Lanthanide metal organic framework reagent for detecting sarin and simulant diethyl chlorophosphate thereof

Abstract

The invention provides a lanthanide metal organic framework reagent for detecting sarin and a simulant diethyl chlorophosphate thereof, and the reagent is composed of a lanthanide metal organic framework material and a solvent N, N-dimethylformamide. The reagent has a ratiometric fluorescence detection function on sarin and a simulant diethyl chlorophosphate, under excitation of 365 nm ultraviolet light, the reagent itself is red fluorescence and turns blue fluorescence after contacting with sarin and a simulant diethyl chlorophosphate, the response time is less than 5 s, and the fluorescence detection limit can reach 95.2 nM. Interference exists when diethyl chlorophosphate and hydrochloric acid are detected in a fluorescence mode, diethyl chlorophosphate and hydrochloric acid can be distinguished through fluorescence colors and fluorescence spectra, and the accuracy and reliability of diethyl chlorophosphate detection are improved. The trace sarin and the simulant diethyl chlorophosphate thereof are detected and analyzed, and the method has the advantages of simplicity in operation, high response speed, high sensitivity, good selectivity, convenience in carrying and the like. And an effective technical support is provided for the detection of trace nerve toxic agents in an actual environment.

Description

Technical Field

[0001] The invention belongs to the field of analysis and detection, and provides a lanthanide metal organic framework reagent for on-site detection of sarin and its simulant diethyl chlorophosphate. Background Art

[0002] Nerve agents refer to toxic chemicals that destroy the normal conduction function of the nervous system. They enter the human body through the respiratory tract, skin and other pathways, inhibit the activity of cholinesterase, and destroy the conduction of nerve impulses. They can cause death within minutes, seriously endangering public and national security. The most representative nerve agents are tabun, sarin, soman and veix, which can be loaded into a variety of ammunition and missiles for use. They are listed as chemical weapons in the first list of the Chemical Weapons Convention 2005. Since sarin nerve agents are highly toxic and extremely harmful, simulants such as diethyl chlorophosphate, which have a chemical structure similar to nerve agents but are less toxic, are usually used to test material properties.

[0003] At present, a variety of detection methods for sarin and its analogue diethyl chlorophosphate have been developed, including mass spectrometry, ion mobility chromatography, bio-enzyme sensors, etc. However, due to its time-consuming, cumbersome, low sensitivity and poor mobility of the equipment, it is not suitable for on-site detection. In contrast, fluorescence detection technology has attracted widespread attention due to its high sensitivity, fast reaction speed, strong specificity, visualization of detection signals and simple operation. Currently, most reports on the detection of sarin and its analogue diethyl chlorophosphate based on fluorescence signals are small molecule luminescence systems. Organic small molecule fluorescent probes with hydroxyl, pyridine, amino or oxime groups as recognition sites can react with sarin and its analogue diethyl chlorophosphate to form protonation or phosphorylation by nucleophilic reaction, thereby changing the processes of photoinduced electron transfer, intramolecular electron transfer or excited state proton transfer, and then realizing fluorescence detection. However, in terms of sensitivity and selectivity, especially the distinction between diethyl chlorophosphate and common interference hydrochloric acid, there are still difficulties.

[0004] Metal-Organic Frameworks (MOF) are a new type of porous material with high porosity and specific surface area. Structurally, MOF materials with diverse functionalities can be prepared by selecting and regulating organic ligands and metal nodes. Lanthanide MOF (Ln-MOF) combines the advantages of lanthanide metals, has excellent luminescence properties and long fluorescence lifetime, and has broad application prospects in the field of fluorescent sensors. However, there are few reports on the detection of diethyl chlorophosphate based on MOF fluorescent sensors. Therefore, it is of great significance to develop a fluorescent sensor based on Ln-MOF materials to detect sarin and its simulant diethyl chlorophosphate, so as to achieve low-cost, high-sensitivity and high-selectivity detection of sarin and its simulant diethyl chlorophosphate. Summary of the invention

[0005] The present invention aims to provide a lanthanide metal organic framework reagent for detecting sarin and its simulant diethyl chlorophosphate, which is composed of a lanthanide metal organic framework material and a solvent N,N-dimethylformamide. The reagent has a ratio fluorescence detection function for sarin and its simulant diethyl chlorophosphate. Under 365nm ultraviolet light excitation, the reagent itself is red fluorescence, and after contacting with sarin and its simulant diethyl chlorophosphate, it becomes blue fluorescence, the response time is less than 5s, and the fluorescence detection limit can reach 95.2nM. There is interference when detecting diethyl chlorophosphate and hydrochloric acid in the fluorescence mode, and diethyl chlorophosphate and hydrochloric acid can be distinguished by fluorescence color and fluorescence spectrum, thereby improving the accuracy and reliability of diethyl chlorophosphate detection. In the process of detecting sarin and its simulant diethyl chlorophosphate, no complicated analytical equipment is required, and the detection and analysis of trace sarin and its simulant diethyl chlorophosphate are realized, which has the advantages of simple operation, fast response speed, high sensitivity, good selectivity and easy carrying. It provides effective technical support for the detection of trace nerve agents in actual environments.

