Design,Synthesis And Properties Of Fluorescent Probes Based On BINOL

In recent years,organic small molecule as fluorescent probes have received extensive attention from researchers due to their advantages such as low detection limit,simple and easy synthesis,rapid reaction time,specific detection,excellent luminescence performance and good biological imaging effect.At present,fluorescent probes have been widely used in toxic and harmful gases detection,biological small molecules detection,heavy metal ions of environment detection and other different fields.Therefore,it is still of great significance to develop a novel organic small molecule fluorescent probe with excellent detection performance.In this thesis,a series of fluorescent probes based on BINOL skeleton were synthesized.These probes can be used for detection of war toxicant mimics(DCP)or biothiols(L-Cys,D-Cys,Hcy and GSH).The research contents of this thesis are as follows:(1)Chapter 1: Several different reaction mechanisms of fluorescence detection(including intramolecular charge transfer,photoinduced electron transfer,fluorescence resonance energy transfer,excimer association and excited state intramolecular proton transfer)and the research progress of BINOL derivatives as fluorescent probes were introduced.(2)Chapter 2: A series of silicon compounds based on BINOL framework as fluorescent probes(FS1,FS2,FS3 and FS4)were designed and synthesized.The fluorescence colors of FS1,FS2,FS3 and FS4 showed green,yellow,orange and green in DMF solution,respectively.They all can realize the specific detection of war poison simulant DCP with the fast responses(within 5 s)and lower detection limit(9.7 n M).With the addition of DCP to the solution of probes,the colors of the fluorescent probes changed from yellow to blue(FS1),from green to light green(FS2),from orange to red(FS3),and from green to colorless(FS4),respectively.Through the TDDFT theoretical calculations and nuclear magnetic experiments,the luminescence mechanism and reaction mechanism of the four fluorescent probes were analyzed.In addition,in terms of practical application,we combined the prepared fluorescent probe and optical fiber sensing technology to prepare an optical fiber sensor that can have high-precision real-time monitoring of DCP steam for the first time.The minimum detection limit is 4.4 ppb which is far lower than the concentration of war poisons that is harmful to humanbeings(7.0 ppb).(3)Chapter 3: We designed and synthesized a series of BINOL derivatives(FP1,FP2,FP3 and FP4).After introducing acryloyl group as recognition group to FP1,FP2,FP3 and FP4,we synthesized four fluorescent probes(FP1B,FP2 B,FP3B and FP4B).They all can the recognize of biothios(L-Cys,D-Cys,Hcy and GSH).Among them,probes FP3 B and FP4 B could distinguish Cys over other amino acids.FP3 B and FP4 B showed fluorescence decreases with Cys in DMF solution,but fluorescence increases were observed with Hcy and GSH.Through the TDDFT theoretical calculations and nuclear magnetic experiments,the luminescence mechanism and reaction mechanism of the four fluorescent probes were studied.