Polysulfide aromatic hydrocarbon compound, preparation method thereof and application of polysulfide aromatic hydrocarbon compound in detection of polarity and / or viscosity
By preparing polysulfide aromatic compounds and introducing thiophenol and galactose groups around the benzene ring, the problem of fluorescent probes being unable to simultaneously detect polarity and viscosity was solved, achieving highly sensitive polarity and viscosity detection.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- JIANGSU UNIV OF SCI & TECH
- Filing Date
- 2026-01-16
- Publication Date
- 2026-04-21
Smart Images
Figure CN121895387A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of fine chemical technology, specifically relating to a polysulfide aromatic compound, its preparation method, and its application in detecting polarity and / or viscosity. Background Technology
[0002] Polarity is a core foundation for chemical separation, drug design, detergent processing, and life processes such as cell membrane formation; viscosity directly affects engineering and physiological processes such as lubricant selection, pipeline transportation, food palatability, coating application, and blood health. In practical applications, the two are closely related and work synergistically. For example, in formulation design (cosmetics, coatings) or process optimization (oil extraction, polymer processing), solubility and rheology must be controlled simultaneously to achieve a precise balance between performance and function. Meanwhile, in the biological field, key microenvironmental parameters, including viscosity and polarity, are related to physiological and pathological states. Viscosity affects the diffusion rate of biomolecules and is associated with metabolic disorders and cancer progression, while polarity shifts are related to abnormal organelle function and lipid droplet accumulation. Detecting these intracellular physiological changes not only provides functional insights into disease states but also offers an important window into cellular pathology research.
[0003] Due to their high sensitivity, spatiotemporal resolution, and non-invasiveness, fluorescent probes have become powerful tools for visualizing biochemical and physical parameters. Common design strategies for sensing viscosity often involve molecular rotors, whose intramolecular rotation is restricted in high-viscosity environments, reducing non-radiative decay. Polarity-sensitive probes often exhibit intramolecular charge transfer effects; the luminescence intensity and wavelength of the probe change significantly with polarity variations. Therefore, enhancing charge transfer can effectively improve polarity detection sensitivity. However, enhanced charge transfer often accompanies an increase in the conjugated system, leading to a reduction in the rotational degrees of freedom of the molecular rotor, thereby decreasing viscosity detection sensitivity. Therefore, fluorescent probes struggle to simultaneously detect polarity and viscosity. Polysulfide aromatic compounds possess photoexcitation-induced aggregation and luminescence properties; they disperse without luminescence in benign solvents but aggregate and emit light in unfavorable solvents or after illumination. This property is related to the polarity and viscosity of the environment, and can therefore be used to design probes for detecting both polarity and viscosity. Summary of the Invention
[0004] To address the shortcomings of existing technologies, such as the difficulty in simultaneously detecting the polarity and viscosity of the environment, the present invention aims to provide a polysulfide aromatic compound, its preparation method, and its application in detecting polarity and / or viscosity.
[0005] The polysulfide aromatic compound of this invention introduces six galactose groups through a substitution reaction, enhancing its water solubility and causing it to exhibit a non-luminescent dispersion in water. Under 365 nm illumination, due to the photoexcitation-induced aggregation and luminescence properties of the polysulfide aromatic compound, its fluorescence gradually increases. In a mixed solvent of water and 1,4-dioxane, with increasing 1,4-dioxane content and decreasing polarity, the fluorescence of the polysulfide aromatic compound blue-shifts from 515 nm to 482 nm, accompanied by a gradual increase in overall intensity. In a mixed solvent of water and glycerol, with increasing glycerol content leading to increased viscosity, the fluorescence enhancement factor of the polysulfide aromatic compound at 500 nm continuously increases.
[0006] To address the problems in the existing technology, the technical solution adopted by this invention is as follows: This invention provides a polysulfide aromatic compound with the structural formula shown in formula (I):
[0007] (I).
