Water-soluble arylacetylene illuminant containing amidinourea and preparation method and application of water-soluble arylacetylene illuminant

Abstract

The invention belongs to the technical field of organic conjugated compounds, and particularly relates to an amidinourea-containing water-soluble arylacetylene illuminant and a preparation method and application thereof.The preparation method of the amidinourea-containing water-soluble arylacetylene illuminant comprises the following steps that (1) in the nitrogen atmosphere, an amidinourea-containing water-soluble arylacetylene illuminant is obtained; the method comprises the following steps: reacting a guanidyl monomer, an alkyne compound, a catalyst and a mixed solvent to obtain a reaction solution; (2) extracting the reaction liquid, drying an organic phase, performing rotary evaporation under reduced pressure to obtain a crude product, and separating and purifying the crude product to obtain an amidinourea-based aromatic acetylene compound; and (3) mixing the amidinourea-based aromatic acetylene compound with dichloromethane, adding trifluoroacetic acid, stirring, carrying out reduced pressure rotary evaporation, washing with an organic solvent, and drying to obtain the amidinourea-containing water-soluble aromatic acetylene illuminant. The water-soluble arylacetylene illuminant containing the amidinourea group is excellent in activity, good in water solubility, stable in chemical property, high in sensitivity and high in selectivity.

Description

Technical Field

[0001] The invention belongs to the technical field of organic conjugated compounds, and in particular relates to a water-soluble aryleneacetylene luminophore containing a guanylurea group, and a preparation method and application thereof. Background Art

[0002] Nitroaromatic compounds are an important class of explosives, which are usually highly explosive and toxic, so the detection of this type of explosives has received widespread attention. Selecting a highly sensitive, highly selective sensor system suitable for detecting trace amounts of nitroaromatic explosives in water is an urgent need for human health, public safety, and environmental protection. So far, significant progress has been made in the detection of nitroaromatic explosives. Instrumental analysis methods represented by Raman spectroscopy, electrochemistry, mass spectrometry, and ion mobility spectroscopy have been developed and applied, but these methods have problems such as complex measurement processes, long time consumption, and low selectivity. Therefore, it is still difficult to quickly, simply, and sensitively identify and detect nitroaromatic explosives.

[0003] Aromatic acetylene compounds are the earliest fluorescent materials used in the detection of nitroaromatic explosives. They are a class of molecules with a rigid structure. Their electron-rich main chain can easily respond to electron-deficient nitroaromatic molecules through an electron transfer mechanism, showing high sensitivity. At the same time, they have the advantages of high quantum yield, strong stability, good biocompatibility and easy modification, which facilitates the precise regulation of their photophysical properties. However, the existing arylacetylene compounds have strong hydrophobicity due to the presence of a rigid structure, which makes them very easy to aggregate in aqueous solution, and then fluorescence quenching occurs, which is not conducive to their identification and detection of explosives in aqueous solution. At the same time, the sensitivity and selectivity need to be improved. Summary of the invention

[0004] In view of the deficiencies in the prior art, the problem to be solved by the present invention is to provide a water-soluble arylene acetylene luminophore containing a guanyl urea group, which has good fluorescence properties; the present invention also provides a preparation method and application thereof, the preparation method is simple, and the product yield is high.

[0005] In order to achieve the above-mentioned invention object and solve the problems existing in the prior art, the technical solution adopted by the present invention is: The water-soluble aryleneacetylene luminophore containing guanylurea group of the present invention has the following structural formula:

[0006] Wherein the structural formula M is one of the following structural formulas: .

[0007] in: The method for preparing the water-soluble arylene acetylene luminophore containing guanyl urea group of the present invention comprises the following steps: (1) tetrahydrofuran and diisopropylamine are mixed, and oxygen and water are removed to obtain a mixed solvent; under a nitrogen atmosphere, a guanidine monomer, an acetylene compound, a catalyst and the mixed solvent are reacted to obtain a reaction solution; (2) extracting the reaction solution, drying the organic phase, and rotary evaporating under reduced pressure to obtain a crude product, and separating and purifying the crude product to obtain a guanylurea aromatic acetylene compound; (3) A guanylurea arylene acetylene compound is mixed with dichloromethane, trifluoroacetic acid is added and stirred, and then rotary evaporation is performed, and then washing is performed with an organic solvent. After drying, a water-soluble arylene acetylene luminophore containing a guanylurea group is obtained.

[0008] The structural formula of the guanidine monomer in step (1) is as follows: ; The acetylene compound is one of phenylacetylene, 1-ethynyl-4-(1,2,2-triphenylvinyl)benzene or 2,5-bis(4-ethynylphenyl)-1,1-dimethyl-3,4-diphenyl-silole; The molar ratio of the guanidine monomer, the acetylene compound and the catalyst is 1-1.4:0.5-4:0.15-0.4; the catalyst is a mixture of bis(triphenylphosphine)palladium chloride and cuprous iodide, and the molar ratio of bis(triphenylphosphine)palladium chloride and cuprous iodide is 1:1.8-2.0.

