CN111205450B - Application and preparation method of tetraphenylethylene isomer - Google Patents

Application and preparation method of tetraphenylethylene isomer Download PDF

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CN111205450B
CN111205450B CN201811405862.7A CN201811405862A CN111205450B CN 111205450 B CN111205450 B CN 111205450B CN 201811405862 A CN201811405862 A CN 201811405862A CN 111205450 B CN111205450 B CN 111205450B
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oeg
tpe
tetraphenylethylene
isomer
assembly
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CN111205450A (en
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唐本忠
彭慧晴
林荣业
石秀娟
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Hong Kong University of Science and Technology HKUST
Shenzhen Research Institute HKUST
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Hong Kong University of Science and Technology HKUST
Shenzhen Research Institute HKUST
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
    • C08G65/33303—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group
    • C08G65/3331—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group cyclic
    • C08G65/33313—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing amino group cyclic aromatic
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6402—Atomic fluorescence; Laser induced fluorescence

Abstract

The invention provides an application and a preparation method of a tetraphenylethylene isomer; the tetraphenylethylene isomer adopts (Z) -TPE-OEG or (E) -TPE-OEG; the chemical formula of the (Z) -TPE-OEG is as follows:
Figure DDA0003769543120000011
(E) -TPE-OEG has the formula:
Figure DDA0003769543120000012
wherein R is 1 、R 2 Is an aromatic group; n is a positive integer. The application and the preparation method of the tetraphenylethylene isomer have wide application and strong practicability.

Description

Application and preparation method of tetraphenylethylene isomer
Technical Field
The invention relates to the technical field of aggregation-induced emission, in particular to an application and a preparation method of a tetraphenylethylene isomer; in particular to application and a preparation method of a tetraphenylethylene isomer, and also relates to a detection reagent at the initial stage of self-assembly and a visual reagent of a temperature response process.
Background
Microscopic visualization of scientific processes, including biological processes, plays an important role in understanding life systems and manipulating industrial production. The above process involves many basic steps such as diffusion, volatilization, polymerization, phase separation, self-assembly, and the like. The self-assembly process achieved by weak interaction is not only very important for living systems but also has been used to build a variety of new functional materials. In recent years, the development of electron microscopes (e.g., transmission microscopes, scanning microscopes, etc.) has enabled a deep understanding of self-assembly. However, the practical operation of these electron microscopes has either required vacuum or special requirements for sample preparation, and thus the study of self-assembly using them has been limited primarily to the observation of static assembly features.
The ultrasensitive, highly selective and non-invasive nature of fluorescence makes fluorescence technology well suited for in situ detection of supramolecular assembly processes. The development of many fluorescence microscopy techniques, especially confocal laser scanning microscopy, has prompted us to achieve real-time high resolution imaging. But conventional molecules tend to undergo fluorescence quenching after being drawn to a distance by weak interactions of supramolecular assembly.
Disclosure of Invention
The invention provides an application and a preparation method of a tetraphenylethylene isomer aiming at the technical problems.
The technical scheme provided by the invention is as follows:
the invention provides an application of a tetraphenylethylene isomer, wherein the tetraphenylethylene isomer adopts (Z) -TPE-OEG or (E) -TPE-OEG; the chemical formula of the (Z) -TPE-OEG is as follows:
Figure GDA0003769543110000021
(E) -TPE-OEG has the formula:
Figure GDA0003769543110000022
wherein R is 1 、R 2 Is an aromatic group;
n is a positive integer;
the tetraphenylethylene isomer was used to detect the initial stage of self-assembly.
In the use of the tetraphenylethylene isomer of the present invention as described above, the tetraphenylethylene isomer is used for indicating the initial assembly concentration at the initial stage of self-assembly by aggregation-induced emission properties.
In the application of the tetraphenylethylene isomer, the tetraphenylethylene isomer adopts (Z) -TPE-OEG; the chemical formula of the (Z) -TPE-OEG is as follows:
Figure GDA0003769543110000023
wherein R is 1 、R 2 Is an aromatic group;
n is a positive integer;
the tetraphenylethylene isomer is used to achieve visualization of the temperature response process.
In the use of the tetraphenylethylene isomers of the present invention as described above, the tetraphenylethylene isomers have different temperature response behaviors at different temperatures.
