube is carried out within the electrochemical window range of-1.6-0V, the scanning speed is 0.1V/s, and the cyclic voltammetry scanning is carried out to detect the luminous intensity.
The working electrode was then placed in a series of different concentrations (1.0X10) prepared in step B2 -14 mol/L，1.0×10 - 13 mol/L，1.0×10 -12 mol/L，1.0×10 -11 mol/L，1.0×10 -10 mol/L，1.0×10 -9 mol/L，1.0×10 - 8 mol/L，1.0×10 -7 mol/L) acetamiprid standard solution, taking out, washing the surface of the electrode, continuously testing the luminous intensity in a phosphate buffer solution containing potassium persulfate under the same test conditions, recording a time-luminous intensity curve, and establishing a linear relation between the luminous intensity difference before and after acetamiprid is added and the acetamiprid concentration logarithmic value to obtain a corresponding linear regression equation. The detection range is 1.0X10 -14 mol/L～1.0×10 -7 mol/L, linear regression equation is DeltaI ECL ＝70194.64-4731.34log C(mol/L)，R 2 =0.9948, the lowest limit of detection is 1.96×10 -15 mol/L。
K 4 PTC to zirconium salt molar ratio adjustment test example 1:
(1) The preparation method of the Zr-PTC (1:1) comprises the following steps:
will be 0.05mmol K 4 PTC was added to 0.05mmol ZrCl 4 In 15mL of the prepared solution (1:1), stirring for 30min and mixing uniformly. Transferring the mixture into a polytetrafluoroethylene-lined high-pressure reaction kettle, heating at 100 ℃ for 12 hours, centrifugally washing the product with deionized water and ethanol for 15 minutes at 10000rpm respectively, and drying at 60 ℃ for 12 hours to obtain red solid which is Zr-PTC (1:1).
(2) The preparation method of the Zr-PTC (1:1)/GCE modified electrode comprises the following steps:
polishing the glassy carbon electrode, sequentially respectively carrying out ultrasonic treatment by using nitric acid, absolute ethyl alcohol and deionized water, naturally airing for standby, transferring 1mg/mL of ethanol solution of Zr-PTC (1:1) to the surface of the glassy carbon electrode by using a microsyringe, baking the glassy carbon electrode by using an infrared lamp until the modification amount is 5.0 mu L, and obtaining the Zr-PTC (1:1)/GCE modified electrode.
Forming a three-electrode system by taking a modified electrode Zr-PTC (1:1)/GCE as a working electrode, a platinum electrode as an auxiliary electrode and Ag/AgCl as a reference electrode; and placing the three-electrode system in a solution containing 0.05mol/L K 2 S 2 O 8 Luminescence intensity was measured in 0.1mol/L PBS buffer at ph=7.4; and (3) in the electrochemical window range of-1.6-0V, the photomultiplier is subjected to high-voltage 800V and scanning speed of 0.1V/s, cyclic voltammetry scanning is carried out, and a T-ECL curve is recorded.
K 4 PTC and zirconium saltMolar ratio adjustment test example 2:
(1) The preparation method of the Zr-PTC (1:2) comprises the following steps:
will be 0.05mmol K 4 PTC was added to 0.1mmol ZrCl 4 In 15mL of the prepared solution (1:2), stirring for 30min and mixing uniformly. Transferring the mixture into a polytetrafluoroethylene-lined high-pressure reaction kettle, heating at 100 ℃ for 12 hours, centrifugally washing the product with deionized water and ethanol for 15 minutes at 10000rpm respectively, and drying at 60 ℃ for 12 hours to obtain red solid which is Zr-PTC (1:2).
(2) The preparation method of the Zr-PTC (1:2)/GCE modified electrode comprises the following steps:
polishing the glassy carbon electrode, sequentially respectively carrying out ultrasonic treatment by using nitric acid, absolute ethyl alcohol and deionized water, naturally airing for standby, transferring 1mg/mL of ethanol solution of Zr-PTC (1:2) to the surface of the glassy carbon electrode by using a microsyringe, baking the glassy carbon electrode by using an infrared lamp until the modification amount is 5.0 mu L, and obtaining the Zr-PTC (1:2)/GCE modified electrode.
