A dual-state regulation dual-color light-molecular sensor with five detection functions, a preparation method and application thereof

Abstract

This invention relates to the field of organic material detection technology, specifically to a molecular sensor with dual-state regulated dual-color light-five-detection function, its preparation method, and its application. The sensor exhibits aggregation-induced red fluorescence emission; in the aggregated state, it detects Hg... 2+ It exhibits four monitoring responses: red fluorescence "on-off", ultraviolet absorption, and different color changes under sunlight and ultraviolet light, in relation to Hg. 2+ Formation of a binary system for Fe 3+ / Cr 3+ It exhibits a red fluorescent "off-on" response; in solution, it responds to CrO4. 2‑ The sensor exhibits multiple detection responses, including different blue fluorescence "on / off" states, UV absorption, and intuitive color changes under UV light, in response to changes in concentration and acidic environment. Furthermore, it is rapid, sensitive, and provides intuitive signals, enabling real-time, in-situ detection of the target. The molecular sensor fabrication process provided by this invention boasts advantages such as high yield and mild synthesis conditions, making it suitable for industrial implementation and creating favorable conditions for its widespread application.

Description

Technical Field

[0001] This invention relates to the field of organic light-emitting material detection technology, specifically to a method for detecting Hg in aggregated state red fluorescence emission signals. 2+ / Cr 3+ / Fe 3+ Solution-state blue fluorescence emission signal for CrO4 2- / Acid-based molecular sensors with multiple detection functions and their applications. Background Technology

[0002] Advances in science and technology have propelled the rapid development of my country's metal industry, but the environmental pollution resulting from this development has hindered its sustainable development. Because metal ions are difficult to degrade and easily accumulate and expand in the food chain, coupled with the insidious, cumulative, and irreversible nature of their pollution, once released into the environment, they can cause enormous harm to ecosystems and the human living environment. When water and food contaminated with metal ions are ingested, these ions can accumulate in the body, causing serious harm. For example, excessive mercury ions can lead to headaches, fatigue, bleeding and erosion of the gums, abdominal pain, interstitial pneumonia, kidney damage, acute gastroenteritis, and even cancer. Chromium is an essential trace element for the human body, but excessive chromium can damage various systems, causing skin allergies, nasal inflammation, gastric ulcers, esophagitis, and even lung cancer. In particular, excessive chromate can cause heavy metal poisoning, leading to dermatitis, eczema, bronchitis, and even inducing lung cancer and nasopharyngeal carcinoma, posing a persistent danger to the environment. Furthermore, with rapid social development, the discharge of various waste acids generated during industrial and agricultural production is increasing daily. When these untreated acids are directly discharged into the soil, they can cause changes in the acidity of the surrounding environment, leading to plant withering, animal death, and causing enormous harm to human production and life. Therefore, developing sensitive and convenient methods for detecting analytes in different systems is of great significance.

[0003] Currently, ion detection generally uses high-performance liquid chromatography (HPLC) and inductively coupled plasma mass spectrometry (ICP-MS), which can accurately monitor the content of analytes in different systems. However, these methods are often limited by high instrument costs, long detection times, high detection costs, and difficulty in on-site detection. Among various detection methods, fluorescent molecular sensors, which offer high sensitivity, low cost, and ease of operation, have gradually become a research hotspot. Fluorescent molecular sensors convert analytical interactions at the molecular level into easily monitorable optical signals, enabling in-situ, real-time, rapid, and sensitive detection. They have been widely used in industrial and agricultural production, environmental monitoring, and other fields. However, most current fluorescent molecular sensors only exhibit sensitive detection performance for a specific ion, have relatively limited functionality, and have significant application limitations. Multifunctional fluorescent molecular sensors not only avoid the preparation process of multiple single-molecule sensors but also offer higher detection efficiency compared to the individual detection of single-function molecular sensors. However, current multifunctional fluorescent molecular sensors are characterized by complex preparation processes and high costs, making it difficult to meet the growing market demand.

[0004] In the construction of fluorescent molecular sensors, luminescent materials are mainly divided into two categories: one type exhibits excellent fluorescence performance in dilute solutions, but its fluorescence performance decreases significantly or is completely quenched in higher concentration solutions or solid states, i.e., aggregation-induced quenching (ACQ). This greatly limits the development and application of solid-state fluorescent sensing materials. In 2001, Professor Benzhong Tang's research group at the Hong Kong University of Science and Technology first reported a material completely opposite to ACQ, namely aggregation-induced emission (AIE) materials, which are also the second type of fluorescent materials. AIE molecules emit weak light or even no fluorescence in solution, but emit strong fluorescence in aggregated states, showing broad application prospects in solid-state light-emitting devices, chemical sensing, and stimulus-responsive materials. To meet different functional requirements, many new organic aggregation-induced emission materials have been designed and developed, such as tetraphenylethylene, triphenylamine, and biphenyl derivatives, leading to new developments in a series of fields, covering bioimaging, optoelectronic materials, and cancer treatment. Imine-based luminescent materials have received widespread attention due to their readily available raw materials, low cost, and easily modifiable structure, but reports on imine-based aggregation-induced emission materials with multiple detection properties are relatively few.