[0008] The aforementioned polysulfide aromatic compound has a benzene ring as its core, with six thiophenol substituents introduced around the benzene ring, and then modified with six galactose groups, denoted as compound HTB-βGal. This compound exhibits photoexcitation-induced aggregation and luminescence properties, but does not emit light when dispersed in water. Under 365 nm illumination, the luminescence of this compound is enhanced, which can be used to detect polarity and viscosity. As the polarity of the environment decreases, the luminescence enhancement factor of this compound increases, and it blue-shifts from 515 nm to 482 nm. As the viscosity of the environment increases, the luminescence enhancement factor of this compound increases further at 500 nm.
[0009] The luminescence mechanism of the polysulfide aromatic compounds is related to charge transfer. When the environmental polarity decreases, their emission wavelength shifts from 515 nm to 482 nm.
[0010] The luminescence mechanism of the polysulfide aromatic compounds is related to the rotation of the CS bond, and the luminescence enhancement at 500 nm increases with increasing ambient viscosity.
[0011] The present invention also provides a method for preparing the above-mentioned polysulfide aromatic compounds, comprising the following steps: (1) Under a nitrogen or inert gas atmosphere, hexahalobenzene, 3-methoxythiophenol and catalyst are reacted in an organic solvent to obtain compound (IV).
[0012] In this step, the hexahalobenzene includes hexabromobenzene, hexafluorobenzene, and hexaiodobenzene, preferably hexahalobenzene; the catalyst includes potassium carbonate, cesium carbonate, triethylamine, etc., preferably potassium carbonate; the mass ratio of hexabromobenzene, 3-methoxybenzenethiophenol, and catalyst is preferably 4.5-5:11-12:9-11; the organic solvent preferably includes one or more of DMF, CH3CN, THF, and NMP; the reaction temperature is preferably 70-80℃, and further, the reaction conditions are preferably stirring at 70-80℃ for 24-48 hours.
[0013]
[0014] (2) Compound (IV) and boron tribromide are reacted in an organic solvent under a nitrogen or inert gas atmosphere to obtain compound (III).
[0015] In this step, the mass-to-volume ratio of compound (IV) and boron tribromide is preferably 300-400 mg: 6-8 mL; the organic solvent preferably includes one or more of DCM, n-hexane, and carbon tetrachloride; the reaction temperature is preferably 15-35°C, and further, the reaction conditions are preferably stirring at room temperature for 10-12 h.
[0016]
[0017] (3) Compound (III), 2,3,4,6-tetraacetoxy-alpha-D-pyranose bromide, and catalyst are reacted in an organic solvent under a nitrogen or inert gas atmosphere to obtain compound (II).
[0018] In this step, the catalyst includes potassium carbonate, cesium carbonate, triethylamine, etc., preferably cesium carbonate; the mass ratio of compound (III), 2,3,4,6-tetraacetoxy-alpha-D-pyranose bromide, and catalyst is preferably 9-11:50-60:70-80; the organic solvent preferably includes one or more of CH3CN, DMF, THF, NMP, etc.; the reaction temperature is preferably 15-35℃, and further, the reaction conditions are preferably room temperature stirring for 8-10 hours.
[0019]
[0020] (4) Under a nitrogen or inert gas atmosphere, compound (II) is added to an organic solvent and the pH is adjusted to 9-11 with sodium methoxide to obtain the polysulfide aromatic compound.
[0021] In this step, the organic solvent preferably includes one or more of MeOH, EtOH, etc.; the reaction temperature is preferably 5-15℃, and further, the reaction conditions are preferably stirring at 5-15℃ for 1-2 hours.
[0022] The above steps further include separating and purifying the reaction products. Preferably, the separation and purification are performed on the reaction solution using one or more of the following methods: dilution, extraction, filtration, solvent removal under reduced pressure, column chromatography, and concentration under reduced pressure.
[0023] Furthermore, the method for preparing the polysulfide aromatic compound includes the following steps: (1) Add hexabromobenzene, 3-methoxythiophenol, and potassium carbonate to a reaction vessel. Dehydrate and deoxygenate the reaction system. Add ultra-dry DMF under a nitrogen atmosphere. Then heat to 70-80℃ and stir for 24-48h. After cooling to room temperature, add DCM and H2O. After extraction, combine the organic phases, remove the solvent under reduced pressure, purify by silica gel column chromatography, and finally concentrate under reduced pressure to obtain a white solid product compound (IV). The preferred proportions of the materials used in this step are: 450-500 mg hexabromobenzene, 1.1-1.2 g 3-methoxythiophenol, 0.9-1.1 g potassium carbonate, 4-8 mL ultra-dry DMF, 15-25 mL DCM, and 5-15 mL H2O.