Forming a three-electrode system by taking a modified electrode Zr-PTC (1:2)/GCE as a working electrode, a platinum electrode as an auxiliary electrode and Ag/AgCl as a reference electrode; and placing the three-electrode system in a solution containing 0.05mol/L K 2 S 2 O 8 Luminescence intensity was measured in 0.1mol/L PBS buffer at ph=7.4; and (3) in the electrochemical window range of-1.6-0V, the photomultiplier is subjected to high-voltage 800V and scanning speed of 0.1V/s, cyclic voltammetry scanning is carried out, and a T-ECL curve is recorded.
K 4 PTC to zirconium salt molar ratio adjustment test example 3:
(1) The preparation method of the Zr-PTC (1:10) comprises the following steps:
will be 0.05mmol K 4 PTC was added to 0.5mmol ZrCl 4 In 15mL of the prepared solution (1:10), stirring for 30min and mixing. Transferring the mixture into a polytetrafluoroethylene-lined high-pressure reaction kettle, heating at 100 ℃ for 12 hours, centrifugally washing the product with deionized water and ethanol for 15 minutes at 10000rpm respectively, and drying at 60 ℃ for 12 hours to obtain red solid which is Zr-PTC (1:10).
(2) The preparation method of the Zr-PTC (1:10)/GCE modified electrode comprises the following steps:
polishing the glassy carbon electrode, sequentially respectively carrying out ultrasonic treatment by using nitric acid, absolute ethyl alcohol and deionized water, naturally airing for standby, transferring 1mg/mL of ethanol solution of Zr-PTC (1:10) to the surface of the glassy carbon electrode by using a microsyringe, baking the glassy carbon electrode by using an infrared lamp until the modification amount is 5.0 mu L, and obtaining the Zr-PTC (1:10)/GCE modified electrode.
Forming a three-electrode system by taking a modified electrode Zr-PTC (1:10)/GCE as a working electrode, a platinum electrode as an auxiliary electrode and Ag/AgCl as a reference electrode; and placing the three-electrode system in a solution containing 0.05mol/L K 2 S 2 O 8 Luminescence intensity was measured in 0.1mol/L PBS buffer at ph=7.4; and (3) in the electrochemical window range of-1.6-0V, the photomultiplier is subjected to high-voltage 800V and scanning speed of 0.1V/s, cyclic voltammetry scanning is carried out, and a T-ECL curve is recorded.
K 4 PTC to zirconium salt molar ratio adjustment test example 4:
(1) The preparation method of the Zr-PTC (1:20) comprises the following steps:
will be 0.05mmol K 4 PTC was added to 1.0mmol ZrCl 4 In 15mL of the prepared solution (1:20), stirring for 30min and mixing. Transferring the mixture into a polytetrafluoroethylene-lined high-pressure reaction kettle, heating at 100 ℃ for 12 hours, centrifugally washing the product with deionized water and ethanol for 15 minutes at 10000rpm respectively, and drying at 60 ℃ for 12 hours to obtain red solid which is Zr-PTC (1:20).
(2) The preparation method of the Zr-PTC (1:20)/GCE modified electrode comprises the following steps:
polishing the glassy carbon electrode, sequentially respectively carrying out ultrasonic treatment by using nitric acid, absolute ethyl alcohol and deionized water, naturally airing for standby, transferring 1mg/mL of ethanol solution of Zr-PTC (1:20) to the surface of the glassy carbon electrode by using a microsyringe, baking the glassy carbon electrode by using an infrared lamp until the modification amount is 5.0 mu L, and obtaining the Zr-PTC (1:20)/GCE modified electrode.
Forming a three-electrode system by taking a modified electrode Zr-PTC (1:20)/GCE as a working electrode, a platinum electrode as an auxiliary electrode and Ag/AgCl as a reference electrode; and placing the three-electrode system in a solution containing 0.05mol/L K 2 S 2 O 8 Luminescence intensity was measured in 0.1mol/L PBS buffer at ph=7.4; and (3) in the electrochemical window range of-1.6-0V, the photomultiplier is subjected to high-voltage 800V and scanning speed of 0.1V/s, cyclic voltammetry scanning is carried out, and a T-ECL curve is recorded.
