Preparation method and application method of an electrochemiluminescence sensor for detecting benzodiazepine 2-chlordiazepoxide

Abstract

The present application belongs to the field of chemiluminescence detection, and particularly relates to a preparation method and application method of an electrochemiluminescence sensor for detecting benzodiazepine 2-chlordiazepoxide. Technical points are as follows: the electrochemiluminescence sensor is obtained by modifying the surface of a glassy carbon electrode with a Cu3(HHTP)2 / PTCA-COF composite material; the Cu3(HHTP)2 / PTCA-COF composite material modification is formed by the adsorption of PTCA-COF on Cu3(HHTP)2. Through the mechanism of the quenching of the ECL signal intensity of the system by 2-chlordiazepoxide, sensitive detection of 2-chlordiazepoxide is realized, the sensing platform can specifically recognize and detect 2-chlordiazepoxide, has high selectivity, and is simple to operate, good in selectivity, low in detection cost, and high in sensitivity.

Description

Technical Field

[0001] This invention relates to the field of chemiluminescence detection, specifically to a method for preparing and applying an electrochemiluminescence sensor for detecting the benzodiazepine drug 2-chlorodiazepam. Background Technology

[0002] Benzodiazepines, as inhibitory new psychoactive substances, have similar hypnotic, sedative, anti-muscle relaxant, and anxiety-relieving effects. However, high doses can produce serious side effects such as drowsiness, coma, hypotension, and respiratory and circulatory depression.

[0003] New benzodiazepines are rampant in the global illicit drug market. Criminals add them to beverages, capsules, or tablets, using their effects to induce rapid drowsiness, hallucinations, and short-term memory loss to commit crimes. Therefore, it is of great significance to develop a simple, rapid, and sensitive method for detecting new psychoactive substances.

[0004] Currently, the main methods for detecting benzodiazepines are capillary electrophoresis (CE), gas chromatography-mass spectrometry (GC-MS), and liquid chromatography-mass spectrometry (LC-MS). These methods have high accuracy, but they often need to be coupled with other methods such as Fourier transform infrared (FT-IR) and nuclear magnetic resonance (NMR). The detection methods are cumbersome and cannot obtain results quickly. They are also expensive and require professional personnel to operate. These problems limit their application in actual sample monitoring. Therefore, there is a need for a simple, rapid, and accurate method for routine analysis and detection of new psychoactive substances in samples.

[0005] In view of the shortcomings of the existing detection methods, the inventors, based on their extensive experience and expertise in this field for many years, combined with theoretical analysis and research innovation, have developed a method for preparing and applying an electrochemiluminescence sensor for detecting the benzodiazepine drug 2-chlorodiazepam. Summary of the Invention

[0006] The purpose of this invention is to develop a method for preparing an electrochemiluminescence sensor for detecting the benzodiazepine drug 2-chlorodiazepam. This method fully utilizes the adsorption effect of PTCA-COF on Cu3(HHTP)2, thereby co-modifying the glassy carbon electrode surface to obtain a Cu3(HHTP)2 / PTCA-COF / GCE electrochemiluminescence sensor. This significantly improves the sensitivity and stability of the electrochemiluminescence. Furthermore, after adding the analyte 2-chlorodiazepam, the ECL signal value of the Cu3(HHTP)2 / PTCA-COF / GCE electrochemiluminescence sensor is significantly reduced, enabling the detection of 2-chlorodiazepam without being affected by other interfering substances, exhibiting good specificity.

[0007] The above-mentioned technical objective of the present invention is achieved through the following technical solution:

[0008] This invention provides a method for preparing an electrochemiluminescence sensor for detecting the benzodiazepine drug 2-chlorodiazepam. The electrochemiluminescence sensor is obtained by modifying the surface of a glassy carbon electrode with Cu3(HHTP)2 / PTCA-COF composite material.

[0009] The modification of Cu3(HHTP)2 / PTCA-COF composite material is formed by the adsorption of Cu3(HHTP)2 by PTCA-COF.

