CN114989093B - Preparation and application of AIE fluorescent material - Google Patents

Preparation and application of AIE fluorescent material Download PDF

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CN114989093B
CN114989093B CN202210755787.7A CN202210755787A CN114989093B CN 114989093 B CN114989093 B CN 114989093B CN 202210755787 A CN202210755787 A CN 202210755787A CN 114989093 B CN114989093 B CN 114989093B
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喻艳华
付成
甘泉
张冬冬
许公女
邓宣凯
何荣祥
鲁望婷
李雯慧
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Abstract

The invention belongs to the field of fluorescent small molecule self-assembly, and particularly discloses three self-assembly fluorescent material synthesis, a preparation method of a self-assembly body and application of the self-assembly body in cation detection. The three fluorescent materials are respectively: (Z) -5- (4-dimethylaminobenzylidene) -2- (2-cyanoethyl) -3-methylimidazole, (Z) -5- (3-dimethylaminobenzylidene) -2- (2-cyanoethyl) -3-methylimidazole, (Z) -5- (4-hydroxy-3, 5-difluorobenzylidene) -2-n-hexyl-3-methylimidazole. All three compounds can form a fibrous structure with fluorescent property and uniform structure through self-assembly in a methanol and water solvent system. Wherein: the (Z) -5- (4-dimethylaminobenzylidene) -2- (2-cyanoethyl) -3-methylimidazolone can identify copper ions and mercury ions in a pure water phase, and can quantitatively detect the mercury ions.

Description

Preparation and application of AIE fluorescent material
Technical Field
The invention belongs to the field of fluorescent small molecule self-assembly, and relates to three self-assembly fluorescent material synthesis, a self-assembly body preparation method and application thereof in cation detection and cytotoxicity.
Background
Luminescent materials with controllable luminescence properties are a focus of attention, and conventional organic fluorescent molecules have fluorescence properties only in dilute solutions due to quenching (ACQ) caused by aggregation, which greatly limits their application in solid luminescent materials. In order to overcome this problem, efforts have been made to incorporate branched or macrocyclic chains into or blend them with polymers having higher glass transition temperatures, but none of the results are ideal. The aggregation-induced emission (AIE) phenomenon found in 2001 by Tang Benzhong institutions et al provides another approach to solve this problem. They developed a new molecule that fluoresces very weakly in solution but emits intense light after aggregation. This abnormal fluorescent behavior is due to the restriction of intramolecular rotation, aggregation-induced planarization, and in some cases the formation of J-aggregates. Many magic molecules with AIE effect have been designed after many years of research.
Molecular self-assembly is the directed association of molecules into nano-or micro-structures through non-covalent interactions. AIE molecules have the advantages of high solid state fluorescence efficiency, variable emission color and the like, and are ideal base stones for constructing luminescent micro/nano structures. AIE molecules can be designed into a novel functional material due to the unique properties of the AIE molecules, and the AIE molecules have wide application in the fields of biology, environment, materials, pharmacy, agriculture and the like. However, classical AIE molecules are difficult to arrange in order due to their non-planar topology and thus difficult to spontaneously assemble into ordered assemblies.
Disclosure of Invention
The green fluorescent protein chromophore (HBI) derivative combined by the applicant subject has AIE effect, and the green fluorescent protein chromophore derivative can form nano material with uniform structure through self-assembly under certain conditions. Because HBI is derived from chromophore of green fluorescent protein, self-assembly of its derivative has better biocompatibility and lower cytotoxicity, so that it has better application in biomedical field. In addition, because the molecular self-assembly is mainly formed by intermolecular hydrogen bonds, pi-pi stacking and other non-covalent bonds, some heavy metal ions can inhibit the molecular self-assembly by the competition of the hydrogen bonds to cause fluorescence change or collapse of the molecular self-assembly by ions to cause fluorescence quenching, thereby realizing the detection of the ions. Heavy metal ions can be detected in pure water phase systems or in cells based on the principle.
Based on the technical principle, the invention has four purposes: (1) Providing several HBI derivatives capable of forming nanomaterials with fluorescent properties by self-assembly; (2) Providing a preparation method of the HBI derivative capable of forming the nanomaterial with fluorescent property through self-assembly; (3) Providing a method for self-assembling the HBI derivative to form a nano material; (4) The method for detecting mercury ions and/or copper ions by using the nanomaterial with fluorescent property is provided.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
1. molecular probe for detecting heavy metal ions (mercury ions and/or copper ions)
The molecular probe is self-assembled in a solvent system by the HBI derivative to form a uniform nanofiber-like structure. The molecular probe is capable of recognizing mercury ions and/or copper ions.