K 4 PTC and zirconium salt moleComparative adjustment test example 5:
(1) The preparation method of the Zr-PTC (1:40) comprises the following steps:
will be 0.05mmol K 4 PTC was added to 2.0mmol ZrCl 4 In 15mL of the prepared solution (1:40), stirring for 30min and mixing. Transferring the mixture into a polytetrafluoroethylene-lined high-pressure reaction kettle, heating at 100 ℃ for 12 hours, centrifugally washing the product with deionized water and ethanol for 15 minutes at 10000rpm respectively, and drying at 60 ℃ for 12 hours to obtain red solid which is Zr-PTC (1:40).
(2) The preparation method of the Zr-PTC (1:40)/GCE modified electrode comprises the following steps:
polishing the glassy carbon electrode, sequentially respectively carrying out ultrasonic treatment by using nitric acid, absolute ethyl alcohol and deionized water, naturally airing for standby, transferring 1mg/mL of ethanol solution of Zr-PTC (1:40) to the surface of the glassy carbon electrode by using a microsyringe, baking the glassy carbon electrode by using an infrared lamp until the modification amount is 5.0 mu L, and obtaining the Zr-PTC (1:40)/GCE modified electrode.
Forming a three-electrode system by taking a modified electrode Zr-PTC (1:40)/GCE as a working electrode, a platinum electrode as an auxiliary electrode and Ag/AgCl as a reference electrode; and placing the three-electrode system in a solution containing 0.05mol/L K 2 S 2 O 8 Luminescence intensity was measured in 0.1mol/L PBS buffer at ph=7.4; and (3) in the electrochemical window range of-1.6-0V, the photomultiplier is subjected to high-voltage 800V and scanning speed of 0.1V/s, cyclic voltammetry scanning is carried out, and a T-ECL curve is recorded.
TABLE 1 comparison of the Performance of different ratio synthesized Zr-PTC luminophores
In addition, in the preparation of the Zr-PTC luminophor material, the invention takes 1:4 as an example, and a temperature adjustment test is carried out, and the test proves that the Zr-PTC luminophor material with good luminescence performance can be obtained under the reaction condition of 80-150 ℃, but the temperature is preferably 90-120 ℃, and the influence of temperature change in the range on the luminescence performance is small, but the temperature is preferably 100 ℃.
Comparative example 1:
(1) The preparation method of the modified electrode Zr-PTC/GCE comprises the following steps:
polishing the glassy carbon electrode, sequentially respectively carrying out ultrasonic treatment with nitric acid, absolute ethyl alcohol and deionized water, naturally airing for standby, transferring 5.0 mu L of ethanol solution of Zr-PTC to the surface of the glassy carbon electrode by a microsyringe, and baking under an infrared lamp to obtain the Zr-PTC/GCE modified electrode
(2) An application method of a working electrode for detecting acetamiprid by an electrochemiluminescence method comprises the following steps:
the modified electrode Zr-PTC/GCE is used as a working electrode, the platinum electrode is used as an auxiliary electrode, and Ag/AgCl is used as a reference electrode to form a three-electrode system. The three-electrode system was placed in a system containing 0.05mol/L K 2 S 2 O 8 The pH=7.4 of 0.1mol/L PBS is used as a blank solution, the high pressure 800V of the photomultiplier tube is carried out within the electrochemical window range of-1.6-0V, the scanning speed is 0.1V/s, and the cyclic voltammetry scanning is carried out to detect the luminous intensity.
The working electrode was then placed in a series of different concentrations (1.0X10) -14 mol/L，1.0×10 -13 mol/L，1.0×10 -12 mol/L，1.0×10 -11 mol/L，1.0×10 -10 mol/L，1.0×10 -9 mol/L，1.0×10 -8 mol/L，1.0×10 -7 mol/L) acetamiprid standard solution, taking out, washing the surface of the electrode, continuously testing the luminous intensity in a phosphate buffer solution containing potassium persulfate under the same test conditions, recording a T-ECL curve, and establishing a linear relation between the luminous intensity difference before and after acetamiprid is added and the acetamiprid concentration logarithmic value to obtain a corresponding linear regression equation.