[0005] 2,5-(bisbutoxy)-terephthalaldehyde, as a bridging unit, can be converted into an imine compound with strong proton-binding ability through nucleophilic addition reactions, thereby increasing the conjugation of organic molecules. Furthermore, the complexation of the imine nitrogen atom with a proton can induce sensitive changes in optical signals. Aminomalenitrile compounds, as flexible conjugated groups, are also attracting increasing attention in the construction of molecular sensors [Monika, A. Verma, MK Tiwari, N. Subba, S. Sah, J. Photochem. Photobio. A: Chem., 2022, 433, 114130; R. Sheng, P. Wang, Y. Gao, Y. Wu, W. Liu, J. Ma, H. Li, S. Wu, Org. Lett., 2008 [10, 5015-5018]. However, currently, molecular sensors with ion detection capabilities in both aggregated and solution states, constructed using 2,5-(bisbutoxy)-terephthalaldehyde as the core unit and complexed with diaminomaleitrile, have not yet been developed. Summary of the Invention

[0006] To address the problems existing in the prior art, this invention provides a method for detecting the emission signal of Hg in the aggregated state of red fluorescence. 2+ / Cr 3+ / Fe 3+ Solution-state blue fluorescence emission signal for acid / CrO4 2- A molecular sensor with multiple detection functions, the molecular sensor is o -Butoxy-modified terephthalaldehyde-maleitrile molecular sensor.

[0007] This invention is achieved through the following technical solution:

[0008] A molecular sensor with dual-state modulation of dual-color light and five-detection function, wherein the sensor is symmetrical. o The structure of the butoxy-modified terephthalaldehyde-maleitrile molecule is as follows:

[0009] .

[0010] The molecular sensor is easy to fabricate and exhibits good aggregation-induced red fluorescence emission performance.

[0011] Another object of the present invention is to provide the said symmetry. o The method for preparing -butoxy-modified terephthalaldehyde-maleitrile molecules includes the following steps:

[0012] 2,5-(bisbutoxy)-terephthalaldehyde was dissolved in an EtOH-DMF mixed solvent, and diaminomaleitrile and concentrated sulfuric acid were added sequentially. The mixture was heated under reflux for 6-8 hours. The reaction solution was cooled to room temperature, filtered, washed with anhydrous ethanol, and dried to obtain an orange solution. o -Butoxy-modified terephthalaldehyde-maleitrile molecule.

[0013] Furthermore, the molar ratio of 2,5-(bisbutoxy)-terephthalaldehyde to diaminomaleitrile is 1:2, the volume ratio of EtOH to DMF in the mixed solvent is 4:1, the amount of mixed solvent added is limited to 20 mL of mixed solvent for every 1 mmol of 2,5-(bisbutoxy)-terephthalaldehyde, and the amount of concentrated sulfuric acid added is 50 μL of concentrated sulfuric acid for every 1 mmol of 2,5-(bisbutoxy)-terephthalaldehyde.

[0014] The symmetry o The reaction formula for preparing the butoxy-modified terephthalaldehyde-maleitrile molecular sensor is as follows:

[0015] .

[0016] A third objective of the present invention is to provide the aforementioned symmetry. o -Butoxy-modified terephthalaldehyde-maleitrile molecules aggregate in Hg 2+ Applications of detection.

[0017] Specifically, the molecular sensor exhibits the following characteristics: in an 80% water-content DMF-water solution, it displays strong red fluorescence emission near 605 nm; 10 times Hg 2+ After its addition, the maximum fluorescence emission intensity of the molecular sensor decreased by 90.8%, and its characteristic broad absorption in the 260-600 nm range disappeared in the UV absorption spectrum, with a maximum absorption appearing near 458 nm; Hg 2+ After addition, the yellowish-brown aggregated solution of the molecular sensor turned flesh-red under sunlight, and its red fluorescence emission disappeared under 365 nm ultraviolet (UV) light irradiation, thus imparting... o -Butoxy-modified terephthalaldehyde-maleitrile molecules against Hg 2+ It features four-signal detection capabilities: red fluorescence emission "on-off", ultraviolet absorption spectrum, and intuitive color changes in solutions under sunlight and ultraviolet light.

[0018] The fourth object of the present invention is to provide the aforementioned o -Butoxy-modified terephthalaldehyde-maleitrile molecules in Fe 3+ Cr 3+ Applications of detection.

[0019] Specifically, the following is observed: In a DMF-water solution with a water content of 80%, the... o Adding 10 times the amount of Hg to the butoxy-modified terephthalaldehyde-maleitrile molecule 2+ The binary system exhibits weak fluorescence emission at 605 nm; when 10 times the amount of Fe is added... 3+ Afterwards, its maximum fluorescence emission was enhanced by 8.5 times; with the addition of 10 times Cr 3+ Afterward, its maximum fluorescence emission increased by 7 times; the addition of other metal ions did not significantly change the weak fluorescence emission of the binary system, thus endowing it with... o -Butoxy-modified terephthalaldehyde-maleitrile molecule-Hg 2+ Binary system red fluorescence emission "off-on" detection of Fe 3+ Cr 3+ performance.