[0009] The deoxygenation and dehydration time in step (1) is 20-30 minutes.

[0010] In the step (1), the mixed solvent is a mixture of tetrahydrofuran and diisopropylamine, the volume ratio of tetrahydrofuran to diisopropylamine is 1.5-1.7:1, and the ratio of guanidine monomer to mixed solvent is 1:34-108, wherein the guanidine monomer is measured in mM and the mixed solvent is measured in ml.

[0011] The reaction time in step (1) is 12-18 hours and the reaction temperature is 60-75°C.

[0012] The extraction in step (2) is performed by mixing dichloromethane and saturated ammonium chloride solution and then extracting for 3-5 times, and drying the organic phase using anhydrous magnesium sulfate; the separation and purification is performed by using an eluent to perform chromatography separation and purification in a chromatographic column, and the eluent is a mixture of petroleum ether, ethyl acetate and triethylamine or a mixture of petroleum ether and dichloromethane; the volume ratio of petroleum ether, ethyl acetate and triethylamine in the mixture of petroleum ether, ethyl acetate and triethylamine is 5-10:1:0.1-0.2, and the volume ratio of petroleum ether to dichloromethane in the mixture of petroleum ether and dichloromethane is 3-5:1.

[0013] In the step (3), the ratio of the guanylurea aromatic acetylene compound, dichloromethane and trifluoroacetic acid is 1:60-100:60-100, wherein the guanylurea aromatic acetylene compound is measured in mM, and the dichloromethane and trifluoroacetic acid are measured in ml; the stirring temperature is 20-30°C, the stirring speed is 200-450 r / min, the stirring time is 6-120 min, and the rotary evaporation times are 3-5 times.

[0014] The organic solvent in step (3) is ether or n-hexane.

[0015] The water-soluble arylene acetylene luminophore containing guanyl urea groups of the present invention is applied to the fluorescence detection of nitroaromatic explosives in aqueous solution.

[0016] The method for testing the luminescent properties of the water-soluble arylene acetylene luminophore containing guanyl urea groups of the present invention is to dissolve the sensor molecules in methanol and perform a performance test at room temperature.

[0017] The water-soluble arylene acetylene luminophore is prepared by a one-pot method in a mixture system of tetrahydrofuran and diisopropylamine using a guanidine monomer and an acetylene compound to synthesize a guanidine-urea arylene acetylene compound containing a Boc group. The guanidine-urea arylene acetylene compound containing a Boc group is then deprotected to obtain a guanidine-urea arylene acetylene luminophore containing a guanidine-urea group. The guanidine-urea arylene acetylene luminophore containing a water-soluble arylene acetylene luminophore can be used for the detection of trace nitroaromatic explosives in aqueous solutions, among which the acetylene compounds are widely applicable and have a high detection efficiency.

[0018] When nitroaromatic explosives are detected, the electrons of the water-soluble arylene acetylene luminophore containing guanylurea groups will jump from the ground state HOMO orbit to the LUMO orbit to enter the excited state under the excitation of photons. The excited state is unstable due to its high energy, and the electrons will be further transferred. Since the LUMO orbital energy level in nitroaromatic explosives is between the HOMO orbital and the LUMO orbital of the water-soluble arylene acetylene luminophore containing guanylurea groups, the electrons will preferentially transfer to the orbit with a smaller energy level difference, that is, the LUMO orbital of the nitroaromatic explosives. The electrons of the water-soluble arylene acetylene luminophore containing guanylurea groups do not return to their HOMO orbital by the original path, resulting in fluorescence quenching. Therefore, the water-soluble arylene acetylene luminophore containing guanylurea groups can detect trace nitroaromatic explosives in aqueous solutions.

[0019] The beneficial effects of the present invention are as follows: The present invention introduces a highly efficient ion receptor guanylurea group as a side chain of a water-soluble arylene acetylene luminophore to improve the water solubility of sensor molecules and the sensitivity of detecting explosives. Guanylurea groups have strong water solubility and high biological activity, can interact with a variety of groups or elements in organisms, and are highly efficient ion receptors. Guanylurea groups in water-soluble arylene acetylene luminophores containing guanylurea groups can increase the solubility of sensor molecules in water phases and increase the sensing activity of sensor molecules, thereby helping sensor molecules to exert better detection performance.

[0020] The present invention introduces a guanylurea side chain into a water-soluble arylene acetylene luminophore, thereby improving the problem that a traditional water-soluble arylene acetylene luminophore is easily aggregated in water, reducing the occurrence of fluorescence quenching, and increasing the toughness of the water-soluble arylene acetylene luminophore containing the guanylurea group on the basis of having a rigid structure, thereby achieving the purpose of highly sensitive and highly selective identification of trace nitroaromatic explosives in an aqueous solution.

