Organic fluorescent probe EDA-ATPM for detecting quizalofop-p-ethyl as well as preparation method and application thereof

Abstract

The invention discloses an organic fluorescent probe EDA-ATPM for detecting quizalofop-p-ethyl as well as a preparation method and application of the organic fluorescent probe EDA-ATPM, and belongs to the technical field of organic synthesis and analytical chemistry. The organic fluorescent probe EDA-ATPM is a compound of ethylenediamine bridged tetraphenylimidazole derivatives, the chemical name of the organic fluorescent probe EDA-ATPM is 1, 2-(pyridine-4-(1, 4, 5-triphenyl-1H-imidazolyl-2-yl)) acetamido ethane, and the molecular formula of the organic fluorescent probe EDA-ATPM is C58H48I2N8O2. KI is used as a catalyst in a nitrogen atmosphere, and 4-(1, 4, 5-triphenyl-1H-imidazolyl-2-yl)-4-(2-pyridine-4-(1, 4, 5-triphenyl-1H-imidazolyl-2-yl)-4-pyridine-4-(1, 4, 5-triphenyl-1H-imidazolyl-2-yl)-4-pyridine-4-( The preparation method comprises the following steps: adding 1, 2, 5-triphenyl-1H-imidazolyl-2-yl) pyridine and 1, 2-chloroacetamido ethane into dry acetonitrile, stirring, refluxing and reacting, filtering a reactant after the reaction is finished, concentrating filtrate under reduced pressure, and separating a light green solid product, namely the organic fluorescent probe EDA-ATPM, by virtue of rapid column chromatography; the organic fluorescent probe EDA-ATPM can form a complex with quizalofop-p-ethyl in a dimethyl sulfoxide-water mixed solution, so that the fluorescence intensity is enhanced, and the organic fluorescent probe EDA-ATPM can be used as an ideal rapid quizalofop-p-ethyl detection fluorescent probe.

Description

Technical Field

[0001] The invention belongs to the technical field of organic synthesis and analytical chemistry, and specifically relates to an organic fluorescent probe EDA-ATPM for detecting quizalofop-p-ethyl and a preparation method and application thereof. Background Art

[0002] Quizalofop-Ph-ethyl is a phenoxycarboxylic acid ester systemic conduction stem and leaf treatment herbicide developed by Nissan Chemical Industries, Ltd. of Japan. As a highly effective herbicide, the mechanism of action of Quizalofop-Ph-ethyl is mainly through absorption by weed stems and leaves, bidirectional conduction upward and downward in the plant body, accumulation at the apical and intercalary meristems, inhibiting cellular fatty acid synthesis and causing weed necrosis. Quizalofop-Ph-ethyl is a highly selective new dryland stem and leaf treatment agent, which is highly selective between grass weeds and dicotyledonous crops, and has a good control effect on grass weeds in broad-leaved crop fields. It is widely used in important crops such as soybeans, sugar beets and cotton to control annual or perennial grass weeds such as foxtail, teff and bermudagrass, and has important agricultural production value.

[0003] However, Quizalofop-PhD is a water-soluble herbicide. Its use in agricultural production will cause it to remain in vegetables and fruits, and penetrate into water and soil under the action of rainwater, and eventually enter the human body through the food chain. The use of Quizalofop-PhD not only increases environmental pollution, but also increases food safety and human disease risks. Studies have shown that if you accidentally come into contact with high concentrations of Quizalofop-PhD, acute poisoning incidents may occur, including cell apoptosis and heart damage, posing a serious threat to human health. The "National Food Safety Standard-Maximum Residue Limits of Pesticides in Food" (GB2763-2021) stipulates that the maximum residues of Quizalofop-PhD in vegetables and fruits, grains and oil crops are 0.2 mg / kg and 0.1 mg / kg, respectively.

