Water-soluble aromatic acetylene luminescent materials containing amidourea groups, their preparation methods and applications

Abstract

The application belongs to the technical field of organic conjugated compounds, and particularly relates to a water-soluble arylene-acetylene luminophore containing amidine urea groups, a preparation method and application thereof. The preparation method of the water-soluble arylene-acetylene luminophore containing amidine urea groups comprises the following steps: (1) under a nitrogen atmosphere, reacting guanidino monomers, acetylenic compounds, a catalyst and a mixed solvent to obtain a reaction solution; (2) extracting the reaction solution, drying an organic phase, and performing rotary evaporation under reduced pressure to obtain a crude product, and then separating and purifying the crude product to obtain an amidine urea group arylene-acetylene compound; (3) mixing the amidine urea group arylene-acetylene compound with dichloromethane, adding trifluoroacetic acid, stirring, performing rotary evaporation under reduced pressure, washing with an organic solvent, and drying to obtain the water-soluble arylene-acetylene luminophore containing amidine urea groups. The water-soluble arylene-acetylene luminophore containing amidine urea groups obtained by the application has excellent activity, good water solubility, stable chemical properties, high sensitivity and strong selectivity.

Description

Technical Field

[0001] This invention belongs to the field of organic conjugated compound technology, specifically relating to a water-soluble aromatic acetylene luminescent material containing an amidourea group, its preparation method, and its application. Background Technology

[0002] Nitroaromatic compounds are an important class of explosives, typically exhibiting high explosiveness and toxicity, thus their detection has received widespread attention. Selecting a highly sensitive, selective, and suitable sensing system for detecting trace amounts of nitroaromatic explosives in water is an urgent need for human health, public safety, and environmental protection. To date, significant progress has been made in the detection of nitroaromatic explosives, with instrumental analytical methods such as Raman spectroscopy, electrochemistry, mass spectrometry, and ion mobility spectroscopy being developed and applied. However, these methods suffer from problems such as complex measurement processes, long measurement times, and low selectivity, making rapid, simple, and sensitive identification and detection of nitroaromatic explosives still challenging.

[0003] Aromatic acetylene compounds were among the first fluorescent materials used for the detection of nitroaromatic explosives. These molecules possess a rigid structure, and their electron-rich backbone readily responds to electron-deficient nitroaromatic molecules through electron transfer mechanisms, exhibiting high sensitivity. They also possess advantages such as high quantum yield, strong stability, good biocompatibility, and ease of modification, facilitating precise control of their photophysical properties. However, the rigid structure of existing aromatic acetylene compounds makes them highly hydrophobic, leading to easy aggregation in aqueous solutions and subsequent fluorescence quenching. This hinders their identification and detection of explosives in aqueous solutions, and their sensitivity and selectivity still need improvement. Summary of the Invention

[0004] To address the shortcomings of existing technologies, the present invention aims to provide a water-soluble aromatic acetylene luminescent material containing an amidourea group, which exhibits excellent fluorescence properties. The invention also provides its preparation method and applications; the preparation method is simple and yields a high product rate.

[0005] To achieve the above-mentioned objectives and solve the problems existing in the prior art, the technical solution adopted by the present invention is as follows:

[0006] The water-soluble aromatic acetylene luminescent material containing an amidourea group described in this invention has the following structural formula:

[0007]

[0008] In the formula, the M structure is one of the following structures:

[0009]

[0010] .

[0011] in:

[0012] The preparation method of the water-soluble aromatic acetylene luminescent material containing an amidourea group according to the present invention includes the following steps:

[0013] (1) Tetrahydrofuran and diisopropylamine were mixed and deoxygenated and dehydrated to obtain a mixed solvent; under a nitrogen atmosphere, guanidine monomers, alkyne compounds, catalysts and the mixed solvent were reacted to obtain a reaction solution;

[0014] (2) The reaction solution was extracted, the organic phase was dried, and the crude product was obtained by rotary evaporation under reduced pressure. The crude product was separated and purified to obtain amidoureidoaryl acetylene compounds.

[0015] (3) Mix the amidoureido-based aromatic acetylene compound with dichloromethane, add trifluoroacetic acid and stir, then rotary evaporate, wash with organic solvent and dry to obtain a water-soluble aromatic acetylene luminescent material containing amidoureido group.

