Fluorescence detection method for organophosphorus acyl fluoride nerve toxic agent based on defected porphyrin metal organic framework material

Abstract

The invention provides an organophosphorus acyl fluoride nerve poison fluorescence detection method based on a defected porphyrin metal organic frame material, and the method constructs the defected metal organic frame material which takes porphyrin as a fluorophore and takes a zirconium cluster as a reaction site. After the defected porphyrin metal organic framework material is added into an organophosphorus acyl fluoride nerve poison solution or atmosphere, a red fluorescence lightening phenomenon is generated based on a dual screening effect of pore size and zirconium cluster coordination activity. In order to facilitate on-site actual detection application, a defective metal organic framework material is loaded on a polyvinyl alcohol hydrogel substrate to prepare a sensing chip, and after an organophosphorus acyl fluoride nerve poison solution is dropwise added, a red fluorescence lightening phenomenon can be generated. And the detection is not interfered by other common neurotoxicants, structural analogues, acidic substances, volatile organic solvents and the like. The method has the advantages of high sensitivity, high specificity, rapidness and visualization, and has a wide application prospect in actual field analysis.

Description

Technical Field

[0001] The invention belongs to the field of nerve agent detection and provides a fluorescence detection method for organic phosphoryl fluoride nerve agents based on defective porphyrin metal organic framework materials. Background Art

[0002] Nerve agents usually act in trace amounts on the acetylcholinesterase (AChE) enzyme in the nervous system, blocking its activity, causing convulsions, suffocation, and death. They are composed of organophosphorus structures and are further divided into three subclasses, such as the G series (e.g., Tabun-GA, Sarin-GB, Soman-GD), the V series (e.g., VX), and the Novichok series. Among them, Sarin and Soman belong to the organophosphoryl fluoride class of nerve agents.

[0003] Nerve agents are extremely lethal and can kill people in a very short time. For example, the aging time of soman is only 2 minutes, which means that its toxicity increases rapidly in a short period of time and is difficult to reverse. Therefore, timely and accurate detection of trace amounts of nerve agents is crucial to minimize their harm to human life and health.

[0004] Among nerve agent detection technologies such as liquid chromatography-mass spectrometry and ion mobility spectrometry, optical analysis represented by fluorescence sensing has great practical prospects and has attracted much attention due to its intuitive results, easy integration, portability and operability.

[0005] The present invention develops a method for fluorescence detection of organophosphoryl fluoride nerve agents based on defective porphyrin metal organic framework materials. The method constructs a defective metal organic framework material (MOF-525) with porphyrin as a fluorophore and zirconium clusters as reaction sites, and based on the dual screening effects of pore size and zirconium cluster coordination activity, realizes highly specific and highly sensitive on-site rapid fluorescence detection of organophosphoryl fluoride nerve agents in the form of detection reagents or polyvinyl alcohol (PVA)-based hydrogel sensor chips. Summary of the invention

[0006] The object of the present invention is to provide a fluorescence detection method for organophosphoryl fluoride nerve agents based on defective porphyrin metal organic framework materials, wherein the defective metal organic framework 525 in the method can realize the red fluorescence lighting detection of organophosphoryl fluoride nerve agents. The material is prepared by solvent thermal reaction under the condition of the presence of a modifier, with zirconium cluster as the coordination recognition site and organic ligand porphyrin as the luminescence center. After adding an organophosphoryl fluoride nerve agent solution or atmosphere, the defective porphyrin metal organic framework material produces a red fluorescence lighting phenomenon based on the dual screening effect of pore size and zirconium cluster coordination activity. In order to facilitate the actual on-site detection application, the defective metal organic framework material is loaded on a polyvinyl alcohol (PVA) hydrogel substrate to form a sensor chip, and after the organophosphoryl fluoride nerve agent solution is added dropwise, a red fluorescence lighting phenomenon can be produced. The detection is not interfered by other common types of nerve agents, structural analogs, acidic substances and volatile organic solvents. The present invention has the advantages of high sensitivity, high specificity, rapidity and visualization, and has broad application prospects in actual on-site analysis. This material has a low detection limit, strong anti-interference ability and short reaction time, and can achieve the purpose of low-cost, visual fluorescence detection of organophosphoryl fluoride nerve agents.