In the use of the above tetraphenylethylene isomer of the present invention, R is 1 By using
Figure GDA0003769543110000031
One of (a) and (b);
R 2 by using
Figure GDA0003769543110000032
One of (1);
n is any one of 1,2, 3, 4, 5, 6 and 7.
The invention also provides a preparation method of the tetraphenylethylene isomer, which adopts the following chemical reaction:
Figure GDA0003769543110000033
wherein R is 1 、R 2 Is an aromatic group;
n is a positive integer.
In the preparation method of the tetraphenyl ethylene isomer, the tetraphenyl ethylene isomer is prepared by reacting 1,2- (4-aminobenzene) -1, 2-diphenylethylene with an acyl chloride compound containing oligomeric ethylene glycol monomethyl ether.
In the process for preparing the tetraphenylethylene isomer of the present invention as described above, R 1 By using
Figure GDA0003769543110000034
One of (1);
R 2 by using
Figure GDA0003769543110000035
One of (a) and (b);
n is any one of 1,2, 3, 4, 5, 6 and 7.
The invention also provides a detection reagent for the initial self-assembly stage, which comprises tetraphenyl ethylene isomer;
the tetraphenylethylene isomer adopts (Z) -TPE-OEG or (E) -TPE-OEG; the chemical formula of the (Z) -TPE-OEG is as follows:
Figure GDA0003769543110000041
(E) -TPE-OEG has the formula:
Figure GDA0003769543110000042
wherein R is 1 、R 2 Is an aromatic group;
n is a positive integer.
In the above-mentioned detection reagent of the present invention, R 1 By using
Figure GDA0003769543110000043
One of (1);
R 2 by using
Figure GDA0003769543110000044
One of (1);
n is any one of 1,2, 3, 4, 5, 6 and 7.
The invention also provides a visual reagent for the temperature response process, which comprises tetraphenylethylene isomer;
the tetraphenylethylene isomer adopts (Z) -TPE-OEG; the chemical formula of the (Z) -TPE-OEG is as follows:
Figure GDA0003769543110000051
wherein R is 1 、R 2 Is an aromatic group;
n is a positive integer.
In the above visual reagent of the present invention, R 1 By using
Figure GDA0003769543110000052
One of (a) and (b);
R 2 by using
Figure GDA0003769543110000053
One of (1);
n is any one of 1,2, 3, 4, 5, 6 and 7.
The implementation of the invention can realize the following beneficial effects: two functional molecules which can be assembled in water are obtained at one time through one-pot reaction. Given that current research approaches to critical concentration of assembly (CMC) are generally limited to testing optical transmittance, their sensitivity is not sufficient to capture the formation of some small assemblies. The characteristics of luminescence after aggregation of the (Z) -TPE-OEG and the (E) -TPE-OEG are detected to find that the two can be assembled under a very low concentration. The (Z) -TPE-OEG has temperature response property. The dehydration of the ether chain of the (Z) -TPE-OEG at the temperature rise limits the fluorescence enhancement of the (Z) -TPE-OEG aqueous solution caused by molecular motion. We can therefore observe this temperature response under a confocal laser scanning microscope. Further, cis-trans isomers (Z) -TPE-OEG and (E) -TPE-OEG modified by oligomeric ethylene glycol monomethyl ether chains are successfully synthesized, and the isomers still retain the aggregation-induced emission property of tetraphenylethylene. Modification of the ether chain confers hydrophilic and hydrophobic assembly behavior on both Z and E cis-trans isomers. The invention realizes the ultra-sensitive detection of the initial stage of the supermolecule assembly and the visualization of the temperature response process of the (Z) -TPE-OEG. The application and the preparation method of the tetraphenylethylene isomer have wide application and strong practicability.