[0016] The structural formula of the guanidino monomer in step (1) is as follows:

[0017] ;

[0018] The alkyne 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-thiophene;

[0019] The molar ratio of guanidino monomer, alkyne compound and 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, with a molar ratio of bis(triphenylphosphine)palladium chloride to cuprous iodide of 1:1.8-2.0.

[0020] The deoxygenation and dehydration time in step (1) is 20-30 minutes.

[0021] In step (1), the mixed solvent is a mixture of tetrahydrofuran and diisopropylamine, with a volume ratio of 1.5-1.7:1 between tetrahydrofuran and diisopropylamine, and a ratio of guanidine monomer to mixed solvent of 1:34-108, wherein the guanidine monomer is in mM and the mixed solvent is in ml.

[0022] The reaction time in step (1) is 12-18h and the reaction temperature is 60-75℃.

[0023] In step (2), the extraction is performed by mixing dichloromethane and saturated ammonium chloride solution and extracting 3-5 times. The organic phase is dried using anhydrous magnesium sulfate. The separation and purification are performed by chromatographic separation and purification using an eluent in a chromatographic column. 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. The volume ratio of petroleum ether to dichloromethane in the mixture of petroleum ether and dichloromethane is 3-5:1.

[0024] In step (3), the ratio of amidoureidoaryl acetylene compound, dichloromethane and trifluoroacetic acid is 1:60-100:60-100, where amidoureidoaryl acetylene compound is calculated in mM, and dichloromethane and trifluoroacetic acid are calculated in ml; the stirring temperature is 20-30℃, the stirring speed is 200-450r / min, the stirring time is 6-120min, and the rotary evaporation is performed 3-5 times.

[0025] The organic solvent in step (3) is diethyl ether or n-hexane.

[0026] The water-soluble aromatic acetylene luminescent material containing an amidourea group described in this invention is used for the fluorescence detection of nitroaromatic explosives in aqueous solutions.

[0027] The method for testing the luminescence properties of the water-soluble aromatic acetylene luminescent material containing an amidourea group of the present invention involves dissolving the sensor molecule in methanol and performing performance testing at room temperature.

[0028] The water-soluble aromatic ethylene acetylene luminescent material is synthesized in a one-pot process using a guanidine monomer and an alkyne compound in a mixture of tetrahydrofuran and diisopropylamine. The resulting compound contains a Boc group and is then deprotected to obtain the water-soluble aromatic ethylene acetylene luminescent material containing the amidouryl group. This material can be used to detect trace amounts of nitroaromatic explosives in aqueous solutions, with a wide range of alkyne compounds as applicable and high detection efficiency.

[0029] When detecting nitroaromatic explosives, electrons in a water-soluble aryl acetylene luminescent material containing an amidineuron group transition from the ground-state HOMO orbital to the LUMO orbital under photon excitation, entering an excited state. Due to its high energy, the excited state is unstable, and further electron transfer occurs. Since the LUMO orbital energy level in nitroaromatic explosives lies between the HOMO and LUMO orbitals of the amidineuron-containing water-soluble aryl acetylene luminescent material, electrons preferentially transfer to the orbital with the smaller energy difference, i.e., the LUMO orbital of the nitroaromatic explosive. The electrons in the amidineuron-containing water-soluble aryl acetylene luminescent material do not return to their HOMO orbital, resulting in fluorescence quenching. Therefore, the amidineuron-containing water-soluble aryl acetylene luminescent material can detect trace amounts of nitroaromatic explosives in aqueous solutions.

[0030] The beneficial effects of this invention are as follows:

[0031] This invention introduces a highly efficient ion-acceptor, the amidourea group, as a side chain of a water-soluble aromatic acetylene luminescent material to improve the water solubility of the sensor molecule and its sensitivity in detecting explosives. The amidourea group possesses strong water solubility and high bioactivity, and can interact with various groups or elements in organisms, making it a highly efficient ion acceptor. The amidourea group in the water-soluble aromatic acetylene luminescent material increases both the solubility of the sensor molecule in the aqueous phase and its sensing activity, thereby helping the sensor molecule to achieve better detection performance.