[0021] The water-soluble arylene acetylene luminophore containing guanylurea groups can realize accurate trace detection by photoinduced electron transfer between the electron-rich groups on the main chain and the electron-deficient nitroaromatic explosives, resulting in fluorescence quenching. The water-soluble arylene acetylene luminophore containing guanylurea groups obtained by the present invention has excellent activity, good water solubility, stable chemical properties, high sensitivity and strong selectivity; the nitroaromatic explosives mainly include 2,4,6-trinitrophenol. Since the strong electron-deficient structure of 2,4,6-trinitrophenol can form specific recognition with the electron-rich structure in the water-soluble arylene acetylene luminophore containing guanylurea groups, the water-soluble arylene acetylene luminophore containing guanylurea groups can be used as a luminescence detector to selectively identify 2,4,6-trinitrophenol in a series of nitroaromatic explosives, thereby realizing specific recognition of 2,4,6-trinitrophenol. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 is the H NMR spectrum of BU1 in Example 1; Figure 2 is the NMR carbon spectrum of BU1 in Example 1; Figure 3 is the mass spectrum of BU1 in Example 1; Figure 4 is the H NMR spectrum of U1 in Example 1; Figure 5 is the NMR carbon spectrum of U1 in Example 1; Figure 6 is the mass spectrum of U1 in Example 1; Figure 7 is the H NMR spectrum of BU2 in Example 2; Figure 8 is the NMR carbon spectrum of BU2 in Example 2; Fig. 9 is the mass spectrum of BU2 in Example 2; Fig.10 is the H NMR spectrum of U2 in Example 2; Fig.11 is the NMR carbon spectrum of U2 in Example 2; Fig.12 is the mass spectrum of U2 in Example 2; Fig.13 is the H NMR spectrum of BU3 in Example 3; Fig.14 is the NMR carbon spectrum of BU3 in Example 3; Fig.15 is the mass spectrum of BU3 in Example 3; Fig.16 is the H NMR spectrum of U3 in Example 3; Fig.17 is the NMR carbon spectrum of U3 in Example 3; Fig.18 is the mass spectrum of U3 in Example 3; Fig.19 The ultraviolet-visible absorption spectrum and fluorescence emission spectrum of the guanylurea aromatic acetylene compound BU1-3 in tetrahydrofuran of the present invention are shown in Figure A, wherein Figure A is an ultraviolet-visible absorption spectrum of the guanylurea aromatic acetylene compound BU1-3 in tetrahydrofuran, and Figure B is a fluorescence emission spectrum of the guanylurea aromatic acetylene compound BU1-3 in tetrahydrofuran; Fig. 20 The ultraviolet-visible absorption spectrum and fluorescence emission spectrum of the water-soluble arylene acetylene luminophore U1-3 containing guanylurea group in the present invention in methanol, wherein Figure A is the ultraviolet-visible absorption spectrum of the water-soluble arylene acetylene luminophore U1-3 containing guanylurea group in methanol, and Figure B is the fluorescence emission spectrum of the water-soluble arylene acetylene luminophore U1-3 containing guanylurea group in methanol; Fig.21 It is a fluorescence spectrum of U1 detecting 2,4,6-trinitrophenol. The curves in the figure correspond from top to bottom to the fluorescence intensity curves after U1 is added to 0μM, 0.2μM, 0.4μM, 0.6μM, 0.8μM, 1μM, 2μM, 4μM, 6μM, 8μM, 10μM and 20μM concentrations of 2,4,6-trinitrophenol aqueous solution respectively; Fig. 22 It is a fluorescence spectrum of U2 detecting 2,4,6-trinitrophenol, and each curve in the figure corresponds from top to bottom to the fluorescence intensity curves after U2 is added to 0μM, 0.2μM, 0.4μM, 0.6μM, 0.8μM, 1μM, 2μM, 4μM, 6μM, 8μM and 10μM concentrations of 2,4,6-trinitrophenol aqueous solution respectively; Fig.23 This is the fluorescence spectrum of U3 detecting 2,4,6-trinitrophenol. The curves in the figure correspond from top to bottom to the fluorescence intensity curves after adding U3 to 0μM, 0.2μM, 0.4μM, 0.6μM, 0.8μM, 1μM, 2μM, 4μM, 6μM, 8μM, 10μM and 20μM concentrations of 2,4,6-trinitrophenol aqueous solution. DETAILED DESCRIPTION

[0023] The present invention is further described below with reference to the embodiments.