[0010] This invention, based on the electrochemiluminescence quenching effect of 2-chlorodiazepam on the Cu3(HHTP)2 / PTCA-COF / GCE system, constructs a novel method for the rapid and sensitive detection of 2-chlorodiazepam. Since PTCA-COF has a good adsorption effect on Cu3(HHTP)2, the combination of the two forms a fluorescence resonance, resulting in a significant enhancement of luminescence intensity. When trace amounts of 2-chlorodiazepam are present, the binding force between 2-chlorodiazepam and Cu3(HHTP)2 is stronger than that between Cu3(HHTP)2 and PTCA-COF, disrupting the fluorescence resonance of Cu3(HHTP)2 / PTCA-COF and significantly reducing the ECL signal of Cu3(HHTP)2 / PTCA-COF. Therefore, this method achieves sensitive detection of 2-chlorodiazepam with high specificity and is unaffected by other impurities. Furthermore, the quenching value (ΔECL) of the ECL signal of the Cu3(HHTP)2 / PTCA-COF sensor system showed a good linear relationship with the concentration of 2-chlorodiazepam.

[0011] Furthermore, the method for preparing the electrochemiluminescence sensor for detecting the benzodiazepine drug 2-chlorodiazepam provided by the present invention includes the following steps:

[0012] S1. Disperse PTCA-COF in DMF and sonicate it to make it uniformly dispersed to obtain a DMF dispersion of PTCA-COF;

[0013] S2. Disperse Cu3(HHTP)2 in DMF and sonicate it to make it uniformly dispersed to obtain a DMF dispersion of Cu3(HHTP)2.

[0014] S3. The DMF dispersion obtained in steps S1 and S2 is drop-coated onto the surface of the pretreated glassy carbon electrode and allowed to air dry naturally to obtain a glassy carbon electrode modified with Cu3(HHTP)2 / PTCA-COF composite material.

[0015] Furthermore, in step S3, the mass ratio of the DMF dispersion of PTCA-COF to the DMF dispersion of Cu3(HHTP)2 is 1:2.

[0016] Furthermore, the molar concentration of the DMF dispersion in both steps S1 and S2 is 0.5 mg / ml.

[0017] Furthermore, PTCA-COF is prepared by the following method: melamine and perylene-3,4,9,10-tetracarboxylic acid dianhydride are mixed and ground to obtain a mixture; the mixture is calcined, washed and dried.

[0018] Furthermore, the preparation method of Cu3(HHTP)2 is as follows: (Cu2(OAc)4•H2O) and HHTP are dissolved in water and ultrasonically dispersed evenly; DMF is added to it, ultrasonically dispersed evenly, and then a hydrothermal synthesis reaction is carried out. After the reaction is completed, the mixture is filtered, washed, and dried.

[0019] Furthermore, the hydrothermal synthesis was carried out at a heating temperature of 80°C for 6 hours.

[0020] The second objective of this invention is to provide a detection method for the benzodiazepine drug 2-chlorodiazepam using the electrochemiluminescence sensor provided by this invention. By utilizing the quenching mechanism of the ECL signal intensity of 2-chlorodiazepam in this system, sensitive detection of 2-chlorodiazepam is successfully achieved. This sensing platform can specifically identify the analyte 2-chlorodiazepam and has high selectivity.

[0021] The above-mentioned technical objective of the present invention is achieved by the following technical solution:

[0022] The present invention provides a detection method for benzodiazepine drug 2-chlorodiazepam using an electrochemiluminescence sensor. The method consists of a three-electrode system with an electrochemiluminescence sensor as the working electrode, Ag / AgCl as the reference electrode, and a platinum wire electrode as the counter electrode. Detection is achieved by generating an electrochemiluminescence signal.

[0023] Specifically, the detection method includes the following steps:

[0024] A1. Prepare a PBS buffer solution for K2S2O8;

[0025] A2. Prepare standard solutions of 2-chlorodiazepam at different concentrations, ranging from 1.0 × 10⁻⁶. -13 ~1.0×10 -8 g / L;

[0026] A3. Using the working electrode, reference electrode, and counter electrode platinum electrode obtained by reacting the 2-chlorodiazepam standard solutions of different concentrations obtained in step A2 with Cu3(HHTP)2 / PTCA-COF / GCE respectively, a three-electrode system was formed and cyclic voltammetry was performed on the electrolyte prepared in step A1. The luminescence intensity-time curve was recorded, and a linear relationship between the luminescence intensity difference ΔECL and the logarithm of the 2-chlorodiazepam concentration was established to obtain the corresponding linear regression equation.