[0006] The lanthanide metal organic framework reagent for detecting sarin and its simulant diethyl chlorophosphate described in the present invention is composed of a carbazole-based lanthanide metal organic framework material and a solvent N,N-dimethylformamide. The specific operation is carried out according to the following steps:

[0007] Prepare reagents:

[0008] a. Dissolve 1,3,6,8-tetrabenzoic acid-carbazole, europium nitrate and o-fluorobenzoic acid in N,N-dimethylformamide, dissolve by ultrasonication, transfer the mixed solution to a reactor, heat to 120°C and react for 48 hours. After the reaction, obtain a white solid powder;

[0009] b. Wash the white solid powder obtained in step a with N,N-dimethylformamide, centrifuge, and dry to obtain a white solid powder;

[0010] c. Dissolve the white solid powder obtained in step b in N,N-dimethylformyl, perform ultrasound until the white solid powder is evenly dispersed, and then add N,N-dimethylformyl to dilute to 0.005 mg / mL to obtain a carbazole-based lanthanide metal organic framework reagent;

[0011] Prepare the test solution:

[0012] d. Dissolve diethyl chlorophosphate, a simulant of the nerve agent sarin, in N,N-dimethylformamide to obtain a standard solution of diethyl chlorophosphate with a concentration of 0.03 M;

[0013] Fluorescence detection of sarin and diethyl chlorophosphate:

[0014] e. Add the carbazole-based lanthanide metal organic framework reagent obtained in step c into a test bottle, and then add diethyl chlorophosphate, a nerve agent sarin simulant prepared in step d. Under the excitation of 365nm ultraviolet light, the fluorescence color changes from red to blue within 5s. When the concentration of diethyl chlorophosphate is 100-300μM, the emission intensity at 433nm has a good linear relationship with the concentration of diethyl chlorophosphate, and the detection limit is 95.2nM. There is interference when detecting diethyl chlorophosphate and hydrochloric acid in the fluorescence mode. Diethyl chlorophosphate and hydrochloric acid are distinguished by fluorescence color or fluorescence spectrum.

[0015] The invention discloses a lanthanide metal organic framework reagent for detecting sarin and its analog diethyl chlorophosphate. The reagent is composed of a carbazole-based lanthanide metal organic framework material and a solvent, N,N-dimethylformamide. (1) The lanthanide metal europium is used as the metal node due to its advantages such as bright visible light emission, large Stokes shift and long lifetime, so that a multi-emission ratiometric fluorescent MOF sensing material can be constructed; (2) 1,3,6,8-tetrabenzoic acid-carbazole is used as the organic ligand because it can act as an "antenna" to absorb photons and sensitize the lanthanide metal europium, thereby making the carbazole-based lanthanide metal organic framework material ratiometric fluorescent sensing reagent emit red fluorescence. In addition, the NH group in the carbazole molecule of the ligand can serve as a recognition site for sarin and diethyl chlorophosphate. At the same time, the ligand has a twisted geometry and four non-coplanar benzene rings, which can provide just the right space for the free diffusion of sarin / diethyl chlorophosphate in the carbazole-based lanthanide metal organic framework material ratiometric fluorescent sensing reagent and inhibit the free rotation of the benzene ring, thereby enhancing the ligand blue light emission; (3) The pore size of the carbazole-based lanthanide metal organic framework material is Its pore size is larger than that of Sarin and diethyl chlorophosphate The van der Waals diameter of the molecule is conducive to the diffusion of sarin / diethyl chlorophosphate molecules into it, and then the specific recognition of sarin / diethyl chlorophosphate is achieved through non-covalent bonds; (4) N,N-dimethylformamide is selected as the solvent because the coordination mode of Eu6 clusters in the carbazole-based lanthanide metal-organic framework material is eight-coordinated and has unsaturated metal sites, which can coordinate with N,N-dimethylformamide solvent molecules, further inhibiting the Eu6 clusters from diffusing into the interior of the lanthanide metal-organic framework. 3+ The molecular vibration of the clusters reduces the energy dissipation of non-radiative transitions and leads to bright red emission. Compared with other solvents, the fluorescence emission in N,N-dimethylformamide is the strongest, and the effect of detecting sarin / diethyl chlorophosphate is the best. Therefore, for the first time, the ratiometric fluorescence detection of sarin and diethyl chlorophosphate was realized using a rotationally suppressed emission lanthanide metal organic framework material.

