Keggin Cluster Modulated Photocatalytic Activity of Aryl Sulfonium Polyoxometalate Hybrids toward Dichromate Reduction.

Dichromate (Cr2O72-) ion having chromium in its +6 oxidation state is a carcinogen and a potential threat to humans and aquatic life. The photocatalytic reduction of toxic Cr(VI) species into less toxic Cr(III) is an important target in heterogeneous catalysis. In this work, the catalytic activities of a series of Keggin cluster-based aryl sulfonium polyoxometalate hybrids, (FPDS)3[PMo12O40] (1), (FPDS)3[PW12O40] (2), (FPDS)4[SiMo12O40] (3), and (FPDS)4[SiW12O40] (4), toward the photocatalytic reduction of Cr(VI) have been analyzed and compared. Here, we used the aryl sulfonium counterions to modulate the POM cluster's solubility in water and stabilize the photogenerated e--h+ pair on the cluster. All of the hybrids 1-4 catalyzed the reduction of Cr(VI) to Cr(III) under ultraviolet (UV) irradiation, and their photocatalytic efficiencies followed the order hybrid 1 > hybrid 3 > hybrid 2 > hybrid 4, with the rate-constant values of 0.048, 0.0056, 0.0035, and 0.0028 min-1, respectively. Hybrid 1 with [PMo12O40]3- Keggin cluster exhibited the best photocatalytic activity in the series yielding a 99% reduction in 120 min. The reasons behind the best photocatalytic activity of hybrid 1 are identified as its low band gap, less charge recombination, and fast photoresponse. The electron-trapping analyses performed using AgNO3 revealed electrons as the main reactive species responsible for the photocatalytic reduction of Cr(VI). A plausible photocatalytic mechanism has also been proposed based on electron-trapping experiments. The present study shows that aryl sulfonium Keggin hybrids can function as efficient photocatalysts for Cr(VI) reduction, and their catalytic efficiency varies with the nature of the Keggin cluster.

Substituent-Controlled Structural, Supramolecular, and Cytotoxic Properties of a Series of 2-Styryl-8-nitro and 2-Styryl-8-hydroxy Quinolines.

Styryl quinolines are biologically active compounds with properties largely depending on the substituents on the styryl and quinoline rings. The supramolecular aspects of this class of compounds are rarely explored. In this study, two new series of styryl quinoline derivatives, bearing -OH and -NO2 groups at the eighthposition of the quinoline ring and -SCH3, -OCH3, and -Br groups on the styryl ring, have been developed, and their structural, supramolecular, and cytotoxic properties have been analyzed. Crystallographic analyses revealed the exciting substituent-dependent structural and supramolecular features of these compounds. In general, the 8 -OH substituted derivatives (SA series) exhibited a non-planar molecular geometry having larger dihedral angles (5.75-59.3°) between the planes of the aromatic rings. At the same time, the 8 -NO2 substituted derivatives (SB series) exhibited a more or less planar molecular geometry, as revealed by the smaller dihedral angles (1.32-3.45°) between the aromatic rings. Multiple O-H···O, C-H···O, O-H···N, and π-π stacking interactions among the molecules lead to fascinating supramolecular architectures such as hydrogen-bonded triple helices, zig-zag 1D chains, π-π stacked infinite chains, and so forth in their crystal lattice. Hirshfeld surface analyses confirmed the existence of strong π-π stacking and other weak bonding interactions in these compounds. The preliminary cytotoxic properties of SA and SB series compounds were evaluated against the human cervical cancer cell lines (HeLa cells), which further highlighted the roles of functional substituents on the aromatic rings. The SA series compounds with the -OH substituent on the quinoline ring exhibited better cytotoxicity than the SB series compounds with a -NO2 substituent. Similarly, the electron-withdrawing group -Br on the styryl ring enhanced the cytotoxicity in both series. The IC50 values were 2.52-4.69 and 2.897-10.37 µM, respectively, for the SA and SB series compounds. Compound S3A having -OH and -Br groups on the quinoline and styryl ring, respectively, exhibited the best IC50 value of 2.52 µM among all the compounds tested. These findings confirm the relevance of the hydroxyl group in the eighth position of quinoline. In short, the present study attempts to provide a systematic analysis of the effects of aromatic ring substituents on the structural, supramolecular, and cytotoxic properties of styryl quinolines for the first time.

A chemosensor for micro- to nano-molar detection of Ag+ and Hg2+ ions in pure aqueous media and its applications in cell imaging.

The pyridine substituted thiourea derivative PTB-1 was synthesized and characterized by spectroscopic techniques as well as by single crystal X-ray crystallography. The metal ion sensing ability of PTB-1 was explored by various experimental (naked-eye, UV-Vis, fluorescence, mass spectrometry and 1H NMR spectroscopy) and theoretical (B3LYP/6-31G**/LANL2DZ) methods. PTB-1 exhibited a highly selective naked-eye detectable color change from colorless to dark brown and UV-Vis spectral changes for the detection of Ag+ with a detection limit of 3.67 µM in aqueous medium. The detection of Ag+ ions was achieved by test paper strip and supported silica methods. In contrast, PTB-1 exhibited a 23-fold enhanced emission at 420 nm in the presence of Hg2+ ions with a nano-molar detection limit of 0.69 nM. Finally, the sensor PTB-1 was applied successfully for the intracellular detection of Hg2+ ions in a HepG2 liver cell line, which was monitored by the use of confocal imaging techniques.