[0024] Example 1 The synthetic route of BU1 is as follows:

[0025] (1) Tetrahydrofuran and diisopropylamine in a volume ratio of 3:2 were mixed, and deoxygenated and dehydrated for 25 min to obtain a mixed solvent; under a nitrogen atmosphere, 0.2 mM guanidine monomer H1, 0.8 mM phenylacetylene, 0.02 mM bis(triphenylphosphine)palladium chloride, 0.04 mM cuprous iodide and 15 mL of the mixed solvent were added into a 50 mL Schlenk reaction tube with a magnetic electron, and reacted at 60 ° C for 12 h to obtain a reaction solution; (2) A mixed solution of dichloromethane and saturated ammonium chloride was added to the reaction solution for extraction three times. The organic phases were combined and dried over anhydrous magnesium sulfate. The crude product was obtained by rotary evaporation under reduced pressure. The crude product was separated and purified by chromatography on a chromatographic column using 1000 mL of a mixed solution of petroleum ether, ethyl acetate and triethylamine as an eluent. The volume ratio of petroleum ether, ethyl acetate and triethylamine was 5:1:0.1 to obtain a guanylurea aromatic acetylene compound BU1 as an orange-yellow solid with a yield of 90%.

[0026] The H NMR spectrum of BU1 is shown in Figure 1 : 1 HNMR (400MHz, CDCl 3 )δ12.43(s,2H),8.51–8.39(m,2H),7.60–7.51(m,4H),7.37–7.30(m,6H),7.03( s,2H),4.24–4.17(m,4H),4.16–3.72(m,8H),1.39(s,18H),1.30–1.21(m,24H).

[0027] The NMR spectrum of BU1 is shown in Figure 2 : 13 CNMR (100MHz, CDCl 3)δ163.4,153.8,153.6,131.9,128.5,128.4,123.4,117.7,95.6,85.4,68.3,44.8,40.5,28.3,28.2,28.1,20.9.

[0028] The mass spectrum of BU1 is shown in Figure 3 : HRMS(ESI):[M+H] + calcdforC 52 H 70 N 8 O 8 :935.5395;found935.5405.

[0029] The synthetic route of U1 is as follows:

[0030] 32 μM BU1 was added to a 10 mL round-bottom flask with a magnet, 2 mL of dichloromethane was added and mixed, and then 2 mL of trifluoroacetic acid was added and stirred for 6 min at a stirring speed of 200 r / min. Then, rotary evaporation was performed 3 times, and then washed with ether three times. After drying, a water-soluble arylene acetylene luminophore U1 containing a guanyl urea group was obtained as a brown-yellow solid with a yield of 97%.

[0031] The H NMR spectrum of U1 is shown in Figure 4 : 1 HNMR (400 MHz, CDCl 3 ) δ 10.76 – 10.60 (m, 2H), 7.54 (h, J = 5.7, 4.3Hz, 4H), 7.43 – 7.33 (m, 6H), 7.03 (s, 2H), 4.24 (s, 4H), 3.79 (s, 8H), 1.25(d, J = 6.4 Hz, 24H).

[0032] The NMR carbon spectrum of U1 is shown in Figure 5 : 13 CNMR (100MHz, CDCl 3 )δ152.7,131.8,129.2,128.8,96.3,84.7,41.9,29.8,20.7.

[0033] The mass spectrum of U1 is shown in Figure 6 : HRMS(ESI):[M+H] +calcdforC 42 H 56 N 8 O 4 :735.4346;found735.4338.

[0034] Example 2 The synthetic route of BU2 is as follows:

[0035] (1) Tetrahydrofuran and diisopropylamine in a volume ratio of 3:2 were mixed, and deoxygenated and dehydrated for 25 min to obtain a mixed solvent; under a nitrogen atmosphere, 0.139 mM guanidine monomer H1, 0.348 mM 1-ethynyl-4-(1,2,2-triphenylvinyl)benzene, 0.0139 mM bis(triphenylphosphine)palladium chloride, 0.027 mM cuprous iodide and 15 mL of the mixed solvent were added to a 50 mL Schlenk reaction tube with a magnetic rod, and the reaction was carried out at 75 ° C for 12 h to obtain a reaction solution; (2) A mixed solution of dichloromethane and saturated ammonium chloride was added to the reaction solution for extraction three times. The organic phases were combined and dried over anhydrous magnesium sulfate. The crude product was obtained by rotary evaporation under reduced pressure. The crude product was separated and purified by chromatography on a chromatographic column using 1100 mL of a mixed solution of petroleum ether, ethyl acetate and triethylamine as an eluent. The volume ratio of petroleum ether, ethyl acetate and triethylamine was 5:1:0.1 to obtain guanylurea aromatic acetylene compound BU2 as a light yellow solid with a yield of 41%.

[0036] The H NMR spectrum of BU2 is shown in Figure 7 : 1 HNMR (400 MHz, CDCl 3 )δ12.41(s,2H),8.44(s,2H),7.34–7.29(m,4H),7.10(dt, J =6.0,3.0Hz,18H),7.02(dq, J =10.1,2.8,2.1Hz,14H),6.97(d, J =8.3Hz,4H),4.15(t, J =5.6Hz,4H),3.80(q, J =5.6Hz,4H),1.37(s,18H),1.24(dd, J =12.3,6.5Hz,24H).

