A colorimetric and ratiometric fluorescent probe compound based on aggregation-induced emission and a preparation method and application thereof

Abstract

The application discloses a colorimetric and ratiometric fluorescent probe compound based on aggregation-induced emission and a preparation method and application thereof, and belongs to the technical field of analysis and detection. The colorimetric and ratiometric fluorescent probe compound is 5-((5-(4-(diphenylamino)phenyl)thiophene-2-yl)methylene)-2,2-dimethyl-1,3-dioxane-4,6-dione. The colorimetric and ratiometric fluorescent probe provided by the application uses an electron-rich double bond as a recognition group, can specifically undergo a nucleophilic addition reaction with sulfite and bisulfite ions, and can accurately and efficiently recognize the sulfite and bisulfite ions. The colorimetric and ratiometric fluorescent probe compound provided by the application is simple in synthesis, easy to prepare, and high in detection sensitivity. The product after response of the colorimetric and ratiometric fluorescent probe provided by the application has dual characteristics of aggregation-induced emission and intramolecular charge transfer, can emit strong fluorescence in a high-concentration aggregation state, and will not have an aggregation quenching phenomenon like traditional fluorescent probes.

Description

Technical Field

[0001] This invention belongs to the field of analytical detection technology, specifically relating to a colorimetric and ratiometric fluorescent probe compound based on aggregation-induced emission, its preparation method, and its application. Background Technology

[0002] Sulfur dioxide (SO2) is a gaseous pollutant primarily originating from the combustion of fossil fuels and industrial production processes. It pollutes the atmosphere through direct emissions or is absorbed by solutions and converted into sulfurous acid (H2SO3) and its salts (HSO3). - SO3 2- Sulfite derivatives (such as sodium sulfite) are widely used in the food industry as preservatives and antioxidants to inhibit enzymatic browning and microbial growth. However, excessive intake is closely associated with various health risks, including respiratory diseases, cardiovascular diseases, neurological dysfunction, and malignant tumors. Given its dual nature as both an environmental pollutant and a food additive, the accurate detection of sulfites has become an important issue in the global food safety and environmental monitoring field. Therefore, the development of new technologies that enable rapid, sensitive, and on-site detection is urgently needed to protect public health and promote environmental governance.

[0003] Currently, while distillation titration, oxidation methods, and instrumental analysis methods (such as ion chromatography and high-performance liquid chromatography) can provide accurate quantification, they generally suffer from limitations such as cumbersome operation, long processing times, and reliance on large instruments and specialized operators, making it difficult to meet the application scenarios of real-time, on-site, and high-throughput screening. In contrast, responsive fluorescent probe technology, with its high sensitivity and selectivity, ease of operation, rapid response (seconds to minutes), and potential visualization (colorimetric) and real-time monitoring capabilities, offers a promising new approach to overcoming these bottlenecks, demonstrating enormous application potential in fields such as environmental analysis, rapid food testing, and bioimaging.

[0004] The development of sulfite fluorescent probes has evolved from an "on-off" single-signal mode to a "ratio-based" self-calibration mode. Early probes were mostly based on enhanced or quenched fluorescence responses, achieving detection through reactions between sulfite ions and specific sites such as aldehyde groups and unsaturated double bonds, inducing changes in intramolecular charge transfer (ICT) or photoinduced electron transfer (PET) processes. However, the fluorescence intensity of these single-signal probes is highly susceptible to interference from various non-specific factors such as probe concentration, fluctuations in the excitation source, and environmental quenchers (e.g., dissolved oxygen, metal ions), leading to insufficient quantitative reliability. Ratio-based probes self-calibrate by monitoring the ratio of fluorescence intensity at two or more wavelengths (I1 / I2), effectively overcoming the inherent limitations of single-signal probes and significantly improving detection accuracy and anti-interference capabilities.

