Preparation method and application of monocrotophos fluorescence detection material

Abstract

The invention discloses a preparation method and application of a monocrotophos fluorescence detection material. The preparation method of the monocrotophos fluorescence detection material comprises the following steps: dissolving zirconium tetrachloride, 2-aminoterephthalic acid, benzoic acid and curcumin in N, N-dimethylformamide to form a reaction solution; performing high-pressure solvent heat treatment on the reaction liquid to generate a solid-liquid mixture; collecting, washing and drying precipitates in the solid-liquid mixture to obtain a precursor; and carrying out thermal activation treatment on the precursor material to obtain the monocrotophos fluorescence detection material. The detection method comprises the step of carrying out fluorescence detection on monocrotophos in a water body to be detected by adopting the monocrotophos fluorescence detection material. The preparation method of the monocrotophos fluorescence detection material and the application of the monocrotophos fluorescence detection material have the advantages of simplicity in operation, low cost, high sensitivity, high specific recognition capability and high anti-interference capability when being used for qualitative and quantitative detection of monocrotophos, and have great application potential in monitoring of monocrotophos in environmental water bodies.

Description

Technical Field

[0001] The present invention relates to the technical field of monocrotophos detection, and in particular to a preparation method and application of a monocrotophos fluorescence detection material. Background Art

[0002] Monocrotophos (MCP) is a highly toxic organophosphorus pesticide that is widely used in agricultural production in my country. Various studies at home and abroad have shown that MCP is an irreversible acetylcholinesterase inhibitor with carcinogenicity, mutagenicity, neurotoxicity and reproductive toxicity. Although MCP has been banned in my country, its residual life is long and it causes great harm to the ecological environment and human health through bioaccumulation and amplification. Therefore, it is necessary to develop sensitive, rapid and selective methods to detect and quantify pesticide residues in water.

[0003] The pesticide analysis techniques reported in the literature include conventional gas chromatography, liquid chromatography, mass spectrometry, high performance liquid chromatography, etc. These methods have high accuracy and reliability and can determine a large number of compounds, but require complex sample pretreatment, sophisticated instruments and long analysis time. Therefore, it is urgent to develop a simple, cost-effective, rapid and sensitive MCP detection method. Summary of the invention

[0004] The technical problem to be solved by the present invention is to provide a simple, economical, effective, rapid and sensitive preparation method of a monocrotophos fluorescent detection material and its application.

[0005] In order to achieve the above object, according to the first aspect of the present invention, a method for preparing a monocrotophos fluorescent detection material is provided, and the technical scheme is as follows:

[0006] The preparation method of the monocrotophos fluorescent detection material comprises the following steps:

[0007] Dissolving zirconium tetrachloride, 2-aminoterephthalic acid, benzoic acid and curcumin in N,N-dimethylformamide to form a reaction solution;

[0008] subjecting the reaction solution to high-pressure solvent thermal treatment to generate a solid-liquid mixture;

[0009] collecting, washing and drying the precipitate in the solid-liquid mixture to obtain a precursor;

[0010] The precursor material is subjected to thermal activation treatment to obtain a long-acting phosphorus fluorescence detection material.

[0011] As a further improvement of the preparation method of the above-mentioned monocrotophos fluorescent detection material: the reaction solution is prepared according to the ratio of adding 1 mmol zirconium tetrachloride, 1 mmol 2-aminoterephthalic acid, 10 mmol benzoic acid and 0.25 mmol curcumin to every 30 mL N,N-dimethylformamide.

[0012] As a further improvement of the preparation method of the above-mentioned long-lasting phosphorus fluorescent detection material: the high-pressure solvent thermal treatment is carried out in a polytetrafluoroethylene-lined reactor, the reaction temperature is 90-110° C., and the reaction time is 18-30 hours.

[0013] As a further improvement of the preparation method of the above-mentioned monocrotophos fluorescent detection material: the precipitate is washed with ethanol and dried at 50-70°C.

[0014] As a further improvement of the preparation method of the above-mentioned long-lasting phosphorus fluorescent detection material: the thermal activation treatment is vacuum activation at 140-160° C. for 8-16 hours.