[0037] The NMR spectrum of BU2 is shown in Figure 8 : 13CNMR (100 MHz, CDCl 3 ) δ 163.3,153.8,153.5,144.2,143.6,143.5,141.7,140.4,131.5,131.4,131.2,131.0,128.9,12 7.9,127.8,126.8,126.7,121.2,117.7,114.5,95.8,85.8,82.1,68.3,40.4,38.9,28.2,20.9.

[0038] The mass spectrum of BU2 is shown in Fig. 9 : HRMS (ESI): [M+Na] + Calculate for C 42 H 52 N 2 O 10 Na: 1465.7405; found 1465.7396.

[0039] The synthetic route of U2 is as follows:

[0040] 21 μM BU2 was added to a 10 mL round-bottom flask with a magnet, 2 mL of dichloromethane was added and mixed, and then 2 mL of trifluoroacetic acid was added and stirred for 1 h at a stirring speed of 250 r / min. Then, rotary evaporation was performed 3 times, and then washed with ether 3 times. After drying, a water-soluble arylene acetylene luminophore U2 containing a guanyl urea group was obtained as a brown-yellow solid with a yield of 81%.

[0041] The H NMR spectrum of U2 is shown in Fig.10 : 1 HNMR (400MHz, CD 3 OD)δ7.27(dd, J =8.1,1.9Hz,3H),7.17–7.06(m,19H),7.05–6.79(m,18H),4.32–4.15(m,4H),3.77(tt, J =10.0,5.2Hz,8H),1.34–1.22(m,24H).

[0042] The NMR carbon spectrum of U2 is shown in Fig.11 : 13 CNMR (100MHz, CDCl 3)δ192.1,152.6,143.4,143.3,140.2,131.8,131.5,131.4,131.1,129.3,128.0,127.8,126.8,46.1,29.8,28.2,20.8.

[0043] The mass spectrum of U2 is shown in Fig.12 : HRMS(ESI):[M+H] + calcdforC 82 H 83 N 8 O 4 :1243.6537;found1243.6530.

[0044] Example 3 The synthetic route of BU3 is as follows:

[0045] (1) tetrahydrofuran and diisopropylamine in a volume ratio of 3:2 were mixed, and deoxygenated and dehydrated for 25 min to obtain a mixed solvent; under a nitrogen atmosphere, 0.2 mM 2,5-di(4-ethynylphenyl)-1,1-dimethyl-3,4-diphenyl-silole, 0.44 mM guanidine monomer H2, 0.02 mM bis(triphenylphosphine)palladium chloride, 0.04 mM cuprous iodide and 15 mL of the mixed solvent were reacted at 65 °C for 18 h to obtain a reaction solution; (2) A mixed solution of dichloromethane and saturated ammonium chloride was added to the reaction solution for extraction three times. The organic phases were combined and dried over anhydrous magnesium sulfate. The crude product was obtained by rotary evaporation under reduced pressure. The crude product was separated and purified by chromatography on a chromatographic column using 1200 mL of a mixed solution of petroleum ether and dichloromethane as an eluent. The volume ratio of petroleum ether to dichloromethane was 3:1. The guanylurea aromatic acetylene compound BU3 was obtained as a light green solid with a yield of 32%.

[0046] The H NMR spectrum of BU3 is shown in Fig.13 : 1 HNMR (400MHz, CDCl 3 )δ12.44(s,2H),8.34(t, J =5.6Hz,2H),7.46–7.38(m,4H),7.27(d, J =1.9Hz,2H),7.25(s,2H),7.07–6.98(m,6H),6.93–6.83(m,8H),6.83–6.75(m,4H),4.11(t, J =5.5Hz,4H),3.77(q,J =5.6Hz,4H),1.47(s,18H),1.25(d, J =7.1Hz,24H),0.48(d, J =2.9Hz,6H).

[0047] The NMR spectrum of BU3 is shown in Fig.14 : 13 CNMR (100MHz, CDCl 3 )δ163.3,158.7,154.6,153.8,153.7,141.7,139.9,138.6,133.1,131.3,130.0,129.0,127 .7,126.6,120.6,116.0,114.8,89.6,88.6,82.3,66.6,44.9,40.3,28.3,21.5,20.9,-3.6.

[0048] The mass spectrum of BU3 is shown in Fig.15 : HRMS(ESI):[M+H] + calcdforC 76 H 91 N 8 O 8 Si:1271.6729;found1271.6752.