[0005] Despite this, the molecular design of most existing ratiometric (and even single-signal) fluorescent probes is typically based on large-planar conjugated structures, which generally face the challenge of aggregation-induced fluorescence quenching (ACQ) at high concentrations or in aggregated states. This characteristic severely limits the working concentration window of the probes, making them unsuitable for high-concentration detection or analysis of complex matrices (such as actual water samples and food extracts), thus restricting their practicality. In recent years, molecular materials with aggregation-induced emission (AIE) properties have provided a revolutionary solution to the ACQ problem. AIE molecules exhibit weak fluorescence in the dispersed state but significantly enhanced luminescence in the aggregated state, perfectly suited for sensing and detection systems requiring high concentrations. However, fluorescent probe designs that organically combine AIE properties, ratiometric signal output, and high selectivity for sulfite recognition are still rarely reported. Furthermore, the synthetic routes of most reported probes are complex, involving multiple steps and low yields, which is not conducive to large-scale preparation and practical application.

[0006] Therefore, developing a novel molecular probe that is easy to synthesize, based on the AIE mechanism, and capable of generating both ratiometric fluorescence and colorimetric dual responses to sulfites (SO2 derivatives) has significant scientific value and broad application prospects for achieving highly sensitive, reliable, rapid, and visual detection of target analytes in complex real-world samples. Summary of the Invention

[0007] To address the shortcomings and deficiencies of the existing technologies, this invention provides a colorimetric and ratiometric fluorescent probe compound based on aggregation-induced emission, its preparation method, and its applications. The provided probe exhibits aggregation-induced emission and intramolecular charge transfer properties, using electron-rich double bonds as recognition sites to achieve the detection of sulfite and bisulfite ions.

[0008] To achieve the above objectives, the present invention provides the following technical solution: One of the technical solutions of this invention is to provide a colorimetric and ratiometric fluorescent probe compound based on aggregation-induced emission, the structural formula of which is shown below: .

[0009] The colorimetric and ratiometric fluorescent probe compound based on aggregation-induced emission provided by this invention is named 5-((5-(4-(diphenylamino)phenyl)thiophen-2-yl)methylene)-2,2-dimethyl-1,3-dioxane-4,6-dione, with the molecular formula C2. 29 H 23 NO4S, with a relative molecular mass of 481.13, is a dark red solid powder. It is sparingly soluble in water but readily soluble in organic solvents such as dichloromethane, tetrahydrofuran, and dimethyl sulfoxide. This compound exhibits good photostability, good chemical stability, and is non-toxic.

[0010] The second technical solution of the present invention provides a method for preparing the above-mentioned colorimetric and ratiometric fluorescent probe compound based on aggregation-induced emission, comprising the following steps: 5-(4-(diphenylamine)phenyl)thiophene-2-carboxaldehyde and 2,2-dimethyl-1,3-dioxane-4,6-dione were co-dissolved in a solvent and reacted by heating to obtain the colorimetric and ratiometric fluorescent probe compound based on aggregation-induced emission.

[0011] Preferably, the molar ratio of 5-(4-(diphenylamine)phenyl)thiophene-2-carboxaldehyde to 2,2-dimethyl-1,3-dioxane-4,6-dione is 1:1 to 1.5.

[0012] Preferably, the solvent is ethanol, and the molar volume ratio of 5-(4-(diphenylamine)phenyl)thiophene-2-carboxaldehyde to ethanol is 1 mmol: 12~18 mL.

[0013] Preferably, the heating reaction is carried out at a temperature of 80~100℃ for 20~24h.

[0014] Preferably, the heating reaction further includes a separation and purification step.

[0015] The third technical solution of the present invention provides an application of the above-mentioned aggregation-induced emission-based colorimetric and ratiometric fluorescent probe compound in the detection of sulfur dioxide derivatives (including sulfite ions and bisulfite ions) in the environment or food.