[0020] The fifth object of the present invention is to provide the aforementioned o -Butoxy-modified terephthalaldehyde-maleitrile molecules in solution state for CrO4 2- Detection applications.

[0021] The specific manifestations are as follows: In a DMF-water solution with a water content of 20%, with the addition of CrO4... 2- As the amount of CrO4 gradually increased, the fluorescence emission intensity of the molecular sensor increased by 29 times near 430 nm. In the ultraviolet absorption spectrum, its maximum absorption at 462 nm gradually disappeared, and two strong absorption peaks appeared near 348 and 262 nm. 2- After addition, the transparent yellowish-brown solution of the molecular sensor turns dark red, and under 365 nm ultraviolet (UV) light irradiation, the solution exhibits almost no fluorescence emission but instead displays blue fluorescence emission, thus imparting... o -Butoxy-modified terephthalaldehyde-maleitrile molecules against CrO4 2- It features four-signal detection functions: blue fluorescence emission "off-on", ultraviolet absorption, and visual color changes under sunlight and ultraviolet light.

[0022] The sixth object of the present invention is to provide the aforementioned o Application of 1-butoxy-modified terephthalaldehyde-maleitrile molecules in solution state for detection in acidic environments.

[0023] Specifically, the results are as follows: In a 20% DMF-water solution, with a gradual increase in the amount of HCl added, the weak maximum fluorescence emission of the symmetric molecular sensor near 535 nm gradually blue-shifts to near 475 nm, accompanied by a 17-fold increase in fluorescence emission intensity. Simultaneously, its maximum absorption at 462 nm blue-shifts to near 425 nm, accompanied by a decrease in absorbance. Under 365 nm ultraviolet (UV) lamp irradiation, the blue fluorescence emission of the molecular sensor solution, which initially showed almost no fluorescence emission, gradually increases, imparting... o Butoxy-modified terephthalaldehyde-maleitrile molecules exhibit a three-signal detection response to changes in acidic environments: blue fluorescence emission "off-on", ultraviolet absorption, and direct fluorescence emission color change.

[0024] Compared with the prior art, the present invention has the following technical effects: o The butyloxy-modified terephthalaldehyde-maleitrile molecular sensor exhibits remarkable aggregation-induced red fluorescence emission due to its symmetrical butyloxy structure. In an 80% DMF-water solution, the aggregated state of this molecular sensor responds to Hg... 2+ It exhibits a four-signal monitoring response: red fluorescence emission "on-off", ultraviolet absorption, and visual color changes under sunlight and ultraviolet light. This is consistent with Hg. 2+ The resulting binary system affects Fe 3+ Cr 3+ This molecular sensor exhibits different red fluorescence "off-on" signal detection responses; in a 20% water-content DMF-water solution, it detects CrO4. 2- The concentration change exhibits a four-signal detection response: blue fluorescence emission "off-on", ultraviolet absorption, and dual-color changes under sunlight and ultraviolet lamp. In acidic environments, it exhibits a three-signal detection response: blue fluorescence emission "off-on", ultraviolet absorption, and a direct color change under ultraviolet lamp. This endows the single-molecule sensor with an aggregated state for detecting Hg. 2+ Cr 3+ Fe 3+ It exhibits a red fluorescence emission signal detection response, and its solution state is responsive to acids and CrO4. 2- It has different blue fluorescence "off-on" detection functions; especially based on the fluorescence emission performance of different states for Cr 3+ and CrO4 2- This invention achieves dual-color light detection response, and the detection signal is fast and intuitive, enabling in-situ, real-time, and field detection of different targets, thus possessing high application value. o The preparation process of the butoxy-modified terephthalaldehyde-maleitrile molecular sensor has advantages such as high yield and mild synthesis conditions, making it suitable for industrial implementation. o The widespread application of 2-butoxy-modified terephthalaldehyde-maleitrile molecular sensors has been facilitated. Attached Figure Description

[0025] Figure 1 for o NMR spectrum of a 2-butoxy-modified terephthalaldehyde-maleitrile molecular sensor.

[0026] Figure 2 for o UV absorption diagram of 1-butoxy-modified terephthalaldehyde-maleitrile molecule in 0-95% THF aqueous solution.

[0027] Figure 3 for o The aggregation and luminescence properties of -butoxy-modified terephthalaldehyde-maleitrile molecules in 0-80% THF aqueous solutions.

[0028] Figure 4 for o The aggregation and luminescence properties of -butoxy-modified terephthalaldehyde-maleitrile molecules in 80-95% THF aqueous solution.

[0029] Figure 5 for o The aggregation and luminescence properties of -butoxy-modified terephthalaldehyde-maleitrile molecules in 0-60% DMF-water solutions.