[0004] However, in my country, quizalofop-p-ethyl is still widely produced and used as an excellent herbicide, and is widely and massively used in agricultural production. In addition, the state has set few limits on the use of quizalofop-p-ethyl in various crops and lacks effective supervision, resulting in a large degree of blindness in the use process and frequent production accidents. Therefore, establishing an effective analysis and detection method for quizalofop-p-ethyl residues and regulating drug use are of great significance to ensuring agricultural production, food safety and people's health.

[0005] To date, many chromatography-based detection methods have been developed for the detection of quizalofop-p-ethyl in the environment and agricultural products, mainly including gas chromatography tandem mass spectrometry (GC-MS), liquid chromatography or high performance liquid chromatography tandem mass spectrometry (LC / HPLC-MS). For example, a Chinese patent with publication number CN108896694A and application date July 5, 2018 discloses an LC-QToF-MS screening and analysis method for pesticide residues in animal food, comprising the following steps: (1) extraction: homogenizing the animal food sample and mixing it with an extraction solvent, extracting by oscillation to obtain an extract, and then removing water and centrifuging the extract to obtain a supernatant; (2) purification: mixing the supernatant obtained in step (1) with a purifier for purification, collecting the supernatant, and then diluting and filtering the supernatant in turn to obtain a sample liquid a; (3) chromatography-mass spectrometry detection: using reverse phase liquid chromatography to separate pesticide residues in the sample liquid a; then using QToFMS with an ESI ion source to screen and analyze the pesticide residues, and using the external standard method for quantification to obtain the content of various pesticide residues including quizalofop-p-ethyl in animal food.

[0006] A Chinese patent with publication number CN106645493A and application date December 29, 2016 provides a method for detecting the residues of quizalofop-p-ethyl and its metabolites in a complex matrix. The method is a matrix solid phase dispersion extraction method, comprising the following steps: (1) extracting the residues in the sample; (2) purifying: measuring the extract in step (2) and adding a purifying agent to perform matrix solid phase dispersion extraction; (3) preparing a standard solution; (4) detecting by high performance liquid chromatography tandem mass spectrometry (HPLCMS / MS); (5) establishing a standard curve; and (6) analyzing the results. The detection method can rapidly, sensitively and accurately determine the residues of quizalofop-p-ethyl and its metabolites.

[0007] The above-mentioned traditional detection method detects the concentration of Quizalofop-PhD by chromatography, but for pesticides such as Quizalofop-PhD, the residual form and stability in different matrices (such as soil, water, plant tissue, etc.) may be different. The complexity and diversity of the samples to be tested may lead to large errors. In addition, the traditional detection method involves the use of precision instruments and equipment, which may not meet the requirements for occasions where rapid detection of Quizalofop-PhD residues is required (such as on-site monitoring, rapid screening, etc.). In addition, the detection cost is expensive, time-consuming, and requires complex pre-treatment, which limits the application of Quizalofop-PhD in certain emergency or rapid detection scenarios.

[0008] Organic fluorescent probes use fluorescent substances as indicators and produce fluorescence under the excitation of light of a certain wavelength, and detect the generated fluorescence to achieve qualitative or quantitative analysis of the substance being detected. As an excellent fluorescent sensor, organic fluorescent probes have excellent biosensitivity, high sensitivity, rapid response, and strong anti-interference ability in cells. They have been successfully used in the detection of various molecules and ions, and play an important role in biological detection, medical diagnosis, environmental monitoring, and materials science. With the continuous advancement of science and technology, the performance research of organic fluorescent probes has continued to mature, and its application fields have become more extensive, but organic fluorescent probes for identifying quizalofop-p-ethyl are rare.

