Synthesis Of Enantioselective Fluorescent Probes Based On Triazole-modified H₈-BINOL And Their Applications

Different enantiomers of chiral molecules often exhibit different properties in terms of biological activity,potency,toxicity,transport mechanisms and metabolic pathways.Therefore it is crucial to distinguish the conformation of chiral compounds such as amino acids.Fluorescence sensor method with the advantages of convenient equipment,high sensitivity,real-time imaging and online monitoring has received wide attention from researchers.BINOL has been widely used as an enantioselective fluorescence sensor due to its C2-axis chirality,good rigid structure and easy modification.H₈-BINOL is a partially hydrogenated derivative of BINOL,which has similar chemical properties with BINOL and is more active because of the electron-giving effect of the alkyl ring,which changes its spatial structure,and can also be used as a good fluorescent material.However,most of the studies are on asymmetric catalysis,and enantioselective recognition is rarely reported.Therefore,in this paper,we designed and synthesized a class of H₈-BINOL-based triazole-modified fluorescent probes to investigate the enantioselective recognition of chiral compounds such as amino acids and chiral small molecules without the involvement of metal ions.In the first chapter,the composition,recognition mechanism and classification of fluorescent probes,as well as the way of evaluating enantioselective fluorescent probes are introduced,click chemistry is introduced as well as the recent research progress of chiral binaphthols and octahydrobinaphthols and derivatives in enantioselectivity are outlined,and the research significance and design ideas of this paper are presented accordingly.In the second chapter,we first designed octahydrobinaphthyl phenol-based fluorescent probes S-Z1 S-Z2 and R-Z1 R-Z2,and showed that:1,the fluorescent probes S-Z1 S-Z2 and R-Z1 R-Z2 can enantioselectively recognize phenylalanine and aspartate,among which phenylalanine has a more significant fluorescence enhancement effect on the probes,and its ef value is higher,which can distinguish and determine their enantiomeric composition,and the other R-Z1 and S-Z2 are able to enantioselectively recognize tyrosine,but their ef values are relatively small.2,The four probes have little selectivity for chiral small molecules,with only octocrylene and octenidine able to substantially burst their fluorescence,and two configurations of2-amino-1-phenylethanol enhancing the fluorescence of the probes to varying degrees.In the third chapter,the fluorescent probes S-Z3 S-Z4 and R-Z3 R-Z4 based on octahydrobinaphthyl phenol were designed firstly,and it was found that:1,the fluorescent probes could enantioselectively recognize phenylalanine and aspartic acid,where aspartic acid enhanced the probes more significantly,and their ef values were higher to have distinguished and determined their enantiomeric composition,and the other S-Z3 and S-Z4 could enantioselectively recognize glutamic acid,and the ef of monosubstituted class was higher.The ef of the monosubstituted class was higher.2,The four probes showed little selectivity for chiral small molecules,and the two conformations of 2-amino-1-phenylethanol enhanced the fluorescence of the probes to different degrees,but the enantioselectivity of the R-type probes was better.Aminobutyric acid of different conformations bursts the probe fluorescence,but its enantioselectivity is less.In the fourth chapter,the fluorescent probes S-Z5 S-Z6 and R-Z5 R-Z6 based on octahydrobinaphthyl phenol were designed firstly,and it was found that:1,The four fluorescent probes can enantioselectively recognize phenylalanine and aspartate and have fluorescence enhancement for them with higher ef-values to distinguish and determine their enantiomeric composition,and the two probes of S-configuration have better enantioselectivity for amino acids.The other S-5Z was able to recognize glutamate enantioselectively and its ef value could reach 15.99.2,The four probes had little selectivity for chiral small molecules,and only octocrylene and octenidine and two conformations of thioester could burst their fluorescence,but the degree of bursting was greater for octocrylene and octenidine,and two conformations of2-amino-1-phenylethanol enhanced the fluorescence of the probes to different degrees.