[0007] The present invention discloses a method for fluorescence detection of organophosphoryl fluoride nerve agents based on defective porphyrin metal organic framework materials, which is carried out according to the following steps:

[0008] Preparation of detection reagents:

[0009] a. Dissolve ZrOCl2·8H2O in 20mL N,N-dimethylformamide, sonicate for 20min, then add porphyrin and mix, sonicate for 20min to obtain a homogeneous solution, then add glacial acetic acid and mix, pour into a Teflon autoclave, heat at 75°C for 72h, centrifuge, collect metal organic framework 525, wash with N,N-dimethylformamide and acetone three times, and dry at 100°C for 12h to obtain metal organic framework 525 powder;

[0010] b. dispersing the metal organic framework 525 powder obtained in step a in an N,N-dimethylformamide solution, ultrasonically treating for 10 min to obtain a uniformly mixed metal organic framework 525 dispersion, and then preparing the dispersion into a 0.03 mg / mL solution, and ultrasonically dissolving it to obtain a detection reagent for identifying organophosphoryl fluoride nerve agents;

[0011] c. Dissolve polyvinyl alcohol in 100 mL of dimethyl sulfoxide-water solution at a volume ratio of 8:2 to form a transparent solution, then heat it in an oil bath at 140°C for 2 hours to obtain a completely dissolved polyvinyl alcohol hydrogel solution, cool it to 60°C, inject the polyvinyl alcohol solution into a glass mold, and let it stand at -20°C for 10 hours to obtain a polyvinyl alcohol hydrogel, then rinse the PVA hydrogel with ultrapure water for 3 times to remove unreacted molecules to obtain a polyvinyl alcohol hydrogel;

[0012] Detection of organophosphoryl fluoride nerve agents using metal organic framework 525 solution:

[0013] d. Take 2 mL of the metal organic framework 525 solution obtained in step b into a test tube, add 50 μL of the organophosphoryl fluoride nerve agent to be detected, and after sufficient reaction, record the fluorescence spectrum and optical photos under 395 nm ultraviolet light excitation conditions to observe the signal changes of the fluorescence characteristic emission peak before and after the reaction;

[0014] Alternatively, 0.03 mg / mL metal organic framework 525 solution is immersed in the polyvinyl alcohol hydrogel obtained in step c to obtain a sensor chip loaded with the metal organic framework 525, 50 mL of organic phosphoryl fluoride nerve agent is drawn and purged onto the sensor chip, and the fluorescence change is observed under 395 nm illumination conditions.

[0015] The present invention discloses a fluorescent detection method for organophosphoryl fluoride nerve agents based on defective porphyrin metal organic framework materials. The defective metal organic framework (MOF-525) described in the method can be obtained by solvent thermal method. The structural formula (I) corresponding to the defective metal organic framework (MOF-525) is:

[0016]

[0017] The present invention discloses a method for fluorescent detection of organophosphoryl fluoride nerve agents based on defective porphyrin metal organic framework materials. The metal organic framework (MOF-525) material in the method can realize red fluorescence lighting detection of organophosphoryl fluoride nerve agents. By changing the amount of the modulator during the synthesis process, a series of metal organic framework (MOF-525) materials are obtained. These materials contain exposed Zr cluster sites and increase the porosity of the material when defects are generated. The inherent red fluorescence of the metal organic framework (MOF-525) gradually weakens with the increase of the defect level, accompanied by the transition of the luminescence mechanism from local excitation to ligand-metal charge transfer excitation. The defect level of the metal organic framework (MOF-525) is 60%, which has specific activity (the extreme value range of the molecular electrostatic potential is 16.5-28.6 kcal / mol) and molecular size. Therefore, the metal organic framework (MOF-525) uses the synergistic screening effect of chemical activity and molecular size to react sensitively and accurately to the target nerve agent, and is not interfered by complex environmental factors such as acidic substances, fluorescent substances, and humidity. The detection limit of organophosphoryl fluoride nerve agents can reach 0.96nM, and the detection linear range is 50-150μM. Within 1s of adding the test substance, a red fluorescent light-up signal is presented.