[0016] The invention discloses a lanthanide metal organic framework reagent for detecting sarin and its simulant diethyl chlorophosphate. The reagent has the characteristics of rapid response, high sensitivity and high selectivity. After adding sarin and its simulant diethyl chlorophosphate, the reagent immediately produces a fluorescence change from red to blue under the excitation of 365nm ultraviolet light, the response time is less than 5s, and the reagent has good selectivity. When diethyl chlorophosphate and hydrochloric acid are detected in a fluorescence mode, interference exists, diethyl chlorophosphate and hydrochloric acid can be distinguished by fluorescence color and fluorescence spectrum, and the accuracy and reliability of diethyl chlorophosphate detection are improved.

[0017] The invention discloses a lanthanide metal organic framework reagent for detecting sarin and its analogue diethyl chlorophosphate. The detection principle of the reagent is as follows: the carbazole NH group in the 1,3,6,8-tetrabenzoic acid-carbazole ligand can form an O...H hydrogen bond interaction with the P=O group in the diethyl chlorophosphate molecule, and at the same time, the H atom of the ligand benzene ring can form a Cl...H van der Waals force with the P-Cl group in the diethyl chlorophosphate molecule. Based on these non-covalent weak interaction forces, the diethyl chlorophosphate molecule can effectively restrict the rotation of the benzene ring in the 1,3,6,8-tetrabenzoic acid-carbazole ligand, thereby reducing the non-radiative transition pathway and enhancing the fluorescence emission of the ligand. Under the excitation of 365nm ultraviolet light, the fluorescence color changes from red to blue, and finally realizes the ratio fluorescence detection of diethyl chlorophosphate. The system has the characteristics of strong specificity, high sensitivity, fast reaction speed, simple operation, and is conducive to popularization and application.

[0018] The rapid, ultrasensitive and highly selective ratiometric fluorescent reagent for detecting diethyl chlorophosphate described in the present invention is mainly used for detecting organophosphorus nerve agents, solving the current problem of being unable to accurately, rapidly, visually and ultrasensitively detect diethyl chlorophosphate.

[0019] A lanthanide metal organic framework reagent for detecting sarin and its analog diethyl chlorophosphate described in the present invention has a reagent effect. Under the excitation of 365nm ultraviolet light, its ratio fluorescence reagent itself is red fluorescence, and within 5s of contact with diethyl chlorophosphate, the fluorescence color changes from red to blue. The dual-mode reagent has high selectivity, is not interfered by common organic solvents (ethyl acetate, tetrahydrofuran, acetone, toluene, ether, methanol, ethanol, dichloromethane, chloroform), structural analogs (diethyl phosphite, dimethyl methylphosphonate, diisopropyl methyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, diethyl cyanophosphate) and acids (formic acid, acetic acid, propionic acid), and can effectively distinguish the interfering substance hydrochloric acid. In addition, this dual-mode reagent has an extremely low detection limit (the detection limit of the fluorescence mode is 95.2nM). The reagent provides an effective technical means for the field of optical detection.

[0020] The invention discloses a lanthanide metal organic framework reagent for detecting sarin and its simulant diethyl chlorophosphate. The reagent comprises the following steps: taking 3 mL of a carbazole-based lanthanide metal organic framework material ratio fluorescence detection reagent with a concentration of 0.005 mg / mL into a test bottle, respectively adding 5 μL, 10 μL, 15 μL, 20 μL, 25 μL, 30 μL, 35 μL and 40 μL of a diethyl chlorophosphate solution with a concentration of 0.03 M, scanning the emission spectrum with a fluorescence spectrometer, and measuring the emission spectrum after the carbazole-based lanthanide metal organic framework material ratio fluorescence detection reagent reacts with diethyl chlorophosphate of different concentrations; and fitting a linear equation with the fluorescence emission intensity at 433 nm as the ordinate and different diethyl chlorophosphate concentrations as the abscissa, thereby determining the fluorescence detection limit of the model detection system. The invention provides a rapid, ultra-sensitive and highly selective ratio fluorescence reagent for the analysis and detection of the nerve agent sarin and its simulant diethyl chlorophosphate. The reagent has the characteristics of high sensitivity, good selectivity and short response time for the detection of the nerve agent sarin and its simulant diethyl chlorophosphate, and can achieve low-cost and real-time detection of sarin and its simulant diethyl chlorophosphate through ratio fluorescence.

