N-Allylbenzimidazole as a strategic surrogate in Rh-catalyzed stereoselective trans-propenylation of aryl C(sp2)-H bond.

A Rh-catalyzed C(sp2)-H propenylation has been reported by taking N-allyl benzimidazole as an allylamine congener. This transformation has been observed for the first time, where a tandem process of C-H allylation followed by alkene isomerization delivers a highly stereoselective trans-propenylated product. Detailed mechanistic studies including the characterization of rhodacycle-intermediates have been conducted to understand the mechanism.

Interface- and Surface-Engineered PdO-RuO2 Hetero-Nanostructures with High Activity for Hydrogen Evolution/Oxidation Reactions.

Active catalysts for HER/HOR are crucial to develop hydrogen-based renewable technologies. The interface of hetero-nanostructures can integrate different components into a single synergistic hybrid with high activity. Here, the synthesis of PdO-RuO2 -C with abundant interfaces/defects was achieved for the hydrogen evolution reaction (HER) and hydrogen oxidation reaction (HOR). It exhibited a current density of 10 mA cm-2 at 44 mV with a Tafel slope of 34 mV dec-1 in 1 m KOH. The HER mass activity was 3 times higher in base and comparable to Pt/C in acid. The stability test confirmed high HER stability. The catalyst also exhibited excellent HOR activity in both media; in alkaline HOR it outperformed Pt/C. The exchange current density i0,m of PdO-RuO2 /C was 522 mA mg-1 in base, which is 58 and 3.4 times higher than those of Pd/C and Pt/C. The HOR activity of PdO-RuO2 /C was 22 and 300 times higher than those of PdO/C in acid and base. Improvement of HER/HOR kinetics in different alkaline electrolytes was observed in the order K+

Platinum Nanostructure/Nitrogen-Doped Carbon Hybrid: Enhancing its Base Media HER/HOR Activity through Bi-functionality of the Catalyst.

The design and synthesis of an active catalyst for the hydrogen evolution reaction/hydrogen oxidation reaction (HER/HOR) are important for the development of hydrogen-based renewable technologies. The synthesis of a hybrid of platinum nanostructures and nitrogen-doped carbon [Pt-(PtOx )-NSs/C] for HER/HOR applications is reported herein. The HER activity of this Pt-(PtOx )-NSs/C catalyst is 4 and 6.5 times better than that of commercial Pt/C in acids and bases, respectively. The catalyst exhibits a current density of 10 mA cm-2 at overpotentials of 5 and 51 mV, with Tafel slopes of 29 and 64 mV dec-1 in 0.5 m H2 SO4 and 0.5 m KOH. This catalyst also showed superior HOR activity at all pH values. The HER/HOR activity of Pt-(PtOx )-NSs/C and PtOx -free Pt-nanostructures on carbon (PtNSs/C) catalysts are comparable in acid. The presence of PtOx in Pt-(PtOx )-NSs/C makes this Pt catalyst more HER/HOR-active in basic media. The activity of the Pt-(PtOx )-NSs/C catalyst is fivefold higher than that of the PtNSs/C catalyst in basic medium, although their activity is comparable in acid. The hydrogen-binding energy and oxophilicity are two equivalent descriptors for HER/HOR in basic media. A bifunctional mechanism for the enhanced alkaline HER/HOR activity of the Pt-(PtOx )-NSs/C catalyst is proposed. In the bifunctional Pt-(PtOx )-NSs/C catalyst, PtOx provides an active site for OH- adsorption to form OHads , which reacts with hydrogen intermediate (Hads ), present at neighbouring Pt sites to form H2 O; this leads to enhancement of the HOR activity in basic medium. This work may provide an opportunity to develop catalysts for various renewable-energy technologies.

Chlorpyrifos induces apoptosis and DNA damage in Drosophila through generation of reactive oxygen species.

The present study investigated the apoptosis and DNA damage inducing potential of chlorpyrifos (CP) in Drosophila melanogaster. Third instar larvae of Drosophila were treated with different concentrations of CP (0.015-15.0 microg/L) for 2-48 h. Reactive oxygen species (ROS) generation, oxidative stress markers, DNA damage and apoptotic cell death end points were measured in them. A significant increase in DNA damage was concomitant with apoptotic mode of cell death in 15.0 microg/L CP-treated organisms for 24 and 48 h. Depolarization in mitochondrial membrane potential and increased casapase-3 and caspase-9 activities in these organisms indicated both as potential targets of CP. A significant positive correlation was observed among ROS generation, apoptosis and DNA damage. The study suggests that (i) ROS may be involved in inducing apoptosis and DNA damage in the CP-exposed larvae of Drosophila and (ii) D. melanogaster may be used as an alternative in vivo animal model for xenobiotics hazard assessment.