[0018] The method for fluorescent detection of organophosphoryl fluoride nerve agents based on defective porphyrin metal organic framework materials described in the present invention has no special restrictions when used, and can quickly complete qualitative and quantitative detection at room temperature without pre-treatment of the analyte. It is simple to operate, economical and practical, has high specificity and sensitivity, and the results are stable and repeatable. The above advantages make the present invention easy to be practically applied and promoted in the field of on-site instant detection.

[0019] The present invention discloses a fluorescent detection method for organophosphoryl fluoride nerve agents based on defective porphyrin metal organic framework materials. Based on defective porphyrin metal organic framework materials, the intrinsic fluorescence can be reduced through a regulator control strategy, and the exposed zirconium cluster recognition sites can be increased at the same time, the intrinsic pore size of the metal organic framework (MOF-525) material can be enlarged, and interferences can be removed by screening. Through coordination, a rapid response <1s is achieved for the target nerve agent, and the target can be specifically identified, without interference from nearly 20 potential coexisting substances, and without interference from hydrochloric acid of different concentrations. Under different water contents and complex environments, characteristic red fluorescence lighting signals can still be continuously output. The present invention has the advantages of high sensitivity, high specificity, rapidity and visualization, and has broad application prospects in on-site analysis of nerve agents.

[0020] The present invention discloses a fluorescence detection method for organophosphoryl fluoride nerve agents based on defective porphyrin metal organic framework materials. In this method, the organophosphoryl fluoride nerve agents to be detected form a coordination effect with the zirconium clusters of the metal organic framework materials to achieve red fluorescence lighting detection. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 The defective metal organic framework (MOF-525) in Example 1 of the present invention is used to detect organophosphoryl fluoride nerve agents;

[0022] Figure 2 The detection effect of defective metal organic framework (MOF-525) solutions of different concentrations on organophosphoryl fluoride nerve agents in Example 2 of the present invention;

[0023] Figure 3The defective metal organic framework (MOF-525) in Example 3 of the present invention detects the fluorescence change before and after the reaction of a series of concentrations of organophosphoryl fluoride nerve agents, and the correlation between the fluorescence intensity and the concentration of the organophosphoryl fluoride nerve agents;

[0024] Figure 4 The defective metal organic framework (MOF-525) in Example 4 of the present invention detects organophosphoryl fluoride nerve agents and other common types of nerve agents, structural analogs, acidic substances and volatile organic solvents;

[0025] Figure 5 The defective metal organic framework (MOF-525) in Example 5 of the present invention detects the detection effect of organophosphoryl fluoride nerve agents in the coexistence of other common types of nerve agents, structural analogs, acidic substances and volatile organic solvents;

[0026] Figure 6 This is a diagram showing the response time of the defective metal organic framework (MOF-525) in Example 6 of the present invention to organophosphoryl fluoride nerve agents;

[0027] Figure 7 The preparation of the PVA hydrogel in Example 7 of the present invention;

[0028] Figure 8 The defective metal organic framework (MOF-525) / PVA hydrogel composite material in Example 8 of the present invention detects the fluorescence changes before and after the atmosphere reaction of a series of concentrations of organophosphoryl fluoride nerve agents, and the correlation between the RGB value of the fluorescence image and the concentration of the organophosphoryl fluoride nerve agents;

[0029] Fig. 9 The defective metal organic framework (MOF-525) / PVA hydrogel composite material in Example 9 of the present invention is effective in detecting organophosphoryl fluoride nerve agents and other common types of nerve agents, structural analogs, acidic substances and volatile organic solvent atmospheres;

[0030] Fig.10 This is the detection effect of the defective metal organic framework (MOF-525) / PVA hydrogel composite material in Example 10 of the present invention on detecting organophosphoryl fluoride nerve agents in a complex environment. DETAILED DESCRIPTION

[0031] The present invention is further described below by means of specific examples, but the invention is not limited to these examples.