[0009] Quizalofop-PhD is currently widely used as a herbicide in the crop industry, but excessive or long-term intake of pesticide residues may have adverse effects on human health, such as causing cancer, neurological diseases, immune system diseases, etc. In order to protect the health of users and contacts, improve food safety, promote sustainable agricultural development, and respond to environmental risks, it is urgent to design an organic fluorescent probe with high sensitivity, high selectivity, high stability and biocompatibility that can be easily applied to various Quizalofop-PhD detection scenarios. Summary of the invention

[0010] In order to solve the problems existing in the prior art, the present invention provides an organic fluorescent probe EDA-ATPM for detecting quizalofop-p-ethyl and a preparation method and application thereof. The organic fluorescent probe EDA-ATPM can form a complex with quizalofop-p-ethyl in a dimethyl sulfoxide-water mixed solution to enhance the fluorescence intensity, and can serve as an ideal fluorescent probe for rapid detection of quizalofop-p-ethyl.

[0011] The technical solution of the present invention is as follows:

[0012] One of the purposes of the present invention is to provide a method for preparing an organic fluorescent probe EDA-ATPM. In a nitrogen atmosphere, KI is used as a catalyst, 4-(1,4,5-triphenyl-1H-imidazolyl-2-yl)pyridine and 1,2-chloroacetylaminoethane are stirred and refluxed in dry acetonitrile for reaction. After the reaction is completed, the reactant is filtered, the filtrate is concentrated under reduced pressure, and the product is separated by rapid column chromatography. The light green solid product after drying is collected, which is the organic fluorescent probe EDA-ATPM.

[0013] Furthermore, the synthesis route of the organic fluorescent probe EDA-ATPM is as follows:

[0014]

[0015] Furthermore, the 4-(1,4,5-triphenyl-1H-imidazolyl-2-yl)pyridine was prepared according to the method of the public document "Analytical Chemistry, 2017, 89(18):10085-10093".

[0016] Furthermore, the 1,2-chloroacetylaminoethane is prepared according to the method of the public document "Journal of Inclusion Phenomena and Macrocyclic Chemistry, 2009, 67 (1-2): 49-54".

[0017] Furthermore, the molar ratio of 4-(1,4,5-triphenyl-1H-imidazolyl-2-yl)pyridine, 1,2-chloroacetylaminoethane and KI is 6-2:1:6-16.

[0018] Furthermore, the stirring and reflux conditions are stirring and reflux in 20-40 mL of dry acetonitrile for 6-24 h.

[0019] Furthermore, the reduced pressure concentration is performed by reducing the pressure with a water pump to evaporate the filtrate to a substantially solvent-free state.

[0020] Furthermore, the detergent used in the rapid column chromatography is a methanol / dichloromethane mixed solution, and the volume ratio of the two is 1:2.

[0021] The second object of the present invention is to provide an organic fluorescent probe EDA-ATPM, wherein the organic fluorescent probe EDA-ATPM is a compound composed of ethylenediamine bridged tetraphenylimidazole derivatives, and its molecular formula is C 58 H 48 I2N8O2, chemical name is 1,2-(pyridine-4-(1,4,5-triphenyl-1H-imidazolyl-2-yl))acetamidoethane.

[0022] Furthermore, the specific structure of the organic fluorescent probe EDA-ATPM is:

[0023]

[0024] Furthermore, the organic fluorescent probe EDA-ATPM appears yellow-green in a dimethyl sulfoxide solution and emits green fluorescence at 513 nm.

[0025] Furthermore, the organic fluorescent probe EDA-ATPM nuclear magnetic resonance hydrogen spectrum (400MHz, DMSO-d6) ppm: 8.79 (bs, 2H, NH), 8.73 (d, J = 8.0 Hz, 4H, ArH), 7.75 (d, J = 8.0 Hz, 4H, ArH), 7.21-7.48 (m, 30H, ArH), 5.29 (bs, 4H, CH2N + ),3.12(bs,4H,NCH2).

[0026] Carbon NMR (100 MHz, DMSO-d6) ppm: 165.14, 146.36, 144.54, 140.61, 140.43, 136.63, 135.89, 133.47, 131.34, 130.65, 130.43, 129.75, 129.25, 129.15, 128.93, 128.03, 127.01, 123.49, 61.27, 38.81. MALDI-TOF-MS (C 58 H 48 I2N8O2)Calcd.For m / z=1142.885,found:889.329(-2I - ),1015.269(-I - ).Anal.Calcd.for C 58 H 48 I2N8O2: C 60.95; H 4.23; N9.80. Found: C 60.91; H 4.19; N 9.74.