Drawings
The invention will be further described with reference to the accompanying drawings and examples, in which:
FIG. 1 shows a schematic structural synthesis of (Z) -TPE-OEG and (E) -TPE-OEG of the present invention;
FIG. 2 shows a high performance liquid chromatogram for separating (Z) -TPE-OEG and (E) -TPE-OEG;
FIG. 3 shows a nuclear Eporhodeit effect spectrum (NOESY) plot of (E) -TPE-OEG;
FIG. 4 shows UV-visible absorption spectra (A) of (Z) -and (E) -TPE-OEG in chloroform solution (10. Mu.M) and chloroform/n-hexane mixed solvent ex ＝350nm；
FIG. 5 is a graph showing luminescence spectra (B) of (Z) -and (E) -TPE-OEG in a chloroform solution (10. Mu.M) and a chloroform/n-hexane mixed solvent;
FIG. 6 shows a graph of the light transmission (A) of (Z) -TPE-OEG at different concentrations;
FIG. 7 shows a graph of light transmission (B) for (E) -TPE-OEG at different concentrations;
FIG. 8 shows the assembled topography at 338 μ M (C) for an aqueous solution of (Z) -TPE-OEG;
FIG. 9 shows the assembled topography at 338 μ M (D) for an aqueous solution of (E) -TPE-OEG;
FIG. 10 shows a graph of fluorescence quantum efficiency versus fluorescence lifetime for (Z) -TPE-OEG at different concentrations;
FIG. 11 shows a graph of fluorescence quantum efficiency versus fluorescence lifetime for (E) -TPE-OEG at different concentrations;
FIG. 12 shows the assembly profile of (Z) -TPE-OEG at low concentration (30 μ M);
FIG. 13 shows the assembled topography of (E) -TPE-OEG at low concentration (30 μ M);
FIG. 14 is a graph showing the change of light transmittance of aqueous solutions of (Z) -and (E) -TPE-OEG with increasing temperature;
FIG. 15 shows a schematic diagram of the reversibility of the (Z) -TPE-OEG temperature response transmittance change;
FIG. 16 shows a graph of the change of fluorescence intensity of an aqueous (Z) -TPE-OEG solution with increasing temperature;
FIG. 17 shows a graph of the reversibility of temperature response of (Z) -TPE-OEG to fluorescence intensity change;
fig. 18 shows a schematic diagram of the temperature response process of the (Z) -TPE-OEG aqueous solution observed using a confocal laser scanning microscope.
Detailed Description
The technical problem to be solved by the invention is as follows: practical operation of electron microscopes imposes requirements on vacuum or on sample preparation, and thus research on self-assembly using them is also largely limited to observing static assembly morphologies. Conventional fluorescent molecules are easily quenched. The technical idea proposed by the invention for solving the technical problem is as follows: the invention adopts the aggregation-induced emission behavior to overcome the problem that fluorescent substance molecules are easy to quench. Molecules with this property do not emit light when they are monodisperse, but rather emit bright fluorescence after assembly. This "light-up" type of fluorescence transition facilitates higher resolution in situ observation of supramolecular assembly processes. Tetraphenylethylene and derivatives thereof are a class of classical molecular motifs with aggregation-induced emission properties. In addition, when the mono-substituted benzophenone is synthesized into the tetraphenyl ethylene compound through the McMurry reaction, cis-trans isomers can be generated. Considering that supramolecular assembly is easily influenced by molecular configuration, we also expect that novel supramolecular materials can be discovered using cis-trans isomers.
In order to make the technical purpose, technical solutions and technical effects of the present invention more clear and facilitate those skilled in the art to understand and implement the present invention, the present invention will be further described in detail with reference to the accompanying drawings and specific embodiments.
The invention respectively synthesizes oligo-polyethylene glycol (OEG) functionalized tetraphenylethylene isomers (Z) -TPE-OEG and (E) -TPE-OEG. Here, the chemical formula of (Z) -TPE-OEG is:
Figure GDA0003769543110000071
(E) -TPE-OEG has the formula:
Figure GDA0003769543110000072
wherein, the chemical formula R 1 And R 2 Is an aromatic group, n is any positive integer, specifically, R 1 And R 2 Or respectively can be
Figure GDA0003769543110000073
Any one of them.
The invention also provides a preparation method of the tetraphenyl ethylene isomer with aggregation-induced emission and hydrophilic-hydrophobic assembly behaviors, which adopts the following chemical reactions:
Figure GDA0003769543110000081
wherein R is 1 、R 2 Is an aromatic group;
n is a positive integer.