[0030] Figure 6 for o The aggregation and luminescence properties of terephthalaldehyde-maleitrile molecules modified with 1-butoxy groups in 60-90% DMF aqueous solution.

[0031] Figure 7 for o- Fluorescence selectivity of butoxy-modified terephthalaldehyde-maleic nitrile molecules for different metal ions in the aggregated state.

[0032] Figure 8 for o UV light images of terephthalaldehyde-maleitrile molecules in their aggregated state interacting with different metal ions.

[0033] Figure 9 for o- The UV absorption selectivity of butoxy-modified terephthalaldehyde-maleitrile molecules for different metal ions in the aggregated state.

[0034] Figure 10 for o Photographs of terephthalaldehyde-maleitrile molecules with different metal ions under sunlight in their aggregated state modified with 1-butoxy groups.

[0035] Figure 11 for o Hg in the aggregated state of -butoxy-modified terephthalaldehyde-maleitrile molecules. 2+ It competes with other metal ions for fluorescence performance.

[0036] Figure 12 for o Fluorescence selectivity of terephthalaldehyde-maleitrile molecules in solution for different anions.

[0037] Figure 13 for o UV-lit images of 1-butoxy-modified terephthalaldehyde-maleitrile molecules interacting with different anions in solution.

[0038] Figure 14 for o Selectivity of terephthalaldehyde-maleitrile molecules for UV absorption of different anions in solution state under -butoxyl-modified conditions.

[0039] Figure 15 for o Photographs of terephthalaldehyde-maleitrile molecules modified with 1-butoxy groups under sunlight with different anions in solution state.

[0040] Figure 16 for o Butoxy-modified terephthalaldehyde-maleitrile molecules in solution at different concentrations of CrO4 2- Fluorescence emission properties.

[0041] Figure 17 for o -Butoxy-modified terephthalaldehyde-maleitrile molecules in solution state CrO4 2- It competes with other anions for fluorescence emission performance.

[0042] Figure 18 for o Fluorescence emission properties of 2-butoxy-modified terephthalaldehyde-maleitrile molecules in solution reacting with HCl of different concentrations.

[0043] Figure 19 for o Photographs under UV light of terephthalaldehyde-maleitrile molecules modified with butoxy groups reacting with HCl of different concentrations in solution.

[0044] Figure 20 for o UV absorption properties of 1-butoxy-modified terephthalaldehyde-maleitrile molecules in solution reacting with HCl of different concentrations.

[0045] Figure 21 for o- Fluorescence emission properties of butoxy-modified terephthalaldehyde-maleitrile molecules reacting with different concentrations of HCl in the aggregated state.

[0046] Figure 22 for oUV absorption properties of terephthalaldehyde-maleitrile molecules in aggregated state reacting with different concentrations of HCl. Detailed Implementation

[0047] The molecular sensor with dual-state modulation, dual-color light, and five-detection function disclosed in this invention has the following molecular structure:

[0048] .

[0049] It can be prepared by a one-step polymerization reaction using 2,5-(bisbutoxy)-terephthalaldehyde and diaminomaleitrile as reactants. The synthesis reaction formula is as follows:

[0050] .

[0051] Example 1

[0052] Preparation of compound A: 1 mmol of 2,5-(bisbutoxy)-terephthalaldehyde was dissolved in 20 mL of EtOH-DMF (4:1), followed by the addition of 2 mmol of diaminomaleitrile and 50 μL of concentrated sulfuric acid. The mixture was heated under reflux for 6 hours. The reaction solution was cooled to room temperature, filtered, washed with anhydrous ethanol, and dried to give an orange compound, 316.2 mg, yield 69%.

[0053] Example 2

[0054] Preparation of compound B: 1 mmol of 2,5-(bisbutoxy)terephthalaldehyde was dissolved in 20 mL of EtOH-DMF (4:1), followed by the addition of 2 mmol of diaminomaleitrile and 50 μL of concentrated sulfuric acid. The mixture was heated under reflux for 8 hours. The reaction solution was cooled to room temperature, filtered, washed with anhydrous ethanol, and dried to give an orange compound, 320.8 mg, yield 70%.

[0055] Compounds A and B obtained in Examples 1 and 2, respectively, were analyzed and determined by NMR. Figure 1 To, see Figure 1 The NMR data are as follows: 1 ¹H NMR (400 MHz, DMSO): δ 8.62 (s, 2H), 8.12 (s, 4H), 7.85 (s, 2H), 4.17 (t, 4H), 1.17 (m, 4H), 1.53 (m, 4H), 0.98 (t, 6H); MS: ion peak m / z 458.45, [theoretical calculated value M]. + [458.22]; indicating that compounds A / B and o The theoretical values ​​for the butoxy-modified terephthalaldehyde-maleitrile molecules are basically consistent. Therefore, the molecular structures of compounds A and B can be confirmed as follows:

[0056] ,Right now o -Butoxy-modified terephthalaldehyde-maleitrile molecule.