Comparative example 2:
(1) The preparation method of the modified electrode GSH-Au NCs/GCE comprises the following steps:
and polishing the glassy carbon electrode, sequentially respectively carrying out ultrasonic treatment by using nitric acid, absolute ethyl alcohol and deionized water, naturally airing for standby, transferring 5.0 mu L of GSH-Au NCs solution by using a microsyringe, dripping the GSH-Au NCs solution on the surface of the glassy carbon electrode, and naturally airing to obtain the GSH-Au NCs/GCE modified electrode.
(2) An application method of a working electrode for detecting acetamiprid by an electrochemiluminescence method comprises the following steps:
the modified electrode GSH-Au NCs/GCE is used as a working electrode, a platinum electrode is used as an auxiliary electrode, and Ag/AgCl is used as a reference electrode to form a three-electrode system. The three-electrode system was placed in a system containing 0.05mol/L K 2 S 2 O 8 The pH=7.4 of 0.1mol/L PBS is used as a blank solution, the high pressure 800V of the photomultiplier tube is carried out within the electrochemical window range of-1.6-0V, the scanning speed is 0.1V/s, and the cyclic voltammetry scanning is carried out to detect the luminous intensity.
The working electrode was then placed in a series of different concentrations (1.0X10) -14 mol/L，1.0×10 -13 mol/L，1.0×10 -12 mol/L，1.0×10 -11 mol/L，1.0×10 -10 mol/L，1.0×10 -9 mol/L，1.0×10 -8 mol/L，1.0×10 -7 mol/L) acetamiprid standard solution, taking out, washing the surface of the electrode, continuously testing the luminous intensity in a phosphate buffer solution containing potassium persulfate under the same test conditions, recording a T-ECL curve, and establishing a linear relation between the luminous intensity difference before and after acetamiprid is added and the acetamiprid concentration logarithmic value to obtain a corresponding linear regression equation.
Comparative example 3:
(1) The preparation method of the modified electrode apt/Zr-PTC/GCE comprises the following steps:
polishing a glassy carbon electrode, sequentially respectively carrying out ultrasonic treatment on the glassy carbon electrode, absolute ethyl alcohol and deionized water, naturally airing for standby, transferring 5.0 mu L of ethanol solution of Zr-PTC to the surface of the glassy carbon electrode by a microsyringe, and baking the solution under an infrared lamp to obtain a Zr-PTC/GCE modified electrode; and 2.5 mu L of 1.0 mu mol/L of apt solution is modified on the surface of the electrode to obtain the apt/Zr-PTC/GCE modified electrode.
(2) An application method of a working electrode for detecting acetamiprid by an electrochemiluminescence method comprises the following steps:
the modified electrode apt/Zr-PTC/GCE is used as a working electrode, a platinum electrode is used as an auxiliary electrode, ag/AgCl is used as a reference electrode, and a three-electrode system is formed. The three-electrode system was placed in a system containing 0.05mol/L K 2 S 2 O 8 Ph=7.4The 0.1mol/L PBS is used as a blank solution, and the high-voltage 800V and the scanning speed 0.1V/s of the photomultiplier tube are carried out in the electrochemical window range of-1.6-0V to detect the luminous intensity by cyclic voltammetry scanning.
The working electrode was then placed in a series of different concentrations (1.0X10) -14 mol/L，1.0×10 -13 mol/L，1.0×10 -12 mol/L，1.0×10 -11 mol/L，1.0×10 -10 mol/L，1.0×10 -9 mol/L，1.0×10 -8 mol/L，1.0×10 -7 mol/L) acetamiprid standard solution, taking out, washing the surface of the electrode, continuously testing the luminous intensity in a phosphate buffer solution containing potassium persulfate under the same test conditions, recording a T-ECL curve, and establishing a linear relation between the luminous intensity difference before and after acetamiprid is added and the acetamiprid concentration logarithmic value to obtain a corresponding linear regression equation.
TABLE 2 determination results of acetamiprid in river water
As shown in Table 2, the samples were tested 3 times in parallel with a relative standard deviation of less than 5% and a labeled recovery ranging from 98% to 103%. The results show that acetamiprid cannot be detected by using the glassy carbon electrode modified by the GSH-Au NCs-cDNA/apt/Zr-PTC composite material alone without modification by using the Zr-PTC, apt/Zr-PTC or GSH-Au NCs, and the acetamiprid can be sensitively, rapidly and accurately detected by using the working electrode and the application method provided by the invention.