[0021] Compared with the prior art, the present invention has the following beneficial effects:

[0022] 1. A lanthanide metal organic framework reagent for detecting sarin and its analog diethyl chlorophosphate according to the present invention, which can achieve high-selective detection of diethyl chlorophosphate in a complex environment;

[0023] 2. A lanthanide metal organic framework reagent for detecting sarin and its analog diethyl chlorophosphate according to the present invention, which can effectively distinguish diethyl chlorophosphate from the interfering substance hydrochloric acid;

[0024] 3. A lanthanide metal organic framework reagent for detecting sarin and its analog diethyl chlorophosphate according to the present invention, wherein the reagent has a high sensitivity for detecting diethyl chlorophosphate by selecting a specific solvent, a detection limit as low as 95.2 nM, a fast detection speed, and can achieve detection in a fluorescence channel within 5 seconds;

[0025] 4. A lanthanide metal organic framework reagent for detecting sarin and its analog diethyl chlorophosphate, the reagent can be directly identified and detected by naked eyes without complicated analytical equipment;

[0026] 5. The lanthanide metal organic framework reagent for detecting sarin and its simulant diethyl chlorophosphate described in the present invention exhibits the same response effect to the real nerve agent sarin as diethyl chlorophosphate, and can fully achieve the purpose of low-cost fluorescence detection of the real nerve agent sarin. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 The van der Waals diameter diagram of sarin and diethyl chlorophosphate obtained by theoretical calculation, where the volume of sarin is 4.2 The volume of diethyl chlorophosphate is

[0028] Figure 2 The topological structure diagram of the carbazole-based lanthanide metal organic framework material of the present invention has a pore size of Its pore size is larger than that of Sarin and diethyl chlorophosphate The van der Waals diameter of the molecule indicates that the topological structure of the carbazole-based lanthanide metal-organic framework material is conducive to the diffusion of sarin / diethyl chlorophosphate molecules into it, and then achieves specific recognition of sarin / diethyl chlorophosphate through non-covalent bonds.

[0029] Figure 3 The figure is the fluorescence emission spectrum of the carbazole-based lanthanide metal-organic framework material of the present invention in N,N-dimethylformamide, tetrahydrofuran, ether, acetone, methanol, ethanol, acetonitrile, dichloromethane, cyclohexane and water. The inset is a fluorescence photograph under 365nm ultraviolet light, indicating that the carbazole-based lanthanide metal-organic framework material has the strongest fluorescence emission in N,N-dimethylformamide.

[0030] Figure 4 This is a phenomenon diagram of the ratio fluorescence reagent of the present invention detecting diethyl chlorophosphate, from left to right are fluorescence photos of the carbazole-based lanthanide metal organic framework material ratio fluorescence detection reagent reacting with 5μL, 10μL, 15μL, 20μL, 25μL, 30μL, 35μL and 40μL of 0.03M diethyl chlorophosphate solution under 365nm ultraviolet light;

[0031] Figure 5 The detection performance diagram in the fluorescence mode is shown after 3 mL of the carbazole-based lanthanide metal organic framework material ratio fluorescence detection reagent with a concentration of 0.005 mg / mL of the present invention reacts with 5 μL, 10 μL, 15 μL, 20 μL, 25 μL, 30 μL, 35 μL and 40 μL of 0.03 M diethyl chlorophosphate solution, wherein Figure 5 The left figure is the emission spectra after detecting different concentrations of diethyl chlorophosphate, and the right figure uses the concentration of diethyl chlorophosphate as the horizontal axis and the intensity of the fluorescence emission peak at 433nm as the vertical axis, and the linear equation obtained by fitting;

[0032] Figure 6This is an optical photograph in fluorescence mode after 3 mL of the carbazole-based lanthanide metal organic framework material ratio fluorescence detection reagent with a concentration of 0.005 mg / mL of the present invention reacts with 50 μL of ethyl acetate, tetrahydrofuran, acetone, toluene, ether, dichloromethane, chloroform, diethyl phosphite, dimethyl methylphosphonate, diisopropyl methyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, diethyl cyanophosphate, formic acid, acetic acid, and propionic acid with a concentration of 0.03 M;

[0033] Figure 7 A bar graph of the emission intensity at 433 nm in fluorescence mode after 3 mL of the carbazole-based lanthanide metal organic framework material ratio fluorescence detection reagent with a concentration of 0.005 mg / mL of the present invention reacts with 50 μL of ethyl acetate, tetrahydrofuran, acetone, toluene, ether, dichloromethane, chloroform, diethyl phosphite, dimethyl methylphosphonate, diisopropyl methyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, diethyl cyanophosphate, formic acid, acetic acid, and propionic acid with a concentration of 0.03 M;