[0032] This invention improves the problem of traditional water-soluble aryl acetylene luminescent materials easily agglomerating in water by introducing an amidourea-based side chain into them, thereby reducing fluorescence quenching. The amidourea-based water-soluble aryl acetylene luminescent material has increased toughness while maintaining a rigid structure, thus achieving the goal of high sensitivity and high selectivity in identifying trace amounts of nitroaromatic explosives in aqueous solutions.

[0033] Amidinium-containing water-soluble aromatic acetylene luminescent emitter can achieve precise trace detection through photoinduced electron transfer between electron-rich groups on the main chain and electron-deficient nitroaromatic explosives, leading to fluorescence quenching. The amidinium-containing water-soluble aromatic acetylene luminescent emitter obtained in this invention exhibits excellent activity, good water solubility, chemical stability, high sensitivity, and strong selectivity. Nitroaromatic explosives mainly include 2,4,6-trinitrophenol. Since the strongly electron-deficient structure of 2,4,6-trinitrophenol can specifically recognize the electron-rich structure in the amidinium-containing water-soluble aromatic acetylene luminescent emitter, using this amidinium-containing water-soluble aromatic acetylene luminescent emitter as a luminescent detector can selectively recognize 2,4,6-trinitrophenol among a range of nitroaromatic explosives, achieving specific recognition of 2,4,6-trinitrophenol. Attached Figure Description

[0034] Figure 1 This is the 1H NMR spectrum of BU1 in Example 1;

[0035] Figure 2 This is the carbon NMR spectrum of BU1 in Example 1;

[0036] Figure 3 This is the mass spectrum of BU1 in Example 1;

[0037] Figure 4 This is the 1H NMR spectrum of U1 in Example 1;

[0038] Figure 5 This is the carbon NMR spectrum of U1 in Example 1;

[0039] Figure 6 This is the mass spectrum of U1 in Example 1;

[0040] Figure 7 This is the 1H NMR spectrum of BU2 in Example 2;

[0041] Figure 8 This is the carbon NMR spectrum of BU2 in Example 2;

[0042] Figure 9 This is the mass spectrum of BU2 in Example 2;

[0043] Figure 10 This is the 1H NMR spectrum of U2 in Example 2;

[0044] Figure 11 This is the carbon NMR spectrum of U2 in Example 2;

[0045] Figure 12 This is the mass spectrum of U2 in Example 2;

[0046] Figure 13 This is the 1H NMR spectrum of BU3 in Example 3;

[0047] Figure 14 This is the carbon NMR spectrum of BU3 in Example 3;

[0048] Figure 15 This is the mass spectrum of BU3 in Example 3;

[0049] Figure 16 This is the 1H NMR spectrum of U3 in Example 3;

[0050] Figure 17 This is the carbon NMR spectrum of U3 in Example 3;

[0051] Figure 18 This is the mass spectrum of U3 in Example 3;

[0052] Figure 19These are the UV-Vis absorption and fluorescence emission spectra of the amidoureidoaryl acetylene compound BU1-3 in tetrahydrofuran, wherein Figure A is the UV-Vis absorption spectrum of the amidoureidoaryl acetylene compound BU1-3 in tetrahydrofuran, and Figure B is the fluorescence emission spectrum of the amidoureidoaryl acetylene compound BU1-3 in tetrahydrofuran.

[0053] Figure 20 The images show the UV-Vis absorption spectrum and fluorescence emission spectrum of the water-soluble aromatic acetylene luminescent material U1-3 containing an amidine urea group in methanol, as described in this invention. Figure A shows the UV-Vis absorption spectrum of the water-soluble aromatic acetylene luminescent material U1-3 containing an amidine urea group in methanol, and Figure B shows the fluorescence emission spectrum of the water-soluble aromatic acetylene luminescent material U1-3 containing an amidine urea group in methanol.

[0054] Figure 21 The graph shows the fluorescence spectra of 2,4,6-trinitrophenol detected by U1. The curves in the graph, from top to bottom, correspond to the fluorescence intensity curves after adding U1 to aqueous solutions of 2,4,6-trinitrophenol at concentrations of 0 μM, 0.2 μM, 0.4 μM, 0.6 μM, 0.8 μM, 1 μM, 2 μM, 4 μM, 6 μM, 8 μM, 10 μM, and 20 μM, respectively.

