Ampyrone appended 1,2,3-triazole as selective fluorescent Cu(II) ion sensor: DFT and docking findings

Abstract

The present report describes the application of the ‘Click Chemistry’ pathway to synthesize a fluorescent probe (APT) based on ampyrone (4-aminoantipyrine), entailing two benzyl groups as the fluorophores coupled to the antipyrine structure through 1,2,3-triazole moieties. Infrared spectroscopy (IR), nuclear magnetic resonance (1H and 13C), and mass spectrometry were the standard spectroscopic methods used to characterize APT. The ion recognition potential of the probe was analyzed through absorption and emission spectroscopy employing a 4:1 combination of CH3CN and H2O, which demonstrated APT to be an efficient sensing agent for Cu(II) ions, wherein the absorption spectrum of the probe displayed a hypsochromic shift with a hyperchromic shift on gradually adding the metal ion solution of Cu(II), whereas quenching of the probe's fluorescence emission on Cu(II) addition was attributed to the chelation-enhanced fluorescence quenching (CHEQ), induced by the d9 electronic configuration of Cu(II). The stoichiometry of the complexation of APT with Cu(II) is indicative of a 1:1 ratio, while the detection limit (LOD) and quantification limit (LOQ) as estimated from the fluorescence titration results were 3.11 µM and 10.35 µM respectively. Furthermore, DFT analysis was also undertaken to yield the energy-optimized structures and HOMO-LUMO density plots of APT and its corresponding Cu(II) complex via the B3LYP/631G+(d,p) level of theory for APT, and LANL2DZ basis set for the APT-Cu(II) complex. Docking analysis of the probe with the synaptic vesicle protein (SV2A) gave glimpses about its anticonvulsant properties.