[0057] Example 3

[0058] o Aggregation properties of butoxy-modified terephthalaldehyde-maleitrile molecules in THF-H2O mixed solvent: at a concentration of 2×10⁻⁶. -4 M o UV absorption spectroscopy tests of the butoxy-modified terephthalaldehyde-maleitrile molecule in THF-H2O mixed solvents with different proportions showed that: in pure THF, the molecular sensor exhibited a maximum absorption peak at 459 nm and a slightly weaker shoulder peak near 482 nm; as the water content in the mixed solvent increased from 0% to 70%, the UV absorption spectrum of the molecular sensor remained almost unchanged; increasing the water content from 70% to 80% resulted in a decrease in absorbance at the absorption peaks at 470 and 494 nm, the appearance of a broad absorption peak without characteristic structure, and a sharp rise in the absorption tail after 510 nm; further increasing the water content in the mixed solvent to 95% resulted in a broad absorption peak without characteristic structure in the UV absorption, indicating... o Butoxy-modified terephthalaldehyde-maleitrile molecules aggregate in a THF-H2O mixed solvent with a water content of over 80%. See details... Figure 2 .

[0059] Example 4

[0060] o Aggregation-induced luminescence properties of β-butoxy-modified terephthalaldehyde-maleitrile molecules in THF-H2O mixed solvents: Fluorescence emission spectroscopy tests of the molecular sensor in THF-H2O mixed solvents with different proportions showed that: as the water content in the mixed solvent increased from 0% to 70%, the weak fluorescence emission of the molecular sensor near 520 nm remained basically unchanged; increasing the water content from 70% to 80% significantly enhanced the fluorescence emission at 520 nm and redshifted it to near 590 nm, as detailed in [see figure]. Figure 3 ; Further increasing the proportion of water in the mixed solvent to 95% slightly reduced the enhanced fluorescence emission mentioned above, see details. Figure 4 ,show o Butoxy-modified terephthalaldehyde-maleitrile molecules exhibit aggregation-induced red fluorescence emission in a mixed solvent of THF-H2O with a slightly higher water content.

[0061] Example 5

[0062] oAggregation-induced luminescence properties of butoxy-modified terephthalaldehyde-maleitrile molecules in DMF-H2O mixed solvent: Fluorescence emission spectroscopy tests of the molecular sensor in DMF-H2O mixed solvents with different proportions showed that: as the water content in the mixed solvent increased from 0% to 30%, the weak fluorescence emission of the molecular sensor near 525 nm remained basically unchanged; as the water content increased from 30% to 60%, its fluorescence emission at 535 nm was significantly enhanced and redshifted to near 608 nm, as detailed in [see...]. Figure 5 ; Further increasing the proportion of water in the mixed solvent to 90% slightly reduced the enhanced fluorescence emission mentioned above, see details below. Figure 6 ,show o Butoxy-modified terephthalaldehyde-maleitrile molecules exhibit aggregation-induced red fluorescence emission in a mixed solvent of DMF-H2O with a slightly higher water content.

[0063] Example 6

[0064] o Butoxy-modified terephthalaldehyde-maleitrile molecule aggregates exhibit fluorescence detection selectivity for different metal ions: in an 80% water-content DMF-water solution, at a concentration of 2×10⁻⁶... -5 mol / L o The butoxy-modified terephthalaldehyde-maleitrile molecular sensor was supplemented with 10 times the amount of Na. + K + Li + Ba 2+ Ca 2+ Cr 3+ Al 3+ Fe 3+ Hg 2+ Co 2+ Pb 2+ Cd 2 + Mn 2+ Ni 2+ Cu 2+ Zn 2+ Fluorescence emission performance tests revealed that the molecular sensor exhibits a maximum fluorescence emission peak at 605 nm; 10 times the amount of Hg 2+ After its addition, its maximum fluorescence emission intensity decreased by 90.8%; other metal ions such as Na + K + Li + Ba 2 + Ca 2+ Cr 3+ Al 3+ Fe 3+ Co 2+Pb 2+ Cd 2+ Mn 2+ Ni 2+ Cu 2+ Zn 2+ After the addition, the fluorescence emission spectrum of the molecular sensor showed almost no significant change, as detailed in [link to documentation]. Figure 7 Under 365 nm ultraviolet (UV) lamp irradiation, o The butoxy-modified terephthalaldehyde-maleitrile molecular sensor exhibits red fluorescence emission in its aggregated state solution, Hg 2+ After the addition of [a specific metal ion], its red fluorescence emission disappeared; after the addition of other metal ions, the red fluorescence emission of the solution remained essentially unchanged. See [the original text for details]. Figure 8 These results indicate that in an aqueous solution of DMF with a water content of 80%... o -Butoxy-modified terephthalaldehyde-maleitrile molecular sensor aggregates for Hg 2+ The ions exhibit a dual-signal monitoring response, which provides an intuitive "on-off" red fluorescence emission and a visually intuitive change in emission color.