[0055] Figure 22 The graph shows the fluorescence spectra of 2,4,6-trinitrophenol detected by U2. The curves in the graph, from top to bottom, correspond to the fluorescence intensity curves after adding U2 to aqueous solutions of 2,4,6-trinitrophenol at concentrations of 0 μM, 0.2 μM, 0.4 μM, 0.6 μM, 0.8 μM, 1 μM, 2 μM, 4 μM, 6 μM, 8 μM and 10 μM, respectively.

[0056] Figure 23 The graph shows the fluorescence spectra of 2,4,6-trinitrophenol detected by U3. The curves in the graph, from top to bottom, correspond to the fluorescence intensity curves after adding U3 to aqueous solutions of 2,4,6-trinitrophenol at concentrations of 0 μM, 0.2 μM, 0.4 μM, 0.6 μM, 0.8 μM, 1 μM, 2 μM, 4 μM, 6 μM, 8 μM, 10 μM, and 20 μM, respectively. Detailed Implementation

[0057] The present invention will be further described below with reference to embodiments.

[0058] Example 1

[0059] The crafting route for BU1 is as follows:

[0060]

[0061] (1) Tetrahydrofuran and diisopropylamine were mixed in a volume ratio of 3:2 and deoxygenated and dehydrated for 25 min to obtain a mixed solvent; under a nitrogen atmosphere, 0.2 mM guanidinyl 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 to a 50 mL Schlenk reaction tube with a magnetic pole and reacted at 60 °C for 12 h to obtain a reaction solution;

[0062] (2) The reaction solution was extracted three times with a mixture of dichloromethane and saturated ammonium chloride. The organic phases were combined and dried with anhydrous magnesium sulfate. The crude product was obtained by rotary evaporation under reduced pressure. The crude product was purified by chromatography using 1000 mL of a mixture of petroleum ether, ethyl acetate and triethylamine as the eluent. The volume ratio of petroleum ether, ethyl acetate and triethylamine was 5:1:0.1. The amidoureidoaryl acetylene compound BU1 was obtained as an orange-yellow solid with a yield of 90%.

[0063] The 1H NMR spectrum of BU1 is shown below. Figure 1 :

[0064] 1 HNMR(400MHz, CDCl3)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).

[0065] The carbon NMR spectrum of BU1 is shown below. Figure 2 :

[0066] 13 CNMR (100MHz, CDCl3) 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.

[0067] Mass spectrometry of BU1 can be found here. Figure 3 :

[0068] HRMS(ESI):[M+H] + calcdforC 52 H 70 N8O8:935.5395;found935.5405.

[0069] The synthesis route of U1 is as follows:

[0070]

[0071] 32 μM BU1 was added to a 10 mL round-bottom flask equipped with a magnetic stir bar, 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, the mixture was rotary evaporated 3 times, washed 3 times with diethyl ether, and dried to obtain water-soluble aromatic acetylene luminescent material U1 containing amidine urea group. It was a brownish-yellow solid with a yield of 97%.

[0072] The 1H NMR spectrum of U1 is shown below. Figure 4 :

[0073] 1 HNMR (400 MHz, CDCl3) 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).

[0074] The carbon NMR spectrum of U1 is shown below. Figure 5 :

[0075] 13 CNMR (100MHz, CDCl3) δ152.7,131.8,129.2,128.8,96.3,84.7,41.9,29.8,20.7.

[0076] Mass spectra of U1 can be found Figure 6 :

[0077] HRMS(ESI):[M+H] + calcdforC 42 H 56 N8O4:735.4346;found735.4338.

[0078] Example 2

[0079] The crafting route for BU2 is as follows:

[0080]

[0081] (1) Tetrahydrofuran and diisopropylamine were mixed in a volume ratio of 3:2 and deoxygenated and dehydrated for 25 min to obtain a mixed solvent. Under a nitrogen atmosphere, 0.139 mM guanidinyl 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 stir bar and reacted at 75 °C for 12 h to obtain a reaction solution.