[0015] In order to achieve the above object, according to the second aspect of the present invention, a monocrotophos fluorescence detection material is provided, and the technical solution is as follows:

[0016] The monocrotophos fluorescent detection material is prepared by the preparation method described in the first aspect above.

[0017] In order to achieve the above object, according to the second aspect of the present invention, a method for detecting monocrotophos is provided, and the technical scheme is as follows:

[0018] The method for detecting monocrotophos comprises the steps of: performing fluorescence detection on monocrotophos in a water body to be detected by using the monocrotophos fluorescence detection material prepared by the method for preparing the monocrotophos fluorescence detection material described in the first aspect.

[0019] As a further improvement of the above-mentioned monocrotophos detection method: the fluorescence intensity of the mixed solution consisting of the monocrotophos fluorescence detection material and the water body to be tested is substituted into the calculation expression to convert the monocrotophos concentration in the water body to be tested;

[0020] The calculation expression is: y=1.01464+0.36444x, R 2 =0.9942;

[0021] Wherein, x is the concentration of monocrotophos in the water to be tested; y is F1 / F0, F1 is the fluorescence intensity of the mixed solution, and F0 is the fluorescence intensity of the monocrotophos fluorescence detection material.

[0022] The preparation method of the monocrotophos fluorescent detection material of the present invention and its application have the following beneficial effects:

[0023] First, the present invention utilizes the fluorescence shut-off and on-off effects of long-lasting phosphorus and fluorescent detection materials before and after mixing, which can realize the rapid qualitative fluorescent detection of long-lasting phosphorus. Secondly, the present invention obtains the calculation expression for the quantitative detection of long-lasting phosphorus through a series of experiments and linear fitting, which can realize the quantitative detection of trace long-lasting phosphorus, and the detection limit is as low as 0.41μg / L. It has been verified that the preparation method of the long-lasting phosphorus fluorescent detection material of the present invention and its application have the advantages of simple operation, low cost, high sensitivity, specific recognition ability and strong anti-interference ability when performing qualitative and quantitative inspections on long-lasting phosphorus, and have great application potential in the monitoring of long-lasting phosphorus in environmental water bodies.

[0024] The present invention is further described below in conjunction with the accompanying drawings and specific embodiments. Additional aspects and advantages of the present invention will be partially given in the following description, partially become apparent from the following description, or be learned through the practice of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] The drawings constituting a part of the present invention are used to assist in understanding the present invention. The contents provided in the drawings and their related descriptions in the present invention can be used to explain the present invention, but do not constitute improper limitations on the present invention. In the drawings:

[0026] Figure 1 It is the fluorescence excitation / emission spectrum of the monocrotophos fluorescence detection material of the present invention and 2-aminoterephthalic acid.

[0027] Figure 2 It is the fluorescence spectrum of the long-lasting phosphorus fluorescence detection material of the present invention in different solvents.

[0028] Figure 3 It is the emission spectrum of the long-acting phosphorus fluorescence detection material of the present invention at different excitation wavelengths.

[0029] Figure 4 The graph is a graph showing the change in fluorescence intensity of the monocrotophos fluorescence detection material of the present invention as the amount of curcumin changes.

[0030] Figure 5 This is a graph showing the change in fluorescence intensity of the monocrotophos fluorescence detection material of the present invention as a function of its own concentration.

[0031] Figure 6 This is a graph showing the change in fluorescence intensity of the long-lasting phosphorus fluorescence detection material of the present invention with the volume concentration of methanol.

[0032] Figure 7 This is a graph showing the change in fluorescence intensity of the monocrotophos fluorescence detection material of the present invention as a function of incubation time.

[0033] Figure 8 This is a graph showing the change in fluorescence intensity of the monocrotophos fluorescence detection material of the present invention as a function of incubation temperature.

[0034] Fig. 9 This is a graph showing the specific recognition ability of the long-lasting phosphorus fluorescent detection material of the present invention.