[0034] Figure 8 An optical photograph in fluorescence mode after 3 mL of the carbazole-based lanthanide metal organic framework material ratio fluorescence detection reagent with a concentration of 0.005 mg / mL of the present invention reacts with 50 μL of diethyl chlorophosphate with a concentration of 0.03 M and 50 μL of a mixed solution of ethyl acetate, tetrahydrofuran, acetone, toluene, ether, dichloromethane, chloroform, diethyl phosphite, dimethyl methylphosphonate, diisopropyl methyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, diethyl cyanophosphate, formic acid, acetic acid, and propionic acid;

[0035] Fig. 9 A bar graph of the emission intensity at 433 nm in fluorescence mode after 3 mL of the carbazole-based lanthanide metal organic framework material ratio fluorescence detection reagent with a concentration of 0.005 mg / mL of the present invention reacts with 50 μL of diethyl chlorophosphate with a concentration of 0.03 M and 50 μL of a mixed solution of ethyl acetate, tetrahydrofuran, acetone, toluene, ether, dichloromethane, chloroform, diethyl phosphite, dimethyl methylphosphonate, diisopropyl methyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, diethyl cyanophosphate, formic acid, acetic acid, and propionic acid with a concentration of 0.03 M;

[0036] Fig.10 This is a detection performance diagram of the reaction of 3 mL of the carbazole-based lanthanide metal organic framework material ratio fluorescence detection reagent with a concentration of 0.005 mg / mL and 10 μL, 30 μL, 50 μL of 0.03 M diethyl chlorophosphate and 10 μL, 30 μL, 50 μL of 0.03 M hydrochloric acid in the fluorescence mode. Fig.10 The left picture is the emission spectrum of hydrochloric acid. Fig.10 The right figure is the emission spectrum of diethyl chlorophosphate;

[0037] Fig.11 In order to realize the distinction between diethyl chlorophosphate and hydrochloric acid, the present invention Fig.10 After the mesocarbazole-based lanthanide metal organic framework material reacted with different concentrations of diethyl chlorophosphate and hydrochloric acid, the fluorescence intensity at 433nm and 613nm was taken as logarithm, and then the principal component analysis diagram was obtained after data processing;

[0038] Fig.12 It is an emission spectrum diagram of the reaction of 3 mL of 0.005 mg / mL carbazole-based lanthanide metal-organic framework material ratio fluorescence detection reagent of the present invention with 100 μL of 0.05 M sarin in fluorescence mode, and the inset is an optical photograph of the reaction in fluorescence mode before and after. DETAILED DESCRIPTION

[0039] The present invention is further described below by means of specific examples, but the invention is not limited to these examples.

[0040] Example 1

[0041] Prepare reagents:

[0042] a. Dissolve 10 mg of 1,3,6,8-tetrabenzoic acid-carbazole, 15 mg of europium nitrate and 350 mg of o-fluorobenzoic acid in 3 mL of N,N-dimethylformamide. After ultrasonic dissolution, transfer the mixed solution to a 5 mL reactor and heat to 120 °C for 48 h. After the reaction, a white solid powder is obtained.

[0043] b. Wash the white solid powder obtained in step a with N,N-dimethylformamide, centrifuge, and dry at 50° C. for 12 h to obtain a white solid powder;

[0044] c. Dissolve 10 mg of the white solid powder obtained in step b in 20 mL of N,N-dimethylformamide to obtain a 0.5 mg / mL carbazole-based lanthanide metal organic framework material solution; perform ultrasound until the white solid powder is evenly dispersed, and then add N,N-dimethylformamide to dilute to 0.005 mg / mL to obtain a carbazole-based lanthanide metal organic framework material reagent;

[0045] d. Take 100 μL of the 0.5 mg / mL carbazole-based lanthanide metal organic framework material reagent obtained in step c, and add 2.9 mL of N,N-dimethylformamide, tetrahydrofuran, ether, acetone, methanol, ethanol, acetonitrile, dichloromethane, cyclohexane and water, respectively. Figure 3 As shown, the carbazole-based lanthanide metal-organic framework reagent has the strongest fluorescence emission in N,N-dimethylformamide.

[0046] Example 2

[0047] Prepare reagents:

[0048] a. Dissolve 10 mg of 1,3,6,8-tetrabenzoic acid-carbazole, 15 mg of europium nitrate and 350 mg of o-fluorobenzoic acid in 3 mL of N,N-dimethylformamide. After ultrasonic dissolution, transfer the mixed solution to a 5 mL reactor and heat to 120 °C for 48 h. After the reaction, a white solid powder is obtained.