The structural formula of the HBI derivative is shown as follows:
Figure BDA0003719518870000021
the chemical names are respectively as follows:
(Z) -5- (4-dimethylaminobenzylidene) -2- (2-cyanoethyl) -3-methylimidazolone, labeled XSG;
(Z) -5- (3-dimethylaminobenzylidene) -2- (2-cyanoethyl) -3-methylimidazolone, labeled FSG;
(Z) -5- (4-hydroxy-3, 5-difluorobenzylidene) -2-n-hexyl-3-methylimidazolone, labeled XWC.
The molecular probe is formed by self-assembly of XSG in a solvent system, wherein the solvent system is a pure water system and a methanol/water system, and the methanol volume ratio in the methanol/water system is 0-20%, for example, the molecular probe can be a methanol/water system with the methanol volume ratio of 20%; preferably, the solvent system is a pure aqueous phase, which is free of organic solvents.
The molecular probe is formed by self-assembly of FSG in a solvent system, wherein the solvent system is a methanol/water system, a tetrahydrofuran/water system, a 1, 3-hexafluoro-2-propanol/water system or a dimethyl sulfoxide/water system, wherein the volume ratio of methanol in the solvent system is 0-20%, the volume ratio of tetrahydrofuran is 0-10%, the volume ratio of 1, 3-hexafluoro-2-propanol is 0-10%, and the volume ratio of dimethyl sulfoxide is 0-5%; preferably, the volume ratio of methanol to tetrahydrofuran in the solvent system is 10% -20%, the volume ratio of 1, 3-hexafluoro-2-propanol is 5% -10%, and the volume ratio of dimethyl sulfoxide is 1% -5%.
The molecular probe is formed by self-assembly of XWC in a solvent system, wherein the solvent system is a methanol/water system, and the volume ratio of methanol in the solvent system is 0-20%; preferably, the volume ratio of methanol in the solvent system is 10-20%.
2. Synthesis method of HBI derivatives XSG, FSG and XWC
The synthetic route for HBI derivatives is shown below:
Figure BDA0003719518870000031
Figure BDA0003719518870000032
wherein: r.t in the route refers to room temperature; r is R 1 4-N, N-dimethyl 4-N (Me) 2 3-N, N-dimethyl 3-N (Me) 2 Or 3, 5-difluoro-4-hydroxy 3,5-F,4-OH; r is R 2 Is propionitrile or n-hexane.
3. Method for self-assembling HBI derivative to form nano material
Dissolving the HBI derivative in a solvent system, uniformly mixing, and standing to obtain the HBI derivative (XSG, FSG and XWC) self-assembled fluorescent material, namely the molecular probe for detecting heavy metal ions.
4. The application of the molecular probe in preparing the probe for detecting heavy metal ions.
The molecular probe can identify mercury ions and/or copper ions, wherein the concentration of copper ions in the solution to be detected is 0-1 mmol/L, and the concentration of mercury ions is 0-1 mmol/L.
In one aspect, the molecular probe may be assembled by ion-inhibiting the probe, resulting in its fluorescence change to detect ions. Preferably, the molecular probe is formed by self-assembly of XSG in a solvent system.
On the other hand, the molecular probe may detect ions by disrupting the assembly with the ions, resulting in a change in fluorescence (quenching) thereof. Preferably, the molecular probe is formed by self-assembly of XSG in a solvent system.
Preferably, the molecular probe is applied to detection of heavy metal ions in a pure water phase system, wherein the molecular probe is formed by self-assembly of XSG in a solvent system, and the solvent system is a pure water phase and does not contain an organic solvent.
Preferably, the molecular probe is applied to qualitative and/or quantitative detection of mercury ion probes in preparation of a pure water phase system, wherein the molecular probe is formed by self-assembly of XSG in a solvent system, and the solvent system is a pure water phase, and does not contain an organic solvent.
Further, the concentration of copper ions in the solution to be measured is 0.01-0.1 mmol/L, and the concentration of mercury ions is 0.01-0.1 mmol/L.
It should be noted that: as used herein, the term "solvent system is a pure aqueous phase, which is free of organic solvent" means that the organic solvent content of the system is extremely small, and the organic solvent content in the solvent system is less than 0.1% and negligible.
Compared with the prior art, the invention has the advantages that:
1. detection of cations using a complexation mechanism is difficult to achieve in the pure water phase in the prior art. The invention can detect cations in a 100% aqueous solvent system by using an XSG molecular probe.