[0035] Fig.10 This is a graph showing the anti-interference ability of the long-lasting phosphorus fluorescence detection material of the present invention.

[0036] Fig.11 It is the fluorescence spectrum of the monocrotophos fluorescence detection material of the present invention at different monocrotophos concentrations.

[0037] Fig.12 This is a relationship curve between the fluorescence enhancement efficiency F1 / F0 and the concentration of monocrotophos when the monocrotophos fluorescence detection material of the present invention detects monocrotophos. DETAILED DESCRIPTION

[0038] The present invention is described clearly and completely below in conjunction with the accompanying drawings. A person skilled in the art will be able to implement the present invention based on these descriptions. Before describing the present invention in conjunction with the accompanying drawings, it should be particularly noted that:

[0039] The technical solutions and technical features provided in each part of the present invention, including the following description, may be combined with each other if there is no conflict.

[0040] In addition, the embodiments of the present invention involved in the following description are generally only a part of the embodiments of the present invention, rather than all the embodiments. Therefore, based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work should fall within the scope of protection of the present invention.

[0041] About the terms and units in the present invention: The terms "include", "have" and any variations thereof in the description and claims of the present invention and related parts are intended to cover non-exclusive inclusions.

[0042] An embodiment of the method for preparing the monocrotophos fluorescent detection material of the present invention comprises the following steps:

[0043] A reaction solution was prepared by adding 1 mmol of zirconium tetrachloride, 1 mmol of 2-aminoterephthalic acid, 10 mmol of benzoic acid and 0.25 mmol of curcumin to every 30 mL of N,N-dimethylformamide;

[0044] 30 mL of the reaction solution was transferred to a polytetrafluoroethylene-lined reactor with a capacity of 200 mL, and the reaction solution was subjected to high-pressure solvent thermal treatment at a reaction temperature of 100° C. for a reaction time of 24 hours to generate a solid-liquid mixture;

[0045] collecting the precipitate in the solid-liquid mixture, washing the precipitate with ethanol, and drying the precipitate at 60° C. to obtain a precursor;

[0046] The precursor material was vacuum activated at 150° C. for 12 hours to obtain a long-acting phosphorus fluorescence detection material.

[0047] An embodiment of the monocrotophos fluorescent detection material of the present invention is prepared by the above-mentioned preparation method.

[0048] An embodiment of the method for detecting monocrotophos of the present invention comprises the steps of: performing fluorescence detection on monocrotophos in a water body to be detected using the monocrotophos fluorescence detection material prepared by the method for preparing the monocrotophos fluorescence detection material described above.

[0049] The test process is as follows: the fluorescence intensity of the mixed solution consisting of the monocrotophos fluorescence detection material and the water body to be tested is substituted into the calculation expression to convert the monocrotophos concentration in the water body to be tested;

[0050] The calculation expression is: y=1.01464+0.36444x, R 2 =0.9942;

[0051] Wherein, x is the concentration of monocrotophos in the water to be tested; y is F1 / F0, F1 is the fluorescence intensity of the mixed solution, and F0 is the fluorescence intensity of the monocrotophos fluorescence detection material.

[0052] The beneficial effects of the present invention are illustrated below through experimental data.

[0053] Figure 1 It is the fluorescence excitation / emission spectrum of the monocrotophos fluorescence detection material of the present invention and 2-aminoterephthalic acid.

[0054] like Figure 1 As shown, when excited at 365nm, due to ligand-metal charge transfer (LMCT), the fluorescence emission peak of the long-lasting phosphorus fluorescence detection material at 445nm is much weaker than the fluorescence emission peak of free 2-aminoterephthalic acid, indicating that before the addition of long-lasting phosphorus, the fluorescence of the long-lasting phosphorus fluorescence detection material under the action of curcumin was in an off state.

[0055] Figure 2 It is the fluorescence spectrum of the long-lasting phosphorus fluorescence detection material of the present invention in different solvents.