[0024] (2) Compound (IV) is added to the reaction vessel. The reaction system is heated to remove water and oxygen under vacuum, with ultra-dry DCM added under N2 atmosphere. Boron tribromide is slowly added dropwise at -20°C and stirred for 1-2 h, then stirred at room temperature for 10-12 h. The solid is collected by filtration and washed with water, EA, and ethanol to obtain a yellow crude product. The product is purified by silica gel column chromatography and finally concentrated under reduced pressure to obtain the yellow product compound (III). In this step, the preferred proportions of the materials used are: 300-400 mg of compound (IV), 4-8 mL of ultra-dry DCM, and 6-8 mL of boron tribromide. The addition of boron tribromide is preferably done by uniformly adding boron tribromide dropwise using a constant pressure dropping funnel.
[0025] (3) Add compound (III), 2,3,4,6-tetraacetoxy-alpha-D-pyranose bromide, and cesium carbonate to the reaction vessel; heat the reaction system under vacuum to remove water and oxygen, add ultra-dry CH3CN under N2 atmosphere, and stir at room temperature for 8-10 h; after the reaction is completed, dilute with DCM and filter, remove the solvent from the filtrate under reduced pressure, purify with silica gel column, and finally concentrate under reduced pressure to obtain the yellow product compound (II). In this step, the preferred proportions of the materials used are: 90-110 mg of compound (III), 500-600 mg of 2,3,4,6-tetraacetoxy-alpha-D-pyranose bromide, 700-800 mg of cesium carbonate, and 10-15 mL of CH3CN.
[0026] (4) Add compound (II) to the reaction vessel, heat the reaction system under vacuum to remove water and oxygen, add ultra-dry MeOH under N2 atmosphere, slowly add a methanol solution of sodium methoxide (54 mg / mL) in an ice bath to adjust the pH to 10, stir for 10-30 min, transfer to 5-15℃ and stir for 1-2 h, then filter. Remove the solvent from the filtrate under reduced pressure to obtain a yellow solid, which is the polysulfide aromatic compound. In this step, the preferred ratio of materials used is: 40-60 mg of compound (II) and 3-5 mL of ultra-dry MeOH.
[0027] Furthermore, the specific process parameters for dehydration and deoxygenation of the reaction system in steps (1)-(4) above are: vacuum pumping for 10-20 minutes, heating to 50°C and holding for 10-20 minutes, and then replacing with nitrogen gas to enter the system.
[0028] The present invention also provides the application of the above-mentioned polysulfide aromatic compounds or polysulfide aromatic compounds prepared by the above-mentioned preparation method in the detection of polarity.
[0029] The applications include the use of polysulfide aromatic compounds for the polarity detection of liquids, determining the polarity based on the ratio of luminescence at 482 nm and 515 nm.
[0030] The present invention also provides the application of the above-mentioned polysulfide aromatic compounds or the polysulfide aromatic compounds prepared by the above-mentioned preparation method in viscosity detection.
[0031] The applications include the use of polysulfide aromatic compounds for viscosity detection of liquids, determining the viscosity based on the luminescence intensity at 500 nm.
[0032] The present invention also provides the application of the above-mentioned polysulfide aromatic compounds or the polysulfide aromatic compounds prepared by the above-mentioned preparation method in the preparation of fluorescent probes for detecting polarity and / or viscosity.
[0033] The present invention also provides a fluorescent probe for detecting polarity and / or viscosity, comprising the above-described polysulfide aromatic compound or the polysulfide aromatic compound prepared by the above-described preparation method.
[0034] The present invention has the following advantages and beneficial effects: 1. This invention uses polysulfide aromatic hydrocarbons as the backbone and connects six galactose groups to improve the water solubility of the compound, so that it presents a non-luminescent dispersed state in water. Under 365nm light, it undergoes photoexcitation-induced aggregation and luminescence, realizing remote non-destructive light-controlled luminescence.