[0082] (2) The reaction solution was extracted three times with a mixture of dichloromethane and saturated ammonium chloride. The organic phases were combined and dried with anhydrous magnesium sulfate. The crude product was obtained by rotary evaporation under reduced pressure. The crude product was purified by chromatography using 1100 mL of a mixture of petroleum ether, ethyl acetate and triethylamine as the eluent. The volume ratio of petroleum ether, ethyl acetate and triethylamine was 5:1:0.1. The aspartate urea aromatic acetylene compound BU2 was obtained as a pale yellow solid with a yield of 41%.

[0083] The 1H NMR spectrum of BU2 is shown below. Figure 7 :

[0084] 1 HNMR (400 MHz, CDCl3)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, 6.5 Hz, 24H).

[0085] The carbon NMR spectrum of BU2 is shown below. Figure 8 :

[0086] 13CNMR (100 MHz, CDCl3) 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.

[0087] Mass spectrometry of BU2 can be found here. Figure 9 :

[0088] HRMS (ESI): [M+Na] + calcd for C 42 H 52 N2O 10 Na: 1465.7405; found 1465.7396.

[0089] The synthesis route of U2 is as follows:

[0090]

[0091] 21 μM BU2 was added to a 10 mL round-bottom flask equipped with a magnetic stir bar, 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, the mixture was rotary evaporated 3 times, washed 3 times with diethyl ether, and dried to obtain water-soluble aromatic ethylene acetylene luminescent material U2 containing amidine urea group. It was a brownish-yellow solid with a yield of 81%.

[0092] The 1H NMR spectrum of U2 is shown below. Figure 10 :

[0093] 1 HNMR (400MHz, CD3OD) δ 7.27 (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).

[0094] The carbon NMR spectrum of U2 is shown below. Figure 11 :

[0095] 13CNMR (100MHz, CDCl3) 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.

[0096] Mass spectra of U2 can be found Figure 12 :

[0097] HRMS(ESI):[M+H] + calcdforC 82 H 83 N8O4:1243.6537;found1243.6530.

[0098] Example 3

[0099] The crafting route for BU3 is as follows:

[0100]

[0101] (1) Tetrahydrofuran and diisopropylamine were mixed in a volume ratio of 3:2 and deoxygenated and dehydrated for 25 min to obtain a mixed solvent; under a nitrogen atmosphere, 0.2 mM 2,5-bis(4-ethynylphenyl)-1,1-dimethyl-3,4-diphenyl-thiophene, 0.44 mM guanidinyl 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;

[0102] (2) The reaction solution was extracted three times with a mixture of dichloromethane and saturated ammonium chloride. The organic phases were combined and dried with anhydrous magnesium sulfate. The crude product was obtained by rotary evaporation under reduced pressure. The crude product was purified by chromatography using 1200 mL of a mixture of petroleum ether and dichloromethane as the eluent. The volume ratio of petroleum ether to dichloromethane was 3:1. The aspartate urea-aryl acetylene compound BU3 was obtained as a light green solid with a yield of 32%.

[0103] The 1H NMR spectrum of BU3 is shown below. Figure 13 :

[0104] 1 HNMR(400MHz,CDCl3)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).

[0105] The carbon NMR spectrum of BU3 is shown below. Figure 14 :

[0106] 13 CNMR (100MHz, CDCl3) 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.

[0107] Mass spectrometry of BU3 can be found here. Figure 15 :

[0108] HRMS(ESI):[M+H] + calcdforC 76 H 91 N8O8Si:1271.6729; found1271.6752.

[0109] The synthesis route for U3 is as follows:

[0110]

[0111] 23.6 μM BU3 was added to a 10 mL round-bottom flask equipped with a magnetic stir bar, 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, the mixture was rotary evaporated three times, washed three times with n-hexane, and dried to obtain a water-soluble aromatic ethylene acetylene luminescent solid U3 containing an amidine urea group, which was a light yellow solid with a yield of 95%.

[0112] The 1H NMR spectrum of U3 is shown below. Figure 16 :

[0113] 1HNMR (400MHz, CD3OD) 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).

[0114] The carbon NMR spectrum of U3 is shown below. Figure 17 :

[0115] 13 CNMR(100MHz,CD3OD)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.

[0116] Mass spectra of U3 can be found Figure 18 :

[0117] HRMS(ESI):[M+H] + calcdforC 66 H 75 N8O4Si:1071.5681;found1071.5685.