[0032] Example 1

[0033] Preparation of detection reagents:

[0034] a. Dissolve 0.117 g 0.36 mmol ZrOCl2·8H2O in 20 mL N,N-dimethylformamide, sonicate for 20 min, then add 0.036 g 0.54 mmol porphyrin and mix, sonicate for 20 min to obtain a homogeneous solution, then add 9 mL glacial acetic acid and mix, pour into a Teflon autoclave, heat at 75 ° C for 72 h, centrifuge, collect the metal organic framework (MOF-525), wash with N,N-dimethylformamide and acetone for 3 times, and dry at 100 ° C for 12 h to obtain a metal organic framework (MOF-525) powder;

[0035] b. The metal organic framework (MOF-525) powder obtained in step a was dispersed in 500 mL of N,N-dimethylformamide solution, and ultrasonicated for 10 min to obtain a uniformly mixed metal organic framework (MOF-525) dispersion, and then the dispersion was configured into a 0.03 mg / mL solution, and ultrasonically dissolved to obtain a detection reagent for organophosphoryl fluoride nerve agents;

[0036] c. Dissolve polyvinyl alcohol in 100 mL of dimethyl sulfoxide-water solution at a volume ratio of 8:2 to form a transparent solution, then heat it in an oil bath at 140°C for 2 hours to obtain a completely dissolved polyvinyl alcohol hydrogel solution, cool it to 60°C, inject the polyvinyl alcohol solution into a glass mold, and let it stand at -20°C for 10 hours to obtain a polyvinyl alcohol hydrogel, then rinse the PVA hydrogel with ultrapure water for 3 times to remove unreacted molecules to obtain a polyvinyl alcohol hydrogel;

[0037] Detection of organophosphoryl fluoride nerve agents using metal organic framework 525 solution:

[0038] d. Take 2 mL of the metal organic framework 525 solution obtained in step b into a test tube, add 50 μL of the organophosphoryl fluoride nerve agent to be detected, and after sufficient reaction, record the fluorescence spectrum and optical photos under 395 nm ultraviolet light excitation conditions to observe the signal changes of the fluorescence characteristic emission peak before and after the reaction; the detection effect of the solution on organophosphoryl fluoride nerve agents is as follows: Figure 1 As shown, under 395nm ultraviolet light, the red fluorescence of the reagent is enhanced. In addition, using a fluorescence spectrometer, the excitation wavelength is selected as 395nm, and the fluorescence characteristic peaks are significantly enhanced at 652nm and 720nm. It is determined that 9mL of acetic acid is the optimal synthesis concentration, and the fluorescence changes before and after the reaction of organophosphoryl fluoride nerve agents are obvious.

[0039] Example 2

[0040] Detection effect of defective metal organic framework (MOF-525) solutions with different concentrations on organophosphoryl fluoride nerve agents:

[0041] Preparation of detection reagent: The defective metal organic framework (MOF-525) solution prepared in step b of Example 1 was dissolved in N,N-dimethylformamide solution to prepare defective metal organic framework (MOF-525) solutions with concentrations of 0.01, 0.02, 0.03, 0.04, 0.05, and 0.1 mg / mL, respectively. Then, 2 mL of the corresponding concentrations of 0.01, 0.02, 0.03, 0.04, 0.05, and 0.1 mg / mL metal organic framework (MOF-525) solutions were taken and placed in test tubes respectively to obtain detection reagents of various concentrations;

[0042] Preparation of organophosphoryl fluoride nerve agent standard solution: Use N,N-dimethylformamide as solvent to prepare a 0.005M organophosphoryl fluoride nerve agent standard solution;

[0043] Detection process: 50 μL of the standard solution of organophosphoryl fluoride nerve agents was added to the defective metal organic framework (MOF-525) solutions with concentrations of 0.01, 0.02, 0.03, 0.04, 0.05, and 0.1 mg / mL, respectively. After sufficient reaction, the excitation wavelength was selected as 395 nm, and the fluorescence spectrum was recorded and the fluorescence image was taken;