[0035] 2. The polysulfide aromatic compounds prepared in this invention exhibit a charge transfer effect within the molecule, resulting in photoexcitation-induced aggregation luminescence properties that are related to the polarity of the environment. In a mixed solvent of water and 1,4-dioxane, as the content of 1,4-dioxane increases and the polarity decreases, the fluorescence of the polysulfide aromatic compounds shifts from 515 nm to 482 nm, accompanied by a gradual increase in overall intensity. The polarity of the environment can be determined by the fluorescence ratio at 515 nm and 482 nm.
[0036] 3. The polysulfide aromatic compounds prepared in this invention have photoexcitation-induced aggregation luminescence properties that are related to the viscosity of the environment because the CS bonds can rotate freely. In a mixed solvent of water and glycerol, the viscosity increases with the increase of glycerol content. The fluorescence enhancement factor of the polysulfide aromatic compounds at 500 nm increases continuously. The viscosity of the environment can be determined by the fluorescence intensity at 500 nm. Attached Figure Description
[0037] Figure 1 This invention presents the photocontrolled fluorescence spectrum of the polysulfide aromatic compound HTB-βGal, used for detecting polarity and viscosity, in a 1,4-dioxane / water mixed solvent at 365 nm. In Figure A, the photocontrolled fluorescence spectrum of compound HTB-βGal in a 1,4-dioxane / water mixed solvent with a 1,4-dioxane volume fraction of 0% is shown, with an excitation wavelength of 405 nm. The x-axis represents wavelength (nm), and the y-axis represents fluorescence intensity (au). Figure B shows the photocontrolled fluorescence spectrum of compound HTB-βGal in a 1,4-dioxane / water mixed solvent with a 1,4-dioxane volume fraction of 60% is shown, with an excitation wavelength of 405 nm. The x-axis represents wavelength (nm), and the y-axis represents fluorescence intensity (au).
[0038] Figure 2This is a spectral change graph of the polysulfide aromatic compound HTB-βGal, used in this invention for detecting polarity and viscosity, in a 1,4-dioxane / water mixed solvent with different volume fractions of 1,4-dioxane (10%, 20%, 30%, 40%, 50%, 60%) after 4 min under 365 nm light-controlled illumination. In the graph, A is the fluorescence spectrum change graph, with an excitation wavelength of 405 nm; the horizontal axis represents wavelength (nm), and the vertical axis represents fluorescence intensity (au). B is the ratio of fluorescence intensity at 482 nm and 515 nm in different polar solvents; the horizontal axis represents the polar dielectric constant, and the vertical axis represents the fluorescence intensity (I). 482nm / I 515nm .
[0039] Figure 3 A represents the change in the fluorescence emission spectrum of the polysulfide aromatic compound HTB-βGal, which is used to detect polarity and viscosity in this invention, in a glycerol / water mixed solvent containing 50% glycerol by volume, under 365 nm light-controlled light. The excitation wavelength is 405 nm. The horizontal axis represents wavelength (nm) and the vertical axis represents fluorescence intensity (au). Figure 3 B represents the fluorescence intensity change at 500 nm of the polysulfide aromatic compound HTB-βGal in a glycerol / water mixed solvent with different volume fractions of glycerol, as detected by this invention. The horizontal axis represents the light control time (s), and the vertical axis represents the fluorescence intensity (au).
[0040] Figure 4 A is the fluorescence emission spectrum of the polysulfide aromatic compound HTB-βGal, which is used to detect polarity and viscosity in this invention, in a glycerol / water mixed solvent with different ratios, under 365 nm light control for 4 min. The excitation wavelength is 405 nm. The horizontal axis is wavelength (nm) and the vertical axis is fluorescence intensity (au). Figure 4 B represents the fluorescence intensity at 500 nm of the polysulfide aromatic compound HTB-βGal in solvents of different viscosities, as determined by this invention for polarity and viscosity. The horizontal axis represents the logarithm of solvent viscosity, lg η, and the vertical axis represents the logarithm of fluorescence intensity at 500 nm, lg I. 500nm . Detailed Implementation
[0041] The present invention will be further illustrated below through examples, the purpose of which is solely to provide a better understanding of the invention. Therefore, the examples given do not limit the scope of protection of the present invention.