[0027] A4. The sample to be tested is detected using the method in step A3 to obtain the luminescence intensity. The luminescence intensity is then substituted into the linear regression equation obtained in step A3 to calculate the concentration of 2-chlorodiazepam in the sample to be tested.

[0028] Furthermore, the cyclic voltammetric scan in step A3 is performed within an electrochemical window of -1.6 to 0 V, with a photomultiplier tube voltage of 800 V and a scan rate of 0.1 V / s.

[0029] Furthermore, in step A3, the amount of 2-chlorodiazepam standard solution used is 5 μL, and the reaction time is 30 min.

[0030] In summary, the present invention has the following beneficial effects:

[0031] This invention designs an electrochemiluminescence sensor (Cu3(HHTP)2 / PTCA-COF / GCE) based on a perylene-bonded organic framework PTCA-COF and a two-dimensional conductive metal-organic framework Cu3(HHTP)2 composite material. The two are combined through adsorption to obtain stable electrochemiluminescence performance. By utilizing the quenching mechanism of 2-chlorodiazepam on the ECL signal intensity of this system, sensitive detection of 2-chlorodiazepam is achieved. This sensing platform can specifically identify the analyte 2-chlorodiazepam, exhibiting high selectivity, and is simple to operate, with good selectivity, low detection cost, and high sensitivity.

[0032] The detection range of this invention is 1.0 × 10⁻⁶. -13 ~1.0×10 -8 g / L, the limit of detection is 2.6×10 g / L. -14 The concentration of g / L is of great significance for promoting the practical application of electrochemiluminescence sensors in the detection of new psychoactive substances. Attached Figure Description

[0033] Figure 1 A simplified flowchart illustrating the preparation of the electrochemiluminescence sensor in this invention and its detection of 2-chlorodiazepam;

[0034] Figure 2 The image shows the ECL response of the electrochemiluminescence sensor constructed in Example 1 after binding with different concentrations of 2-chlorodiazepam.

[0035] Figure 3 The standard curve of the difference in luminescence intensity (ΔECL) before and after the addition of 2-chlorodiazepam in Example 1 versus the logarithm of the 2-chlorodiazepam concentration is shown.

[0036] Figure 4 This is a scanning electron microscope image of the Cu3(HHTP)2 / PTCA-COF composite material prepared in Example 1. Detailed Implementation

[0037] To further illustrate the technical means and effects adopted by the present invention to achieve the intended purpose, the preparation method and application method of an electrochemiluminescence sensor for detecting the benzodiazepine drug 2-chlorodiazepam, based on the present invention, are described in detail below, including its specific implementation method, features, and effects.

[0038] In this specific embodiment, the preparation method of 2-chlorodiazepam standard solutions of different concentrations is as follows: prepare a 2-chlorodiazepam solution, and then dilute it with anhydrous ethanol to obtain a series of 2-chlorodiazepam standard solutions of different concentrations. In this embodiment, the concentration of 2-chlorodiazepam in the 2-chlorodiazepam standard solutions is (a) 1.0 × 10⁻⁶. -8 g / L; (b) 1.0×10 -9 g / L; (c) 1.0×10 -10 g / L; (d) 1.0×10 -11 g / L; (e) 1.0 × 10 -12 g / L; (f) 1.0×10 -13 g / L.

[0039] Example 1: Preparation and application method of an electrochemiluminescence sensor for detecting the benzodiazepine drug 2-chlorodiazepam.