[0027] The third object of the present invention is to provide an application of an organic fluorescent probe EDA-ATPM in a rapid and sensitive detection environment for quizalofop-p-ethyl.

[0028] Furthermore, in a dimethyl sulfoxide-water mixed solution, the organic fluorescent probe EDA-ATPM emits a weak green fluorescence at 522 nm and can form a 1:1 complex with quizalofop-p-ethyl, significantly enhancing its fluorescence intensity. Within a certain range, the degree of fluorescence enhancement is proportional to the concentration of quizalofop-p-ethyl. The quizalofop-p-ethyl content in the solution can be obtained by comparing the fluorescence intensity value with the quizalofop-p-ethyl concentration gradient change standard curve.

[0029] Furthermore, the volume ratio of the two in the dimethyl sulfoxide-water mixed solution is 5:95.

[0030] Furthermore, the organic fluorescent probe EDA-ATPM was prepared into a solution of a certain concentration, and a series of quizalofop-p-ethyl solutions with gradient concentrations were prepared at molar multiples of 0, 0.02, 0.04, 0.06, 0.08, 0.1, 0.2, 0.4, 0.6, 0.8, 1.0, 2.0, 4.0, 6.0, 8.0, and 10.0 of this concentration. The organic fluorescent probe EDA-ATPM was thoroughly shaken and mixed with the quizalofop-p-ethyl series solutions of different concentrations one by one, and the fluorescence intensity of the mixed solution was measured to establish a standard curve of the gradient change of quizalofop-p-ethyl concentration with the quizalofop-p-ethyl concentration as the horizontal axis and the fluorescence intensity of the mixed solution as the vertical axis.

[0031] Furthermore, the organic fluorescent probe EDA-ATPM is mixed with a solution of unknown concentration containing quizalofop-ethyl pesticide, the fluorescence intensity value of the mixed solution is measured and compared with the standard curve of quizalofop-ethyl concentration gradient change, and the content of quizalofop-ethyl in the solution of unknown concentration can be read from the curve.

[0032] Compared with the prior art, the beneficial effects of the present invention are:

[0033] 1. The present invention discloses for the first time a compound 1,2-(pyridine-4-(1,4,5-triphenyl-1H-imidazolyl-2-yl))acetamidoethane, which is a tetraphenylimidazole derivative bridged by ethylenediamine, and uses it as an organic fluorescent probe EDA-ATPM. The organic fluorescent probe EDA-ATPM is yellow-green in a dimethyl sulfoxide solution, emits green fluorescence at 513nm, and emits weak green fluorescence at 522nm in a dimethyl sulfoxide-water (V / V, 5:95) mixed solution. When quizalofop-ethyl is present in a solution environment, the organic fluorescent probe EDA-ATPM can form a 1:1 complex with quizalofop-ethyl, significantly enhancing the fluorescence intensity, and within a certain range, the degree of fluorescence enhancement is proportional to the concentration of quizalofop-ethyl, which can be applied to the sensitive detection of quizalofop-ethyl in various environments, and is an ideal fluorescent probe for rapid detection of quizalofop-ethyl.

[0034] 2. The present invention constructs a novel organic fluorescent probe EDA-ATPM with high sensitivity, high selectivity and high stability. By designing a specific recognition unit, the organic fluorescent probe can produce a specific fluorescent signal for Quizalofop-Phase-III, and can overcome the interference of other substances to detect very low concentrations of the target molecule Quizalofop-Phase-III, with a detection limit of up to 3.05 μM, ensuring the accuracy of detecting Quizalofop-Phase-III pesticides in complex environments and real samples. In addition, the organic fluorescent probe EDA-ATPM can also realize real-time quantitative detection and visualization detection, monitor the distribution and residue of Quizalofop-Phase-III in various environments, and is suitable for various Quizalofop-Phase-III detection scenarios that require rapid response, and intuitively display the detection results through visualization of fluorescent signals.