[0118] Detection application experiments of BU1-3 and U1-3

[0119] Experiment 1: To detect the properties of amidineuryl aryl acetylene compound BU1-3 and water-soluble amidineuryl aryl acetylene luminescent material U1-3.

[0120] The amidoureidoyl aryl acetylene compound BU1-3 was dissolved in tetrahydrofuran, and its UV-Vis absorption and fluorescence spectra were detected. The water-soluble aryl acetylene luminescent material U1-3 containing amidoureidoyl groups was dissolved in methanol, and its UV-Vis absorption and fluorescence spectra were detected.

[0121] Experiment 2: Fluorescence detection of 2,4,6-trinitrophenol was achieved using U1, a water-soluble aromatic acetylene luminescent material containing amidourea groups.

[0122] A 1 mM methanol solution of U1 and a 20 mM aqueous solution of 2,4,6-trinitrophenol were prepared. During the test, 15 μL of the methanol solution of U1 was added to a quartz cuvette, followed by 2985 μL of water. The initial fluorescence emission spectrum was measured. Then, 50 μM of the 2,4,6-trinitrophenol aqueous solution was added, and its fluorescence spectrum was measured. The changes in fluorescence intensity were compared, and the fluorescence quenching efficiency was calculated to be 94%.

[0123] Experiment 3: Fluorescence detection of 2,4,6-trinitrophenol was achieved using U2, a water-soluble aromatic acetylene luminescent material containing amidourea groups.

[0124] A 1 mM methanol solution of U2 and a 20 mM aqueous solution of 2,4,6-trinitrophenol were prepared. During testing, 15 μL of the methanol solution of U2 was added to a quartz cuvette, followed by 2985 μL of water. The initial fluorescence emission spectrum was measured. Then, 50 μM of the 2,4,6-trinitrophenol aqueous solution was added, and its fluorescence spectrum was measured. The changes in fluorescence intensity were compared, and the fluorescence quenching efficiency was calculated to be 98%.

[0125] Experiment 4: Fluorescence detection of 2,4,6-trinitrophenol was achieved using U3, a water-soluble aromatic acetylene luminescent material containing amidourea groups.

[0126] A 1 mM methanol solution of U3 and a 20 mM aqueous solution of 2,4,6-trinitrophenol were prepared. During testing, 15 μL of the methanol solution of U3 was added to a quartz cuvette, followed by 2985 μL of water. The initial fluorescence emission spectrum was measured. Then, 50 μM of the 2,4,6-trinitrophenol aqueous solution was added, and its fluorescence spectrum was measured. The changes in fluorescence intensity were compared, and the fluorescence quenching efficiency was calculated to be 96%.

[0127] Experiment 5: Prepare a methanol solution of U1 with a concentration of 1 mM. Then, following the method in Experiment 2, 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 respectively. Calculate the fluorescence quenching efficiencies as 10%, 70%, 27%, 17%, 7%, and 14% respectively.

[0128] Experiment 6: Prepare a methanol solution of U2 with a concentration of 1 mM. Then, following the method in Experiment 2, 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 respectively. Calculate the fluorescence quenching efficiencies as 18%, 43%, 35%, 19%, 8% and 4% respectively.

[0129] Experiment 7: Prepare a methanol solution of U3 with a concentration of 1 mM. Then, following the method in Experiment 2, 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 respectively. Calculate the fluorescence quenching efficiencies as 9%, 35%, 44%, 5%, 17% and 5% respectively.

[0130] The characteristic spectra of amidoureido-based aromatic acetylene compound BU1-3 and amidoureido-based water-soluble aromatic acetylene luminescent material U1-3 can be obtained by the method in Experiment 1. The data from Experiments 2-7 show that amidoureido-based water-soluble aromatic acetylene luminescent material U1-3 can selectively recognize 2,4,6-trinitrophenol in nitroaromatic explosives.

