Renewable Energy via Photocatalysis

The generation of renewable energy through photocatalysis is an attractive option to utilize the abundantly available solar radiation for a sustainable future. Photocatalysis refers to charge-carrier, i.e. electron and hole, mediated reactions occurring on a semiconductor surface in presence of ultraviolet or visible light radiation. Photocatalysis is a well established advanced oxidation technique for the decontamination of toxic organic pollutants to CO2 and H2O. However, the generation of energy in the form of hydrogen, hydrocarbon fuels and electricity via photocatalysis is an upcoming field with great many technical challenges towards practical implementation. This review will describe the fundamental reaction mechanism of (i) photocatalytic water splitting, (ii) photocatalytic H-2 generation in presence of different sacrificial agents, (iii) H-2 and electricity generation in a photofuel cell, (iv) photocatalytic reduction of CO2 to hydrocarbons and useful chemicals, and (v) photocatalytic water-gas shift reaction. A historic and recent perspective of the above conversion techniques, especially with regard to the development of TiO2-based and non-TiO2 materials is provided. The activity of different materials for the above reactions based on quantifiers like reaction rate, quantum yield and incident-photon-to-current efficiency is compared, and key design considerations of the ``best'' photocatalyst or photoelectrode is outlined. An overall assessment of the research area indicates that the presently achieved quantum efficiencies for the above reactions are rather moderate in the visible region, and the goal is to develop a catalyst that absorbs visible radiation, provides good charge-carrier separation, and exhibits high stability for long periods of usage.

Gold nanoparticles anchored reduced graphene oxide as catalyst for oxygen electrode of rechargeable Li-O-2 cells

Gold nanoparticles decorated reduced graphene oxide (Au-RGO) catalyst for O-2 electrode is prepared by in situ reduction of Au3+ ions and graphene oxide dispersed in water. The Au nanoparticles are uniformly distributed on the two-dimensional RGO layers. Li-O-2 cells assembled in a non-aqueous electrolyte using Au-RGO catalyst exhibit an initial discharge capacity as high as 5.89 mA h cm-(2) (5230 mA h g(-1))at a current density of 0.1 mA cm(-2). The voltage gap between the charge and discharge curves is less for Li-O-2(Au-RGO) cell in comparison with Li-O-2(RGO) cell. The Li-O-2(Au-RGO) cells are cycled over about 120 charge-discharge cycles. The results suggest that Au-RGO is a promising catalyst for rechargeable Li-O-2 cells.

Nucleosynthesis in the outflows associated with accretion disks of type II collapsars

We investigate nucleosynthesis inside the outflows from gamma-ray burst (GRB) accretion disks formed by the Type II collapsars. In these collapsars, massive stars undergo core collapse to form a proto-neutron star initially, and a mild supernova (SN) explosion is driven. The SN ejecta lack momentum, and subsequently this newly formed neutron star gets transformed to a stellar mass black hole via massive fallback. The hydrodynamics and the nucleosynthesis in these accretion disks have been studied extensively in the past. Several heavy elements are synthesized in the disk, and much of these heavy elements are ejected from the disk via winds and outflows. We study nucleosynthesis in the outflows launched from these disks by using an adiabatic, spherically expanding outflow model, to understand which of these elements thus synthesized in the disk survive in the outflow. While studying this, we find that many new elements like isotopes of titanium, copper, zinc, etc., are present in the outflows. Ni-56 is abundantly synthesized in most of the cases in the outflow, which implies that the outflows from these disks in a majority of cases will lead to an observable SN explosion. It is mainly present when outflow is considered from the He-rich, Ni-56/Fe-54-rich zones of the disks. However, outflow from the Si-rich zone of the disk remains rich in silicon. Although emission lines of many of these heavy elements have been observed in the X-ray afterglows of several GRBs by Chandra, BeppoSAX, XMM-Newton, etc., Swift seems to have not yet detected these lines.