[0049] b. Wash the white solid powder obtained in step a with N,N-dimethylformamide, centrifuge, and dry at 50° C. for 12 h to obtain a white solid powder;

[0050] c. Dissolve 10 mg of the white solid powder obtained in step b in 20 mL of N,N-dimethylformamide to obtain a 0.5 mg / mL carbazole-based lanthanide metal organic framework material solution, perform ultrasound until the white solid powder is evenly dispersed, and then add N,N-dimethylformamide to dilute to 0.005 mg / mL to obtain a carbazole-based lanthanide metal organic framework material reagent;

[0051] Prepare the test solution:

[0052] d. Take 18.3 μL of the nerve agent sarin simulant diethyl chlorophosphate and dissolve it in 3.98 mL of N,N-dimethylformamide to obtain a standard solution of diethyl chlorophosphate with a concentration of 0.03 M;

[0053] Fluorescence detection of the nerve agent sarin simulant diethyl chlorophosphate:

[0054] e. Add the carbazole-based lanthanide metal organic framework material ratio fluorescence detection reagent obtained in step c into the test bottle, and then add the nerve agent sarin simulant diethyl chlorophosphate prepared in step d. Figure 4 As shown, under the excitation of 365nm ultraviolet light, the fluorescence color changes from red to blue within 5s.

[0055] Example 3

[0056] Prepare reagents:

[0057] a. Dissolve 10 mg of 1,3,6,8-tetrabenzoic acid-carbazole, 15 mg of europium nitrate and 350 mg of o-fluorobenzoic acid in 3 mL of N,N-dimethylformamide. After ultrasonic dissolution, transfer the mixed solution to a 5 mL reactor and heat to 120 °C for 48 h. After the reaction, a white solid powder is obtained.

[0058] b. Wash the white solid powder obtained in step a with N,N-dimethylformamide, centrifuge, and dry at 50° C. for 12 h to obtain a white solid powder;

[0059] c. Dissolve 10 mg of the white solid powder obtained in step b in 20 mL of N,N-dimethylformamide to obtain a 0.5 mg / mL carbazole-based lanthanide metal organic framework material solution, perform ultrasound until the white solid powder is evenly dispersed, and then add N,N-dimethylformamide to dilute to 0.005 mg / mL to obtain a carbazole-based lanthanide metal organic framework material reagent;

[0060] Preparation of test solution

[0061] d. Take 18.3 μL of the nerve agent sarin simulant diethyl chlorophosphate and dissolve it in 3.98 mL of N,N-dimethylformamide to obtain a standard solution of diethyl chlorophosphate with a concentration of 0.03 M;

[0062] Fluorescence detection of the nerve agent sarin simulant diethyl chlorophosphate:

[0063] e. After reacting 3 mL of the 0.005 mg / mL carbazole-based lanthanide metal organic framework reagent obtained in step c with 5 μL, 10 μL, 15 μL, 20 μL, 25 μL, 30 μL, 35 μL and 40 μL of 0.03 M diethyl chlorophosphate solution, the emission spectrum was scanned on a fluorescence spectrometer to compare the emission spectra. Figure 5 It can be seen that the emission intensity at 433 nm is linearly related to the concentration of diethyl chlorophosphate, and the detection line reaches 95.2 nM.

[0064] Example 4

[0065] Prepare reagents:

[0066] a. Dissolve 10 mg of 1,3,6,8-tetrabenzoic acid-carbazole, 15 mg of europium nitrate and 350 mg of o-fluorobenzoic acid in 3 mL of N,N-dimethylformamide. After ultrasonic dissolution, transfer the mixed solution to a 5 mL reactor and heat to 120 °C for 48 h. After the reaction, a white solid powder is obtained.

[0067] b. Wash the white solid powder obtained in step a with N,N-dimethylformamide, centrifuge, and dry at 50° C. for 12 h to obtain a white solid powder;

[0068] c. Dissolve 10 mg of the white solid powder obtained in step b in 20 mL of N,N-dimethylformamide to obtain a 0.5 mg / mL carbazole-based lanthanide metal organic framework material solution, perform ultrasound until the white solid powder is evenly dispersed, and then add N,N-dimethylformamide to dilute to 0.005 mg / mL to obtain a carbazole-based lanthanide metal organic framework material reagent;

[0069] Preparation of test solution

[0070] d. Take 18.3 μL of the nerve agent sarin simulant diethyl chlorophosphate and dissolve it in 3.98 mL of N,N-dimethylformamide to obtain a standard solution of diethyl chlorophosphate with a concentration of 0.03 M;

[0071] Fluorescence detection of the nerve agent sarin simulant diethyl chlorophosphate:

[0072] e. After reacting 3 mL of the 0.005 mg / mL carbazole-based lanthanide metal organic framework reagent obtained in step c with 50 μL of 0.03 M ethyl acetate, tetrahydrofuran, acetone, toluene, ether, dichloromethane, chloroform, diethyl phosphite, dimethyl methylphosphonate, diisopropyl methyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, diethyl cyanophosphate, and formic acid, acetic acid, and propionic acid interferences, take photos with a smart phone, and then perform fluorescence spectrum testing. By comparing the color and fluorescence intensity of the photos in the fluorescence mode, the fluorescence intensity of the samples can be determined. Figure 6 and Figure 7 It can be seen that it has good selectivity.