[0044] Detection effect: The detection effect of 2 mL of defective metal organic framework (MOF-525) solution with concentrations of 0.01, 0.02, 0.03, 0.04, 0.05, and 0.1 mg / mL on organophosphoryl fluoride nerve agents is as follows: Figure 2 As shown, under the irradiation of 395nm ultraviolet light, the red fluorescence of the reagent is enhanced; when the concentrations are 0.01, 0.02, 0.03, 0.04, 0.05, and 0.1 mg / mL, respectively, the fluorescence changes of the reagent before and after the reaction of organic phosphoryl fluoride nerve agents are more obvious at 0.03 mg / mL, so the defective metal organic framework (MOF-525) solution is selected as the optimal detection concentration in this concentration range.

[0045] Example 3

[0046] Defective metal organic framework (MOF-525) solution detection of a series of organophosphoryl fluoride nerve agents:

[0047] Preparation of detection reagent: dissolve the defective metal organic framework (MOF-525) solution prepared in step b of Example 1 in N,N-dimethylformamide solution to prepare a defective metal organic framework (MOF-525) solution with a concentration of 0.03 mg / mL, take 2 mL into a test tube to obtain a detection reagent;

[0048] Preparation of organophosphoryl fluoride nerve agents: Use N,N-dimethylformamide as solvent to prepare organophosphoryl fluoride nerve agent standard solutions with concentrations of 25, 50, 75, 100, 125, 150, 200, 300, and 600 μmol / L;

[0049] Detection process: Take 50 μL of the prepared organophosphoryl fluoride nerve agent standard solution and add it to the detection reagent. After sufficient reaction, select the excitation wavelength as 395 nm, measure the fluorescence spectrum, and draw a linear curve at the product characteristic peak of 652 nm;

[0050] Detection effect: Figure 3 As shown, the concentration change of defective metal organic framework (MOF-525) solution in N,N-dimethylformamide solution system for detecting organophosphoryl fluoride nerve agents shows a good linear relationship in the range of 50-150 μmol / L. Therefore, the detection reagent can quantitatively detect organophosphoryl fluoride nerve agents.

[0051] Example 4

[0052] Selective testing of defective metal-organic framework (MOF-525) solutions for detecting organophosphoryl fluoride nerve agents

[0053] Preparation of detection reagent: dissolve the defective metal organic framework (MOF-525) solution prepared in step b of Example 1 in N,N-dimethylformamide solution to prepare a defective metal organic framework (MOF-525) solution with a concentration of 0.03 mg / mL, take 2 mL into a test tube to obtain a detection reagent;

[0054] Preparation of test solution: Using N,N-dimethylformamide as solvent, prepare 0.05M and 0.5M hydrochloric acid, common nerve agent simulants and volatile organic solvents such as diethyl chlorophosphate, diethyl cyanophosphate, propafluoride, methanol, ethanol, acetone, acetonitrile, dichloromethane, ethyl acetate, hydrochloric acid, tributyl phosphate, triethyl phosphate, n-hexane, cyclohexane or VX (VX), as interferences for the detection of organophosphoryl fluoride nerve agents, to prepare a solution with a corresponding concentration of 0.1mmol / L;

[0055] Detection process: Add 50 μL of 0.05M and 0.5M hydrochloric acid, common nerve agent simulants and volatile organic solvents or 0.05 mol / L of organic phosphoryl fluoride nerve agents to the prepared detection reagent. After sufficient reaction, select an excitation wavelength of 395 nm and record the fluorescence spectrum and optical photographs.

[0056] Detection effect: The detection effect of defective metal organic framework (MOF-525) solution on the detection of organophosphoryl fluoride nerve agents and their interferents is as follows Figure 4As shown, the addition of organophosphoryl fluoride nerve agents leads to an increase in the red fluorescence of the detection reagent, while the fluorescence remains unchanged after the addition of other interferents, indicating that the defective metal organic framework (MOF-525) has good selectivity for organophosphoryl fluoride nerve agents.