Versatility of azide in serendipitous assembly of Copper(II) Magnetic Polyclusters

Engineering at the molecular level is one of the most exciting new developments for the generation of functional materials. However, the concept of designing polynuclear extended structures from bottom up is still not mature. Although progress has been made with secondary building units (SBUs) in metal organic frameworks (MOFs), the control seems to be just an illusion when it comes to bridging ligands such as the azide ion. When we say that the azido ligand is versatile in its bridging capabilities, what we mean is that it would be difficult to predict or control its bridging properties. However, this kind of serendipity is not always bad news. For example, scientists have shown that the azido ligand can mediate magnetic exchanges between paramagnetic metals in a predictable fashion (usually depending upon the bonding geometries). Therefore, it is a well-respected ligand in polynuclear assemblies. Serendipitous assemblies offer new magnetic structures that we may not otherwise even think about synthesizing. The azido ligand forms a variety of complexes with copper(II) using different blocking amines or pyridine based ligands. Its structural nature changes upon changing the substitution on amine, as well as the amount of blocking ligand. In principle, if we take any of these complexes and provide more coordination sites to the bridging azido ligands by removing a fraction of the blocking ligands, we can get new complexes with intricate structural networks and therefore different magnetic properties with the same components as used for the parent complex. In this Account, we mainly discuss the development of a number of new topological and magnetic exchange systems synthesized using this concept. Not all of these new complexes can be grouped according to their basic building structures or even by the ratio of the metal to blocking ligand. Therefore, we divided the discussion by the nuclearity of the basic building structures. Some of the complexes with the same nuclearities have very similar or even almost identical basic structures. However, the way these building units are joined together (by the azido bridges) to form the overall extended structures differ almost in every case. The complexes having the Cu-6 core are particularly interesting from a structural point of view. Although they have almost identical basic structures, some of them are extended in three dimensions, but two of them are extended in two dimensions by two different bridging networks. In the complexes having linear Cu-4 basic units, we find that using similar ligands does not always give the same bridging networks even within the basic building structures. These complexes have also enriched the field of molecular magnetism. One of the complexes with a Cu-3 building unit has provided us with the opportunity to study the competing behavior of two different kinds of magnetic exchange mechanism (ferromagnetic and antiferromagnetic) acting simultaneously between two metal ions. Through density functional theory calculations, we showed how they work independently and their additive nature to produce the overall effect. The exciting methodology for the generation of copper(II) polyclusters presented in this Account will provide the opportunity to explore analogous serendipitous assembly of diverse structures with interesting magnetic behavior using other transition metal ions having more than one unpaired electrons.

Pt-6(II) nanoscopic cages with an organometallic backbone as sensors for picric acid

An organometallic building block 1,3,5-tris(4-trans-Pt(PEt3)(2)I(ethynyl)phenyl)benzene (1) incorporating Pt-ethynyl functionality has been synthesized and characterized. 2 + 3] self-assembly of its nitrate analogue 1,3,5-tris(4-trans-Pt(PEt3)(2)(ONO2)(ethynyl)phenyl)benzene (2) with ``clip'' type bidentate donors (L-1-L-3) separately afforded three trigonal prismatic architectures (3a-3c), respectively. All these prisms were characterized and their shapes/sizes are predicted through geometry optimization employing molecular mechanics universal force field (MMUFF) simulation. The extended p-conjugation including the presence of Pt-ethynyl functionality makes them electron rich as well as luminescent in nature. Macrocycles 3b and 3c exhibit fluorescence quenching in solution upon addition of picric acid PA], which is a common constituent of many explosives. Interestingly, the non-responsive nature of fluorescent intensity towards other electron-deficient nitro-aromatic explosives (NAEs) makes them promising selective sensors for PA with a detection limit predicted to be ppb level. Furthermore, solid-state quenching of fluorescent intensity of the thin film of 3b upon exposure to saturated vapor of picric acid has drawn special attention for infield applications.