[0016] The response mechanism of this colorimetric and ratiometric fluorescent probe to sodium bisulfite is as follows: the probe molecule has a D-π-A structure of "triphenylamine (donor)-thiophene (π-bridge)-Mischel acid (acceptor)," in which the bisulfite ion selectively recognizes and adds to the carbon-carbon double bond between the Mischel acid acceptor unit and the thiophene bridge. This addition reaction disrupts the conjugated structure of the molecule, inhibits the intramolecular charge transfer process, and leads to a significant blue shift in the fluorescence emission wavelength and a change in the absorption spectrum, thereby achieving dual-signal detection of ratiometric fluorescence and colorimetric fluorescence. The reaction mechanism diagram of the ratiometric fluorescent probe (TPA-MA) based on aggregation-induced emission properties and the bisulfite ion is shown below. Figure 13 The response mechanism of sulfite is similar.

[0017] The beneficial technical effects of the present invention are as follows: The colorimetric and ratiometric fluorescent probe of the present invention utilizes electron-rich double bonds as recognition groups, which can specifically undergo nucleophilic addition reactions with sulfite and bisulfite ions. Therefore, the probe can accurately and efficiently identify sulfite and bisulfite ions.

[0018] The colorimetric and ratiometric fluorescent probe compounds of the present invention are simple to synthesize, easy to prepare, and have high detection sensitivity.

[0019] The product of the colorimetric and ratiometric fluorescent probe of the present invention has dual characteristics of aggregation-induced emission and intramolecular charge transfer. It can emit strong fluorescence in a high-concentration aggregation state without the aggregation quenching phenomenon that occurs with traditional fluorescent probes.

[0020] The colorimetric and ratiometric fluorescent probe of this invention emits at a wavelength of 655 nm before the response and at 435 nm after the response, exhibiting a significant shift and marked change. This makes it a high-performance ratiometric fluorescent probe. It minimizes spontaneous interference from external environmental factors such as the instrument, thereby improving detection accuracy.

[0021] The colorimetric and ratiometric fluorescent probe of this invention enables sensitive detection of sulfite ions and can be used to detect sulfite ions in food and the environment. Attached Figure Description

[0022] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0023] Figure 1 The synthetic route of 5-((5-(4-(diphenylamino)phenyl)thiophen-2-yl)methylene)-2,2-dimethyl-1,3-dioxane-4,6-dione is shown in the embodiments of the present invention.

[0024] Figure 2 The 1H NMR spectrum of 5-((5-(4-(diphenylamino)phenyl)thiophen-2-yl)methylene)-2,2-dimethyl-1,3-dioxane-4,6-dione prepared in Example 1.

[0025] Figure 3 The mass spectrum of 5-((5-(4-(diphenylamino)phenyl)thiophen-2-yl)methylene)-2,2-dimethyl-1,3-dioxane-4,6-dione prepared in Example 1.

[0026] Figure 4 The image shows the absorption spectra of the colorimetric and ratiometric fluorescent probe TPA-MA in Application Example 1 in response to different concentrations of bisulfite ions.

[0027] Figure 5 This demonstrates the relationship between the absorbance ratio of the colorimetric and ratiometric fluorescent probe TPA-MA at 547 nm and 348 nm and the concentration of bisulfite ions in Example 1.

[0028] Figure 6 The fluorescence spectra of the colorimetric and ratiometric fluorescent probe TPA-MA in Application Example 1 in response to different concentrations of bisulfite ions under 340 nm excitation are shown.

[0029] Figure 7 The fluorescence spectra of the colorimetric and ratiometric fluorescent probe TPA-MA in Application Example 1 in response to different concentrations of bisulfite ions under 540 nm excitation are shown.

[0030] Figure 8 This shows the relationship between the fluorescence intensity ratio at 435 nm and 655 nm and the concentration of bisulfite ions after excitation of the colorimetric and ratiometric fluorescent probe TPA-MA in Example 1.