Preferably, R 1 And R 2 Are respectively as
Figure GDA0003769543110000082
n is 3. FIG. 1 shows R 1 And R 2 Are respectively as
Figure GDA0003769543110000083
The synthetic structure schematic diagram of (Z) -TPE-OEG and (E) -TPE-OEG when n is 3 comprises the following specific steps: 181-1810 mg of compound 1, i.e. 1,2- (4-aminophenyl) -1, 2-stilbene (0.5-5.0 mmol) and triethylamine (Et) 3 N, 101-1515mg, 1.0-10.0 mmol) is slowly added into a dichloromethane solution of 626-7828 mg of the compound 2, namely the oligoethylene glycol monomethyl ether acyl chloride compound (1.0-12.5 mmol) and stirred for 24 hours. The reaction solution was rotary evaporated and the crude product was simply separated by silica gel column to obtain a mixture of (Z) -TPE-OEG and (E) -TPE-OEG. The mixture was successfully separated into pure products of (Z) -TPE-OEG and (E) -TPE-OEG by high performance liquid chromatography. The following provides anSix specific examples of chemical reactions occur:
table 1 five specific examples of generating (Z) -TPE-OEG and (E) -TPE-OEG
Figure GDA0003769543110000084
Figure GDA0003769543110000091
As can be seen from Table 1, when example 3 is adopted, the yield is highest, the total yield is as high as 93%, and the yield of (E) -TPE-OEG is 2-3 times higher than that of (Z) -TPE-OEG; an excess of compound 2 is advantageous for an increase in the yield of the product. The molar amount of triethylamine is preferably not less than twice that of compound 1.
In this example, (Z) -TPE-OEG and (E) -TPE-OEG can be separated by high performance liquid chromatography, as shown in FIG. 2. The spatial configuration of the molecule can be confirmed by a two-dimensional nuclear magnetic spectrum, as shown in fig. 3. The aggregation-induced emission properties can be confirmed by absorption and emission spectra, as shown in fig. 4 and 5. The (Z) -TPE-OEG and the (E) -TPE-OEG have different assembly behaviors, wherein the Z-configuration can be assembled into a vesicle structure, and the E-configuration can be assembled into a micelle structure. The aggregation-induced emission properties of both were found to be assembled at very low concentrations. Molecules demonstrating aggregation-induced emission properties can be used to monitor the initial stages of self-assembly with great sensitivity. Dehydration of the OEG chain in (Z) -TPE-OEG at elevated temperatures causes the molecular motion of tetraphenylethylene to be restricted, resulting in its fluorescence enhancement. Therefore, we successfully observed the temperature response process of (Z) -TPE-OEG by using a confocal laser scanning microscope.
1. Separation of (Z) -TPE-OEG and (E) -TPE-OEG
As shown in FIG. 2, (Z) -TPE-OEG and (E) -TPE-OEG have different retention times on the HPLC column, respectively 8.5min and 16.0min, and the two compound solutions are respectively connected to obtain pure stereoisomer compounds.
2. Molecular Structure confirmation of (Z) -TPE-OEG and (E) -TPE-OEG
As shown in FIG. 1, in the E-configuration molecule, the benzene ring A without any modification on the tetraphenylethylene molecule is on the same side of the central double bond as the benzene ring B modified by OEG chain, which means that they are closer in space distance. The Nuclear Oreochromiser Effect Spectra (NOESY) of compounds with retention times of 8.5min and 16min were studied, respectively. The results show that the compound with 16min retention time has space interaction between the benzene ring A and the proton resonance signal on the benzene ring B (signal in circle of FIG. 3). Therefore, the compound with a retention time of 16min was (E) -TPE-OEG. Correspondingly, the compound with a residence time of 8.5min was (Z) -TPE-OEG.
3. Photophysical properties of (Z) -TPE-UPy and (E) -TPE-UPy
As shown in FIGS. 4 and 5, the UV-visible absorption spectra of (Z) -TPE-OEG and (E) -TPE-OEG chloroform solutions (10 μ M) are the same, and the extinction coefficient of (Z) -TPE-OEG is slightly higher than that of (E) -TPE-OEG, and the signals of the chloroform solutions are very weak in the luminescence spectra. As the volume fraction of n-hexane in chloroform increases, the (Z) -TPE-OEG and the (E) -TPE-OEG are aggregated, the absorption spectrum is red-shifted, and the fluorescence intensity is greatly enhanced. The above results indicate that both (Z) -and (E) -TPE-OEG have aggregation-induced emission properties.