[0057] Example 5

[0058] The detection effect of defective metal organic framework (MOF-525) on the coexistence of organophosphoryl fluoride nerve agents and other common types of nerve agents, structural analogs, acids and volatile organic solvents:

[0059] Preparation of detection reagent: dissolve the defective metal organic framework (MOF-525) solution prepared in step b of Example 1 in N,N-dimethylformamide solution to prepare a defective metal organic framework (MOF-525) solution with a concentration of 0.03 mg / mL, take 2 mL into a test tube to obtain a detection reagent;

[0060] Preparation of test solution: Using N,N-dimethylformamide as solvent, prepare 0.05M and 0.5M hydrochloric acid, common nerve agent simulants and volatile organic solvents such as diethyl chlorophosphate, diethyl cyanophosphate, chlorpyrifos, methanol, ethanol, acetone, acetonitrile, dichloromethane, hydrochloric acid, tributyl phosphate, triethyl phosphate, n-hexane, cyclohexane or VX (VX), as interferences for the detection of organophosphoryl fluoride nerve agents, to prepare a solution with a corresponding concentration of 0.1mmol / L;

[0061] Detection process: Add 50 μL of 0.05M and 0.5M hydrochloric acid, common nerve agent simulants and volatile organic solvents, and 0.005 mol / L of organic phosphoryl fluoride nerve agents to the prepared detection reagent. After sufficient reaction, select an excitation wavelength of 395 nm and record the fluorescence spectrum and optical photographs.

[0062] Detection effect: The detection effect of defective metal organic framework (MOF-525) solution on the detection of organophosphoryl fluoride nerve agents and interferences is as follows Figure 5 As shown, the addition of organophosphoryl fluoride nerve agents leads to an increase in the red fluorescence of the detection reagent, while the fluorescence remains unchanged after the addition of other interferents, indicating that the defective metal organic framework (MOF-525) has good anti-interference properties against organophosphoryl fluoride nerve agents.

[0063] Example 6

[0064] Effect of defective metal organic framework (MOF-525) on the response time of organophosphoryl fluoride nerve agents:

[0065] Preparation of detection reagent: Dissolve the defective metal organic framework (MOF-525) solution prepared in step b of Example 1 in N,N-dimethylformamide solution to prepare a defective metal organic framework (MOF-525) solution with a concentration of 0.03 mg / mL, take 2 mL into a test tube to obtain a detection reagent;

[0066] Preparation of organophosphoryl fluoride nerve agent standard solution: Prepare a 0.5M organophosphoryl fluoride nerve agent standard solution in N,N-dimethylformamide as solvent;

[0067] Detection process: Add 100 μL of 0.5 mol / L organophosphoryl fluoride nerve agent to the prepared detection reagent, and after sufficient reaction, select the excitation wavelength of 395 nm and record the optical photograph;

[0068] Detection effect: The detection effect of defective metal organic framework (MOF-525) solution on the detection of organophosphoryl fluoride nerve agents is as follows Figure 6 As shown, the addition of organophosphoryl fluoride nerve agents leads to an increase in the red fluorescence of the detection reagent, and the response is rapid, <1s.

[0069] Example 7

[0070] Preparation of polyvinyl alcohol (PVA) hydrogel:

[0071] 15 g of polyvinyl alcohol in a volume ratio of 8:2 in step c of Example 1 was dissolved in 100 mL of dimethyl sulfoxide-water solution to form a transparent solution, which was then heated in an oil bath at 140° C. for 2 h to obtain a completely dissolved polyvinyl alcohol hydrogel solution. After cooling to 60° C., the polyvinyl alcohol solution was injected into a glass mold and allowed to stand at -20° C. for 10 hours to obtain a polyvinyl alcohol hydrogel. The PVA hydrogel was then rinsed with ultrapure water for 3 times to remove unreacted molecules.

[0072] A 0.03 mg / mL metal organic framework (MOF-525) solution was immersed in the obtained polyvinyl alcohol hydrogel to obtain a sensor chip loaded with a defective metal organic framework (MOF-525); 50 mL of organic phosphoryl fluoride nerve agent atmosphere was drawn and purged onto the sensor chip loaded with the defective metal organic framework (MOF-525) / polyvinyl alcohol hydrogel, and the fluorescence change was observed under 395 nm illumination. The effect was as follows: Figure 7 shown.