2. The mercury ions can inhibit the assembly of the HBI derivative (XSG, FSG, XWC), and the naked eye detection of the mercury ions can be realized.
3. The invention can be used forQuantitative detection of Hg in pure water phase solvent system by XSG molecular probe 2+ 。
Drawings
Fig. 1: fluorescence microscopy of 1mg/mL of XSG self-assembly in different solvents (a, c, d, e) and 0.17mg/mL of XSG self-assembly in ultra pure water; a is 20% methanol/water v/v, b is 100% water, c is 10% THF/water v/v, d is 10% HFP/water v/v, e is 5% DMSO/water v/v.
Fig. 2: fluorescence microscopy (a-c) and scanning electron microscopy (d-g) of the self-assembly process of XSG in 1mg/mL, 20% aqueous methanol (v/v).
Fig. 3: fluorescence microscopy images of FSG self-assembly in different solvents at 1mg/mL (a-e); a is 20% v/v methanol/water, b is 10% v/v THF/water, c is 10% v/v isopropanol/water, d is 10% v/v HFP/water, e is 5% v/v DMSO/water.
Fig. 4: fluorescence microscopy (a-c) and scanning electron microscopy (d-g) of FSG self-assembled in 1mg/mL, 20% aqueous methanol (v/v).
Fig. 5: fluorescence microscopy of XWC self-assembly in 1mg/mL in different solvents (a-d): a is methanol/water with a v/v of 20%, b is acetonitrile/water with a v/v of 20%, c is DMSO/water with a v/v of 5%, d is DMF/water with a v/v of 5%.
Fig. 6: XWC was self-assembled in 1mg/mL, 20% methanol in water (v/v) for fluorescence microscopy (a) and scanning electron microscopy (b, c).
Fig. 7: XSG, FSG, XWC molecular fluorescence spectra in 1mg/mL, 20% aqueous methanol (v/v).
Fig. 8:0.1mg/mL XSG in pure water blank (a) and 1.6mmol/L Cu, respectively 2+ (b)、Hg 2+ (c)、Na + (d)、Ag + (e)、Ca 2+ (f)、K + (g)、Mg 2+ (h)、Zn 2+ (j) Fluorescence microscopy of self-assembly in aqueous solution (TRITC mode test).
Fig. 9:0.1mg/mL XSG forms a self-assembly body in pure water, and then fluorescence spectrum is tested, and assembly morphology is observed through a fluorescence microscope; then 10. Mu.L of mercury ions and copper ions (final concentration of both ions is 1 mmol/L) were added to the assembled solution, respectively, and the fluorescence intensity of the XSG solution was measured after 3 hours (excitation wavelength is 509nm, slit width is 5nm to 5 nm), and the assembled morphology was observed by a fluorescence microscope (TRITC mode test).
Fig. 10:0.1mg/mL of XSG is shown in a molecular fluorescence spectrum (10 a) of the pure water solution when the concentration of mercury ions ranges from 0.01 mmol/L to 1 mmol/L; hg in FIG. a 2+ The curves corresponding to the concentrations of 0.01-0.1 mmol/L are independently plotted to obtain FIG. 10b, and the fluorescence value at 533nm in the graph can be taken to obtain the line graph on the right of FIG. 10b and obtain the linear fitting graph thereof.
Fig. 11: XSG, FSG, XWC at a concentration of 10 respectively -5 、10 -6 、10 -7 Human glioma cell cytotoxicity test pattern at mol/L.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples.
Example 1: preparation of HBI derivatives XSG, FSG and XWC
1. Synthesis of Compound 2
A500 mL eggplant-shaped bottle is taken, 200mL of diethyl ether, 32mL of deionized water and 10g of glycine methyl ester hydrochloride are added, then 11g of anhydrous potassium carbonate is added, stirring is carried out for 10min, and then 9.8g of ethyl acetamidine hydrochloride is added for reaction for 10min. The aqueous and organic phases were separated by a separatory funnel, 200mL diethyl ether was added again to the aqueous phase and the reaction was continued for 10min, and the organic phases were combined. Anhydrous magnesium sulfate is added into the organic phase, and the mixture is dried, filtered and spin-dried to obtain a pale yellow liquid product 2.