Localized Surface Plasmon Resonance (LSPR) is the excitation of free electrons by an electromagnetic field, which causes a significant enhancement of the optical signal based on collective oscillations in the metal nanostructures. Besides being applied to the fields of surface Raman spectroscopy and fluorescence, the plasma resonance can be combined with electrochemiluminescence to form an ECL-LSPR mechanism and enhance ECL signals. The electrochemiluminescence method has the advantages of high sensitivity, low instrument price, good reproducibility, good selectivity and the like. The key to the present invention to utilize plasmon resonance to increase sensitivity is based on LSPR efficiency between donor and acceptor, which is largely dependent on spectral overlap between donor emission and acceptor absorption. Thus, by linking the aptamer and selecting the appropriate donor, acceptor, is the key to make up ECL-LSPR.
3,4,9, 10-perylene tetracarboxylic dianhydride (PTCDA) is a 5-ring polycyclic aromatic hydrocarbon with low toxicity and rich carboxyl modification. K is reacted to give + Modification on PTCDA, synthesis of yellow intermediate K 4 PTC. Then the mixture is synthesized by hydrothermal synthesis method through Zr 4+ Strong bond with carboxyl group, zr 4+ Substitution K + The red product Zr-PTC is obtained. Zr-PTC is used as a novel luminescent material, and has high luminous intensity. The invention uses Zr-PTC as ECL luminophor and co-reactant (K) 2 S 2 O 8 ) And (3) reacting to construct the solid ECL sensing platform.
In the embodiment of the invention, acetamiprid is used as a detection object, a luminous body is modified on the surface of a Glassy Carbon Electrode (GCE), and the acetamiprid is sensitively detected through a plasma resonance mechanism formed by an aptamer and a complementary DNA linking receptor.
The present invention is not limited to the above-mentioned embodiments, but is not limited to the above-mentioned embodiments, and any simple modification, equivalent changes and modification made to the above-mentioned embodiments according to the technical matters of the present invention can be made by those skilled in the art without departing from the scope of the present invention.
Claims (10)
1. A Zr-PTC luminophor material is characterized in that the Zr-based MOF material is made of perylene tetracarboxylic acid potassium K 4 The mixture of PTC and zirconium salt solution is heated and reacted in autoclave to obtain the solidA bulk material; k (K) 4 The molar ratio of the PTC to the zirconium salt is 1:1-4.
2. The Zr-PTC light-emitting material according to claim 1, wherein the heating reaction temperature is 80-150 ℃.
3. The Zr-PTC emitter material according to claim 1, wherein the zirconium salt is any one or more of zirconium chloride, zirconium nitrate, zirconium acetate.
4. An electrochemical luminescence sensor, characterized by comprising the Zr-PTC luminophor material according to any of claims 1 to 3 as a donor modified on the surface of an electrode, an aptamer apt with carboxyl modified on the surface of the Zr-PTC luminophor material, GSH-Au NCs modified on the surface of an electrode as an acceptor, the Zr-PTC and GSH-Au NCs being connected by an aptamer complementary strand cDNA and forming a plasmon resonance mechanism.
5. The method for manufacturing an electrochemical luminescence sensor according to claim 4, comprising: polishing the electrode, sequentially respectively carrying out ultrasonic treatment on the electrode, the absolute ethyl alcohol and the deionized water, and naturally airing the electrode for later use; transferring the ethanol solution of Zr-PTC to the surface of the electrode, and drying at room temperature to obtain a Zr-PTC modified electrode; dripping an aptamer apt on the surface of a Zr-PTC modified electrode, and then dripping GSH-Au NCs-cDNA dispersion liquid to obtain the electrochemical luminescence sensor;
GSH-Au NCs-cDNA dispersion was prepared by the following method: and fully mixing the aptamer complementary strand cDNA activated by EDC and NHS solution with GSH-Au NCs.