[0073] Example 8

[0074] Defective metal organic framework (MOF-525) / PVA hydrogel composite material detects the fluorescence changes of organophosphoryl fluoride nerve agents before and after the atmospheric reaction of a series of concentrations, and its correlation with organophosphoryl fluoride nerve agents:

[0075] Detection reagent configuration: The defective metal organic framework (MOF-525) solution prepared in step b of Example 1 is dissolved in an N,N-dimethylformamide solution to prepare a defective metal organic framework (MOF-525) solution with a concentration of 0.03 mg / mL, and then immersed in the polyvinyl alcohol (PVA) hydrogel obtained in step c of Example 1 to obtain a sensor chip loaded with a defective metal organic framework (MOF-525);

[0076] Preparation of the atmosphere of the test object: Place the liquid organophosphoryl fluoride nerve agent in a syringe, heat it in an oven to saturated steam, and dilute it to 5ppm, 2.5ppm, 1ppm, 500ppb, 250ppb, 125ppb, 100ppb, 50ppb, and 25ppb atmospheres in sequence;

[0077] Detection process: 50 mL of organic phosphoryl fluoride nerve agent atmosphere was drawn and purged onto the sensor chip loaded with defective metal organic framework (MOF-525) / polyvinyl alcohol (PVA) hydrogel, and the fluorescence changes were observed under 395 nm illumination;

[0078] Detection effect: The detection effect of defective metal organic framework (MOF-525) solution on the detection of organophosphoryl fluoride nerve agents and interferences is as follows Figure 8 As shown, the addition of organophosphoryl fluoride nerve agents leads to an enhancement of the red fluorescence of the detection composite material, and a good linear relationship is shown between 250ppb-5ppm. Therefore, the composite material can quantitatively detect organophosphoryl fluoride nerve agents.

[0079] Example 9

[0080] The detection effect of defective metal organic framework (MOF-525) / PVA hydrogel composite material on the detection of organophosphoryl fluoride nerve agents and other common types of nerve agents, structural analogs, acidic substances and volatile organic solvent atmospheres:

[0081] Detection reagent configuration: The defective metal organic framework (MOF-525) solution prepared in step b of Example 1 is dissolved in an N,N-dimethylformamide solution to prepare a defective metal organic framework (MOF-525) solution with a concentration of 0.03 mg / mL. The 0.03 mg / mL metal organic framework (MOF-525) solution is immersed in the polyvinyl alcohol (PVA) hydrogel obtained in step c of Example 1 to obtain a sensor chip loaded with a defective metal organic framework (MOF-525);

[0082] Preparation of atmosphere for the test object: 0.05M and 0.5M hydrochloric acid, common nerve agent simulants and volatile organic solvents such as diethyl chlorophosphate, diethyl cyanophosphate, propanediol, methanol, ethanol, acetone, acetonitrile, dichloromethane, hydrochloric acid, tributyl phosphate, triethyl phosphate, n-hexane, cyclohexane or VX (VX), as interferences for the detection of organophosphoryl fluoride nerve agents, prepare the corresponding saturated atmosphere;

[0083] Detection process: 50 mL of organic phosphoryl fluoride nerve agents, 0.05 M and 0.5 M hydrochloric acid, common nerve agent simulants and volatile organic solvents were drawn and purged onto the sensor chip loaded with defective metal organic framework (MOF-525) / PVA hydrogel, and the fluorescence changes were observed under 395 nm illumination.

[0084] Detection effect: The detection effect of defective metal organic framework (MOF-525) / PVA composite material on the detection of organophosphoryl fluoride nerve agents and their interferents is as follows Fig. 9 As shown, the addition of organophosphoryl fluoride nerve agents leads to an enhancement of the red fluorescence of the detection reagent, while the fluorescence remains unchanged after the addition of other interferents, indicating that the defective metal organic framework (MOF-525) / PVA composite material has good selectivity for organophosphoryl fluoride nerve agents.