Preparation of XSG
A50 mL dry eggplant-shaped bottle was taken, 4-dimethylaminobenzaldehyde (1.49 g,10 mmol) and 3-aminopropionitrile (77 mg,11 mol) were added thereto, and 20mL of absolute ethanol was used as a solvent, followed by stirring at room temperature under nitrogen atmosphere for 12 hours. The corresponding schiff base is obtained after the solvent is dried. Then, freshly prepared compound 2 (1.25 g,11 mmol) was added and stirred at room temperature for 12h with 20mL of absolute ethanol as solvent. After the reaction is finished, spin-drying the solvent, and separating and purifying by column chromatography to obtain a final product XSG: (Z) -5- (4-dimethylaminobenzylidene) -2- (2-cyanoethyl) -3-methylimidazolone.
HRMS：calculated for[M+H]:283.15,measured:283.1551； 1 H NMR(400MHz,DMSO,298K):δ(ppm):8.07(d,J＝8.8Hz,2H),6.91(s,1H),6.76(d,J＝8.9Hz,2H),3.85(t,J＝6.5Hz,2H),3.01(s,6H),2.88(t,J＝6.5Hz,2H),2.39(s,3H)； 13 C NMR(101MHz,DMSO,298K):δ(ppm):169.81,159.45,151.90,134.44,134.24,127.75,121.85,119.17,112.13,40.07,36.17,17.58,15.68.
Preparation of FSG
A50 mL dry eggplant-shaped bottle was taken, 3-dimethylaminobenzaldehyde (1.49 g,10 mmol) and 3-aminopropionitrile (77 mg,11 mol) were added thereto, and 20mL of absolute ethanol was used as a solvent, followed by stirring at room temperature under nitrogen atmosphere for 12 hours. The corresponding schiff base is obtained after the solvent is dried. Then, freshly prepared compound 2 (1.25 g,11 mmol) was added and stirred at room temperature for 12h with 20mL of absolute ethanol as solvent. After the reaction is finished, spin-drying the solvent, and separating and purifying by column chromatography to obtain a final product FSG: (Z) -5- (3-dimethylaminobenzylidene) -2- (2-cyanoethyl) -3-methylimidazolone.
HRMS：calculated for[M+H]:283.15,measured:283.1547； 1 H NMR(400MHz,DMSO,298K):δ(ppm):7.62–7.56(m,1H),7.25(t,J＝8.0Hz,1H),6.97(s,1H),6.82–6.78(m,1H),3.87(t,J＝6.6Hz,1H),2.92(s,1H),2.42(s,1H)； 13 CNMR(101MHz,DMSO,298K):δ(ppm):170.15,163.05,150.97,138.25,134.77,129.59,127.36,120.67,119.11,116.43,114.94,40.53,36.28,17.54,15.95.
Preparation of XWC
50mL of a dried eggplant-shaped bottle was taken, 3, 5-fluoro, 4-hydroxybenzaldehyde (1.58 g,10 mmol) and n-hexylamine (1.45 mL,11 mol) were added, and the mixture was stirred at room temperature for 12 hours under a nitrogen atmosphere using 20mL of absolute ethanol as a solvent. The corresponding schiff base is obtained after the solvent is dried. Then, freshly prepared compound 2 (1.25 g,11 mmol) was added and stirred at room temperature for 12h with 20mL of absolute ethanol as solvent. After the reaction is finished, spin-drying the solvent, and separating and purifying by column chromatography to obtain a final product XWC: (Z) -5- (4-hydroxy-3, 5-difluorobenzylidene) -2-n-hexyl-3-methylimidazolone.
HRMS：calculated for[M+H]:322.15，measured:322.1524； 1 H NMR(400MHz,DMSO,298K):δ(ppm):8.05(d,J＝9.0Hz,2H),6.85(s,1H),6.74(d,J＝9.1Hz,2H),3.53(t,J＝7.3Hz,2H),3.01(s,6H),2.33(s,3H),1.68–1.43(m,2H),1.26(m,6H),0.86(t,J＝6.8Hz,3H)； 13 C NMR(101MHz,DMSO,298K):δ(ppm):170.10,164.48,153.53,151.13,138.62,136.15,125.18,123.38,115.75,40.33,31.25,28.96,26.28,22.45,15.91,14.34.