4. Hydrophilic and hydrophobic Assembly behavior of (Z) -TPE-OEG and (E) -TPE-OEG
The proton resonance signals of (Z) -TPE-OEG and (E) -TPE-OEG in deuterated water become wider, indicating that they have intermolecular interactions in water. The light transmittance of the two aqueous solutions with different concentrations is tested, and the critical assembly concentrations of the (Z) -TPE-OEG and the (E) -TPE-OEG are respectively 156 and 162 mu M. Freezing aqueous solution of isomer (338 μ M) found that (Z) -TPE-OEG can form vesicles and (E) -TPE-OEG can form micelle structure, as shown in FIGS. 6-9.
5. Ultrasensitive detection of self-assembly initial stage using (Z) -TPE-OEG and (E) -TPE-OEG aggregation-induced emission properties
The molecules with aggregation-induced emission properties have very low fluorescence quantum efficiency and very weak fluorescence intensity in a completely dissolved state. Therefore, we believe that the fluorescence quantum efficiency (Φ) should occur at the critical assembly concentration for (Z) -TPE-OEG and (E) -TPE-OEG AF ) And fluorescence lifetime (. Tau.) F ) Is performed. However, as shown in FIG. 10-FIG. 13 shows that the results of the experiment show that the (. PHI.) of (Z) -TPE-OEG and (E) -TPE-OEG AF And τ F The critical turning points for sharp increases were 1.7 and 1.0 μ M, respectively. This result is two orders of magnitude lower than the 156 and 162 μ M obtained by transmittance. It is shown that the cis-trans isomer already undergoes molecular assembly at very low concentrations and aggregation causes an increase in fluorescence. Freezing the dilute solution of cis-trans isomers found that at this concentration (Z) -TPE-OEG and (E) -TPE-OEG had formed a micelle structure of 3-6 nm in water. Too small an assembly morphology is not amenable to detection by transmission rate transitions. The high sensitivity of fluorescence allows us to successfully capture the initial stages of self-assembly. This result is believed to be of some instructive significance for other assembly systems.
6. Temperature response behavior of (Z) -TPE-UPy
The increase in temperature easily breaks the hydrogen bonding between the OEG chains and the water molecules, causing the OEG chains to agglomerate in the water. Molecules containing OEG chains are likely to exhibit temperature response behavior. As shown in FIG. 14, the light transmittance of (Z) -TPE-OEG aqueous solution (3 mM) at 39.2 ℃ decreases sharply with increasing temperature. Indicating that the molecules are aggregated. In contrast, no significant temperature response behavior occurred up to 52.0 ℃ in aqueous (E) -TPE-OEG solutions of the same concentration. The temperature is controlled to be changed between 39.0 ℃ and 39.5 ℃, and the temperature response behavior of the (Z) -TPE-OEG is proved to have good reversibility, as shown in FIG. 15.
7. Visualization of temperature response process by using aggregation-induced emission property of (Z) -TPE-OEG
Dehydration of the OEG chain in the (Z) -TPE-OEG molecule at elevated temperatures may cause the tetraphenylethylene molecule to be restricted in motion. At the same time, the molecules aggregate due to the reduced solubility, which also increases fluorescence. For the above reasons, we expect that the critical phase transition temperature of (Z) -TPE-OEG can be detected by testing the change of fluorescence at different temperatures. As shown in FIG. 16, the fluorescence intensity started to increase at 38.0 ℃ until 43 ℃ reached a plateau. As shown in FIG. 17, the fluorescence signal has good reversibility with temperature change. Confirmation of fluorescence may also be used to reflect the temperature response behavior of the molecule.
