The Design,syntheses And Properties Of Fluorescent Probes Based On Azole Derivatives

Fluorescent probes for detection of various ions and neutral analytes have been widely used in many fields such as physiology,pharmacology,biology,and environmental sciences,and so on.The development of fluorescent probes has been continued for about 150 years due to their simplicity and high selectivity.Therefore,the design and synthesis of fluorescent probes have been an important topic.In this dissertation,a series of fluorescent probes has been established.Diverse azole groups(benzimidazole,naphthoimidazole and benzoxazole)and different aryl moieties were used as skeleton and fluorophore.These probes have been used for the detection of CN~-or thiol–containing amino acids(L-Cys,D-Cys,Hcy,and GSH).The concrete contents are as follows:1.In this part,the development of fluorescent probes with good detection and recognition of cations,anions,gases,reactive oxygen and nitrogen species,chemical warfare agents(CWAs),amino acids,biomacromolecules and chiral compounds was introduced.2.A series of fluorescence“turn–on”probes(PY,AN,NA,B1 and B2)have been developed and successfully applied to detect cyanide anions based on Michael–addition reaction and FRET mechanism.These probes demonstrated good selectivity,high sensitivity and very fast recognition for CN~-.Especially,the fluorescence response of probe NA finished within 3 seconds.Low LODs(down to63 nM)are also obtained in these probes with remarkable fluorescence enhancement factors.In addition,fluorescence colors of these probes turned to blue,yellow or orange upon sensing CN~-.In UV vis mode,all of them showed ratiometric response for CN~-.~1H NMR titration experiments and TDDFT calculations were taken to verify the mechanism of the specific reaction and fluorescence properties of the corresponding compounds.Moreover,silica gels plates with these probes were also fabricated and utilized to detect cyanide.3.A series of probes((R)-a,(R)-b,(R)-c,(R)-d,(R)-e,(R)-f,(R)-g,(R)-h,(R)-i,(S)-a,(S)-b,and(S)-c)for thiol-containing amino acid have been synthesized,in which 1,1?–binaphthol(BINOL),various azole group were used as ligands to obtain the boron complexes,and 2,4-Dinitrobenzenesulfonylchl group was as recognition group to detection of thiol-containing amino acid.The photophysical properties and DFT calculations of the probes were studied.4.The probes((R)-a,(R)-b,(R)-c,(R)-d,(R)-e,(R)-f,(R)-g,(R)-h,(R)-i,(S)-a,(S)-b,and(S)-c)were successfully applied to detect L-Cys,D-Cys?Hcy and GSH.In particularly,the fluorescence response of probe(R)-d for Cys finished within 60 s.Low limits of detection(down to 15 nM,(R)-e for L-Cys)are also procured in these probes with excellent fluorescence enhancement.Furthermore,fluorescence colors of these probes turned to be blue,cyan,or yellow upon the addition of thiol-containingamino acid(L-Cys,D-Cys,Hcy,and GSH).~1H NMR titration experiments were taken to verify the mechanism of the specific reaction.