[0031] Figure 9 The ratio of fluorescence intensity at 435 nm to 655 nm after adding a solution containing potential interfering substances to the colorimetric and ratiometric fluorescent probe TPA-MA in Application Example 2 and then exciting it is given.

[0032] Figure 10 The ratio of fluorescence intensity at 435 nm to 655 nm after adding a solution containing potential interfering substances + bisulfite ions to the colorimetric and ratiometric fluorescent probe TPA-MA in Application Example 3 and exciting it is used to measure the fluorescence intensity ratio at 435 nm to 655 nm.

[0033] Figure 11 The fluorescence spectra of the colorimetric and ratiometric fluorescent probe TPA-MA in different ratios of dimethyl sulfoxide / water mixed solutions are shown in Application Example 4.

[0034] Figure 12 The graph shows the fluorescence intensity of the colorimetric and ratiometric fluorescent probe TPA-MA at 650 nm as a function of different water percentages in Application Example 4.

[0035] Figure 13 This diagram illustrates the reaction mechanism of the ratiometric fluorescent probe (TPA-MA) based on aggregation-induced emission properties with bisulfite ions, as described in this invention. Detailed Implementation

[0036] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention. It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the present invention.

[0037] It should be noted that any aspects not described in detail in this invention are conventional practices in the field and are not the focus of this invention.

[0038] Furthermore, regarding the numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Any stated value or intermediate value within a stated range, as well as each smaller range between any other stated value or intermediate value within said range, are also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0039] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar to or equivalent to those described herein may be used in the implementation or testing of this invention.

[0040] The terms “include,” “including,” “have,” “contain,” etc., used in this article are all open-ended terms, meaning that they include but are not limited to.

[0041] The synthetic route diagram of 5-((5-(4-(diphenylamino)phenyl)thiophen-2-yl)methylene)-2,2-dimethyl-1,3-dioxane-4,6-dione in the embodiments of the present invention is shown below. Figure 1 .

[0042] Example 1 5-(4-(diphenylamino)phenyl)thiophene-2-carboxaldehyde (410 mg, 1.15 mmol) and 2,2-dimethyl-1,3-dioxane-4,6-dione (249 mg, 1.725 mmol) were placed in a sealed tube and dissolved in 20.8 mL of ethanol. The mixture was then heated in an oil bath to 100 °C for 24 h. After the reaction, the organic solvent was removed by rotary evaporation. The resulting solid was purified by silica gel chromatography with a solvent ratio of petroleum ether:dichloromethane = 2:1 (V / V) to give 456 mg of dark red solid 5-((5-(4-(diphenylamino)phenyl)thiophene-2-yl)methylene)-2,2-dimethyl-1,3-dioxane-4,6-dione (yield: 82%).

[0043] The 5-((5-(4-(diphenylamino)phenyl)thiophene-2-yl)methylene)-2,2-dimethyl-1,3-dioxane-4,6-dione (TPA-MA) prepared in Example 1 was characterized by 1H NMR spectroscopy and mass spectrometry. Its 1H NMR spectrum is shown in [Figure 1]. Figure 2 Mass spectrum can be found Figure 3 .

[0044] The data for the proton NMR spectrum are as follows: 1H NMR (400 MHz, DMSO) δ 8.61 (s, 1H), 8.24 (s, 1H), 7.72 (s, 2H), 7.68 (s, 1H), 7.38 (d, J = 12.7 Hz, 4H), 7.18 – 7.11 (m,6H), 6.96 (d, J = 6.7 Hz, 2H), 1.71 (s, 6H).

[0045] Among them, 1.71 ppm corresponds to the characteristic proton peak of methyl, 8.61 ppm and 8.24 ppm correspond to the characteristic proton peak of benzene ring on thiophene structure, and 7.72 ppm, 7.38 ppm, 7.18-7.11 ppm and 6.96 ppm correspond to the characteristic proton peak of triphenylamine structure.