[0049] The synthetic route of U3 is as follows:

[0050] 23.6 μM BU3 was added to a 10 mL round-bottom flask with a magnet, 1.5 mL of dichloromethane was added and mixed, and then 1.5 mL of trifluoroacetic acid was added and stirred for 2 h at a stirring speed of 250 r / min. Then, rotary evaporation was performed for 3 times, and then washed with n-hexane for 3 times. After drying, a water-soluble arylene acetylene luminophore U3 containing a guanyl urea group was obtained as a beige solid with a yield of 95%.

[0051] The H NMR spectrum of U3 is shown in Fig.16 : 1 HNMR (400MHz, CD 3 OD)δ7.41–6.69(m,26H),4.35–4.21(m,4H),3.89–3.66(m,8H),1.35–1.28(m,24H),0.45–0.04(m,6H).

[0052] The NMR carbon spectrum of U3 is shown in Fig.17 : 13 CNMR (100MHz, CD 3 OD)δ163.4,157.1,153.4,132.9,132.2,131.4,131.3,130.8,129.4,128.8, 115.5,115.3,96.8,67.0,53.5,47.8,42.0,20.9,20.9,19.2,9.1,7.6,0.4.

[0053] The mass spectrum of U3 is shown in Fig.18 : HRMS(ESI):[M+H] + calcdforC 66 H 75 N 8 O 4 Si:1071.5681;found1071.5685.

[0054] BU1-3 and U1-3 detection application experiment Experiment 1: Detect the properties of the guanylurea arylene acetylene compound BU1-3 and the guanylurea-containing water-soluble arylene acetylene luminophore U1-3.

[0055] The guanylurea arylene acetylene compound BU1-3 is dissolved in tetrahydrofuran, and its ultraviolet visible absorption spectrum and fluorescence spectrum are detected; the guanylurea-containing water-soluble arylene acetylene luminophore U1-3 is dissolved in methanol, and its ultraviolet visible absorption spectrum and fluorescence spectrum are detected.

[0056] Experiment 2: Fluorescence detection of 2,4,6-trinitrophenol was achieved using the water-soluble arylene acetylene luminophore U1 containing a guanyl urea group.

[0057] Prepare a 1mM U1 methanol solution and a 20mM 2,4,6-trinitrophenol aqueous solution. During the test, add 15μL of U1 methanol solution to the quartz cuvette, then add 2985μL of water, test the initial fluorescence emission spectrum, then add 50μM 2,4,6-trinitrophenol aqueous solution, and test its fluorescence spectrum, compare the changes in fluorescence intensity, and calculate the fluorescence quenching efficiency to be 94%.

[0058] Experiment 3: Use the water-soluble arylene acetylene luminophore U2 containing guanyl urea group to realize the fluorescence detection of 2,4,6-trinitrophenol.

[0059] Prepare a 1mM U2 methanol solution and a 20mM 2,4,6-trinitrophenol aqueous solution. During the test, add 15μL of U2 methanol solution to the quartz cuvette, then add 2985μL of water, test the initial fluorescence emission spectrum, then add 50μM 2,4,6-trinitrophenol aqueous solution, and test its fluorescence spectrum, compare the changes in fluorescence intensity, and calculate the fluorescence quenching efficiency to be 98%.

[0060] Experiment 4: Fluorescence detection of 2,4,6-trinitrophenol was achieved using the water-soluble aryleneacetylene luminophore U3 containing guanyl urea groups.

[0061] Prepare a 1mM U3 methanol solution and a 20mM 2,4,6-trinitrophenol aqueous solution. During the test, add 15μL of U3 methanol solution to the quartz cuvette, then add 2985μL of water, test the initial fluorescence emission spectrum, then add 50μM 2,4,6-trinitrophenol aqueous solution, and test its fluorescence spectrum, compare the changes in fluorescence intensity, and calculate the fluorescence quenching efficiency to be 96%.

[0062] Experiment 5: Prepare a methanol solution of U1 with a concentration of 1 mM. Then, refer to the method of Experiment 2 to test the fluorescence characteristics of nitrobenzene aqueous solution, 4-nitroaniline aqueous solution, 2-nitrophenol aqueous solution, 4-nitrophenol aqueous solution, 2,4-dinitrobenzene aqueous solution and 2,4-dinitrotoluene aqueous solution. The fluorescence quenching efficiencies are calculated to be 10%, 70%, 27%, 17%, 7% and 14%, respectively.

[0063] Experiment 6: Prepare a methanol solution of U2 with a concentration of 1 mM. Then, refer to the method of Experiment 2 to test the fluorescence characteristics of nitrobenzene aqueous solution, 4-nitroaniline aqueous solution, 2-nitrophenol aqueous solution, 4-nitrophenol aqueous solution, 2,4-dinitrobenzene aqueous solution and 2,4-dinitrotoluene aqueous solution. The fluorescence quenching efficiencies are calculated to be 18%, 43%, 35%, 19%, 8% and 4%, respectively.