[0042] Example 1 A polysulfide aromatic compound for detecting polarity and viscosity, wherein the polysulfide aromatic compound has a benzene ring as its core, with six thiophenol substituents introduced around the benzene ring, and then modified with six galactose groups, denoted as compound HTB-βGal. This compound exhibits photoexcitation-induced aggregation and luminescence properties, but does not emit light when dispersed in water. Under 365 nm illumination, the luminescence of this compound is enhanced, and it can be used to detect polarity and viscosity. As the ambient polarity decreases, the luminescence enhancement factor of this compound increases, and it blue-shifts from 515 nm to 482 nm. As the ambient viscosity increases, the luminescence enhancement factor of this compound increases at 500 nm. The structural formula of the polysulfide aromatic compound HTB-βGal for detecting polarity and viscosity is shown in formula (I):
[0043] (I).
[0044] The luminescence mechanism of the polysulfide aromatic compound HTB-βGal, which is used to detect polarity and viscosity, is related to charge transfer. When the environmental polarity decreases, its emission wavelength shifts from 515 nm to 482 nm.
[0045] The luminescence mechanism of the polysulfide aromatic compound HTB-βGal, which is used to detect polarity and viscosity, is related to the rotation of the CS bond. As the ambient viscosity increases, the luminescence enhancement at 500 nm increases by a factor of 1.
[0046] The method for preparing the polysulfide aromatic compound HTB-βGal, which is used for detecting polarity and viscosity, includes the following steps: (1) Hexabromobenzene (500 mg, 0.907 mmol), 3-methoxythiophenol (1144 mg, 8.17 mmol), and potassium carbonate (988 mg, 7.16 mmol) were added to a 50 mL Shrek tube. The reaction system was dehydrated and deoxygenated. 6 mL of ultra-dry DMF was injected under a nitrogen atmosphere using a syringe. The mixture was then heated to 75 °C and stirred for 48 h. After cooling to room temperature, 20 mL of DCM and 10 mL of H2O were added. The organic phases were extracted and combined. The solvent was removed under reduced pressure. The mixture was purified by silica gel column chromatography with a volume ratio of PE:DCM = 4:3. Finally, the white solid product compound (IV) (707 mg, yield 86.1%) was obtained by concentration under reduced pressure.
[0047]
[0048] 1 H NMR (400 MHz, CDCl3) δ 7.04 (t, J = 8.2 Hz, 6H), 6.65 – 6.59 (m,6H), 6.56 – 6.48 (m, 12H), 3.69 (s, 18H). 13C NMR (101 MHz, DMSO- d 6) δ 158.00,146.81, 129.91, 127.89, 114.81, 55.11. HRMS-ESI (m / z): [M + H] + Calcd forC 48 H 42 O6S6 + 907.1379 found 907.1357, [M + Na] + Calcd for C 48 H 42 O6S6Na + 929.1198 found929.1197, [M + K] + Calcd for C 48 H 42 O6S6K + 945.0938 found 945.0939.
[0049] (2) Compound (IV) (400 mg, 0.44 mmol) was added to a 100 mL three-necked flask. The reaction system was heated under vacuum to remove water and oxygen. 8 mL of ultra-dry DCM was injected using a syringe under N2 atmosphere. Boron tribromide (6.62 mL, 13.23 mmol) was slowly added dropwise at -20 °C and stirred for 1 h. Then, the mixture was stirred at room temperature for 12 h. The solid was collected by filtration and washed with water, EA, and ethanol to obtain a yellow crude product. The crude product was purified by silica gel column chromatography using a DCM:MeOH volume ratio of 25:1. Finally, the product compound (III) (326 mg, yield 84.5%) was obtained by concentration under reduced pressure.
[0050]
[0051] 1 H NMR (400 MHz, DMSO- d 6) δ 9.56 (s, 6H), 6.53 (d, J = 6.4 Hz, 6H), 6.42 (t, J = 2.1 Hz, 6H), 6.26 (d, J = 7.7 Hz, 6H). 13 C NMR (101 MHz, DMSO- d6) δ157.85, 147.25, 138.57, 130.19, 117.38, 113.66, 113.29. HRMS-ESI (m / z): [M +H] + Calcd for C 42 H 31 O6S6 + 823.0440 found 823.0446.