Example 2: XSG, FSG, XWC self-assembled material and its preparation method
1. XSG self-assembly
(1) Effect of solvent on XSG self-assembly
Accurately weighing five parts of XSG of 1mg, wherein four parts of the XSG are respectively dissolved in 200 mu L of methanol, 100 mu L of Tetrahydrofuran (THF), 100 mu L of 1, 3-hexafluoro-2-propanol (HFP) and 50 mu L of dimethyl sulfoxide (DMSO), respectively adding 800 mu L, 900 mu L and 950 mu L of ultrapure water respectively, uniformly mixing by an oscillator, standing for 2 hours to obtain self-assemblies of the XSG, respectively transferring the solutions containing the self-assemblies onto a glass plate, and testing the self-assembly morphology of the XSG in different solvent systems by a fluorescence microscope after the self-assemblies are naturally dried, as shown in (a, c-e) of fig. 1: a methanol/water (v/v: 2/8), c THF/water (v/v: 1/9), dHFP/water (v/v: 1/9), e DMSO (v/v: 0.5/9.5). 1 part of ultrapure water (heated in a water bath at 80 ℃ C. For 1 hour) was dissolved in 6mL of the solution, naturally cooled to room temperature and allowed to stand for 3 hours to obtain a self-assembly of XSG, which was tested for self-assembly by a fluorescence microscope as shown in FIG. 1 (b).
As shown in FIG. 1, XSG can form fibrous nano materials with uniform structures through self-assembly in a methanol/water and pure water solvent system, and the fibrous nano materials all show green fluorescence. In other solvent systems, the self-assembled structure is more complex and the unordered state is more. Thus, a suitable solvent system for self-assembly of XSG is methanol/water or pure water.
(2) Assembly process of XSG in mixed solvent of methanol and water
At room temperature, 1mg of XSG is accurately weighed and dissolved in 200 mu L of methanol solvent, after complete dissolution, 800 mu L of ultrapure water is added, an oscillator is adopted to mix the methanol/ultrapure water solution containing XSG, after standing for 0min, 30min and 2h, the solution is respectively transferred to a glass plate and a silicon wafer, the glass plate and the silicon wafer are put into a freeze dryer for freeze drying, and the morphology is tested by a fluorescence microscope (a sample on the glass plate) and an ultra-high resolution cold field scanning electron microscope (a sample on the silicon wafer).
As shown in fig. 2, when water is added to the methanol solution containing XSG, XSG immediately forms fine fiber spherical nanomaterial by self-assembly due to poor solubility of XSG in water (fig. 2a,2 d), and as time goes by, such fine fiber spheres are entangled with each other into a thicker rod shape (fig. 2b and 2 e), and finally assembled into a uniform structure of nanorods (fig. 2c and 2 f), and its sectional view (fig. 2 g) shows that it is a solid rod structure.
2. Self-assembly of FSG
(1) Solvent effects on FSG self-assembly
Accurately weighing five parts of FSG (1 mg), respectively dissolving in 200 mu L of methanol, 100 mu L of Tetrahydrofuran (THF), 100 mu L of isopropanol, 100 mu L of 1, 3-hexafluoro-2-propanol (HFP) and 50 mu L of dimethyl sulfoxide (DMSO), respectively adding 800 mu L, 900 mu L and 950 mu L of ultrapure water respectively, uniformly mixing by an oscillator, standing for 2 hours to obtain self-assemblies of the FSG, respectively transferring solutions containing the self-assemblies onto a glass plate, and testing the self-assembly conditions by a fluorescence microscope after the solutions are naturally dried, wherein the self-assemblies are shown in the following figures 3 (a-e): a methanol/water (v/v: 2/8), b THF/water (v/v: 1/9), c isopropanol/water (v/v: 1/9), dHFP/water (v/v: 1/9), e DMSO (v/v: 0.5/9.5).
As shown in fig. 3, FSG cannot form a nano-material with a uniform structure through self-assembly in an isopropanol/water solvent system, and can form a nano-fiber material with green fluorescence property in other solvent systems, and fibers formed by FSG are finer than those formed by XSG.
(2) FSG assembling process in mixed solvent of methanol and water
1mg of FSG is accurately weighed and dissolved into 200 mu L of methanol solvent at room temperature, 800 mu L of ultrapure water is added after complete dissolution, an oscillator is adopted to mix methanol/ultrapure water solution containing FSG, the solution is respectively transferred onto a glass plate and a silicon wafer after standing for 0min, 30min and 2h, the glass plate and the silicon wafer are put into a freeze dryer for freeze drying, and the morphology is tested through a fluorescence microscope (a sample on the glass plate) and an ultra-high resolution cold field scanning electron microscope (a sample on the silicon wafer).
As shown in fig. 4, when water is added to the methanol solution containing FSG, FSG immediately forms a more fine fiber spherical nanomaterial than XSG by self-assembly due to poor solubility of FSG in water (fig. 4a,4 d), and as time goes by, the fine fiber spheres are entangled with each other into a thicker rod shape (fig. 4b and 4 e), and finally assembled into a uniform structure of nanofiber-like structure (fig. 4c and 4 f), the cross-sectional view (fig. 4 g) shows that it is a solid rod-like structure.