Heat shock proteins in toxicology: how close and how far?

The response to stress triggers activation of the genes involved in cell survival and/or cell death. Stress response is a ubiquitous feature of cells that is induced under stress conditions. As a part of this response a set of genes called stress genes are induced to synthesize a group of proteins called heat shock proteins (Hsps). The Hsps play an essential role as molecular chaperones by assisting the correct folding of nascent and stress-accumulated misfolded proteins, and by preventing their aggregation. Because of their sensitivity to even minor assaults, Hsps are suitable as an early warning bio-indicator of cellular hazard. Despite having enormous use in toxicology, the current state of knowledge in defining a mechanism of action or accurately predicting toxicity based on stress gene expression warrants further investigation. The goal of this review is to summarize current developments in the application of stress genes and their products 'Hsps' in toxicology with a brief discussion of the caveats. While focusing on hsp70 because of its higher conservation across the taxa and since it is one of the first to be induced under stress conditions, we will also discuss other members of the stress gene family.

Adverse effect of organophosphate compounds, dichlorvos and chlorpyrifos in the reproductive tissues of transgenic Drosophila melanogaster: 70kDa heat shock protein as a marker of cellular damage.

The study highlights the adverse effects of organophosphate compounds dichlorvos and chlorpyrifos on reproduction in Drosophila. Freshly eclosed first instar larvae of Drosophila melanogaster transgenic for hsp70 (hsp70-lacZ) Bg(9) were fed on 0.015-150.0ppb dichlorvos and chlorpyrifos mixed food. Virgin flies eclosing from the normal and contaminated food were pair-mated to examine the effect of the test chemicals on reproduction of the exposed organisms. Expression of hsp70, sex peptide (SP or Acp70A), accessory gland protein (Acp36DE) and tissue damage was examined in reproductive organs of adult fly. Exposed organisms exhibited a dose-dependent significantly reduced reproductive outcome and males were found to be more sensitive than females. Hsp70 expression was restricted only within the testis lobes of male fly while it was not induced in the ovary of the female. In concurrence with absence of hsp70 expression in the accessory glands of male fly, tissue damage was evident in them. Acp70A and Acp36DE expression were found to be significantly downregulated at the higher concentrations of the test chemicals. The study suggests that (i) dichlorvos is more deleterious to fly reproduction compared to chlorpyrifos with an adverse effect on Acp70A and Acp36DE expression required to facilitate normal reproduction; (ii) hsp70 may be used as a marker of cellular damage against dichlorvos and chlorpyrifos in Drosophila.

Induction of hsp70, alterations in oxidative stress markers and apoptosis against dichlorvos exposure in transgenic Drosophila melanogaster: modulation by reactive oxygen species.

We examined a hypothesis that reactive oxygen species (ROS) generated by organophosphate compound dichlorvos modulates Hsp70 expression and anti-oxidant defense enzymes and acts as a signaling molecule for apoptosis in the exposed organism. Dichlorvos (0.015-15.0 ppb) without or with inhibitors of Hsp70, superoxide dismutase (SOD) and catalase (CAT) were fed to the third instar larvae of Drosophila melanogaster transgenic for hsp70 (hsp70-lacZ) Bg(9) to examine Hsp70 expression, oxidative stress and apoptotic markers. A concentration- and time-dependent significant increase in ROS generation accompanied by a significant upregulation of Hsp70 preceded changes in antioxidant defense enzyme activities and contents of glutathione, malondialdehyde and protein carbonyl in the treated organisms. An inhibitory effect on SOD and CAT activities significantly upregulated ROS generation and Hsp70 expression in the exposed organism while inhibition of Hsp70 significantly affected oxidative stress markers induced by the test chemical. A comparison made among ROS generation, Hsp70 expression and apoptotic markers showed that ROS generation is positively correlated with Hsp70 expression and apoptotic cell death end points indicating involvement of ROS in the overall adversity caused by the test chemical to the organism. The study suggests that (a) Hsp70 and anti-oxidant enzymes work together for cellular defense against xenobiotic hazard in D. melanogaster and (b) free radicals may modulate Hsp70 expression and apoptosis in the exposed organism.