[0065] Example 7

[0066] o Butoxy-modified terephthalaldehyde-maleitrile molecular aggregates exhibit UV selectivity for different metal ions: In an 80% water-content DMF-water solution at a concentration of 2×10⁻⁶... -5 mol / L o Adding 10 times the amount of Na to the butoxy-modified terephthalaldehyde-maleitrile molecular sensor + K + Li + Ba 2+ Ca 2+ Cr 3+ Al 3+ Fe 3+ Hg 2+ Co 2+ Pb 2+ Cd 2+ Mn 2+ Ni 2+ Cu 2+ Zn 2+ UV absorption performance testing revealed that the molecular sensor exhibits a broad, structure-free absorption in the 260-600 nm range; Na + K + Li + Ba 2+ Ca 2+ Cr 3+ Al 3+ Fe 3+Co 2+ Pb 2+ Cd 2+ Mn 2+ Ni 2+ Cu 2+ Zn 2+ After the addition of metal ions, its ultraviolet absorption spectrum showed almost no significant change; Hg 2+ After its addition, the molecular sensor exhibits a maximum absorption near 458 nm; see [link to details] for more information. Figure 9 Under the sunlight, o The butoxy-modified terephthalaldehyde-maleitrile molecular sensor aggregate solution appears yellowish-brown, Hg 2+ After the addition of this substance, the solution turned flesh-colored. The color of the solution remained largely unchanged after the addition of other metal ions. See the attached table for specific results. Figure 10 These results indicate that in an aqueous solution of DMF with a water content of 80%, o -Butoxy-modified terephthalaldehyde-maleitrile molecular sensor aggregates for Hg 2+ The ions exhibit a four-signal monitoring response, including red fluorescence emission "on-off", ultraviolet absorption, and two intuitive color changes under sunlight and ultraviolet light.

[0067] Example 8

[0068] o -Butoxy-modified terephthalaldehyde-maleitrile molecular sensor Hg in aggregated state 2+ Optical competitiveness with other metal ions: In an aqueous solution of DMF- with a water content of 80% and a concentration of 2×10⁻⁶, -5 mol / L o The butoxy-modified terephthalaldehyde-maleitrile molecular sensor was simultaneously supplemented with 10 times the amount of Hg. 2+ Fluorescence emission spectroscopy studies of mixed systems with other different metal ions showed that the addition of 10 times the amount of Hg to this molecular sensor... 2+ Subsequently, its binary system exhibits a weak maximum fluorescence emission near 605 nm; when K... + Mg 2+ Li + Ca 2+ Ba 2+ Na + Co 2+ Cu 2+ Cd 2+ Zn 2+ Mn 2+ Al 3+ Hg 2+ Pb 2+ and Ni 2+ Metal ions and Hg 2+ Join at the same timeo After the butoxy-modified terephthalaldehyde-maleitrile molecule solution, the ternary mixed system and the molecular sensor with Hg 2+ The fluorescence emission spectrum of the binary system is similar; however, this molecular sensor is similar to that of Hg. 2+ Adding Fe to a binary system 3+ Subsequently, its maximum fluorescence emission blue-shifted to 591 nm, and the fluorescence emission was enhanced by 8.5 times; with the addition of Cr 3+ Subsequently, its maximum fluorescence emission blue-shifted to 593 nm, and the fluorescence emission was enhanced by 7 times. For details, please refer to [link to relevant documentation]. Figure 11 ,show o- Butoxy-modified terephthalaldehyde-maleitrile molecules not only affect Hg 2+ It exhibits good selective detection performance, compared with Hg 2+ The resulting binary system affects Cr 3+ Fe 3+ It has different red fluorescence emission "off-on" detection performance.

[0069] Example 9

[0070] o The butoxy-modified terephthalaldehyde-maleitrile molecular sensor's fluorescence detection function for different anions in solution state: in a 20% aqueous DMF-water solution, at a concentration of 1×10⁻⁶... -5 mol / L o The butyloxy-modified terephthalaldehyde-maleitrile molecular sensor exhibits almost no fluorescence emission; 10 times that of CrO4 2- After its addition, its fluorescence emission at 430 nm was significantly enhanced, with the intensity increasing by 29 times; other anions such as SO42- 2- HSO4 - HSO3 - SO3 2- NO3 - NO2 - CO3 2- S2O3 2- SCN - IO3 - C2O4 2- SiO3 2- HCO3 - F - Cl - ,Br - After joining, o The weak fluorescence emission spectrum of the butoxy-modified terephthalaldehyde-maleic nitrile molecule did not change significantly; see the detailed results below. Figure 12 Under 365 nm ultraviolet (UV) lamp irradiation, oThe butoxy-modified terephthalaldehyde-maleitrile molecular sensor solution showed almost no fluorescence emission, CrO4 2- After its addition, the solution exhibits blue fluorescence emission, while SO4... 2- HSO4 - HSO3 - SO3 2- NO3 - NO2 - CO3 2- S2O3 2- SCN - IO3 - C2O4 2- SiO3 2- HCO3 - F - Cl - ,Br - After the addition of ions, the mixture showed virtually no fluorescence emission; see the results below. Figure 13 These results indicate that o -Butoxy-modified terephthalaldehyde-maleitrile molecular sensor solution state for CrO4 2- It features fluorescence emission "off-on" and intuitive blue fluorescence color change detection response.