[0035] 3. The present invention also provides a preparation method of an organic fluorescent probe EDA-ATPM, wherein the synthesis method of the raw materials 4-(1,4,5-triphenyl-1H-imidazolyl-2-yl)pyridine and 1,2-chloroacetylaminoethane is relatively mature, the synthesis path is simple and easy to operate, and no complicated pretreatment or special reaction equipment is required. At the same time, the high yield and purity of the probe molecule can be ensured, and the synthesis cost is relatively low, which is suitable for large-scale production. In addition, the organic fluorescent probe EDA-ATPM is not easy to decompose or inactivate during storage and use, has good stability, can maintain its fluorescence characteristics under different environmental conditions, and can meet the large demand for detecting quizalofop-ethyl in practical applications. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 This is an infrared spectrum of the functional group structure of the organic fluorescent probe EDA-ATPM described in Example 1 of the present invention;

[0037] Figure 2 This is a hydrogen nuclear magnetic resonance spectrum of the organic fluorescent probe EDA-ATPM structure described in Example 1 of the present invention;

[0038] Figure 3 This is the carbon nuclear magnetic resonance spectrum of the organic fluorescent probe EDA-ATPM structure described in Example 1 of the present invention;

[0039] Figure 4 This is a mass spectrum of the organic fluorescent probe EDA-ATPM structure described in Example 1 of the present invention;

[0040] Figure 5 1.0×10 -5 mol / L of the organic fluorescent probe EDA-ATPM was mixed with 1.0×10 -5 mol / L fluorescence emission spectra of various common pesticide molecules or ions mixed, where 1 = EDA-ATPM, 2 = 1 + Quizalofop-Ph-ethyl, 3 = 1 + Pymetrozine, 4 = 1 + Imidacloprid, 5 = 1 + Glufosinate, 6 = 1 + Glyphosate Isopropylamine, 7 = 1 + Mancozeb, 8 = 1 + Methimazole, 9 = 1 + Thiophanate-Methyl, 10 = 1 + Methimsulfuron-methyl, 11 = 1 + Bromoxynil Octanoyl, 12 = 1 + Cypermethrin, 13 = 1 + Metaldehyde, 14 = 1 + Tricyclazole, 15 = 1 + Cartap, 16 = 1 + Na + , 18=1+K + , 19=1+Al 3+ , 20 = 1 + Ba 2+ , 21=1+Ca 2+ , 22=1+Mg 2+ , 23=1+Cu2 + , 24=1+Zn 2+ , 25 = 1 +

[0041] NH4 + , 26=1+SO4 2- , 27=1+Cl - , 28=1+PO4 3- , 29=1+NO3 - ,30=1+

[0042] HPO4 2- ,The illustration is the fluorescence comparison before and after identification of Quizalofop-P-ethyl;

[0043] Figure 6 1.0×10 -5 mol / L of the organic fluorescent probe EDA-ATPM after mixing with different concentrations of Quizalofop-P-ethyl in dimethyl sulfoxide-water solution (V / V, 5:95);

[0044] Figure 7 The performance test of the present invention is based on Figure 6 The standard curve of quizalofop-ethyl concentration gradient change and fluorescence intensity change established by fluorescence emission spectrum;

