Quantum chemical elucidation of the turn-on luminescence mechanism in two new Schiff bases as selective chemosensors of Zn2+: synthesis, theory and bioimaging applications

摘要

We report the synthesis and characterization of two new selective zinc sensors ( S , E )-11-amino-8-((2,4-di- tert -butyl-1-hydroxybenzylidene) amino)-11-oxopentanoic acid ( A ) and ( S , E )-11-amino-8-((8-hydroxybenzylidene)amino)-11-oxopentanoic acid ( B ) based on a Schiff base and an amino acid. The fluorescent probes, after binding to Zn ~(2+) ions, presented an enhancement in fluorescent emission intensity up to 30 times ( ? = A 50.10 and B 18.14%). The estimated LOD for compounds A and B was 1.17 and 1.20 μM respectively (mixture of acetonitrile?:?water 1?:?1). Theoretical research has enabled us to rationalize the behaviours of the two selective sensors to Zn ~(2+) synthesized in this work. Our results showed that in the free sensors, PET and ESIPT are responsible for the quenching of the luminescence and that the turn-on of luminescence upon coordination to Zn ~(2+) is mainly induced by the elimination of the PET, which is deeply analysed through EDA, NOCV, molecular structures, excited states and electronic transitions via TD-DFT computations. Confocal fluorescence microscopy experiments demonstrate that compound A could be used as a fluorescent probe for Zn ~(2+) in living cells.