[0056] like Figure 2 As shown, the emission wavelength position and fluorescence intensity of the long-lasting phosphorus fluorescence detection material changed in different solvents (water, methanol, acetonitrile, ethanol, dimethylformamide, dimethyl sulfoxide, acetone, tetrahydrofuran), among which the long-lasting phosphorus fluorescence detection material had the best fluorescence performance in methanol.

[0057] Figure 3 It is the emission spectrum of the long-acting phosphorus fluorescence detection material of the present invention at different excitation wavelengths.

[0058] like Figure 3 As shown, the emission wavelength position of the long-term phosphorus fluorescent detection material does not change with the change of the excitation wavelength, reflecting the non-excitation dependence of the long-term phosphorus fluorescent detection material. Among them, when the excitation wavelength is 350nm, the intensity of the fluorescence emission peak of the long-term phosphorus fluorescent detection material is the highest.

[0059] Figure 4 The graph is a variation diagram of the fluorescence intensity of the monocrotophos fluorescent detection material of the present invention with the change of the amount of curcumin. The fluorescence detection liquid and the fluorescence detection parameters are: 60 μL of monocrotophos fluorescent detection material solution (0.25 g / L, ultrapure water-soluble) and 600 μL of monocrotophos solution (methanol-soluble) are added to a quartz cuvette in sequence, and the volume is fixed to 1500 μL with ultrapure water, and incubated at 25°C for 5 minutes to obtain the fluorescence detection liquid; the volume of methanol in the fluorescence detection liquid is 40%; the fluorescence intensity of the fluorescence emission peak under 350nm excitation.

[0060] like Figure 4 As shown, the fluorescence intensity of the monocrotophos fluorescent detection material shows a trend of first increasing and then decreasing with the increase of curcumin dosage. When the curcumin dosage is 0.25 mmol, the fluorescence intensity of the obtained monocrotophos fluorescent detection material is the highest.

[0061] Figure 5 This is a graph showing the change in fluorescence intensity of the monocrotophos fluorescence detection material of the present invention as a function of its own concentration.

[0062] like Figure 5 As shown, the fluorescence intensity of the long-lasting phosphorus fluorescent detection material shows a trend of first increasing and then decreasing with the increase of its own concentration (the concentration of the long-lasting phosphorus fluorescent detection material in the fluorescent detection solution is 0.0025g / L, 0.005g / L, 0.01g / L, 0.015g / L, and 0.02g / L). When the concentration is 0.01g / L, the fluorescence intensity of the long-lasting phosphorus fluorescent detection material is the highest.

[0063] Figure 6 This is a graph showing the change in fluorescence intensity of the long-lasting phosphorus fluorescence detection material of the present invention with the volume concentration of methanol.

[0064] like Figure 6 As shown, the fluorescence intensity of the long-lasting phosphorus fluorescence detection material shows a trend of first increasing and then decreasing with the increase of the volume concentration of methanol (the volume concentration of methanol in the fluorescence detection solution is 10%, 20%, 40%, 60%, and 80%). When the volume concentration of methanol in the mixture of methanol and water is 40%, the fluorescence intensity of the long-lasting phosphorus fluorescence detection material is the highest.

[0065] Figure 7 This is a graph showing the change in fluorescence intensity of the monocrotophos fluorescence detection material of the present invention as a function of incubation time.

[0066] like Figure 7 As shown, the fluorescence intensity of the long-lasting phosphorus fluorescent detection material shows a trend of first increasing and then decreasing with the incubation time (incubation time is 0 minutes, 3 minutes, 5 minutes, 10 minutes, 15 minutes, 20 minutes, 30 minutes, 45 minutes, and 60 minutes). When the incubation time is 5 minutes, the fluorescence intensity of the long-lasting phosphorus fluorescent detection material is the highest.

[0067] Figure 8 This is a graph showing the change in fluorescence intensity of the monocrotophos fluorescence detection material of the present invention as a function of incubation temperature.

[0068] like Figure 8 As shown, the fluorescence intensity of the long-lasting phosphorus fluorescence detection material shows a trend of first increasing and then stabilizing with the increase of incubation temperature (incubation temperature is 20°C, 25°C, 35°C, 45°C, 55°C). When the incubation temperature reaches 25°C, the fluorescence intensity of the long-lasting phosphorus fluorescence detection material reaches the maximum value.