[0071] Example 10

[0072] o The butoxy-modified terephthalaldehyde-maleitrile molecular sensor's UV absorption detection function for different anions in solution state: in a 20% aqueous DMF-water solution, at a concentration of 1×10⁻⁶... -5 mol / L o The butyloxy-modified terephthalaldehyde-maleitrile molecular sensor exhibits a maximum absorption peak near 462 nm and a weak absorption peak at 275 nm; 10 times CrO4 2- After its addition, the molecular sensor exhibited a disappearance of its maximum absorption at 462 nm and a new absorption peak at 348 nm. Simultaneously, its absorption at 275 nm blue-shifted to 262 nm, accompanied by increased absorbance. Other anions, such as SO42-, also showed similar effects. 2- HSO4 - HSO3 - SO3 2- NO3 - NO2 - CO3 2- S2O3 2- SCN - IO3 - C2O4 2- SiO3 2- HCO3- F - Cl - ,Br - After joining, o The UV absorption spectrum of the butoxy-modified terephthalaldehyde-maleitrile molecule showed no significant change. (See attached image for details.) Figure 14 Under the sunlight, o The butoxy-modified terephthalaldehyde-maleitrile molecular sensor solution is a transparent yellowish-brown color, CrO4 2- After the addition, the solution turned dark red. The yellowish-brown transparent mixture remained essentially unchanged after the addition of the other anions mentioned above. See [link to specific results] for details. Figure 15 These results indicate that in an aqueous solution of DMF with a water content of 20%, o -Butoxy-modified terephthalaldehyde-maleitrile molecular sensor for CrO4 2- It features a four-signal detection response, including blue fluorescence emission "off-on", ultraviolet absorption, and dual color changes under sunlight and ultraviolet light.

[0073] Example 11

[0074] o -Butoxy-modified terephthalaldehyde-maleitrile molecular sensor solution state for different concentrations of CrO4 2- Fluorescent detection function of ions: In a DMF- aqueous solution with a water content of 20%, the concentration is 1×10⁻⁶. -5 mol / L o -Butoxy-modified terephthalaldehyde-maleitrile molecular sensor with different concentrations of CrO4 2- The fluorescence emission spectrum in its presence is as follows: with CrO4 2- As the concentration increased from 0 to 20 molar amounts, the maximum fluorescence emission intensity of the molecular sensor gradually increased near 430 nm; subsequently, with further increases in CrO4... 2- The fluorescence emission spectrum remains essentially unchanged regardless of the concentration; see the attached diagram for details. Figure 16 ;show o -Butoxy-modified terephthalaldehyde-maleitrile molecular sensor for CrO4 2- It possesses sensitive and intuitive fluorescence "off-on" recognition potential.

[0075] Example 12

[0076] o CrO4 in the solution of -butoxy-modified terephthalaldehyde-maleitrile molecular sensor 2- Spectroscopic competitiveness with other anions: In a 20% aqueous solution of DMF-, at a concentration of 1×10⁻⁶... -5 mol / L oThe butoxy-modified terephthalaldehyde-maleitrile molecule is simultaneously incorporating 10 times the amount of CrO4. 2- Fluorescence emission spectroscopy studies of other mixed systems with different anions have shown that: o Adding 10 times the amount of CrO4 to the butoxy-modified terephthalaldehyde-maleitrile molecule 2- Subsequently, the binary system exhibits a strong maximum fluorescence emission near 430 nm; when SO42-... 2- HSO4 - HSO3 - SO3 2- NO3 - NO2 - CO3 2- S2O3 2- SCN - IO3 - C2O4 2- SiO3 2- HCO3 - F - Cl - ,Br - Plasma and CrO4 2- Join at the same time o After α-butoxy-modified terephthalaldehyde-maleitrile molecule solution, the fluorescence emission spectrum of the ternary system and o -Butoxy-modified terephthalaldehyde-maleitrile molecule-CrO4 2- The binary system exhibits similar fluorescence spectra, displaying strong blue fluorescence emission. For details, please refer to [link to results]. Figure 17 These indicate o -Butoxy-modified terephthalaldehyde-maleitrile molecules against CrO4 2- It exhibits good selective detection performance.