Remarkable anticancer activity of ferrocenylterpyridine platinum(II) complexes in visible light with low dark toxicity

Ferrocenyl platinum(II) complexes (1-3), viz. Pt(Fc-tpy)Cl]Cl (1), Pt(Fc-tpy)(NPC)]Cl (2, HNPC = N-propargyl carbazole) and Pt(Fc-bpa)Cl]Cl (3), were prepared, characterized and their anti-proliferative properties in visible light in human keratinocyte (HaCaT) cell lines have been studied. Pt(Ph-tpy)Cl]Cl (4) was prepared and used as a control. Complexes 1 and 3, structurally characterized by X-ray crystallography, show distorted square-planar geometry for the platinum(II) centre. Complexes 1 and 2 having the Fc-tpy ligand showed an intense absorption band at similar to 590 nm. The ferrocenyl complexes are redox active showing the Fc(+)-Fc couple near 0.6 V vs. SCE in DMF-0.1 M tetrabutylammonium perchlorate (TBAP). Complexes 1-3 showed external binding to calf thymus DNA. Both 1 and 2 showed remarkable photocytotoxicity in HaCaT cell lines giving respective IC50 values of 9.8 and 12.0 mu M in visible light of 400-700 nm with low dark toxicity (IC50 > 60 mu M). Fluorescent imaging studies showed the spread of the complexes throughout the cell localising both in cytoplasm and the nucleus. The ferrocenyl complexes triggered apoptosis on light exposure as evidenced from the Annexin V-FITC/PI and DNA ladder formation assays. Spectral studies revealed the formation of ferrocenium ions upon photo-irradiation generating cytotoxic hydroxyl radicals via a Fenton type mechanism. The results are rationalized from a TDDFT study that shows involvement of ferrocene and the platinum coordinated terpyridine moiety as respective HOMO and LUMO.

Pd-Catalyzed Cross-Coupling Reactions of Hydrazones: Regioselective Synthesis of Highly Branched Dienes

The regioselective formation of highly branched dienes is a challenging task. Design and exploration of alternative working models to achieve such a regioselectivity to accomplish highly branched dienes is considered to be a historical advancement of Heck reaction to construct branched dienes. On the basis of the utility of carbene transfer reactions, in the reaction of hydrazones with Pd(II) under oxidative conditions, we envisioned obtaining a Pd-bis-carbene complex with alpha-hydrogens, which can lead to branched dienes. Herein, we report a novel Pd-catalyzed selective coupling reaction of hydrazones in the presence of t-BuOLi and benzoquinone to form the corresponding branched dienes. The utility of the Pd catalyst for the cross-coupling reactions for synthesizing branched conjugated dienes is rare. The reaction is very versatile and compatible with a variety of functional groups and is useful in synthesizing heterocyclic molecules. We anticipate that this Pd-catalyzed cross-coupling reaction will open new avenues for synthesizing useful compounds.

Thermodynamics of NdRhO3 and phase relations in the system Nd-Rh-O

Phase equilibrium experiments indicate that NdRhO3 is the only ternary oxide in the system Nd-Rh-O at 1273 K; it has orthorhombically-distorted perovskite structure. By employing a solid-state electrochemical cell incorporating calcia-stabilized zirconia as the electrolyte, thermodynamic properties of NdRhO3 are determined. The standard Gibbs energy of formation of NdRhO3 from its component binary oxides in the temperature ranges from 900 to 1300 K can be expressed as: 1/2Rh(2)O(3) (ortho)+1/2Nd(2)O(3)(hex)=NdRhO3(ortho), Delta(f(o,x))G(0)/J mol(-1)( +/- 197) = - 66256+5.64 (T/K). The decomposition temperature of NdRhO3 computed from extrapolated thermodynamic data is 1803 (+/- 4) K in pure oxygen and 1692 (+/- 4) K in air at standard pressure. Oxygen partial pressure-composition diagram and three-dimensional chemical potential diagram at 1273 K are developed from thermodynamic data obtained in this study and auxiliary information from the literature. Equilibrium temperature-composition phase diagrams at constant oxygen partial pressures are also constructed. (C) 2013 Elsevier Ltd. All rights reserved.