[0045] Figure 8 The graph of the change in fluorescence intensity of the organic fluorescent probe EDA-ATPM described in the performance test of the present invention before and after adding other objects to a mixed solution of quizalofop-p-ethyl in dimethyl sulfoxide-water solution (V / V, 5:95), wherein 1=EDA-ATPM+quizalofop-p-ethyl, 2=1+pymetrozine, 3=1+imidacloprid, 4=1+glufosinate, 5=1+glyphosate isopropylamine salt, 6=1+mancozeb, 7=1+mefacyl, 8=1+thiophanate-methyl, 9=1+sulfuron-methyl, 10=1+bromoxynil octanoate, 11=1+chlorpyrifos, 12=1+spirulinamidol ethanolamine salt, 13=1+metaaldehyde, 14=1+tricyclazole, 15=1+carbazide, 16=1+Na + , 17=1+K + , 18=1+Al 3+ , 19 = 1 + Ba 2+ , 20=1+Ca 2+ , 21=1+Mg 2+ , 22=1+Cu 2+ , 23=1+Zn 2+ , 24=1+NH4 + , 25=1+SO4 2- , 26=1+Cl - , 27=1+PO4 3- , 28 = 1 + NO3- , 29=1+HPO4 2- . DETAILED DESCRIPTION

[0046] The present invention is further described below in conjunction with preferred embodiments. The endpoints of the ranges disclosed in the present invention and any values ​​are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, and these numerical ranges should be deemed to be specifically disclosed herein.

[0047] The experimental methods in the following examples, unless otherwise specified, are conventional methods and are performed according to the techniques or conditions described in the literature in the art or according to the product instructions.

[0048] Unless otherwise specified, the materials and reagents used in the following examples can be obtained from commercial sources.

[0049] In the following examples, 4-(1,4,5-triphenyl-1H-imidazolyl-2-yl)pyridine was prepared according to the method of the public document "Analytical Chemistry, 2017, 89(18): 10085-10093".

[0050] The 1,2-chloroacetylaminoethane in the following examples was prepared according to the method of the public document “Journal of Inclusion Phenomena and Macrocyclic Chemistry, 2009, 67(1-2):49-54”.

[0051] Example 1

[0052] This embodiment provides a method for preparing an organic fluorescent probe EDA-ATPM for detecting Quizalofop-P-ethyl, which specifically comprises the following steps:

[0053] S1. Under nitrogen atmosphere, 4-(1,4,5-triphenyl-1H-imidazolyl-2-yl)pyridine (2 mmol), 1,2-chloroacetamidoethane (1 mmol) and KI (6 mmol) were stirred and refluxed in 40 mL of dry acetonitrile for 24 hours;

[0054] S2. The reaction progress was monitored by TLC. After the reaction was completed, the reactants were filtered, and the filtrate was evaporated to a substantially solvent-free state by reducing the pressure through a water pump. The product was separated by rapid column chromatography (eluent: methanol / dichloromethane = 1:2, V / V). The light green solid product was collected and dried, which was the organic fluorescent probe EDA-ATPM, with a yield of 67%.

[0055] The infrared spectra of the functional group structures of the organic fluorescent probe EDA-ATPM prepared in this embodiment are shown in FIG. Figure 1 As shown; the nuclear magnetic resonance hydrogen spectrum is shown Figure 2 As shown; the carbon NMR spectrum is as shown Figure 3 As shown; the mass spectrum is as Figure 4 shown.

[0056] Example 2

[0057] This embodiment provides a method for preparing an organic fluorescent probe EDA-ATPM for detecting Quizalofop-P-ethyl, which specifically comprises the following steps:

[0058] S1. Under nitrogen atmosphere, 4-(1,4,5-triphenyl-1H-imidazolyl-2-yl)pyridine (6 mmol), 1,2-chloroacetamidoethane (1 mmol) and KI (12 mmol) were stirred and refluxed in 30 mL of dry acetonitrile for 6 hours;

[0059] S2. The reaction progress was monitored by TLC. After the reaction was completed, the reactants were filtered, and the filtrate was evaporated to a substantially solvent-free state by reducing the pressure through a water pump. The product was separated by rapid column chromatography (eluent: methanol / dichloromethane = 1:2, V / V). The light green solid product was collected and dried, which was the organic fluorescent probe EDA-ATPM, with a yield of 59%.