[0085] Example 10

[0086] Detection effect of defective metal organic framework (MOF-525) / PVA hydrogel composite material on organophosphoryl fluoride nerve agents in complex environment:

[0087] Detection reagent configuration: The defective metal organic framework (MOF-525) solution prepared in step b of Example 1 is dissolved in an N,N-dimethylformamide solution to prepare a defective metal organic framework (MOF-525) solution with a concentration of 0.03 mg / mL, and then immersed in the polyvinyl alcohol (PVA) hydrogel obtained in step c of Example 1 to obtain a sensor chip loaded with a defective metal organic framework (MOF-525);

[0088] Preparation of atmosphere for the test object: Preparation of atmosphere for the test object: Place the liquid organophosphoryl fluoride nerve agent in a syringe, heat it in an oven to saturated steam, and dilute it to 5 ppm in sequence;

[0089] Detection process: 50 mL of organic phosphoryl fluoride nerve agent atmosphere was extracted and purged onto the sensor chip loaded with defective metal organic framework (MOF-525) / polyvinyl alcohol (PVA) hydrogel, and tested in an environment with a water content of 0-80%, four volatile acids of hydrofluoric acid, nitric acid, acetic acid or hydrochloric acid, and different interferences of fluorescein, dust or fiber, and the fluorescence changes were observed under 395 nm illumination;

[0090] Detection effect: The detection effect of defective metal organic framework (MOF-525) / PVA composite material on the detection of organophosphoryl fluoride nerve agents and their interferents is as follows Fig.10 As shown, the addition of organophosphoryl fluoride nerve agents leads to an increase in the red fluorescence of the detection reagent, while the fluorescence remains unchanged after the addition of other interferents, indicating that the defective metal organic framework (MOF-525) / PVA composite material has good anti-interference properties against organophosphoryl fluoride nerve agents.

Claims

1. A fluorescence detection method for organophosphoryl fluoride nerve agents based on defective porphyrin metal organic framework materials, characterized in that: Follow these steps: Prepare detection reagents: a. Dissolve ZrOCl2·8H2O in 20 mL N,N-dimethylformamide, sonicate for 20 min, then add porphyrin and mix, sonicate for 20 min to obtain a homogeneous solution, then add glacial acetic acid and mix, pour into a Teflon autoclave, heat at 75°C for 72 h, centrifuge, collect metal organic framework 525, wash with N,N-dimethylformamide and acetone for 3 times, and dry at 100°C for 12 h to obtain metal organic framework 525 powder; b. dispersing the metal organic framework 525 powder obtained in step a in an N,N-dimethylformamide solution, ultrasonicating for 10 minutes to obtain a uniformly mixed metal organic framework 525 dispersion, and then configuring the dispersion into a 0.03 mg / mL solution, and ultrasonically dissolving it to obtain a detection reagent for identifying organophosphoryl fluoride nerve agents; c. Dissolve polyvinyl alcohol in 100 mL of dimethyl sulfoxide-water solution at a volume ratio of 8:2 to form a transparent solution, then heat it in an oil bath at 140°C for 2 h to obtain a completely dissolved polyvinyl alcohol hydrogel solution. After cooling to 60°C, inject the polyvinyl alcohol solution into a glass mold and let it stand at -20°C for 10 hours to obtain a polyvinyl alcohol hydrogel. Rinse the PVA hydrogel three times with ultrapure water to remove unreacted molecules to obtain a polyvinyl alcohol hydrogel. Detection of organophosphoryl fluoride nerve agents using metal organic framework 525 solution: d. Take 2 mL of the metal organic framework 525 solution obtained in step b into a test tube, add 50 μL of the organophosphoryl fluoride nerve agent to be detected, and after sufficient reaction, record the fluorescence spectrum and optical photos under 395 nm ultraviolet light excitation conditions to observe the signal changes of the fluorescence characteristic emission peak before and after the reaction; Alternatively, 0.03 mg / mL metal organic framework 525 solution is immersed in the polyvinyl alcohol hydrogel obtained in step c to obtain a sensor chip loaded with the metal organic framework 525, 50 mL of organophosphoryl fluoride nerve agent is drawn and purged onto the sensor chip, and the fluorescence change is observed under 395 nm illumination.

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