[0069] exist Figure 5-8 In the condition screening shown, F1 / F0 represents the fluorescence enhancement efficiency (the same below), wherein the preparation of the fluorescence detection liquid corresponding to F1 is: 60 μL of the monocrotophos fluorescence detection material solution (ultrapure water-soluble, the same below) and the monocrotophos solution (methanol-soluble, the same below) are added to the quartz cuvette in sequence, and the volume is fixed to 1500 μL with ultrapure water to obtain the fluorescence detection liquid; the preparation of the fluorescence detection liquid corresponding to F0 is: 60 μL of the monocrotophos fluorescence detection material solution and methanol are added to the quartz cuvette in sequence, and the volume is fixed to 1500 μL with ultrapure water; the concentration of the monocrotophos fluorescence detection material in the two detection liquids corresponding to a group of F1 / F0 is the same, and the concentration of monocrotophos is 6.67 mg / L; the fluorescence intensity of the fluorescence emission peak of the test liquid under 350nm excitation is tested. The following fluorescence test can be adaptively adjusted under the optimal conditions.

[0070] Fig. 9 This is a graph showing the specific recognition ability of the long-lasting phosphorus fluorescent detection material of the present invention.

[0071] like Fig. 9 As shown, when monocrotophos is replaced by phoxim, isocarbophos, dimethoate, trichlorfon, tributyl phosphate, trioctyl phosphate, tri(2-chloropropyl) phosphate, triphenyl phosphate, and tricresyl phosphate, the fluorescence enhancement efficiency F1 / F0 is significantly reduced, indicating that the monocrotophos fluorescent detection material of the present invention has excellent specific recognition ability for monocrotophos.

[0072] Fig.10 This is a graph showing the anti-interference ability of the long-lasting phosphorus fluorescence detection material of the present invention.

[0073] like Fig.10 As shown in Figure 2, when a high concentration of Na is added to the fluorescent detection solution + , K + 、Al 3+ , Ba 2+ , Ca 2+ 、Cd 2+ 、Co 2+ Cr 3+ Mg 2+ , Mn 2+ 、Zn 2+ , Pb 2+ 、NO3 - Br - ,I - , Cl - Afterwards, the fluorescence intensity of the fluorescent detection liquid changed very little, and the fluorescence turning-on effect of monocrotophos was still very obvious, indicating that the influence of interfering ions on the fluorescence enhancement effect of monocrotophos was negligible. The monocrotophos fluorescent detection material of the present invention has excellent anti-interference ability to monocrotophos.

[0074] Fig.11 It is the fluorescence spectrum of the monocrotophos fluorescence detection material of the present invention at different monocrotophos concentrations. Fig.12 This is a relationship curve between the fluorescence enhancement efficiency F1 / F0 and the concentration of monocrotophos when the monocrotophos fluorescence detection material of the present invention detects monocrotophos.

[0075] like Fig.11 As shown in the figure, the fluorescence intensity of the fluorescent detection solution changes linearly with the concentration of monocrotophos. Fig.12 As shown in the figure, the relationship between the fluorescence enhancement efficiency F1 / F0 and the concentration of monocrotophos was fitted to obtain y=1.01464+0.36444x, R 2 =0.9942, x is the concentration of monocrotophos in the fluorescence detection solution; y is the fluorescence enhancement efficiency F1 / F0.

[0076] In actual application, the fluorescence intensity of the mixed solution composed of the monocrotophos fluorescence detection material and the water body to be tested is substituted into the calculation expression, and the monocrotophos concentration in the water body to be tested can be obtained by conversion. The following is a spiked test to illustrate the practicality of the above technical expression.