D-A-D-structured conducting polymer-modified electrodes for detection of lead(II) ions in water

Donor-acceptor-donor-structured thiophene derivative-based conducting polymer poly(7,9-dithiophene-2yl-8H-cyclopentaa]acenaphthalene-8-one) was chemically synthesized. This polymer was used to modify both glassy-carbon and carbon-paste electrode, which was used to detect lead(II) ions present in water in the range of 1 mM to 0.1 mu M. Cyclic voltammetry confirms the formation of the co-ordination complex between the soft segment of polymer and the dissolved lead ion. Anodic stripping voltammetry was carried out by the modified electrode to determine the lower limit of detection of dissolved lead(II) species in the solution. Differential adsorptive stripping and impedance measurements were also conducted to find the lowest possible response of the as-synthesized polymer to lead(II) ion in water. The electrochemical performance of the modified electrodes at different pH (4, 7 and 9) environments was carried out by stripping voltammetry, to get optimum sensitivity and stability under these conditions. Finally, interference analysis was carried out to detect the modified electrode's sensitivity towards lead ion affinity in water.

Self-assembly of discrete metallamacrocycles employing half-sandwich octahedral diruthenium(II) building units and imidazole-based ligands

Equimolar combination of a series of binuclear half-sandwich p-cymene ruthenium(II) building units Ru-2(mu-eta(4)-C2O4)(MeOH)(2)(eta(6)-p-cymene)(2)](OTf)(2) 1a](OTf)(2), Ru-2(mu-eta(4)-N,N'-diphenyloxamidato)( MeOH)(2)(eta(6)-p-cymene)(2)](OTf)(2) 1b](OTf)(2) and Ru-2(mu-eta(4)-C6H2O4)(MeOH)(2)(eta(6)-p-cymene)(2)](OTf)(2) 1c](OTf)(2) separately with imidazole-based ditopic ligands (L-1-L-2) in methanol yielded a series of tetranuclear metallamacrocycles 2-7](OTf)(4), respectively L-1 = 1,4-bis(imidazole-1-yl)benzene; L-2 = 4,4'-bis(imidazole-1-yl)biphenyl; OTf- = O3SCF3-]. Similarly, the reaction of Ru-2(mu-eta(4)-C2O4)(MeOH)(2)(eta(6)-p-cymene)2](OTf)(2) 1a](OTf)(2) with a triazine-based tritopic ligand 1,3,5-tris(imidazole-1-yl) triazine (L3) in 3: 2 M ratio afforded an unexpected tetranuclear macrocycle 8](OTf)(4) instead of an expected trigonal prismatic cage 8a](OTf)(6). All the self-assembled macrocycles 2-8](OTf)(4) were isolated in moderate to high yields and were fully characterized by multinuclear H-1, F-19] NMR, IR and electrospray ionization mass spectrometry (ESI-MS). In addition, X-ray diffraction study on the single crystals of 3](OTf)(4) and 8](OTf)(4) also indicated the formation 2 + 2] self-assembled macrocycles. Despite the possibility of formation of different conformational isomeric macrocycles (syn-and anti) and polymeric product due to free rotation of ligand sites of imidazole linkers, the selective formation of single conformational isomer (anti) as the only product is quite interesting. Furthermore, the photo-and electrochemical properties of these assemblies have been studied using UV/Vis absorption and cyclic voltammetry analysis. (c) 2013 Elsevier B.V. All rights reserved.

Transcriptional Repression of Tumor Suppressor CDC73, Encoding an RNA Polymerase II Interactor, by Wilms Tumor 1 Protein (WT1) Promotes Cell Proliferation IMPLICATION FOR CANCER THERAPEUTICS