[0073] Example 5

[0074] Prepare reagents:

[0075] a. Dissolve 10 mg of 1,3,6,8-tetrabenzoic acid-carbazole, 15 mg of europium nitrate and 350 mg of o-fluorobenzoic acid in 3 mL of N,N-dimethylformamide. After ultrasonic dissolution, transfer the mixed solution to a 5 mL reactor and heat to 120 °C for 48 h. After the reaction, a white solid powder is obtained.

[0076] b. Wash the white solid powder obtained in step a with N,N-dimethylformamide, centrifuge, and dry at 50° C. for 12 h to obtain a white solid powder;

[0077] c. Dissolve 10 mg of the white solid powder obtained in step b in 20 mL of N,N-dimethylformamide to obtain a 0.5 mg / mL carbazole-based lanthanide metal organic framework material solution, perform ultrasound until the white solid powder is evenly dispersed, and then add N,N-dimethylformamide to dilute to 0.005 mg / mL to obtain a carbazole-based lanthanide metal organic framework material reagent;

[0078] Preparation of test solution

[0079] d. Take 18.3 μL of the nerve agent sarin simulant diethyl chlorophosphate and dissolve it in 3.98 mL of N,N-dimethylformamide to obtain a standard solution of diethyl chlorophosphate with a concentration of 0.03 M;

[0080] Fluorescence detection of the nerve agent sarin simulant diethyl chlorophosphate:

[0081] After reacting 3 mL of the 0.005 mg / mL carbazole-based lanthanide metal organic framework reagent obtained in step c with 50 μL of 0.03 M diethyl chlorophosphate and 50 μL of a mixed solution of 0.03 M ethyl acetate, tetrahydrofuran, acetone, toluene, ether, dichloromethane, chloroform, diethyl phosphite, dimethyl methylphosphonate, diisopropyl methyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, diethyl cyanophosphate, formic acid, acetic acid, and propionic acid, a photo was taken with a smart phone, and then a fluorescence spectrum test was performed. By comparing the color and fluorescence intensity of the photos in the fluorescence mode, the fluorescence intensity of the photos was determined. Figure 8 and Fig. 9 It can be seen that it has good anti-interference ability.

[0082] Example 6

[0083] Prepare reagents:

[0084] a. Dissolve 10 mg of 1,3,6,8-tetrabenzoic acid-carbazole, 15 mg of europium nitrate and 350 mg of o-fluorobenzoic acid in 3 mL of N,N-dimethylformamide. After ultrasonic dissolution, transfer the mixed solution to a 5 mL reactor and heat to 120 °C for 48 h. After the reaction, a white solid powder is obtained.

[0085] b. Wash the white solid powder obtained in step a with N,N-dimethylformamide, centrifuge, and dry at 50° C. for 12 h to obtain a white solid powder;

[0086] c. Dissolve 10 mg of the white solid powder obtained in step b in 20 mL of N,N-dimethylformamide to obtain a 0.5 mg / mL carbazole-based lanthanide metal organic framework material solution, perform ultrasound until the white solid powder is evenly dispersed, and then add N,N-dimethylformamide to dilute to 0.005 mg / mL to obtain a carbazole-based lanthanide metal organic framework material reagent;

[0087] Preparation of test solution

[0088] d. Take 18.3 μL of the nerve agent sarin simulant diethyl chlorophosphate and dissolve it in 3.98 mL of N,N-dimethylformamide to obtain a standard solution of diethyl chlorophosphate with a concentration of 0.03 M;

[0089] Fluorescence detection of the nerve agent sarin simulant diethyl chlorophosphate:

[0090] After 3 mL of the 0.005 mg / mL carbazole-based lanthanide metal organic framework reagent obtained in step c reacted with 10 μL, 30 μL, and 50 μL of 0.03 M diethyl chlorophosphate and 10 μL, 30 μL, and 50 μL of 0.03 M hydrochloric acid, the emission spectrum was scanned on a fluorescence spectrometer. By comparing the reaction of the carbazole-based lanthanide metal organic framework material with different concentrations of diethyl chlorophosphate and hydrochloric acid, as shown in FIG. Fig.10 As shown in the figure, the principal component analysis of the fluorescence spectrum obtained by taking the logarithm of the fluorescence intensity at 433nm and 613nm Fig.11 It can be seen that different concentrations of diethyl chlorophosphate and hydrochloric acid are divided into separate clusters, and the diethyl chlorophosphate clusters and the hydrochloric acid clusters have a linear relationship, which shows that the ratio fluorescence detection reagent of carbazole-based lanthanide metal organic framework material can not only distinguish diethyl chlorophosphate from hydrochloric acid, but also preliminarily infer the approximate concentrations of diethyl chlorophosphate and hydrochloric acid through the positions of the clusters. Therefore, the ratio fluorescence detection reagent described in the present invention can effectively distinguish diethyl chlorophosphate from hydrochloric acid.

[0091] Example 7

[0092] Prepare reagents:

[0093] a. Dissolve 10 mg of 1,3,6,8-tetrabenzoic acid-carbazole, 15 mg of europium nitrate and 350 mg of o-fluorobenzoic acid in 3 mL of N,N-dimethylformamide. After ultrasonic dissolution, transfer the mixed solution to a 5 mL reactor and heat to 120 °C for 48 h. After the reaction, a white solid powder is obtained.

[0094] b. Wash the white solid powder obtained in step a with N,N-dimethylformamide, centrifuge, and dry at 50° C. for 12 h to obtain a white solid powder;

[0095] c. Dissolve 10 mg of the white solid powder obtained in step b in 20 mL of N,N-dimethylformamide to obtain a 0.5 mg / mL carbazole-based lanthanide metal organic framework material solution, perform ultrasound until the white solid powder is evenly dispersed, and then add N,N-dimethylformamide to dilute to 0.005 mg / mL to obtain a carbazole-based lanthanide metal organic framework material ratio fluorescence detection reagent;

[0096] Fluorescence detection of the nerve agent Sarin:

[0097] After 3 mL of the 0.005 mg / mL carbazole-based lanthanide metal organic framework reagent obtained in step c reacted with 100 μL of 0.05 M sarin, the emission spectrum was scanned on a fluorescence spectrometer in the fluorescence mode. By comparing the emission spectrum Fig.12 It can be seen that the emission at 433 nm is significantly enhanced, and the fluorescence under 365 nm UV light changes from red to blue.

[0098] The above embodiments describe the present invention. It should be understood that, without violating the spirit of the present invention, the ratio of the reagent components in the present invention can be adjusted, and the sarin and diethyl chlorophosphate tests used in other fields are also applicable, and these changes also fall within the scope of the present invention.

Claims

1. A lanthanide metal organic framework reagent for detecting sarin and its analog diethyl chlorophosphate, characterized in that The reagent is composed of a carbazole-based lanthanide metal organic framework material and a solvent, N,N-dimethylformamide, and the specific operation is carried out according to the following steps: Prepare reagents: a. Dissolve 1,3,6,8-tetrabenzoic acid-carbazole, europium nitrate and o-fluorobenzoic acid in N,N-dimethylformamide, dissolve by ultrasonication, transfer the mixed solution to a reactor, heat to 120°C and react for 48 h. After the reaction, a white solid powder is obtained. b. Wash the white solid powder obtained in step a with N,N-dimethylformamide, centrifuge, and dry to obtain a white solid powder; c. Dissolve the white solid powder obtained in step b in N,N-dimethylformyl, perform ultrasound until the white solid powder is evenly dispersed, and then add N,N-dimethylformyl to dilute to 0.005 mg / mL to obtain a carbazole-based lanthanide metal organic framework reagent; Prepare the test solution: d. Dissolve diethyl chlorophosphate, a simulant of the nerve agent sarin, in N,N-dimethylformamide to obtain a standard solution of diethyl chlorophosphate with a concentration of 0.03 M; Fluorescence detection of sarin and diethyl chlorophosphate: e. Add the carbazole-based lanthanide metal organic framework reagent obtained in step c into a test bottle, and then add diethyl chlorophosphate, a nerve agent sarin simulant prepared in step d. Under the excitation of 365 nm ultraviolet light, the fluorescence color changes from red to blue within 5 s. When the concentration of diethyl chlorophosphate is 100-300 μM, the emission intensity at 433 nm has a good linear relationship with the concentration of diethyl chlorophosphate. The detection limit is 95.2 nM. There is interference when detecting diethyl chlorophosphate and hydrochloric acid in the fluorescence mode. Diethyl chlorophosphate and hydrochloric acid are distinguished by fluorescence color or fluorescence spectrum.

Images