[0040] Fabrication of electrochemiluminescence sensors:

[0041] Preparation of S1 and PTCA-COF:

[0042] 0.63 g of melamine and 1.96 g of perylene-3,4,9,10-tetracarboxylic acid dianhydride were mixed and ground in an agate mortar for 0.5 hours. Next, the synthesized mixture was transferred from the agate mortar to an alumina crucible and calcined at 325 °C with a heating rate of 5 °C / min. It was then cooled to room temperature and washed with deionized water. The resulting PTCA-COF material was dried overnight at 80 °C for further use.

[0043] Preparation of S2 and Cu3(HHTP)2 materials:

[0044] 39 mg of copper acetate hydrate (Cu2(OAc)4·H2O) and 35 mg of HHTP (2,3,6,7,10,11-hexahydroxytriphenylene) were dissolved in 7.5 mL of water and sonicated for 5 minutes. Then, 0.75 mL of DMF was added dropwise to the mixture, followed by sonication for 5 minutes. The solution was then transferred to a reaction vessel and heated at 80 °C for 6 hours. The resulting blue powder was centrifuged and washed twice, once in water, once in ethanol, and once in acetone, to obtain Cu3(HHTP)2.

[0045] S3. Prepare a 0.5 mg / mL DMF dispersion from the PTCA-COF; prepare a 0.5 mg / mL DMF dispersion from the Cu3(HHTP)2.

[0046] S4. After polishing the glassy carbon electrode to a mirror finish on chamois leather with polishing powder (Al2O3), it is ultrasonically cleaned sequentially with nitric acid solution, ethanol solution, and ultrapure water, and then dried at room temperature to obtain the pretreated glassy carbon electrode. Using a microsyringe, 2 μL of a 0.5 mg / mL PTCA-COF DMF dispersion is sequentially transferred and allowed to air dry. Then, 4 μL of a 0.5 mg / mL Cu3(HHTP)2 DMF dispersion is dropped onto the electrode and allowed to air dry again to obtain the Cu3(HHTP)2 / PTCA-COF modified glassy carbon electrode. The Cu3(HHTP)2 / PTCA-COF / GCE electrode serves as the sensing element for electrochemiluminescence testing.

[0047] A method for detecting 2-chlorodiazepam based on a Cu3(HHTP)2 / PTCA-COF / GCE sensor

[0048] A1. Drawing the standard curve

[0049] Equal amounts of standard solutions of 2-chlorodiazepam at different concentrations were modified onto the aforementioned electrochemiluminescence sensor and reacted for the same amount of time to allow the sensor to bind 2-chlorodiazepam. A three-electrode system was then constructed using 2-chlorodiazepam / Cu3(HHTP)2 / PTCA-COF / GCE as the working electrode, Ag / AgCl as the reference electrode, and a platinum electrode as the counter electrode. A PBS buffer solution containing 0.1 mol / L K2S2O8 at pH 7.4 was used as the electrolyte. Electrolysis was performed within an electrochemical window of -1.6 to 0 V, with a photomultiplier tube voltage of 800 V and a scan rate of 0.1 V. Cyclic voltammetry scans were performed at V / s, and the luminescence intensity-time curve was recorded. A linear relationship was established between the difference in luminescence intensity (ΔECL) before and after the electrochemiluminescence sensor binds to 2-chlorodiazepam and the logarithm of the concentration of 2-chlorodiazepam in the 2-chlorodiazepam standard solution, yielding the corresponding linear regression equation: ΔECL = 15620.44 + 1048.49LogC (g / L), with a detection range of 1.0 × 10⁻⁶. -13 ~1.0×10 -8 g / L, detection limit is 2.6×10 g / L. -14 g / L;

[0050] A2. Sample Detection

[0051] Take 50 μL of the smoke liquid of the sample to be tested and put it into 200 μL of ethanol to obtain a diluent. Dilute the diluent into several equal portions. Add 2-chlorodiazepam standard solutions of different concentrations to the above diluent. After the reaction is complete, centrifuge at 3000 rpm for 5 min and collect the supernatant. Take 5 μL of the supernatant to modify the surface of Cu3(HHTP)2 / PTCA-COF / GCE electrochemiluminescence sensor. Calculate the concentration of 2-chlorodiazepam in the sample to be tested according to the linear regression equation obtained in step A1. The results are listed in Table 1.

