Click Chemistry-Based Synthesis And Application Of Lanthanide Complex-Based Luminescent Probes

The time-resolved luminescence assay based on luminescent lanthanide-complex probe has obtained a remarkable achievement and plays increasingly important role in clinical diagnosis and life science. In this thesis,several lanthanide complex-based luminescence probes for some small bio active molecules have been designed and synthesized by conjugating luminescent lanthanide complex modified by azido group(4- azido-2, 2 6’,2"-terpyridine-6, 6-diyl}bis-(methylenenitrilo)tetrakis(acetic acid)) with some analyte-recognition moieties modified by alkyne group through click chemistry reaction. And the luminescence properties and response behaviors to hypochlorous acid have been investigated.Through click chemistry reaction, two luminescent lanthanide-complex probes,Eu{4’-[4-(4-amino-3-nitrophenoxy)methyIene-lH-l,2,3-triazol]-2, 2 6\ 2”-terpyridine-6, 6"-diyl}bis-(methylenenitrilo)tetrakis(acetic acid)(ANMTTTA-Eu) and Eu{4[4-(4-aminomethylene)-1H-1,2,3-triazol]-2, 26\ 2"-terpyridine-6, 6 "-diyl}bis-(methylenenitrilo)tetrakis(acetic acid)(AMTTTA-Eu), have been designed and synthesized for the specific recognition and time-gated luminescence detection of hypochlorous acid(HOCl) in aqueous media. The probe, ANMTTTA-Eu itself is almost non-luminescent, the reaction of ANMTTTA-Eu with HOCl results a sixty-fold luminescence enhancement of the probe. The probe has several favorable features including high chemical specificity for HOCl, kinetic and thermodynamic stability, high water soluble solubility, large reaction rate constant, high sensitivity and a signal that is independent of pH over a wide range. It will be a useful tool for luminescent detection of HOCl in complex biosystem. The probe, AMTTTA-Eu also showed luminescence response to HOCl, but inI present of HOCl the luminescence of AMTTTA-Eu has only increased three times,which resulted a quite low signal-to-noise ratio. So the flither studies on AMTTTA-Euwere not going on.Then,a further exploratory effort was made to develop some new time-gated luminescence probe for small bioactive molecules and ions. The time-gated luminescence probe for nitric oxide(NO), 3,4-diamino phenoxy have been developed by coupling a recognizer of NO with luminescent lanthanide complex through click chemistry reaction. And the another time-gated luminescence probe for Zn〕,dimethyl pyridine amino have been developed using the samestrategy. We have prepared the precursors of ligands, the preparation of two luminescent lanthanide-complex probe and studies on their application was going on.