[0052] (3) Compound (III) (100 mg, 0.12 mmol), 2,3,4,6-tetraacetoxy-alpha-D-pyranose bromide (600 mg, 1.46 mmol), and cesium carbonate (714 mg, 2.01 mmol) were added to a 50 mL Shrek tube. The reaction system was heated to remove water and oxygen under vacuum. 12 mL of ultra-dry CH3CN was added by syringe under N2 atmosphere and stirred at room temperature for 8 h. The reaction was terminated by diluting with DCM and filtering. The solvent in the filtrate was removed under reduced pressure. Column chromatography was performed with DCM:MeOH = 200:3 as the eluent. The filtrate was purified by silica gel column chromatography and finally concentrated under reduced pressure to obtain the yellow product compound (II) (2601 mg, yield 76.1%).
[0053]
[0054] 1 H NMR (400 MHz, DMSO- d 6) δ 7.21 (t, J = 8.1 Hz, 6H), 6.79 (s, 6H), 6.76 – 6.73 (m, 6H), 6.44 (d, J = 8.0 Hz, 6H), 5.45 (d, J = 7.8 Hz, 6H), 5.34(d, J = 3.7 Hz, 6H), 5.26 (dd, J = 10.4, 3.5 Hz, 6H), 5.18 (dd, J = 10.3, 7.7Hz, 6H), 4.40 (t, J = 6.2 Hz, 6H), 4.11 – 3.95 (m, 12H), 2.13 (s, 18H), 2.00(s, 18H), 1.94 (s, 18H), 1.82 (s, 18H). 13 C NMR (101 MHz, DMSO- d6) δ 169.98,169.86, 169.53, 169.22, 156.79, 147.37, 138.86, 130.48, 120.71, 114.66,114.03, 97.35, 70.51, 70.10, 68.30, 67.31, 61.59, 54.92, 20.88, 20.41, 20.35,20.31. HRMS-ESI (m / z): [M + Na] + Calcd for C 126 H 138 O 60 S 60 Na + 2826.5998 found2826.4219.
[0055] (4) Add compound (II) (100 mg, 0.04 mmol) to a 50 mL double-necked flask reaction vessel. Heat the reaction system under vacuum to remove water and oxygen. Add 4 mL of ultra-dry MeOH with a syringe under N2 atmosphere. Add a methanol solution of sodium methoxide (54 mg / mL) slowly dropwise under ice bath to adjust the pH to 10. Stir for 10 min, then stir at 5-15℃ for 1 h. Filter the solution. Remove the solvent from the filtrate under reduced pressure to obtain a yellow solid as product HTB-βGal(I) (26 mg, yield 41%).
[0056]
[0057] 1 H NMR (400 MHz, DMSO- d 6) δ 7.22 (t, J = 8.1 Hz, 6H), 6.80 (d, J = 9.1Hz, 6H), 6.75 (s, 6H), 6.40 (d, J = 8.5 Hz, 6H), 5.17 (d, J = 5.3 Hz, 6H), 4.87 (s, 6H), 4.79 (d, J = 7.6 Hz, 6H), 4.66 (s, 6H), 4.52 (s, 6H), 3.68 (s,6H), 3.51 (d, J = 30.2 Hz, 30H). 13 C NMR (101 MHz, DMSO- d6) δ 157.91, 147.63,138.57, 130.56, 120.02, 114.95, 114.02, 100.93, 75.41, 73.22, 70.34, 68.06,60.32, 54.95. HRMS-ESI (m / z): [M + Na] + Calcd for C 78 H 90 O 36 S6Na + 1817.3429 found1817.3402.