[0046] The mass spectrum shows that the mass-to-charge ratio of the product is 481.16 [M]. + The mass-to-charge ratio [C] predicted by theory. 29 H 23 NO4S] + 481.13 is consistent.

[0047] Therefore, the synthesized product can be identified as the final product through NMR and mass spectrometry analysis.

[0048] Example 2 5-(4-(diphenylamino)phenyl)thiophene-2-carboxaldehyde (160 mg, 0.45 mmol) and 2,2-dimethyl-1,3-dioxane-4,6-dione (65 mg, 0.45 mmol) were placed in a sealed tube and dissolved in 5.4 mL of ethanol. The mixture was then heated to 80 °C in an oil bath for 20 h. After the reaction was completed, the organic solvent was removed by rotary evaporation. The resulting solid was purified by silica gel chromatography with a solvent ratio of petroleum ether:dichloromethane = 2:1 (V / V) to give 161 mg of dark red solid 5-((5-(4-(diphenylamino)phenyl)thiophene-2-yl)methylene)-2,2-dimethyl-1,3-dioxane-4,6-dione (yield: 74%).

[0049] The characterization results of the final product obtained in this embodiment are the same as those in Example 1.

[0050] Example 3 5-(4-(diphenylamino)phenyl)thiophene-2-carboxaldehyde (325 mg, 0.91 mmol) and 2,2-dimethyl-1,3-dioxane-4,6-dione (165 mg, 1.14 mmol) were placed in a sealed tube and dissolved in 14.6 mL of ethanol. The mixture was then heated to 90 °C in an oil bath for 22 h. After the reaction was completed, the organic solvent was removed by rotary evaporation. The resulting solid was purified by silica gel chromatography with a solvent ratio of petroleum ether:dichloromethane = 2:1 (V / V) to give 341 mg of dark red solid 5-((5-(4-(diphenylamino)phenyl)thiophene-2-yl)methylene)-2,2-dimethyl-1,3-dioxane-4,6-dione (yield: 77%).

[0051] The characterization results of the final product obtained in this embodiment are the same as those in Example 1.

[0052] Application Example 1 The colorimetric and ratiometric fluorescent probe TPA-MA prepared in Example 1 of this invention was used to detect bisulfite ions. The specific method is as follows: Prepare a 1 mM TPA-MA dimethyl sulfoxide stock solution. During testing, the final TPA-MA concentration was controlled to 10 μM in a mixture of ethanol and PBS buffer (pH=7.4) at a volume ratio of 3:7. Bisulfite ions were prepared by dissolving sodium bisulfite solid in ultrapure water to prepare a 10 mM stock solution, which was then diluted to a series of final concentrations: 0, 1, 2.5, 5, 7.5, 10, 12.5, 15, 20, 25, and 30 μM. The total volume of the test system was 3 mL, and the temperature was 25℃.

[0053] Absorption spectra: The absorption spectra of the colorimetric and ratiometric fluorescent probe TPA-MA in response to different concentrations of bisulfite ions are shown in the figure. Figure 4 The absorbance ratio of the colorimetric and ratiometric fluorescent probe TPA-MA at 547 nm to 348 nm (A) 547 / A 348 The relationship between the concentration of ions and bisulfite ions is shown in the figure. Figure 5 .

[0054] like Figure 4 and Figure 5 As shown, with the increase of bisulfite ion concentration, the absorption peak of the system at 547 nm gradually decreases, and the solution color changes from pink to colorless, indicating that the probe has a significant colorimetric response, proving that the probe has a highly sensitive colorimetric detection capability.

[0055] Fluorescence Spectroscopy: The fluorescence spectra of the colorimetric and ratiometric fluorescent probe TPA-MA in response to different concentrations of bisulfite ions under 340 nm excitation are shown in the figure. Figure 6The fluorescence spectra of the colorimetric and ratiometric fluorescent probe TPA-MA in response to different concentrations of bisulfite ions under 540 nm excitation are shown below. Figure 7 The ratio of fluorescence intensity at 435 nm and 655 nm after excitation (F 435 / F 655 The relationship between the concentration of ions and bisulfite ions is shown in the figure. Figure 8 .