[0131] Results analysis:

[0132] The UV-Vis absorption and fluorescence emission spectra of amidinuryl aryl acetylene compound BU1-3 in tetrahydrofuran are shown below. Figure 19 The corresponding photophysical data are shown in Table 1. Combined with... Figure 19 As shown in Table 1, BU1 has absorption peaks at 310 nm and 360 nm, and a fluorescence emission peak at 404 nm. Compared with BU1, BU2, which contains a tetraphenylethylene luminescent group, exhibits a red shift in both its absorption and emission peaks, located at 380 nm and 455 nm, respectively. BU3, which contains a thiophene luminescent group, has absorption peaks at 295 nm and 386 nm, and a fluorescence emission peak at 530 nm. The Stokes shift of BU1 and BU2 is 303 cm⁻¹. -1 and 434cm -1 The displacement of BU3 Stokes reached 704cm. -1 BU1 exhibits a high quantum yield of 72.64% in tetrahydrofuran solution and displays bright blue fluorescence. Tetrahydrofuran is a good solvent for BU2 and BU3, which possess aggregation-induced emission properties. BU2 and BU3 exhibit a well-dispersed state in tetrahydrofuran, displaying only weak blue and green fluorescence under UV excitation. Measurements showed that the quantum yields of BU2 and BU3 in tetrahydrofuran solution were only 0.38% and 3.61%, respectively. Meanwhile, the fluorescence lifetimes of BU1-3 in tetrahydrofuran are all in the range of 1.07-1.53 ​​ns.

[0133]

[0134] In Table 1: [a] Maximum UV-Vis absorption wavelength; [b] Maximum fluorescence emission wavelength; [c] Stokes shift; [d] Absolute fluorescence quantum yield; [e] Fluorescence lifetime.

[0135] The UV-Vis absorption and fluorescence emission spectra of the water-soluble aromatic acetylene luminescent material U1-3 containing an amidine urea group in methanol are shown below. Figure 20 The corresponding photophysical data are shown in Table 2. Combined with... Figure 20As shown in Table 2, U1 has absorption peaks at 305 nm and 355 nm, and a fluorescence emission peak at 395 nm. Compared with U1, the absorption and emission peaks of U2, which contains a tetraphenylethylene luminescent group, both exhibit a certain degree of red shift, located at 365 nm and 448 nm, respectively. U3, which contains a thiophene luminescent group, has an absorption peak at 265 nm and a fluorescence emission peak at 424 nm. The Stokes shift of U1 is 285 cm⁻¹. -1 The Stokes displacement of U2 is 508cm. -1 The Stokes displacement of the U3 reached 1415cm. -1 U1 exhibited a quantum yield of 91.09% in methanol solution, displaying bright blue-violet fluorescence. Methanol, however, is a benign solvent for U2 and U3, which possess aggregation-induced emission properties. U2 and U3 showed a well-dispersed state in methanol, exhibiting only weak blue fluorescence under UV excitation. Measurements revealed that the quantum yields of U2 and U3 in methanol solution were only 0.54% and 2.72%, respectively. Meanwhile, the fluorescence lifetimes of U1 and U2 in tetrahydrofuran were 1.59 ns and 1.39 ns, respectively, while the fluorescence lifetime of U3 in tetrahydrofuran reached 3.04 ns.

[0136]

[0137] In Table 2: [a] Maximum UV-Vis absorption wavelength; [b] Maximum fluorescence emission wavelength; [c] Stokes shift; [d] Fluorescence quantum yield; [e] Fluorescence lifetime.

[0138] The water-soluble aromatic ethylene acetylene luminescent material U1-3 containing an amidine urea group can achieve highly sensitive detection of 2,4,6-trinitrophenol in aqueous solutions through fluorescence quenching. Aqueous solutions of 2,4,6-trinitrophenol with different concentration gradients were prepared, and then detected using the same amount of the water-soluble aromatic ethylene acetylene luminescent material U1-3. The detection results are as follows: Figure 21-23 As shown in Table 3, with the continuous increase of the concentration of 2,4,6-trinitrophenol, the fluorescence intensity of the water-soluble aromatic acetylene luminescent material U1-3 containing amidourea gradually decreased. The degree of decrease in fluorescence intensity was affected by the conjugation length and ionic side chain composition of the water-soluble aromatic acetylene luminescent material containing amidourea. The quenching constant of 2,4,6-trinitrophenol on U1-3 was determined in aqueous solution. K sv The detection limits (LODs) were calculated. The quenching constant of 2,4,6-trinitrophenol for U2 was as high as 6.8 × 10⁻⁶. 6 M -1 Meanwhile, the detection limit of U2 for 2,4,6-trinitrophenol can be as low as 1 nM.