[0058] Example 2 The light-controlled time-dependent fluorescence spectra of the polysulfide aromatic compound HTB-βGal in different proportions of 1,4-dioxane / water mixed solvents in Example 1: The polysulfide aromatic compound HTB-βGal prepared in Example 1 was dissolved in water to a final concentration of 20 μM. The solution was then irradiated at 365 nm (0.03 mW / cm²). 2 Under these conditions, the green fluorescence at 515 nm gradually increased with increasing irradiation time (0s, 30s, 60s, 90s, 120s, 150s, 180s, 210s, 240s), as shown in the figure. Figure 1 As shown in Figure A, in a 1,4-dioxane / water mixed solvent with a 1,4-dioxane volume fraction of 60%, under the same illumination, the fluorescence of HTB-βGal is significantly enhanced at 482 nm, as shown in Figure A. Figure 1 As shown in B. Figure 1 The graphs show the fluorescence spectra of the polysulfide aromatic compound HTB-βGal (20 μM) in a 1,4-dioxane / water mixed solvent under 365 nm light control. Graph A shows the fluorescence spectra of HTB-βGal in a solvent (water) with a 1,4-dioxane volume fraction of 0%; Graph B shows the fluorescence spectra of HTB-βGal in a solvent with a 1,4-dioxane volume fraction of 60%. The excitation wavelength is 405 nm, with the horizontal axis representing wavelength (nm) and the vertical axis representing fluorescence intensity (µA).
[0059] Example 3 Fluorescence spectra and standard curves of the polar response of the polysulfide aromatic compound HTB-βGal in Example 1: The polysulfide aromatic compound HTB-βGal (20 μM) prepared in Example 1 was dissolved in solvents of different polarities (different proportions of 1,4-dioxane / water mixed solvents, with 1,4-dioxane volume fractions of 0%, 10%, 20%, 30%, 40%, 50%, and 60%). The sensing performance of HTB-βGal under 365 nm illumination in different polar solvents was tested. With increasing 1,4-dioxane volume fraction, solvent polarity decreased, fluorescence enhanced, and a significant blue shift in the maximum emission wavelength occurred, from 515 nm (green) to 482 nm (blue). Figure 2 As shown in Figure A. The fluorescence ratio I of HTB-βGal. 482nm / I 515nm The dielectric constant of the solvent exhibits a good linear relationship, with a correlation coefficient reaching R0. 2 =0.9921, as Figure 2 As shown in B. Figure 2 The following are the spectra of the polysulfide aromatic compound HTB-βGal (20 μM) of this invention after 4 min of controlled fluorescence at 365 nm in different ratios of 1,4-dioxane / water mixed solvents. Figure A shows the fluorescence spectrum changes, with an excitation wavelength of 405 nm. The x-axis represents wavelength (nm), and the y-axis represents fluorescence intensity (µA). Figure B shows the ratio of fluorescence intensity at 482 nm and 515 nm in solvents of different polarities (different ratios of 1,4-dioxane / water mixed solvents). The x-axis represents dielectric constant, and the y-axis represents fluorescence intensity (µA). 482nm / I 515nm .
[0060] Example 4 The photocontrolled fluorescence spectrum of the HTB-βGal viscosity response of the polysulfide aromatic compound in Example 1: The polysulfide aromatic compound HTB-βGal (20 μM) was irradiated at 365 nm (0.03 mW / cm²). 2 In a glycerol / water mixed solvent with a glycerol volume fraction of 50%, the fluorescence intensity of HTB-βGal at 500 nm gradually increased over time (0 s, 30 s, 60 s, 90 s, 120 s, 150 s, 180 s, 210 s, 240 s), as shown below. Figure 3 As shown in Figure A. Simultaneously, with the increase of glycerol content (i.e., viscosity), the emission intensity of HTB-βGal also increases accordingly, as shown in Figure A. Figure 3 As shown in B. Figure 3A shows the fluorescence emission spectrum of the polysulfide aromatic compound HTB-βGal (20 μM) of the present invention in a glycerol / water mixed solvent with a glycerol volume fraction of 50% under 365 nm light control. The excitation wavelength is 405 nm. The horizontal axis represents wavelength (nm) and the vertical axis represents fluorescence intensity (au). B shows the fluorescence intensity change of the polysulfide aromatic compound HTB-βGal (20 μM) of the present invention at 500 nm in glycerol / water mixed solvents with different volume fractions of glycerol. The horizontal axis represents light control time (s) and the vertical axis represents fluorescence intensity (au).