[0060] Example 3

[0061] This embodiment provides a method for preparing an organic fluorescent probe EDA-ATPM for detecting Quizalofop-P-ethyl, which specifically comprises the following steps:

[0062] S1. Under nitrogen atmosphere, 4-(1,4,5-triphenyl-1H-imidazolyl-2-yl)pyridine (4 mmol), 1,2-chloroacetamidoethane (1 mmol) and KI (16 mmol) were stirred and refluxed in 20 mL of dry acetonitrile for 12 hours;

[0063] S2. The reaction progress was monitored by TLC. After the reaction was completed, the reactants were filtered, and the filtrate was evaporated to a substantially solvent-free state by reducing the pressure with a water pump. The product was separated by rapid column chromatography (eluent: methanol / dichloromethane = 1:2, V / V). The light green solid product was collected and dried, which was the organic fluorescent probe EDA-ATPM, with a yield of 71%.

[0064] Performance Testing

[0065] 1. Selective testing

[0066] In a dimethyl sulfoxide-water solution (V / V, 5:95), 1.0×10 -5mol / L organic fluorescent probe EDA-ATPM and 1.0×10 -5 mol / L of various common pesticide molecules or ions were mixed, and the fluorescence intensity was measured respectively. The fluorescence emission spectrum was constructed with the wavelength as the horizontal axis and the fluorescence intensity as the vertical axis.

[0067] Fluorescence emission spectra such as Figure 5 As shown, in the tests of various pesticide molecules or ions, the organic fluorescent probe EDA-ATPM only responded significantly to Quizalofop-Ph-ethyl and the fluorescence was significantly enhanced, indicating that the organic fluorescent probe EDA-ATPM can perform good selective recognition on Quizalofop-Ph-ethyl.

[0068] 2. Correlation test

[0069] In a dimethyl sulfoxide-water solution (V / V, 5:95), 1.0×10 -5 mol / L organic fluorescent probe EDA-ATPM was mixed with quizalofop-p-ethyl solutions of different concentrations. The concentrations of quizalofop-p-ethyl were 0, 0.02, 0.04, 0.06, 0.08, 0.1, 0.2, 0.4, 0.6, 0.8, 1.0, 2.0, 4.0, 6.0, 8.0 and 10.0 molar multiples of the concentration of the organic fluorescent probe EDA-ATPM, respectively. The fluorescence emission spectrum was constructed with the wavelength as the abscissa and the fluorescence intensity as the ordinate, and a standard curve of the concentration gradient change and the fluorescence intensity change of quizalofop-p-ethyl was established based on this.

[0070] Fluorescence emission spectra such as Figure 6 As shown in Figure 1, the fluorescence intensity of the organic fluorescent probe EDA-ATPM showed a significant upward trend with the increase of the concentration of quizalofop-p-ethyl. The standard curve of the change of the concentration gradient of quizalofop-p-ethyl and the change of the fluorescence intensity is shown in Figure 1. Figure 7 As shown, when the concentration of quizalofop-ethyl was 0~1×10 -6 In the range of mol / L, the enhancement of the fluorescence intensity of the mixed system of organic fluorescent probe EDA-ATPM and quizalofop-p-ethyl is linearly related to the concentration of quizalofop-p-ethyl, with good correlation, and can be used as a standard working curve for the control detection of quizalofop-p-ethyl concentration.

[0071] 3. Sensitivity test

[0072] In a dimethyl sulfoxide-water solution (V / V, 5:95), 1.0×10 -5 mol / L organic fluorescent probe EDA-ATPM and quizalofop-p-ethyl before and after adding other interfering objects. The concentration of the mixed system after adding other interfering objects is 2.0×10 -5 mol / L.

[0073] like Figure 8As shown in the fluorescence intensity change graph, the detection of Quizalofop-Ph-ethyl by the organic fluorescent probe EDA-ATPM of the present invention is not disturbed after adding other objects, indicating that the organic fluorescent probe EDA-ATPM has the characteristic of high sensitivity in the detection of Quizalofop-Ph-ethyl.

