The Synthesis And Application Study Of Aie Fluorescent Probes Based On Triphenylamine And Tetraphenylethene

Triphenylamine(TPA) is a common fluorescence core which has propeller-type structure. TPA derivatives have attracted researchers much attention in biological engineering, chemical probes, photoelectric materials and piezochromism sensors, due to its unique and excellent photoelectric properties. However, most of TPA derivatives exhibit typical Aggregration-Caused-Quenching(ACQ) effect which mainly caused by the large conjugation structure is easily selfassembly through ?-? stacking, limited their widely applications. Thus, it is of great significance to convert TPA derivatives from ACQ to AIE. Up to now, the common strategy is decorated TPA by AIE molecules such as tetraphenylethylene(TPE). Nevertheless, this kind of method could not solve the problem fundamentally. Therefore, it is much worth researching TPA derivatives to possess an AIE property by simple reaction.In addition, TPE and its derivatives are also a kind of novel fluorescent molecules which have propeller-type structure. Because of the restriction of intramolecular rotation(RIR) and intramolecular vibrations(RIV) effect, these fluorescent molecules exhibit representative AIE properties. This kinds of probes have been widely used in the fields of biology and medicine. To make the long-term cell tracing come true, there needs some good biocompatibility molecules to decorate TPE(such as c histon). However, this types of materials have been rarely reported until now. Although the fluorescence molecules show perfect biocompatibility and have a long term tracing, bad solvability in neutral and alkaline water and organic solvent limited the app lication in cell imaging. Thus, there's a great significance and value to synthesize a kind of target molecules that have good water solubility and biocompatibility, and can be used to long-terms cellular tracing.According to the properties, a series of fluorescence probes(have AIE property) have been synthesized via taking TPA and TPE as matrixes in this paper. O n the one hand, a series of TPA-based probes are synthesized by K noevenagel condensation reaction, Vilsmeier Haack and Heck reaction, putting forward the mechanism of AIE phenomenon by studying the photophysical property of target molecules. And using the target molecules as probe to selectively recognize tetrabutylammonium fluoride and tetrabutylammonium iodide and amine acid. On the other hand, synthesized TPE derivative which can react with N-isopropylacrylamide by free radical reaction. Then, we obtained a series of water soluble molecules and chosen the best ratio of NIPAM and DDBV to study the AIE property and its cytotoxicity and cell tracing ability. The thesis consists of three parts as following:1. Taking triphenylamine as a raw material and two red emission molecules INDTPA and IND- TPAT have been synthesized through Vilsmeier Haack reaction, Suzuki cross coupling reaction and K noevenagel condensation reaction. The basic performance of those two red emission molecules are studied by XRD, UV-vis absorbance spectrum and fluorescence spectrum. Both of them show excellent piezochromic and AIE property. Then, explained the mechanism of AIE phenomenon and the difference between two red emission materials by the density functional theory. Besides, IND- TPA and IND-TPAT contain C=C double bond which is activated by two adjacent carbonyl groups. As we all know that this kind of double bond is unstable in alkali surroundings. Moreover, heavy-atom is another important factor to affect emission. The result show that both of them can be used to selective recognition tetrabutylammonium fluoride and tetrabutylammonium iodide in THF solution, which could be easily detected by naked-eyes under visible light and UVlight.2. A series of triphenylamine derivatives are synthesized which have formyl and methyl acrylate groups by Vilsmeier Haack and Heck reaction. Then, TLC testing plates are prepared for the target molecules to detected the fatty amine by a untouched way. The results show that the molecule which has two formyls and one methyl acrylate groups exerted excellent performance. In order to achieve the selective recognition of amino acids in aqueous solution, the molecule is decorated by watersoluble molecule PEG. The result shows that the amphiphilic probe has obvious AIE property and can be used to selective recognition and quantitative analysis of lysine in water. The recognition mechanism is studied by synthesizing schiff base and coresponding experiments. After that, making pyrene as a target molecule and lysine as stimulating source to simulate a drug quantitative release system in aqueous solution. The mechanism is explained by scanning electron microscope(SEM) and spectrum study. At last, established a quantitative drug release system by using lysine as a stimulating source in aqueous solution.3. 4,4'-(2,2-diphenylethene-1,1-diyl)bis(vinylbenzene)(DDBV) is synthesized by Suzuki coupling reaction. Then, a series of water-soluble fluorescent copolymers are synthesized by different feed ratios of N-isopropylacrylamide with DDBV through radical reaction. These molecules show good water soluble and fluorescent stability. The molar ratio of NIPAm to DDBV are confirmed by the integral of nuclear magnetic. The lower critical solution temperature(LCST) is determined by using Variable temperature ultraviolet test. Then, choosing the molecule which LCST is close to body temperature(37.5 o C) as target molecule. The formation mechanism is explained by variable temperature NMR, scanning electron microscope(SEM) and dynamic light scattering(DLS) measurement. Finally, this copolymer is used as tracer agent for long-term cell imaging. The result shows that this molecule can stay in cells for a long time(at least 10 passages), making the water soluble AIE molecule for long-term cellular tracing applications come true.