[0061] Example 5 Fluorescence spectra and standard curves of the viscosity response of the polysulfide aromatic compound HTB-βGal in Example 1: The probe HTB-βGal (20 μM) prepared in Example 1 was dissolved in glycerol / water mixed solvents with different volume fractions of glycerol (0%, 10%, 20%, 30%, 40%, 50%). The emission wavelength remained basically constant. As the glycerol content increased, the viscosity increased, and the fluorescence intensity increased significantly after 4 minutes of light control. Figure 4 As shown in Figure A. The logarithm of the HTB-βGal fluorescence intensity, lg I. 500nm The correlation coefficient η exhibits a good linear relationship with the logarithm of the solvent viscosity, lg η, reaching R0. 2 =0.9894, such as Figure 4 As shown in B. Figure 4 Image A shows the fluorescence emission spectra of the polysulfide aromatic compound HTB-βGal (20 μM) of this invention in glycerol / water mixed solvents of different ratios after 4 min under 365 nm light-controlled illumination. The excitation wavelength was 405 nm. The horizontal axis represents wavelength (nm), and the vertical axis represents fluorescence intensity (au). Image B shows the fluorescence intensity of HTB-βGal in solvents of different viscosities (glycerol / water mixed solvents of different ratios). The horizontal axis represents the logarithm of viscosity lg η, and the vertical axis represents the logarithm of fluorescence intensity at 500 nm lg I. 500 nm .
[0062] The above embodiments are only used to help illustrate the present invention and are not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included within the protection scope of the present invention.
Claims
1. A polysulfide aromatic compound, characterized in that, The structural formula is shown in equation (I): （I）。 2. The method for preparing the polysulfide aromatic compound according to claim 1, characterized in that, Includes the following steps: (1) Under a nitrogen or inert gas atmosphere, hexahalobenzene, 3-methoxythiophenol and catalyst are reacted in an organic solvent to give compound (IV). (2) Compound (IV) and boron tribromide are reacted in an organic solvent under a nitrogen or inert gas atmosphere to give compound (III). (3) Compound (III), 2,3,4,6-tetraacetoxy-alpha-D-pyranose bromide, and catalyst were reacted in an organic solvent under a nitrogen or inert gas atmosphere to obtain compound (II); (4) Under a nitrogen or inert gas atmosphere, compound (II) is added to an organic solvent and the pH is adjusted to 9-11 with sodium methoxide to obtain the polysulfide aromatic compound.
3. The method for preparing polysulfide aromatic compounds according to claim 2, characterized in that: In step (1), The hexahalobenzenes mentioned include hexabromobenzene, hexafluorobenzene, and hexaiodobenzene; The catalysts include potassium carbonate, cesium carbonate, and triethylamine; The organic solvents include one or more of DMF, CH3CN, THF, and NMP; The reaction temperature is 70-80℃.
4. The method for preparing polysulfide aromatic compounds according to claim 2, characterized in that: In step (2), The organic solvents include one or more of DMF, n-hexane, and carbon tetrachloride; The reaction temperature is 15-35℃.
5. The method for preparing polysulfide aromatic compounds according to claim 2, characterized in that: In step (3), The catalysts include potassium carbonate, cesium carbonate, and triethylamine; The organic solvents include one or more of CH3CN, DMF, THF, and NMP; The reaction temperature is 15-35℃.
6. The method for preparing polysulfide aromatic compounds according to claim 2, characterized in that: In step (4), The organic solvents include one or more of MeOH and EtOH; The reaction temperature is 5-15℃.
7. The use of the polysulfide aromatic compound of claim 1 or the polysulfide aromatic compound obtained by any one of claims 2-6 in the detection of polarity and / or viscosity.
8. The application according to claim 7, characterized in that: The applications include the use of polysulfide aromatic compounds for the polarity detection of liquids, determining the polarity based on the ratio of luminescence at 482 nm and 515 nm. And / or: The applications include the use of polysulfide aromatic compounds for viscosity detection of liquids, determining the viscosity based on the luminescence intensity at 500 nm.
9. The use of the polysulfide aromatic compound of claim 1 or the polysulfide aromatic compound obtained by any one of claims 2-6 in the preparation of fluorescent probes for detecting polarity and / or viscosity.
10. A fluorescent probe for detecting polarity and / or viscosity, characterized in that: It includes the polysulfide aromatic compound of claim 1 or the polysulfide aromatic compound obtained by any one of the preparation methods of claims 2-6.