[0056] like Figures 6-8 As shown, under 340 nm excitation, the fluorescence intensity at 435 nm increases accordingly; under 540 nm excitation, the fluorescence intensity at 655 nm decreases with increasing bisulfite concentration. The ratio of fluorescence intensity at 435 nm to 655 nm (F...) 435 / F 655 The concentration of R shows a linear relationship with the concentration of bisulfite in the range of 0–10 μM. 2 =0.98.

[0057] The above results show that the TPA-MA probe prepared in this invention exhibits significant ratiometric responses in both UV-Vis absorption and fluorescence emission, demonstrating high sensitivity and good quantitative ability, making it suitable for rapid and visual detection of bisulfite ions in complex systems.

[0058] Application Example 2 The selectivity of the colorimetric and ratiometric fluorescent probe TPA-MA prepared in Example 1 of this invention was tested using the following specific method: TPA-MA was prepared as a 1.0 mM dimethyl sulfoxide stock solution. The test was conducted in an ethanol:PBS buffer (pH=7.4) = 3:7 v / v system, controlling the final TPA-MA concentration to 10 μM. Equivalent amounts (or higher concentrations) of potential interfering substances were added to the system, including: H₂S, NaClO, NaClO₄, H₂O₂, Na₂S, cysteine ​​(Cys), glutathione (GSH), ascorbic acid (AA), K₂CO₃, Na₂SO₄, NaNO₃, Na₂S₂O₃, KCl, and homocysteine ​​(Hcy). NaHSO₃ and Na₂SO₃ were used as target controls, and a blank control group was set up. The total test volume was 3 mL, and the temperature was controlled at 25℃. The fluorescence intensity at 435 nm and 655 nm was measured using excitation wavelengths of 340 nm and 540 nm, respectively, and their ratio (F) was calculated. 435 / F 655 ).

[0059] The ratio of fluorescence intensity (F) at 435 nm to 655 nm after the colorimetric and ratiometric fluorescent probe TPA-MA is added to a solution containing potential interfering substances and excited. 435 / F655 )See Figure 9 .

[0060] like Figure 9 As shown, under the same conditions, the system with only NaHSO3 or Na2SO3 added showed a significant increase in fluorescence intensity ratio, while the fluorescence ratio changes caused by other common anions and cations, reactive oxygen species and biothiols were much lower than the response of the target analyte, indicating that the probe has excellent selective recognition ability for bisulfite / sulfite.

[0061] Application Example 3 The anti-interference performance of the colorimetric and ratiometric fluorescent probe TPA-MA prepared in Example 1 was tested using the following methods: A 1.0 mM TPA-MA dimethyl sulfoxide stock solution was prepared. In an ethanol / PBS buffer (pH=7.4) 3:7 v / v system, the final concentration of TPA-MA was controlled to 10 μM, and a certain concentration (20 μM) of bisulfite ions was added. Subsequently, various potential interfering substances were added to this coexistence system, including: NaClO4, H2O2, cysteine ​​(Cys), glutathione (GSH), ascorbic acid (AA), K2CO3, Na2SO4, Na2S2O3, KCl, and homocysteine ​​(Hcy). The total volume of the test system was 3 mL, and the temperature was 25℃. Excitation was performed at 340 nm and 540 nm, and the fluorescence intensity at 435 nm and 655 nm was measured, and their ratio (F) was calculated. 435 / F 655 ).

[0062] The ratio of fluorescence intensity (F) at 435 nm to 655 nm after the colorimetric and ratiometric fluorescent probe TPA-MA is excited by adding a solution containing potential interfering substances + bisulfite ions. 435 / F 655 )See Figure 10 .