[0052] In this embodiment, PTCA-COF is used as the substrate material, and a composite material is obtained by secondary drop-coating of Cu3(HHTP)2, with the morphology as shown in the figure. Figure 4 The two can be stably bound through adsorption interactions, thereby enhancing the electrochemiluminescence stability of the PTCA-COF monomer.

[0053] Furthermore, Cu3(HHTP)2 can significantly enhance the electrochemiluminescence intensity of the material alone, enabling the detection of 2-chlorodiazepam. When trace amounts of 2-chlorodiazepam are present, the interaction between PTCA-COF and 2-chlorodiazepam increases the ECL intensity value, achieving quantitative detection of 2-chlorodiazepam. This sensor exhibits good conductivity, stability, and selectivity. Compared to other detection methods, this method also has a wider detection range and a lower detection limit, enabling trace detection of 2-chlorodiazepam.

[0054] Comparative Example 1

[0055] Fabrication of PTCA-COF / GCE sensor

[0056] Using a microsyringe, 2 μL of the PTCA-COF DMF dispersion prepared in Example 1 was transferred onto the surface of a pretreated glassy carbon electrode (pretreatment method as in Example 1) to obtain a PTCA-COF / GCE chemically modified electrode. After air drying, a PTCA-COF / GCE sensor was obtained, which can be used as a sensing element for electrochemiluminescence testing.

[0057] A method for detecting 2-chlorodiazepam based on a PTCA-COF / GCE sensor

[0058] A1. Drawing the standard curve

[0059] Using the PTCA-COF / GCE sensor prepared above as the sensing element, equal amounts of 2-chlorodiazepam standard solutions of different concentrations were modified on the sensor surface and reacted for 30 min. This sensor was then used as the working electrode, with Ag / AgCl as the reference electrode and a platinum electrode as the counter electrode, forming a three-electrode system. The luminescence intensity was measured using 0.1 mol / L PBS buffer (pH 7.4) containing 0.1 mol / L K₂S₂O₈ as the electrolyte. Cyclic voltammetry was performed within the electrochemical window of -1.6 to 0 V, with a photomultiplier tube voltage of 800 V and a scan rate of 0.1 V / s. The luminescence intensity-time curve was recorded, and a linear relationship was established between the difference in luminescence intensity before and after binding to 2-chlorodiazepam and the logarithm of the 2-chlorodiazepam concentration in the standard solution. The corresponding linear regression equation was obtained.

[0060] A2. Sample Detection

[0061] Take 50 μL of the sample liquid to be tested and put it into 200 μL of ethanol to obtain a diluent. Dilute the diluent into several equal portions. Add 2-chlorodiazepam standard solutions of different concentrations to the above diluent. After the reaction is complete, centrifuge at 3000 rpm for 5 min and collect the supernatant. Take 5 μL of the supernatant and modify the surface of the PTCA-COF / GCE electrochemiluminescence sensor. Calculate the concentration of 2-chlorodiazepam in the sample to be tested according to the linear regression equation obtained in step A1. The results are listed in Table 1.

[0062] Comparative Example 2:

[0063] Fabrication of Cu3(HHTP)2 / GCE sensor

[0064] 4 μL of the DMF dispersion of Cu3(HHTP)2 prepared in Example 1 was transferred using a microsyringe and dropped onto the surface of a pretreated glassy carbon electrode (pretreatment method is the same as in Example 1) to obtain a Cu3(HHTP)2 / GCE chemically modified electrode. After natural drying, a Cu3(HHTP)2 / GCE sensor was obtained as a sensing element for electrochemiluminescence testing.