[0077] Example 13

[0078] o The optical detection function of the butoxy-modified terephthalaldehyde-maleitrile molecular sensor solution under different acidic environments: in a 20% water content DMF-water solution, at a concentration of 1×10⁻⁶... -5 mol / L o The fluorescence emission spectra of the butoxy-modified terephthalaldehyde-maleitrile molecule in the presence of different concentrations of HCl are as follows: As the concentration of added HCl increases from 0 to 80 molar equivalents, the maximum fluorescence emission of this molecular sensor blue-shifts from approximately 535 nm to 475 nm, and the fluorescence emission intensity increases by 17-fold. See the detailed results below. Figure 18Studies of its ultraviolet absorption spectroscopy properties show that as the HCl concentration increases from 0 to 80 molar amounts, the maximum absorption of this molecular sensor near 462 nm gradually blue-shifts to 425 nm, accompanied by a decrease in absorbance. Subsequently, when the HCl concentration is further increased, even to 200 molar amounts, its ultraviolet absorption spectrum remains essentially unchanged. For detailed results, please refer to [link to relevant documentation]. Figure 19 Under 365nm ultraviolet (UV) light irradiation, o The butoxy-modified terephthalaldehyde-maleitrile molecular sensor solution showed almost no fluorescence emission. However, as the HCl concentration increased from 0 to 80 molar amounts, the blue fluorescence emission gradually increased. Further increases in HCl concentration did not significantly alter the blue fluorescence emission. (See attached table for details.) Figure 20 These results indicate o The butoxy-modified terephthalaldehyde-maleitrile molecular sensor solution exhibits the potential for detection of three signals: sensitive blue fluorescence emission "on-off", intuitive fluorescence color change, and ultraviolet absorption, in response to changes in acidic environment.

[0079] Example 14

[0080] o The butoxy-modified terephthalaldehyde-maleitrile molecular sensor exhibits optical detection capabilities in various acidic environments: in an 80% water-content DMF-water solution, at a concentration of 1×10⁻⁶... -5 mol / L o The fluorescence emission spectra of the butoxy-modified terephthalaldehyde-maleitrile molecule in the presence of different concentrations of HCl are as follows: With increasing HCl concentration from 0 to 500 molar equivalents, the maximum fluorescence emission intensity of this molecular sensor near 610 nm shows almost no change. See the detailed results below. Figure 21 Studies of its ultraviolet absorption spectroscopy properties showed that as the HCl concentration increased from 0 to 500 molar amounts, the molecular sensor's structureless absorption spectrum remained unchanged in the 260-600 nm range. For detailed results, please refer to [link to relevant documentation]. Figure 22 ;show o The -butoxy-modified terephthalaldehyde-maleitrile molecular sensor exhibits no sensitive optical signal detection response to changes in acidic environments.

Claims

1. A bistate regulation dual-color light-molecular sensor with five detection functions, the sensor is symmetrical o - a butoxy modified, aggregation-induced emission performance, terephthaldehyde-maleonitrile molecule, the structure is: 。 2. A method of preparing a molecular sensor as claimed in claim 1, characterized in that: Comprising the following steps: 2,5-(bis-butoxy) terephthaldehyde was dissolved in a mixed solvent of EtOH-DMF, diamino maleonitrile and concentrated sulfuric acid were added successively, and the reaction was heated to reflux for 6-8 hours. The reaction solution was cooled to room temperature, filtered, washed with anhydrous ethanol, and dried to obtain o - butoxy-modified terephthaldehyde-maleonitrile molecules.

3. The method of claim 2, wherein the molecular sensor is prepared by: The molar ratio of 2,5-(dibutoxy) benzene-1,4-dialdehyde and diamino maleonitrile is 1:2, the volume ratio of EtOH and DMF in the mixed solvent is 4:1, the adding amount of the mixed solvent is limited to 20 mL mixed solvent per 1 mmol 2,5-(dibutoxy) benzene-1,4-dialdehyde, and the adding amount of concentrated sulfuric acid is 50 μL concentrated sulfuric acid per 1 mmol 2,5-(dibutoxy) benzene-1,4-dialdehyde.

4. Use of the molecular sensor aggregate according to claim 1 for the detection of Hg 2+ which does not involve the diagnosis and treatment of diseases, characterized in that: The molecular sensor exhibits four-signal monitoring response of red fluorescence emission "on-off", UV absorption, direct color change of solution under sunlight and UV light in DMF-water solution with water content of 80% 2+ The molecular sensor exhibits four-signal monitoring response of red fluorescence emission "on-off", UV absorption, direct color change of solution under sunlight and UV light in DMF-water solution with water content of 80% 5. Use of the molecular sensor aggregate according to claim 1 for the detection of Fe 3+ , Cr 3+ without involving the diagnosis and treatment of diseases. In DMF-water solution with 80% water content, the molecular sensor-Hg 2+ The binary system has a weak fluorescence emission at 605 nm; Fe 3+ , Cr 3+ After adding, the maximum fluorescence emission of the binary system presents different degrees of red fluorescence emission "off-on" response.

6. Use of a molecular sensor solution as claimed in claim 1 in the detection of Cr04 2- applications not related to the diagnosis and treatment of diseases, characterized in that: In DMF-aqueous solution with 20% water content, the molecular sensor solution meets CrO4 2- exhibited blue fluorescence emission "off-on", UV absorption, sunlight and UV light dual color change four signal detection potential.

7. The use of a molecular sensor solution state to acidic environment detection according to claim 1, characterized by: In a DMF-water solution with a water content of 20%, the molecular sensor can exhibit three signal detection responses of blue fluorescence emission "off-on", ultraviolet absorption and intuitive color change under ultraviolet light in response to changes in acidic environment.

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