3. Self-assembly of XWC
(1) Influence of solvent on XWC self-assembly
Accurately weighing four XWC parts, respectively dissolving in 200 mu L of methanol, 200 mu L of acetonitrile, 50 mu L of DMSO and 50 mu L of N, N-Dimethylformamide (DMF), respectively adding 800 mu L of ultrapure water, 950 mu L of ultrapure water and 950 mu L of ultrapure water, mixing uniformly by an oscillator, standing for 6 hours to obtain a self-assembly body of XWC, taking a solution point containing the self-assembly body onto a glass plate, and testing the self-assembly morphology of the XWC in different solvent systems by a fluorescence microscope after the solution point is naturally dried, as shown in (a-d) of fig. 5: a methanol/water (v/v: 2/8), b acetonitrile/water (v/v: 2/8), c DMSO/water (v/v: 0.9/9.5), dDMF/water (v/v: 0.5/9.5).
As shown in fig. 5, the solvent has a great influence on the assembly of XWC, and XWC can form a nano rod-like structure with a uniform structure in a mixed system of methanol and water, and a wide and flat rod-like structure in a mixed solvent system of acetonitrile and water. Very fine filiform structures are formed in the more polar DMSO and DMF systems.
(2) Assembly morphology research of XWC in methanol and water mixed solvent system
1mg of XWC is accurately weighed and dissolved in 200 mu L of methanol solvent at room temperature, 800 mu L of ultrapure water is added after the XWC is completely dissolved, the mixture is mixed by an oscillator, the self-assembly of the XWC is obtained after the mixture is stood for 6 hours, a solution point containing the self-assembly is taken on a glass plate, the glass plate is placed into a freeze dryer for freeze drying, and the self-assembly condition of the glass plate is tested by a fluorescence microscope, as shown in figure 6a. The solution containing the self-assembly was spotted onto a silicon wafer, which was freeze-dried in a freeze dryer, and its morphology was tested by ultra-high resolution cold field scanning electron microscopy as shown in fig. 6 (b-c).
As shown in fig. 6a, the self-assembly of XWC is also a rod-like structure which is more straight than XSG, FSG, and the cross section (fig. 6 c) is also a solid rod-like structure.
4. XSG, FSG, XWC fluorescent Properties
1mg of XSG, FSG, XWC is respectively and accurately weighed and dissolved in 200 mu L of methanol solvent, 800 mu L of ultrapure water is respectively and correspondingly added after the solution is completely dissolved, and after the solution is uniformly mixed by an oscillator, fluorescence emission spectra of the solution are respectively tested. And then standing for 6 hours, and testing fluorescence emission spectra of the materials after self-assembly of the materials is completed. The excitation wavelength of the test XSG was 516nm, and the slit width was 5nm-5nm, as shown in FIG. 7a; the excitation wavelength of the test FSG was 445nm and the slit width was 5nm-5nm as shown in FIG. 7b; the excitation wavelength of the XWC was 415nm and the slit width was 5nm-5nm as shown in FIG. 7c.
As shown in FIG. 7a, XSG increases fluorescence intensity after assembly by about 7.7 times over before assembly, and the fluorescence optimum emission wavelength red shifts from 549nm before assembly to 593nm after assembly; FIG. 7b shows that the fluorescence intensity after FSG assembly is enhanced about 250 times over that before assembly, and that the fluorescence optimum emission wavelength blue shifts from 540nm before assembly to 536nm after assembly; FIG. 7c shows that three fluorescence emission peaks appear after XWC is assembled, wherein the intensity of the highest fluorescence emission peak is enhanced by about 36 times, the corresponding fluorescence emission wavelength is red shifted from 522nm before assembly to 549nm after assembly, and in addition, fluorescence emission peaks of 482 and 518nm appear in XWC.
Example 3: detection application of XSG to cations
(1) XSG response to various cations
Cu of 160mmol/L was formulated separately 2+ 、Hg 2+ 、Na + 、Ag + 、Ca 2+ 、K + 、Mg 2+ 、Zn 2+ The method comprises the following steps of: respectively weighing a certain amount of copper nitrate trihydrate, mercury perchlorate trihydrate, sodium chloride, silver nitrate, anhydrous calcium chloride, potassium chloride, anhydrous magnesium sulfate and zinc chloride, addingIn a 10mL EP tube, a proper amount of water was dissolved by a pipette and sonicated for 0.5min.