[0065] A method for detecting 2-chlorodiazepam based on a Cu3(HHTP)2 / GCE sensor

[0066] A1. Drawing the standard curve

[0067] Using the Cu3(HHTP)2 / GCE sensor prepared above as the sensing element, equal amounts of 2-chlorodiazepam standard solutions of different concentrations were modified on the sensor surface and reacted for 30 min. This sensor was then used as the working electrode, with Ag / AgCl as the reference electrode and a platinum electrode as the counter electrode, forming a three-electrode system. The luminescence intensity was measured using 0.1 mol / L PBS buffer (pH 7.4) containing 0.1 mol / L K2S2O8 as the electrolyte. Cyclic voltammetry was performed within the electrochemical window of -1.6 to 0 V, with a photomultiplier tube voltage of 800 V and a scan rate of 0.1 V / s. The luminescence intensity-time curve was recorded, and a linear relationship was established between the difference in luminescence intensity before and after binding to 2-chlorodiazepam and the logarithm of the 2-chlorodiazepam concentration in the standard solution. The corresponding linear regression equation was obtained.

[0068] A2. Sample Detection

[0069] Take 50 μL of the sample's liquid and dissolve it in 200 μL of ethanol to obtain a diluent. Dilute the diluent in several equal portions. Add 2-chlorodiazepam standard solutions of different concentrations to the diluent, and after sufficient reaction, centrifuge at 3000 rpm for 5 min. Collect the supernatant. Take 5 μL of the supernatant and modify it on the surface of the Cu3(HHTP)2 / GCE electrochemiluminescence sensor. Calculate the concentration of 2-chlorodiazepam in the sample using the linear regression equation obtained in step A1. The results are listed in Table 1.

[0070] Table 1. Measurement results of the samples to be tested

[0071]

[0072] Remark: The average of three measurements

[0073] In this specific embodiment, the e-cigarette liquid diluent used in the test sample was taken from the same batch of e-cigarette liquid, and its composition and other properties were completely consistent.

[0074] As shown in Table 1, the samples were measured in parallel three times, and the spiked recoveries ranged from 95% to 102%, with a relative standard deviation of less than 5%, indicating good recovery performance. The above experimental results demonstrate that 2-chlorodiazepam cannot be detected by assembling a sensing element after modifying a glassy carbon electrode with PTCA-COF or Cu3(HHTP)2 alone without modification using the PTCA-COF / Cu3(HHTP)2 composite material. Therefore, the sensor of this invention can be used to detect 2-chlorodiazepam in electronic cigarettes.

[0075] Based on the above verification, this invention demonstrates a novel method for the rapid and sensitive detection of 2-chlorodiazepam, utilizing the electrochemiluminescence quenching effect of 2-chlorodiazepam on the Cu3(HHTP)2 / PTCA-COF / GCE system. Due to the excellent adsorption capacity of PTCA-COF for Cu3(HHTP)2, the ECL signal of Cu3(HHTP)2 / PTCA-COF significantly decreases in the presence of trace amounts of 2-chlorodiazepam.

[0076] Furthermore, the quenching value (ΔECL) of the ECL signal in the Cu3(HHTP)2 / PTCA-COF sensor system exhibits a good linear relationship with the concentration of 2-chlorodiazepam. The electrochemiluminescence method used in this invention not only possesses advantages such as high sensitivity, good reproducibility, good selectivity, and a wide linear range, but also has great application potential for the quantitative analysis of 2-chlorodiazepam in e-cigarettes. It is one of the ideal methods for the rapid quantitative analysis of the novel benzodiazepine drug 2-chlorodiazepam in e-cigarettes.

[0077] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Although the present invention has been shown above with reference to preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some modifications or alterations to the above-disclosed technical content to create equivalent embodiments without departing from the scope of the present invention. Any simple modifications, equivalent changes, and alterations made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the scope of the present invention.

Claims

1. A method for preparing an electrochemiluminescence sensor for detecting benzodiazepine designer drug 2-chlorodiazepam, characterized by, The electrochemiluminescence sensor is obtained by modifying the surface of a glassy carbon electrode with a Cu3(HHTP)2 / PTCA-COF composite material. The Cu3(HHTP)2 / PTCA-COF composite material modification is formed by the adsorption of PTCA-COF to Cu3(HHTP)2.