Generally, dehydration of OEG causes a decrease in molecular solubility resulting in precipitation. Researchers are used to decorrelate temperature response behavior by observing the generation of precipitates. However, this misses many details that may exist in the process. The aggregation-induced emission property of the (Z) -TPE-OEG makes it possible to observe the temperature response behavior of the (Z) -TPE-OEG in situ in an aqueous solution by using a confocal laser scanning microscope. As shown in FIG. 18, it was found that the temperature response behavior of (Z) -TPE-OEG can be divided into different stages by observation under a microscope. Just after the temperature has started to rise, as with many compounds, the solubility of (Z) -TPE-OEG increases, which in turn reduces the solution fluorescence. When the temperature is further increased, the generation of fluorescent aggregates starts. It is believed that this is a result of the increased molecular solubility resulting from the increased temperature competing with the decreased molecular solubility resulting from dehydration of the OEG chains. At this temperature stage, dehydration dominates the reduction of molecular solubility, and thus the molecules aggregate and fluorescence increases. When the temperature is lowered, the aggregates of (Z) -TPE-OEG in the solution are dissociated, and the fluorescence disappears. But passes through a stage of lowest fluorescence intensity before the temperature is reduced to the initial temperature. At this stage, the molecular solubility enhancement predominates, with the weakest fluorescence. The method is the first case of in-situ real-time observation of the molecular phase transition temperature response behavior under a confocal laser scanning microscope by using aggregation-induced emission, and lays a foundation for deeper understanding and utilization of the temperature response property.
While the present invention has been described with reference to the embodiments shown in the drawings, the present invention is not limited to the embodiments, which are illustrative and not restrictive, and it will be apparent to those skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope of the invention as defined in the appended claims.

Claims (8)

1. The application of the tetraphenylethylene isomer is characterized in that the tetraphenylethylene isomer adopts (Z) -TPE-OEG or (E) -TPE-OEG; the chemical formula of the (Z) -TPE-OEG is as follows:
Figure FDA0003885714060000011
(E) -TPE-OEG has the formula:
Figure FDA0003885714060000012
wherein the tetraphenylethylene isomer is used for detecting the initial stage of self-assembly;
R 1 by using
Figure FDA0003885714060000013
One of (a) and (b);
R 2 by using
Figure FDA0003885714060000014
One of (1);
n is any one of 1,2, 3, 4, 5, 6 and 7.
2. The use of the tetraphenylethylene isomer of claim 1, wherein said tetraphenylethylene isomer is used to indicate the initial assembly concentration at the initial stage of self-assembly by aggregation-induced emission properties.
3. The application of the tetraphenylethylene isomer is characterized in that the tetraphenylethylene isomer adopts (Z) -TPE-OEG; the chemical formula of the (Z) -TPE-OEG is as follows:
Figure FDA0003885714060000021
wherein the tetraphenylethylene isomer is used to effect visualization of a temperature response process;
R 1 by using
Figure FDA0003885714060000022
One of (1);
R 2 by using
Figure FDA0003885714060000023
One of (1);
n is any one of 1,2, 3, 4, 5, 6 and 7.
4. Use of the tetraphenylethylene isomers according to claim 3 characterized in that said tetraphenylethylene isomers have different temperature response behavior at different temperatures.
5. The preparation method of the tetraphenylethylene isomer is characterized by adopting the following chemical reaction:
Figure FDA0003885714060000024
wherein R is 1 By using
Figure FDA0003885714060000025
One of (1);
R 2 by using
Figure FDA0003885714060000031
One of (1);
n is any one of 1,2, 3, 4, 5, 6 and 7.
6. The method for preparing the tetraphenyl ethylene isomer of claim 5, wherein the tetraphenyl ethylene isomer is obtained by reacting 1,2- (4-aminobenzene) -1, 2-stilbene with an acyl chloride compound containing oligo (ethylene glycol monomethyl ether).
7. A detection reagent for an initial stage of self-assembly, comprising a tetraphenylethylene isomer;
the tetraphenylethylene isomer adopts (Z) -TPE-OEG or (E) -TPE-OEG; the chemical formula of the (Z) -TPE-OEG is as follows:
Figure FDA0003885714060000032
(E) -TPE-OEG has the formula:
Figure FDA0003885714060000033
wherein the content of the first and second substances,
R 1 by using
Figure FDA0003885714060000034
One of (1);
R 2 by using
Figure FDA0003885714060000035
One of (1);
n is any one of 1,2, 3, 4, 5, 6 and 7.
8. An agent for visualizing a temperature-responsive process, comprising a tetraphenylethylene isomer;
the tetraphenylethylene isomer adopts (Z) -TPE-OEG; the chemical formula of the (Z) -TPE-OEG is as follows:
Figure FDA0003885714060000041
wherein the content of the first and second substances,
R 1 by using
Figure FDA0003885714060000042
One of (1);
R 2 by using
Figure FDA0003885714060000043
One of (1);
n is any one of 1,2, 3, 4, 5, 6 and 7.
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