[0139]

Claims

1. A water-soluble aromatic acetylene luminescent material containing an amidourea group, characterized in that, The structural formula is as follows: The structure of M is one of the following structural formulas: 。 2. A method for preparing the aramidourea-containing water-soluble arylene ethynylene light emitter according to claim 1, characterized by, The method comprises the following steps: (1) mixing tetrahydrofuran and diisopropylamine to remove oxygen and water to obtain a mixed solvent; under a nitrogen atmosphere, reacting guanidino monomer, alkyne compound and catalyst with the mixed solvent to obtain a reaction solution; the structure of the guanidino monomer is as follows: or ; The alkyne compound is one of phenylacetylene, 1-ethynyl-4-(1,2,2-triphenylvinyl) benzene or 2,5-di(4-ethynylphenyl)-1,1-dimethyl-3,4-diphenyl-thiophene; (2) extracting the reaction solution, drying the organic phase, and performing rotary evaporation under reduced pressure to obtain a crude product, which is separated and purified to obtain an amidine urea arylene acetylene compound; (3) mixing the amidine urea arylene acetylene compound with dichloromethane, adding trifluoroacetic acid, stirring, performing rotary evaporation, washing with an organic solvent, and drying to obtain an amidine urea-containing water-soluble arylene acetylene luminophore.

3. The method for preparing a water-soluble aromatic acetylene luminescent material containing an amidourea group according to claim 2, characterized in that, In step (1), the molar ratio of the guanidino monomer, alkyne compound and catalyst is 1-1.4:0.5-4:0.15-0.4; the catalyst is a mixture of dichlorobis(triphenylphosphine)palladium and cuprous iodide, and the molar ratio of dichlorobis(triphenylphosphine)palladium to cuprous iodide is 1:1.8-2.

0.

4. The method for preparing a water-soluble aromatic acetylene luminescent material containing an amidourea group according to claim 2, characterized in that, In step (1), the time for removing oxygen and water is 20-30 min.

5. The method for preparing a water-soluble aromatic acetylene luminescent material containing an amidourea group according to claim 2, characterized in that, In step (1), the mixed solvent is a mixture of tetrahydrofuran and diisopropylamine, and the volume ratio of tetrahydrofuran to diisopropylamine is 1.5-1.7:1; the ratio of the guanidino monomer to the mixed solvent is 1:34-108, wherein the guanidino monomer is in mM and the mixed solvent is in ml.

6. The method for preparing a water-soluble aromatic acetylene luminescent material containing an amidourea group according to claim 2, characterized in that, In step (1), the reaction time is 12-18 h, and the reaction temperature is 60-75°C.

7. The method for preparing a water-soluble aromatic acetylene luminescent material containing an amidourea group according to claim 2, characterized in that, In step (2), the extraction is performed 3-5 times after mixing dichloromethane and saturated ammonium chloride solution; the drying is performed using anhydrous magnesium sulfate; the separation and purification are performed by chromatographic separation and purification using an eluent in a chromatographic column; the eluent is a mixture of petroleum ether, ethyl acetate and triethylamine or a mixture of petroleum ether and dichloromethane; in the mixture of petroleum ether, ethyl acetate and triethylamine, the volume ratio of petroleum ether, ethyl acetate and triethylamine is 5-10:1:0.1-0.2; in the mixture of petroleum ether and dichloromethane, the volume ratio of petroleum ether to dichloromethane is 3-5:

1.

8. The method for preparing a water-soluble aromatic acetylene luminescent material containing an amidourea group according to claim 2, characterized in that, In step (3), the ratio of the amidine urea arylene acetylene compound, dichloromethane and trifluoroacetic acid is 1:60-100:60-100, wherein the amidine urea arylene acetylene compound is in mM, and dichloromethane and trifluoroacetic acid are 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.

9. The method for preparing a water-soluble aromatic acetylene luminescent material containing an amidourea group according to claim 2, characterized in that, In step (3), the organic solvent is diethyl ether or n-hexane.

10. Use of the arid urea-containing water-soluble aryleneacetylene light-emitting body according to claim 1, characterized by, The amidine urea-containing water-soluble arylene acetylene luminophore is applied to the fluorescence detection of nitroaromatic explosive in an aqueous solution.

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