2. The method for preparing an electrochemiluminescence sensor for detecting benzodiazepine 2-chlordiazepoxide according to claim 1, characterized in that, The method comprises the following steps: S1, dispersing PTCA-COF in DMF, and ultrasonically dispersing the PTCA-COF to obtain a DMF dispersion of PTCA-COF; S2, dispersing Cu3(HHTP)2 in DMF, and ultrasonically dispersing the Cu3(HHTP)2 to obtain a DMF dispersion of Cu3(HHTP)2; S3, dropping the two dispersions obtained in steps S1 and S2 on the surface of a pretreated glassy carbon electrode, and naturally air-drying to obtain a Cu3(HHTP)2 / PTCA-COF composite material modified glassy carbon electrode.

3. The method for preparing an electrochemiluminescence sensor for detecting benzodiazepine 2-chlordiazepoxide according to claim 2, characterized in that, In step S3, the mass ratio of the DMF dispersion of PTCA-COF to the DMF dispersion of Cu3(HHTP)2 is 1:

2.

4. The method for preparing an electrochemiluminescence sensor for detecting benzodiazepine designer drug 2-chlordiazepoxide according to claim 2, characterized in that, The molar concentration of the DMF dispersions in steps S1 and S2 is 0.5 mg / ml.

5. The method for preparing an electrochemiluminescence sensor for detecting benzodiazepine designer drug 2-chlordiazepoxide according to claim 2, characterized in that, The PTCA-COF is prepared by the following method: mixing and grinding melamine and perylene-3,4,9,10-tetracarboxylic dianhydride to obtain a mixture; calcining the mixture, and washing and drying.

6. The method for preparing an electrochemiluminescence sensor for detecting benzodiazepine designer drug 2-chlordiazepoxide according to claim 2, characterized in that, The Cu3(HHTP)2 is prepared by the following method: dissolving (Cu2(OAc)4·H2O) and HHTP in water, and ultrasonically dispersing the mixture; adding DMF, ultrasonically dispersing the mixture, and then performing a hydrothermal synthesis reaction; after the reaction is completed, filtering, washing, and drying.

7. The method for detecting 2-chlordiazepoxide, a benzodiazepine drug, by using the electrochemiluminescence sensor prepared according to the method of any one of claims 1 to 6, characterized by, The electrochemiluminescence sensor is used as a working electrode, Ag / AgCl is used as a reference electrode, and a platinum wire electrode is used as a counter electrode to form a three-electrode system, and the detection is completed through the generated electrochemiluminescence signal.

8. The method for detecting the electrochemiluminescence sensor for detecting benzodiazepine 2-chlordiazepoxide according to claim 7, characterized in that, The method comprises the following steps: A1, preparing a K2S2O8 PBS buffer solution; A2, 2-chlorodiazepam standard solution of different concentrations was prepared, with a concentration range of 1.0 x 10 -13 ~ 1.0 x 10 -8 g / L; A3, using different concentrations of 2-chlordiazepoxide standard solution in step A2 to react with the working electrode obtained after the reaction of Cu3(HHTP)2 / PTCA-COF / GCE, the reference electrode, and the counter electrode platinum electrode, and then performing cyclic voltammetry scanning on the electrolyte prepared in step A1 to record the luminescence intensity-time curve, and establishing a linear relationship between the luminescence intensity difference ΔECL and the logarithmic value of the 2-chlordiazepoxide concentration to obtain a corresponding linear regression equation; A4, detecting the sample to be tested by the method in step A3, obtaining the luminescence intensity, and substituting the luminescence intensity into the linear regression equation obtained in step A3 to calculate the concentration of 2-chlordiazepoxide in the sample to be tested.

9. The method for detecting the electrochemiluminescence sensor for detecting benzodiazepine 2-chlordiazepoxide according to claim 8, characterized in that, The cyclic voltammetry scanning in step A3 is performed in an electrochemical window range of -1.6-0 V, the photomultiplier high voltage is 800 V, and the scanning speed is 0.1 V / s.

10. The method of claim 7, wherein the electrochemiluminescent sensor for detecting the benzodiazepine designer drug 2-chlorodeschlorisone is characterized by, The amount of 2-chlordiazepoxide standard solution used in step A3 is 5 μL, and the reaction time is 30 min.

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