[0074] It should be noted that, in this article, relational terms such as "first" and "second" are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. The terms "include", "comprises" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device. In the absence of further restrictions, the elements defined by the sentence "comprises a ..." do not exclude the presence of other identical elements in the process, method, article or device including the elements.

[0075] The above are only preferred embodiments of the present application and do not constitute any form of limitation to the present application. Any technician familiar with the profession can make some changes or modify the technical contents disclosed above into equivalent embodiments with equivalent changes without departing from the scope of the technical solution of the present application. However, any simple modification, equivalent change and modification made to the above embodiments based on the technical essence of the present application without departing from the content of the technical solution of the present application still fall within the scope of the technical solution of the present application.

Claims

1. A method for preparing an organic fluorescent probe EDA-ATPM, characterized in that: In a nitrogen atmosphere, KI is used as a catalyst, 4-(1,4,5-triphenyl-1H-imidazolyl-2-yl)pyridine and 1,2-chloroacetylaminoethane are stirred and refluxed in dry acetonitrile to react. After the reaction is completed, the reactant is filtered, the filtrate is concentrated under reduced pressure, and the product is separated by rapid column chromatography. The light green solid product is collected and dried, which is the organic fluorescent probe EDA-ATPM.

2. The method for preparing an organic fluorescent probe EDA-ATPM according to claim 1, characterized in that: The molar ratio of the 4-(1,4,5-triphenyl-1H-imidazolyl-2-yl)pyridine, 1,2-chloroacetylaminoethane and KI is 6-2:1:6-16.

3. The method for preparing an organic fluorescent probe EDA-ATPM according to claim 1, characterized in that: The stirring and reflux conditions are stirring and reflux in 20-40 mL of dry acetonitrile for 6-24 hours.

4. The method for preparing an organic fluorescent probe EDA-ATPM according to claim 1, characterized in that: The reduced pressure concentration is carried out by reducing the pressure with a water pump to evaporate the filtrate to a substantially solvent-free state.

5. The method for preparing an organic fluorescent probe EDA-ATPM according to claim 1, characterized in that: The washing solvent used in the flash column chromatography is a methanol / dichloromethane mixed solution, and the volume ratio of the two is 1:

2.

6. An organic fluorescent probe EDA-ATPM prepared according to any one of claims 1 to 5, characterized in that: The organic fluorescent probe EDA-ATPM is a compound composed of ethylenediamine bridging tetraphenylimidazole derivatives, and its molecular formula is C 58 H 48 I2N8O2, chemical name is 1,2-(pyridine-4-(1,4,5-triphenyl-1H-imidazolyl-2-yl))acetamidoethane.

7. The organic fluorescent probe EDA-ATPM according to claim 6, characterized in that: The specific structure of the organic fluorescent probe EDA-ATPM is:

8. The organic fluorescent probe EDA-ATPM according to claim 6, characterized in that: The organic fluorescent probe EDA-ATPM appears yellow-green in a dimethyl sulfoxide solution and emits green fluorescence at 513 nm.

9. Use of the organic fluorescent probe EDA-ATPM according to any one of claims 6 to 8 in rapid and sensitive detection of quizalofop-p-ethyl in an environment.

10. The use of an organic fluorescent probe EDA-ATPM in a rapid and sensitive detection environment of quizalofop-p-ethyl according to claim 9, characterized in that: In a dimethyl sulfoxide-water mixed solution, the organic fluorescent probe EDA-ATPM emits a weak green fluorescence at 522 nm and can form a 1:1 complex with quizalofop-p-ethyl, significantly enhancing its fluorescence intensity. Within a certain range, the degree of fluorescence enhancement is proportional to the concentration of quizalofop-p-ethyl. The quizalofop-p-ethyl content in the solution can be obtained by comparing the fluorescence intensity value with the standard curve of the quizalofop-p-ethyl concentration gradient change.

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