6. The method for manufacturing an electrochemical luminescence sensor according to claim 5, wherein the method for manufacturing Zr-PTC comprises the following steps:
s1, dissolving perylene tetracarboxylic dianhydride and KOH in deionized water to obtain a yellowish green solution, and heating and stirring in a water bath to obtain a compound;
s2, obtaining the product in the step S1Precipitating the compound with ethanol, centrifuging and drying to obtain yellow powdery solid, namely perylene tetracarboxylic acid potassium K 4 PTC；
S3, K is taken 4 Dripping PTC into zirconium salt solution, stirring and mixing uniformly to obtain a mixture;
s4, transferring the mixture obtained in the step S3 into a polytetrafluoroethylene-lined high-pressure reaction kettle, reacting at 90-120 ℃ for 10-14 h, centrifugally washing the obtained product with deionized water and ethanol, and drying to obtain a red solid, namely Zr-PTC.
7. The method of preparing an electrochemical luminescence sensor according to claim 5, wherein the method of preparing GSH-Au NCs-cDNA comprises the following steps:
A1. an amount of HAuCl 4 Mixing the solution with glutathione solution in deionized water;
A2. the mixed solution of A1 is stirred gently, heated in water bath overnight, and the dark yellow solution with orange fluorescence is obtained, namely GSH-Au NCs;
A3. and (3) dripping a certain amount of cDNA into EDC and NHS solution, mixing the cDNA with GSH-Au NCs after shaking at a constant speed, and obtaining the GSH-Au NCs-cDNA after shaking for a period of time.
8. The method for manufacturing an electrochemical luminescence sensor according to claim 5, wherein the Zr-PTC dispensing amount is 5.0 μl, and the concentration is 1.0mg/mL; the drop amount of apt is 2.5 mu L, and the concentration is 1.0 mu mol/L; the dropping amount of the GSH-Au NCs-cDNA dispersion liquid is 5 mu L, wherein the concentration of cDNA is 0.5 mu M, and the concentration is 0.5 mu mol/L; the incubation times for apt and cDNA were 12h and 2h, respectively.
9. An electrochemiluminescence method for detecting acetamiprid is characterized in that a three-electrode system is formed by taking the electrochemiluminescence sensor as a working electrode, an Ag/AgCl electrode as a reference electrode and a platinum electrode as an auxiliary electrode to perform electrochemiluminescence detection on acetamiprid;
the aptamer nucleotide sequence is as follows:
cDNA: 5'-HOOC-gcg ATc AAg AAc cgc Tcg AgA cAA ATT AcA-3'；
apt: 5'- HOOC-TgT AAT TTg TcT gcA gcg gTT cTT gAT cgc TgA cAc cAT ATT ATg AAg A-3'。
10. the electrochemiluminescence method for detecting acetamiprid according to claim 9, wherein the specific steps are as follows:
B1. preparing phosphate buffer solution containing potassium persulfate;
B2. preparation of acetamiprid standard solutions with different concentrations:
acetamiprid is prepared into 1.0X10 by using absolute ethyl alcohol -5 Diluting the mol/L solution into a series of acetamiprid standard solutions with different concentrations, wherein the concentration range is 1.0X10 -14 mol/L ~ 1.0 × 10 -5 mol/L；
B3. Drawing a standard curve:
taking the electrochemical luminescence sensor as a working electrode, taking a platinum electrode as an auxiliary electrode and taking Ag/AgCl as a reference electrode to form a three-electrode system; placing a three-electrode system in phosphate buffer solution containing potassium persulfate as a blank solution, and carrying out cyclic voltammetry scanning to detect the luminous intensity within an electrochemical window range of-1.6-0V at a high pressure of 800V and a scanning speed of 0.1V/s; soaking the working electrode in a series of acetamiprid standard solutions with different concentrations prepared in the step B2 for a certain time, taking out the working electrode, flushing the surface of the electrode, continuously testing the luminous intensity of the working electrode in a phosphate buffer solution containing potassium persulfate under the same test conditions, recording a time-luminous intensity curve, and establishing a linear relation between the luminous intensity difference before and after acetamiprid is added and the acetamiprid concentration logarithmic value to obtain a corresponding linear regression equation;
B4. and (3) detecting acetamiprid to-be-detected liquid: and detecting the luminous intensity of the acetamiprid to-be-detected liquid by referring to the B3 three-electrode system and the cyclic voltammetry scanning condition, and calculating the acetamiprid concentration in the acetamiprid to-be-detected liquid based on the linear regression equation.
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