[0077] The process of the spike test is as follows: remove the particulate matter in the tap water and lake water for standby; first test the fluorescence intensity (F0) of the first mixture consisting of 60 μL of monocrotophos fluorescence detection material solution, 600 μL of methanol and 840 μL of pure water; then test the fluorescence intensity (F1) of the second mixture consisting of 60 μL of monocrotophos fluorescence detection material solution, 600 μL of monocrotophos methanol solution and 840 μL of tap water or lake water, and the spiked concentration of monocrotophos in the second mixture is 0.5 mg / L or 1 mg / L; then substitute the F0 and F1 obtained by the test into the calculation expression to obtain the calculated concentration of monocrotophos concentration. The specific spike test results are shown in Table 1.

[0078] As can be seen from Table 1, the recovery rate of the spiked test is 98.8-105.3%, and the relative standard deviation is less than 4.25%, indicating that the detection method of the present invention has good accuracy and reproducibility, and has great potential in the field of environmental analysis. Compared with the electrochemical method and the chromatographic method, it has the advantages of high sensitivity, strong anti-interference ability, simple operation, etc., and is an innovative method for detecting monocrotophos.

[0079] Table 1

[0080]

[0081] In the present invention, the ultraviolet-visible absorption spectrum was tested using a USB-4000 UV-vis spectrometer (Ocean Optics, USA); the fluorescence emission spectrum was measured on a FLS1000-stm steady-state / transient fluorescence spectrometer (Edinburgh, UK), and the excitation slit width and emission slit width were 2 nm and 1.5 nm, respectively.

[0082] The above is a description of the relevant contents of the present invention. A person skilled in the art will be able to implement the present invention based on these descriptions. Based on the above contents of the present invention, all other embodiments obtained by a person skilled in the art without creative work shall fall within the scope of protection of the present invention.

Claims

1. A method for preparing a monocrotophos fluorescent detection material, characterized in that: The following steps are involved: Dissolving zirconium tetrachloride, 2-aminoterephthalic acid, benzoic acid and curcumin in N,N-dimethylformamide to form a reaction solution; subjecting the reaction solution to high pressure solvent thermal treatment to generate a solid-liquid mixture; collecting, washing and drying the precipitate in the solid-liquid mixture to obtain a precursor; The precursor material is subjected to thermal activation treatment to obtain a long-acting phosphorus fluorescence detection material.

2. The method for preparing the monocrotophos fluorescent detection material according to claim 1, characterized in that: The reaction solution was prepared by adding 1 mmol of zirconium tetrachloride, 1 mmol of 2-aminoterephthalic acid, 10 mmol of benzoic acid and 0.25 mmol of curcumin to every 30 mL of N,N-dimethylformamide.

3. The method for preparing the monocrotophos fluorescent detection material according to claim 1, characterized in that: The high-pressure solvent thermal treatment is carried out in a polytetrafluoroethylene-lined reactor, the reaction temperature is 90 to 110° C., and the reaction time is 18 to 30 hours.

4. The method for preparing the monocrotophos fluorescent detection material according to claim 1, characterized in that: The precipitate was washed with ethanol and dried at 50-70°C.

5. The method for preparing the monocrotophos fluorescent detection material according to claim 1, characterized in that: The thermal activation treatment is vacuum activation at 140-160° C. for 8-16 hours.

6. The monocrotophos fluorescence detection material is characterized by: The compound is prepared by the preparation method according to any one of claims 1 to 5.

7. A method for detecting monocrotophos, characterized in that: The method comprises the following steps: using the monocrotophos fluorescent detection material prepared by the method for preparing the monocrotophos fluorescent detection material according to any one of claims 1 to 5 to perform fluorescence detection on monocrotophos in a water body to be detected.

8. The method for detecting monocrotophos according to claim 7, characterized in that: Substituting the fluorescence intensity of the mixed solution consisting of the monocrotophos fluorescence detection material and the water body to be tested into the calculation expression, the concentration of monocrotophos in the water body to be tested is converted; The calculation expression is: y=1.01464+0.36444x, R 2 =0.9942; Wherein, x is the concentration of monocrotophos in the water to be tested; y is F1 / F0, F1 is the fluorescence intensity of the mixed solution, and F0 is the fluorescence intensity of the monocrotophos fluorescence detection material.

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