The electrocatalytic behaviour of Ti-supported RuOz, prepared by thermal decomposition of RuC13, as substrate for oxygen evolution was investigated by a variety of techniques. B.E.T. adsorption experiments showed that the RuOz layers are highly porous with large surface area values which, however, decrease rapidly as the annealing temperature increases above -300°C. Both the charge involved in the cyclic voltammograms and the oxygen evolution rates are dependent on the true (rather than apparent) area of these electrode surfaces, and also on the pH of the solution. The results for oxygen evolution are discussed in terms of electrochemically generated unstable surface oxides whose decomposition is catalysed by protons in acid, and hydroxide ions in base.The lower reactivity of the oxide at intermediate pH value is attributed on the one hand to loss of protons by OH groups, resulting in oxygen bridging, and on the other to lack of enhanced coordination of surface ruthenium species by OH-ions, which in this pH region are present only at low activity. The charge associated with voltammetric sweeps is accounted for in terms of surface redox processes rather than bulk penetration of protons into the oxide. The need for surface area measurements as a guide to the interpretation of the electrochemical data in the case of these oxide systems is stressed.

β-Sitosterol (BS), a major bioactive constituent present in plants and vegetables has shown potent anticancer effect against many human cancer cells, but the underlying mechanism remain elusive on NSCLC cancers. We found that BS significantly inhibited the growth of A549 cells without harming normal human lung and PBMC cells. Further, BS treatment triggered apoptosis via ROS mediated mitochondrial dysregulation as evidenced by caspase-3 & 9 activation, Annexin-V/PI positive cells, PARP inactivation, loss of MMP, Bcl-2-Bax ratio alteration and cytochrome c release. Moreover, generation of ROS species and subsequent DNA stand break were found upon BS treatment which was reversed by addition of ROS scavenger (NAC). Indeed BS treatment increased p53 expression and its phosphorylation at Ser15, while silencing the p53 expression by pifithrin-α, BS induced apoptosis was reduced in A549 cells. Furthermore, BS induced apoptosis was also observed in NCI-H460 cells (p53 wild) but not in the NCI-H23 cells (p53 mutant). Down-regulation of Trx/Trx1 reductase contributed to the BS induced ROS accumulation and mitochondrial mediated apoptotic cell death in A549 and NCI-H460 cells. Taken together, our findings provide evidence for the novel anti-cancer mechanism of BS which could be developed as a promising chemotherapeutic drug against NSCLC cancers.

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Anchoring groups play an important role in dye sensitized solar cells (DSCs). In order to acquire a suitable anchoring group for DSCs, a deeper understanding of the effect of anchoring groups on the ground and excited state properties of the dye is significant. In this context, various anchoring group connected pyrene derivatives are successfully synthesized and well characterized by using (1)H, (13)C-NMR, FT-IR and EI-MS spectrometry. The anchoring groups employed are carboxylic acid, malonic acid, acrylic acid, malononitrile, cyanoacrylic acid, rhodanine and rhodanine-3-acetic acid. The optimized geometries, HOMO-LUMO energy gap, light harvesting efficiency (LHE) and electronic absorption spectra of these dyes are studied by using density functional theory (DFT) calculations. The results show that pyrene connected with anchoring groups with weak electron pulling strength (PC, PAC and PMC) has a larger HOMO-LUMO energy gap, whereas that connected with anchoring groups with strong electron pulling strength (PCC, PMN, PR and PRA) has a reduced HOMO-LUMO energy gap. These molecules with a reduced energy gap are primarily preferred for DSC applications. Moreover, P, PC, PAC and PMC molecules undergo π→π* transition, whereas PCC, PMN, PR and PRA molecules show significant charge transfer along with π→π* transition. UV-visible absorption spectral studies on these dyes reveal that connecting various anchoring groups with different electron pulling abilities enables the pyrene chromophore to absorb in the longer wavelength region. Notably, an efficient bathochromic shift is observed for PCC, PMN, PR and PRA molecules in both electronic absorption and fluorescence spectral measurements, which suggests that the excitation is delocalized throughout the entire π-system of the molecules. Both theoretical and spectral studies reveal that dyes with an ICT character (PCC, PMN, PR and PRA) are suitable for dye sensitized solar cell applications.

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