Probing the interaction of uranyl(VI) complex with bovine serum albumin via in-depth experimental and computational perspectives.

Interaction aspects of uranyl(VI) complexes as well as the coordinated ONNO-donor ligand with bovine serum albumin (BSA) were investigated by the fluorescence spectroscopy and computational insights. Under optimal physiological condition, it was observed that there was significant decrease in fluorescence intensity of BSA upon interaction with uranyl(VI) complexes as well as the ligand. The mechanism of interaction between the uranyl(VI) complex and BSA protein was examined by fluorescence measurement. The Stern-Volmer constant, binding affinity, binding constant, standard free energy, and fluorescence lifetime decay profile of BSA in the absence as well as in the presence of uranyl(VI) complex were determined. Furthermore, the conformational binding of uranyl(VI) complexes with BSA protein was explored via molecular docking studies, and confirmed that there is a strong affinity between the Trp-213 residue in the binding pocket of sub-domain IIA and uranyl(VI) complex.

Detailed characterization of dioxouranium(vi) complexes with a symmetrical tetradentate N2O2-benzil bis(isonicotinoyl hydrazone) ligand.

The reactions of UO2(OAc)2·2H2O with benzil bis(isonicotinoyl hydrazone) ligand (H2L) in varied solvent media resulted in the formation of a series of new dioxouranium(vi) complexes 1-3 of the type UO2(L)(X), [where 1, X = DMF; 2, X = DMSO; 3, X = H2O]. The complexes were systematically characterized by elemental analysis, UV-Visible spectroscopy, TGA, mass spectrometry, cyclic voltammetry, and powder X-ray diffraction study. Among all the complexes, 1 was confirmed by single-crystal X-ray diffraction study. It was found that 1 preferred a distorted pentagonal bipyramidal geometry, in which an equatorial coordination plane was formed by the ONNO-tetradentate cavity of the deprotonated hydrazone ligand along with an additional oxygen atom of the coordinated solvent molecule. Thermal analysis suggested that complexes 1 and 3 undergo weight loss in the temperature range 180-210 °C and 100-120 °C, respectively, due to the ready release of their coordinated solvent molecules. Complexes 1-3 exhibited analogous UV-Visible absorption bands and the intense band between 300-600 nm was assigned to the M ← L and n → π* transitions. Weakly resolved reduction waves assigned to {UO2}2+/{UO2}+ couple were observed for complexes 1 and 2 {1, -1.76 V; 2, -1.75 V; vs. ferrocenium/ferrocene (Fc+/Fc)} in DMSO solution, signifying the feeble electron-donating nature of the L2- ligand. Powder X-ray diffraction study suggested that the crystallite size of all the complexes was in the nanoscale range. Further analysis using density functional theory (DFT) calculations provided structural insights as well as information on the electronic properties of both complex 1 and the ligand.

Triazole derived azo-azomethine dye as a new colorimetric anion chemosensor.

In the pursue of developing anion sensors, an efficient triazole derived azo-azomethine dye chemosensor (S) that differentially senses F‾ and AcO‾ ions has been reported. The ions recognition ability of S was investigated by colorimetric and UV-visible spectroscopic methods. Interestingly, this chemosensor molecule is virtually inactive in presence of other anions such as Cl‾, Br‾ and I‾ and HSO4‾. We have further presented a ratiometric approach to differentiate F‾ and AcO‾ ions. The reversibility of F‾ ion binding with S was established by the addition of Ca(NO3)2 to the fluoride bound S, which led to the regeneration of S. The quantum chemical calculation of energies of unbound and bound S has been employed using Density Functional Theory (DFT) to understand the interaction between chemosensor and anions. Evidence in support of fluoride-induced deprotonation of a O-H bond during the detection of F⁻ ion has been demonstrated by employing 1H NMR titration experiments.