[0064] Experiment 7: Prepare a methanol solution of U3 with a concentration of 1 mM. Then, refer to the method of Experiment 2 to test the fluorescence characteristics of nitrobenzene aqueous solution, 4-nitroaniline aqueous solution, 2-nitrophenol aqueous solution, 4-nitrophenol aqueous solution, 2,4-dinitrobenzene aqueous solution and 2,4-dinitrotoluene aqueous solution. The fluorescence quenching efficiencies are calculated to be 9%, 35%, 44%, 5%, 17% and 5%, respectively.

[0065] The characteristic spectra of the guanylurea aromatic acetylene compound BU1-3 and the water-soluble aromatic acetylene luminophore U1-3 containing the guanylurea group can be obtained by the detection method of Experiment 1; the data of Experiments 2-7 show that the water-soluble aromatic acetylene luminophore U1-3 containing the guanylurea group can selectively identify 2,4,6-trinitrophenol among nitroaromatic explosives.

[0066] Result analysis: The UV-visible absorption spectrum and fluorescence emission spectrum of guanylurea aromatic acetylene compound BU1-3 in tetrahydrofuran are shown in Fig.19 , the corresponding photophysical data are shown in Table 1. Fig.19 As can be seen from Table 1, BU1 has absorption peaks at 310nm and 360nm, and a fluorescence emission peak at 404nm; compared with BU1, BU2 containing tetraphenylethylene luminescent groups has a certain degree of red shift in its absorption peak and emission peak, which are located at 380nm and 455nm respectively; BU3 containing silole luminescent groups has absorption peaks at 295nm and 386nm, and a fluorescence emission peak at 530nm. The Stokes shift of BU1 and BU2 is 303cm -1 and 434cm -1 , and the BU3 Stokes shift reaches 704cm -1 . The quantum yield of BU1 in tetrahydrofuran solution is as high as 72.64%, showing bright blue fluorescence; and tetrahydrofuran is a good solvent for BU2 and BU3 with aggregation-induced emission properties. BU2 and BU3 are well dispersed in tetrahydrofuran and only show weak blue fluorescence and green fluorescence under ultraviolet light excitation. It was found that the quantum yield of BU2 and BU3 in tetrahydrofuran solution is only 0.38% and 3.61%. At the same time, the fluorescence lifetimes of BU1-3 in tetrahydrofuran are all in the range of 1.07-1.53ns.

[0067]

[0068] In Table 1: [a] UV-visible maximum absorption wavelength; [b] fluorescence maximum emission wavelength; [c] Stokes shift; [d] fluorescence absolute quantum yield; [e] fluorescence lifetime.

[0069] The UV-visible absorption spectrum and fluorescence emission spectrum of water-soluble arylene acetylene luminophore U1-3 in methanol are shown in Fig. 20 The corresponding photophysical data are shown in Table 2. Fig. 20As can be seen from Table 2, U1 has absorption peaks at 305nm and 355nm, and a fluorescence emission peak at 395nm; compared with U1, the absorption peak and emission peak of U2 containing tetraphenylethylene luminescent group are red-shifted to a certain extent, located at 365nm and 448nm respectively; U3 containing silole luminescent group has an absorption peak at 265nm and a fluorescence emission peak at 424nm. The Stokes shift of U1 is 285cm -1 , the Stokes shift of U2 is 508 cm -1 , the Stokes shift of U3 reached 1415cm -1 . The quantum yield of U1 in methanol solution reached 91.09%, showing bright blue-purple fluorescence; methanol is a good solvent for U2 and U3 with aggregation-induced emission properties. U2 and U3 are well dispersed in methanol and only show weak blue fluorescence under ultraviolet light excitation. It was found that the quantum yield of U2 and U3 in methanol solution was only 0.54% and 2.72%. At the same time, the fluorescence lifetimes of U1 and U2 in tetrahydrofuran are 1.59ns and 1.39ns, and the fluorescence lifetime of U3 in tetrahydrofuran reaches 3.04ns.

[0070]

[0071] In Table 2: [a] UV-visible maximum absorption wavelength; [b] fluorescence maximum emission wavelength; [c] Stokes shift; [d] fluorescence quantum yield; [e] fluorescence lifetime.

[0072] The water-soluble aryleneacetylene luminophore U1-3 containing guanylurea groups can achieve high-sensitivity detection of 2,4,6-trinitrophenol by fluorescence quenching in aqueous solution. Aqueous solutions of 2,4,6-trinitrophenol with different concentration gradients were prepared, and then the same amount of water-soluble aryleneacetylene luminophore U1-3 containing guanylurea groups was used to detect them. The detection results are as follows: Figure 21-23 As shown in Table 3, as the concentration of 2,4,6-trinitrophenol increases, the fluorescence intensity of the water-soluble arylene acetylene luminophore U1-3 gradually decreases, and the degree of decrease in fluorescence intensity is affected by the conjugation length and ionic side chain composition of the water-soluble arylene acetylene luminophore containing guanidine urea groups. The quenching constant ( K sv ), and the corresponding detection limit (LOD) was calculated. The quenching constant of 2,4,6-trinitrophenol for U2 was as high as 6.8×10 6 M -1 At the same time, the detection limit of U2 for 2,4,6-trinitrophenol can be as low as 1nM.