Accurately weighing 3mg of XSG into an EP tube, adding 30mL of ultrapure water, heating in a water bath at 80 ℃ for one hour to form a hot solution, transferring 8 parts of 3mL of 0.1mg/mL of XSG into the EP tube, and then adding 30 mu L of Cu-containing water respectively 2+ 、Hg 2+ 、Na + 、Ag + 、Ca 2+ 、K + 、Mg 2+ 、Zn 2+ The final concentration of the aqueous solution was 1.6mmol/L, and the aqueous solution was allowed to stand for 6 hours, and the solution was transferred to a glass plate, respectively, and the self-assembly effect of different metal ions on XSG was observed by using a fluorescence microscope. FIG. 8 shows pure water voids (8 a), cu 2+ (8b)、Hg 2+ (8c)、Na + (8d)、Ag + (8e)、Ca 2+ (8f)、K + (8g)、Mg 2+ (8h)、Zn 2+ (8j)。
As shown in FIG. 8, cu 2+ Ions and Hg 2+ Ions can inhibit XSG self-assembly, and other metal ions have no effect on XSG self-assembly. Description Cu can be detected using XSG self-assembly 2+ Ions and Hg 2+ Ions. Likewise, the self-assembly condition of FSG and XWC in a solvent system can be utilized to detect Cu 2+ Ions and Hg 2+ Ions.
(2) XSG assembly is respectively to Cu 2+ Ions and Hg 2+ Ion response conditions
Accurately weighing 2mg of XSG into an EP tube, adding 20mL of ultrapure water, heating in a water bath at 80 ℃ for one hour to form a hot solution, respectively transferring 3mL of 0.1mg/mL of XSG aqueous solution into a cuvette, self-assembling for 3 hours, testing fluorescence spectrum after the assembly of the XSG is completed, transferring part of the solution onto a glass plate, and observing the assembly morphology through a fluorescence microscope after the solution is naturally dried; then 18.7 mu L Hg-containing solution system was added separately 2+ And Cu 2+ The final concentration of the aqueous solution was 1mmol/L. After standing for 3 hours, testing the fluorescence spectrum of the glass plate, respectively transferring part of the solution to the glass plate, and observing the assembly morphology of the glass plate through a fluorescence microscope after the glass plate is naturally dried.
As shown in FIG. 9, the self-assembly of XSG in pure water phaseThe maximum fluorescence spectrum at about 600nm (FIG. 9 d), FIG. 9a shows the morphology of the self-assembled XSG in pure water phase, and FIG. 9c shows Cu addition 2+ The morphology of the self-assembled body of XSG of (C) indicates Cu 2+ XSG self-assemblies can be partially broken down (fig. 9 c), resulting in a decrease in their fluorescence intensity (fig. 9 d). FIG. 9b is a graph of Hg addition 2+ The morphology of the self-assembled body of XSG of (1) indicates Hg 2+ The XSG self-assembly can be completely disrupted (FIG. 9 b), resulting in complete quenching of its fluorescence intensity (FIG. 9 d), so Cu can be detected separately using this method 2+ And Hg of 2+ . Similarly, cu can be detected after formation of an assembly in a solvent system using FSG, XWC 2+ Ions and Hg 2+ Ions.
(3) XSG vs Hg 2+ Quantitative detection
Accurately weighing 2mg of XSG into an EP tube, adding 20mL of ultrapure water, heating in a water bath at 80 ℃ for one hour to form a hot solution, respectively transferring 3mL of 0.1mg/mL of XSG aqueous solution into a cuvette, self-assembling for 3 hours, testing fluorescence spectrum after the assembly of the XSG is completed, and then respectively adding 10 mu L of Hg with different concentrations 2+ The fluorescence intensity of the aqueous solution was measured after standing for 3 hours while the final concentration was kept at 0.01 to 1mmol/L, to obtain FIG. 10a, and the fluorescence intensity corresponding to the concentration of 0.01 to 0.1mmol/L was plotted from FIG. 10a to obtain FIG. 10b.
FIG. 10a shows Hg 2+ The addition of (2) significantly reduces the fluorescence intensity of the XSG self-assembly body, so that the maximum fluorescence emission peak of the XSG self-assembly body is blue-shifted from 600nm to 540nm; FIG. 10b shows the following Hg 2+ The fluorescence of the XSG self-assembly gradually decreases with increasing concentration. Linear fitting Hg at 533nm in the range of 0.01-0.1 mmol/L 2+ The concentration and the fluorescence value are found to have a certain linear relation, and Hg can be quantitatively detected by the method 2+ Is a concentration of (3). At the same time, the detection of Cu in pure water phase can be realized by utilizing XSG self-assembly 2+ And Hg of 2 + The method comprises the steps of carrying out a first treatment on the surface of the And can realize naked eye detection of Hg in pure water phase 2+ And quantitative detection thereof.