[0063] like Figure 10 As shown, the fluorescence intensity ratio of the system remained at a high level in the presence of bisulfite and other interfering substances, similar to the results of the control group containing only bisulfite. This indicates that these common substances do not affect the probe's specific recognition of bisulfite. These results demonstrate that the probe exhibits excellent anti-interference ability against bisulfite in complex matrices.

[0064] Application Example 4 The aggregation-induced emission properties of the colorimetric and ratiometric fluorescent probe TPA-MA prepared in Example 1 were tested using the following methods: A 1.0 mM TPA-MA dimethyl sulfoxide stock solution was prepared. During testing, the final probe concentration was controlled at 10 μM, and the solvent was a mixture of dimethyl sulfoxide and water, with water volume fractions set sequentially to 0%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 95%, and 99%. The total test volume was 3 mL, and the temperature was 25℃. The fluorescence emission spectra of each system were measured at an excitation wavelength of 540 nm. The results are as follows: Figure 11 and Figure 12 As shown, when the water content ranges from 0% to 70% by volume, the probe molecules aggregate, and their fluorescence intensity gradually increases, reaching a maximum at a certain water content (70%). At this point, intramolecular motion is most fully restricted, and the ICT luminescence process is most efficient. As the water content continues to increase (from 70% to 99%), excessively strong hydrophobic interactions may cause the probe molecules to form excessively large, dense, or irregularly shaped aggregates. The resulting excessively large aggregates or precipitation slightly decrease the fluorescence intensity, exhibiting typical aggregation-induced luminescence characteristics. This property indicates that the TPA-MA probe can maintain strong fluorescence emission in aqueous media or in an aggregated state, effectively overcoming the problem of fluorescence quenching caused by aggregation in traditional fluorescent probes. This provides a significant advantage for its detection applications in aqueous environments or under solid / high concentration conditions.

[0065] The embodiments described above are merely preferred embodiments of the present invention and are not intended to limit the scope of the present invention. Various modifications and improvements made by those skilled in the art to the technical solutions of the present invention without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.

Claims

1. A colorimetric and ratiometric fluorescent probe compound based on aggregation-induced emission, characterized in that, The structural formula of the colorimetric and ratiometric fluorescent probe compound based on aggregation-induced emission is shown below: 。 2. A method for preparing the colorimetric and ratiometric fluorescent probe compound based on aggregation-induced emission as described in claim 1, characterized in that, Includes the following steps: 5-(4-(diphenylamine)phenyl)thiophene-2-carboxaldehyde and 2,2-dimethyl-1,3-dioxane-4,6-dione were co-dissolved in a solvent and reacted by heating to obtain the colorimetric and ratiometric fluorescent probe compound based on aggregation-induced emission.

3. The method for preparing the colorimetric and ratiometric fluorescent probe compound based on aggregation-induced emission according to claim 2, characterized in that, The molar ratio of 5-(4-(diphenylamine)phenyl)thiophene-2-carboxaldehyde to 2,2-dimethyl-1,3-dioxane-4,6-dione is 1:1 to 1.

5.

4. The method for preparing the colorimetric and ratiometric fluorescent probe compound based on aggregation-induced emission according to claim 2, characterized in that, The solvent is ethanol, and the molar volume ratio of 5-(4-(diphenylamine)phenyl)thiophene-2-carboxaldehyde to ethanol is 1 mmol: 12~18 mL.

5. The method for preparing the colorimetric and ratiometric fluorescent probe compound based on aggregation-induced emission according to claim 2, characterized in that, The heating reaction is carried out at a temperature of 80~100℃ for 20~24h.

6. The method for preparing the colorimetric and ratiometric fluorescent probe compound based on aggregation-induced emission according to claim 2, characterized in that, The heating reaction is followed by a separation and purification step.

7. The application of the aggregation-induced emission-based colorimetric and ratiometric fluorescent probe compound of claim 1 in the detection of sulfur dioxide derivatives in the environment or food.

Images