[0073]

Claims

1. A water-soluble aryleneacetylene luminophore containing a guanylurea group, characterized in that: The structural formula is as follows: Wherein the structural formula M is one of the following structural formulas: 。 2. A method for preparing a water-soluble aryleneacetylene luminophore containing a guanylurea group according to claim 1, characterized in that: The following steps are involved: (1) tetrahydrofuran and diisopropylamine are mixed, and oxygen and water are removed to obtain a mixed solvent; under a nitrogen atmosphere, a guanidine monomer, an acetylene compound, a catalyst and the mixed solvent are reacted to obtain a reaction solution; (2) extracting the reaction solution, drying the organic phase, and rotary evaporating under reduced pressure to obtain a crude product, and separating and purifying the crude product to obtain a guanylurea aromatic acetylene compound; (3) A guanylurea arylene acetylene compound is mixed with dichloromethane, trifluoroacetic acid is added and stirred, and then rotary evaporation is performed, and then washing is performed with an organic solvent. After drying, a water-soluble arylene acetylene luminophore containing a guanylurea group is obtained.

3. The method for preparing a water-soluble aryleneacetylene luminophore containing a guanylurea group according to claim 2, characterized in that: The structural formula of the guanidine monomer in step (1) is as follows: or ; The acetylene compound is one of phenylacetylene, 1-ethynyl-4-(1,2,2-triphenylvinyl)benzene or 2,5-bis(4-ethynylphenyl)-1,1-dimethyl-3,4-diphenyl-silole; The molar ratio of the guanidine monomer, the acetylene compound and the catalyst is 1-1.4:0.5-4:0.15-0.4; the catalyst is a mixture of bis(triphenylphosphine)palladium chloride and cuprous iodide, and the molar ratio of bis(triphenylphosphine)palladium chloride and cuprous iodide is 1:1.8-2.

0.

4. The method for preparing a water-soluble aryleneacetylene luminophore containing a guanylurea group according to claim 2, characterized in that: The deoxygenation and dehydration time in step (1) is 20-30 minutes.

5. The method for preparing a water-soluble aryleneacetylene luminophore containing a guanylurea group according to claim 2, characterized in that: In step (1), the mixed solvent is a mixture of tetrahydrofuran and diisopropylamine, the volume ratio of tetrahydrofuran to diisopropylamine is 1.5-1.7:1, and the ratio of guanidine monomer to mixed solvent is 1:34-108, wherein the guanidine monomer is measured in mM and the mixed solvent is measured in ml.

6. The method for preparing a water-soluble aryleneacetylene luminophore containing a guanylurea group according to claim 2, characterized in that: The reaction time in step (1) is 12-18 hours, and the reaction temperature is 60-75°C.

7. The method for preparing a water-soluble aryleneacetylene luminophore containing a guanylurea group according to claim 2, characterized in that: The extraction in step (2) is to mix dichloromethane and saturated ammonium chloride solution and then extract for 3-5 times, and dry the organic phase using anhydrous magnesium sulfate; the separation and purification is to use an eluent to perform chromatography separation and purification in a chromatographic column, and the eluent is a mixture of petroleum ether, ethyl acetate and triethylamine or a mixture of petroleum ether and dichloromethane; the volume ratio of petroleum ether, ethyl acetate and triethylamine in the mixture of petroleum ether, ethyl acetate and triethylamine is 5-10:1:0.1-0.2, and the volume ratio of petroleum ether to dichloromethane in the mixture of petroleum ether and dichloromethane is 3-5:

1.

8. The method for preparing a water-soluble aryleneacetylene luminophore containing a guanylurea group according to claim 2, characterized in that: In step (3), the ratio of the guanylurea aromatic acetylene compound, dichloromethane and trifluoroacetic acid is 1:60-100:60-100, wherein the guanylurea aromatic acetylene compound is measured in mM, and the dichloromethane and trifluoroacetic acid are measured in ml; the stirring temperature is 20-30° C., the stirring speed is 200-450 r / min, the stirring time is 6-120 min, and the number of rotary evaporation is 3-5 times.

9. The method for preparing a water-soluble aryleneacetylene luminophore containing a guanylurea group according to claim 2, characterized in that: In step (3), the organic solvent is ether or n-hexane.

10. An application of the water-soluble aryleneacetylene luminophore containing guanylurea group according to claim 1, characterized in that: The water-soluble arylene acetylene luminophore containing guanyl urea group is applied to the fluorescence detection of nitroaromatic explosives in aqueous solution.

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