Example 4: MTT test of XSG, FSG, XWC
U87 (human glioma cell line) cells were cultured in 24-well plates at 30000 cells/well in DMEM, 10% Fetal Bovine Serum (FBS), 0.1% diabody (penicillin, streptomycin) and 5% carbon dioxide at 37℃for 24 hours, then 10. Mu.L of XSG, FSG, XWC DMSO solutions were added respectively, the final concentrations of XSG, FSG, XWC were 0.1. Mu.mol/L, 1. Mu.mol/L and 10. Mu.mol/L respectively, incubated for 24 hours, 50. Mu.L of CCK-8 kit was taken and incubated in the aforementioned U87 cells at 37℃for 2 hours, and the multi-labeled microwell plates were tested for absorbance at 450 nm.
FIG. 11 shows that XSG, FSG, XWC has very low cytotoxicity to U87 cells in the concentration range of 0.1 to 10. Mu. Mol/L.

Claims (8)

1. An AIE molecule, wherein the AIE molecule has the structural formula:
Figure FDA0004177297700000011
2. the AIE molecule of claim 1, wherein the AIE molecule is synthesized by the following route:
Figure FDA0004177297700000012
3. a molecular probe for detecting heavy metal ions, which is characterized in that the molecular probe is self-assembled in a solvent system by the XSG of claim 1 to form a uniform nanofiber structure, wherein the solvent system is a pure water system and a methanol/water system, and the methanol volume ratio in the methanol/water system is 0-20%; or (b)
The molecular probe forms a uniform nanofiber-like structure by self-assembly of the FSG of claim 1 in a solvent system, wherein the solvent system is a methanol/water system, a tetrahydrofuran/water system, a 1, 3-hexafluoro-2-propanol/water system or a dimethyl sulfoxide/water system, wherein the volume ratio of methanol in the solvent system is 0-20%, the volume ratio of tetrahydrofuran is 0-10%, the volume ratio of 1, 3-hexafluoro-2-propanol is 0-10%, and the volume ratio of dimethyl sulfoxide is 0-5%; or (b)
The molecular probe is self-assembled in a solvent system by XWC according to claim 1 to form a uniform nanofiber-like structure, wherein the solvent system is a methanol/water system, and the volume ratio of methanol in the solvent system is 0-20%;
the molecular probe is capable of recognizing mercury ions and/or copper ions.
4. A molecular probe for detecting heavy metal ions according to claim 3, wherein the molecular probe is self-assembled in a solvent system by XSG according to claim 1 to form a uniform nanofiber-like structure, the solvent system is a pure water system and a methanol/water system, and the methanol volume ratio in the methanol/water system is 0-20%; or (b)
The molecular probe forms a uniform nanofiber-like structure by self-assembly of the FSG of claim 1 in a solvent system, wherein the solvent system is a methanol/water system, a tetrahydrofuran/water system, a 1, 3-hexafluoro-2-propanol/water system or a dimethyl sulfoxide/water system, wherein the volume ratio of methanol in the solvent system is 10-20%, the volume ratio of tetrahydrofuran is 5-10%, the volume ratio of 1, 3-hexafluoro-2-propanol is 5-10%, and the volume ratio of dimethyl sulfoxide is 1-5%; or (b)
The molecular probe is self-assembled in a solvent system by XWC according to claim 1 to form a uniform nanofiber-like structure, wherein the solvent system is a methanol/water system, and the volume ratio of methanol in the solvent system is 10% -20%.
5. The use of a molecular probe for detecting heavy metal ions according to any one of claims 3 to 4 for preparing a probe for detecting mercury ions and/or copper ions.
6. The use according to claim 5, wherein the molecular probe detects ions by disrupting the assembly of ions, resulting in a change in their fluorescence.
7. The use of a molecular probe for detecting heavy metal ions according to any one of claims 3-4 for the detection of mercury ions and/or copper ions in the preparation of pure aqueous systems, characterized in that the molecular probe is self-assembled from XSG according to claim 1 in a solvent system to form a uniform nanofibrous structure.
8. Use of a molecular probe for detecting heavy metal ions according to any one of claims 3-4 for qualitative and/or quantitative detection of mercury ions in the preparation of a pure aqueous phase system, characterized in that the molecular probe is self-assembled from XSG according to claim 1 in a solvent system to form a uniform nanofibrous structure.
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