The Wilms tumor 1 gene (WT1) can either repress or induce the expression of genes. Inconsistent with its tumor suppressor role, elevated WT1 levels have been observed in leukemia and solid tumors. WT1 has also been suggested to act as an oncogene by inducing the expression of MYC and BCL-2. However, these are only the correlational studies, and no functional study has been performed to date. Consistent with its tumor suppressor role, CDC73 binds to RNA polymerase II as part of a PAF1 transcriptional regulatory complex and causes transcriptional repression of oncogenes MYC and CCND1. It also represses beta-catenin-mediated transcription. Based on the reduced level of CDC73 in oral squamous cell carcinoma (OSCC) samples in the absence of loss-of-heterozygosity, promoter methylation, and mutations, we speculated that an inhibitory transcription factor is regulating its expression. The bioinformatics analysis predicted WT1 as an inhibitory transcription factor to regulate the CDC73 level. Our results showed that overexpression of WT1 decreased CDC73 levels and promoted proliferation of OSCC cells. ChIP and EMSA results demonstrated binding of WT1 to the CDC73 promoter. The 5-azacytidine treatment of OSCC cells led to an up-regulation of WT1 with a concomitant down-regulation of CDC73, further suggesting regulation of CDC73 by WT1. Exogenous CDC73 attenuated the protumorigenic activity of WT1 by apoptosis induction. An inverse correlation between expression levels of CDC73 and WT1 was observed in OSCC samples. These observations indicated that WT1 functions as an oncogene by repressing the expression of CDC73 in OSCC. We suggest that targeting WT1 could be a therapeutic strategy for cancer, including OSCC.

Template-free multicomponent coordination-driven self-assembly of Pd(II)/Pt(II) molecular cages

Recent years have seen a tremendous increase in the interest for constructing hollowed-out molecular frameworks, for their potential uses. Metal-ligand coordination-driven self-assembly has provided multitudes of opportunities in the formation of molecular architectures of desired shapes and sizes, with the help of the information already coded in the components. This article summarizes the recent developments in the construction of multicomponent molecular cages through this process, with a focus on the decreasing relevance of templates, and use of these systems in catalysis/host-guest chemistry.

Phase equilibria in the system Sm-Rh-O and thermodynamic and thermal studies on SmRhO3

Using isothermal equilibration, phase relations are established in the system Sm-Rh-O at 1273 K. SmRhO3 with GdFeO3-type perovskite structure is found to be the only ternary phase. Solid-state electrochemical cells, containing calcia-stabilized zirconia as an electrolyte, are used to measure the thermodynamic properties of SmRhO3 formed from their binary component oxides Rh2O3 (ortho) and Sm2O3 (C-type and B-type) in two different temperature ranges. Results suggest that C-type Sm2O3 with cubic structure transforms to B-type Sm2O3 with monoclinic structure at 1110 K. The standard Gibbs energy of transformation is . Standard Gibbs energy of formation of SmRhO3 from binary component oxides Rh2O3 and Sm2O3 with B-type rare earth oxide structure can be expressed as . The decomposition temperature of SmRhO3 estimated from the extrapolation of electrochemical data is 1665 (+/- 2) K in air and 1773 (+/- 3) K in pure oxygen. Temperature-composition diagrams at constant oxygen pressures are constructed for the system Sm-Rh-O. Employing the thermodynamic data for SmRhO3 from emf measurement and auxiliary data for other phases from the literature, oxygen potential-composition phase diagram and 3-D chemical potential diagram for the system Sm-Rh-O at 1273 K are developed.

mu-Oxamido binuclear copper (II) complexes: Synthesis, crystal structure, DNA interaction and antibacterial studies

Four binuclear copper (II) complexes Cu(oxpn)Cu(B)](2+) (2-5) bridged by N, N'-bis3-(methylamino) propyl] oxamide (oxpn), where, B is N, N-donor heterocyclic bases (viz. 2,2'-bipyridine (bpy, 2), 1,10-phenathroline (phen, 3), dipyrido3,2-d:2',3'-f]quinoxaline (dpq, 4) and dipyrido3,2-a:2',3'-c]phenazine (dppz, 5) are synthesized, characterized by different spectroscopic and single crystal X-ray data technique. The phen (3) and dpq (4) complexes were structurally characterized by X-ray data analysis. Their DNA binding, oxidative cleavage and antibactirial activities were studied. The dpq (4) and dppz (5) complexes are avid binders to the Calf thymus DNA (CT-DNA). The phen (3), dpq (4) and dppz (5) complexes show efficient oxidative cleavage of supercoiled DNA (SC DNA) through hydroxyl radical ((OH)-O-center dot) pathway in the presence of Mercaptopropionic acid (MPA). (C) 2013 Elsevier Ltd. All rights reserved.