Synthesis and photocatalytic properties of AgLi1/3Ru2/3]O-2: A new delafossite oxide

A new delafossite oxide, AgLi1/3Ru2/3]O-2, synthesized by ion-exchanging interlayer-Li+ with Ag+ in layered Li2RuO3, is reported. The transformation of layered Li2RuO3 (monoclinic, space group C2/c) to AgLi1/3Ru2/3]O-2 possessing a delafossite structure (space group R (3) over barm) has been established with powder X-ray diffraction. The successful conversion of LiLi1/3Ru2/3]O-2 to AgLi1/3Ru2/3]O-2 is further confirmed by EDAX analysis. The diffuse reflectance spectrum of AgLi1/3Ru2/3]O-2 shows broad absorption in the UV-visible region suggesting its use as a photocatalyst. The photocatalytic activity of AgLi1/3Ru2/3]O-2 has been investigated by degrading various dyes. It showed significant photocatalytic activity for dye degradation both under UV and solar radiation. (C) 2010 Elsevier B.V. All rights reserved.

The modulation of radiation in an electron-positron plasma

The modulational instability of a large-amplitude, linearly polarized electromagnetic wave propagating in an electron-positron plasma is considered, including the combined effect of relativistic mass variation of the plasma particles, harmonic generation, and the non-resonant, finite-frequency electrostatic density perturbations, all caused by the large-amplitude radiation field. The radiation from many strong sources, such as AGN and pulsars, has been observed to vary over a host of time-scales. It is possible that the extremely rapid variations in the non-thermal continuum of AGN, as well as in the non-thermal radio radiation from pulsars, can be accounted for by the modulational instabilities to which radiation may be subjected during its propagation out of the emission region.

Vesicle and Stable Monolayer Formation from Simple ``Click'' Chemistry Adducts in Water

Click chemistry has been successfully extended into the field of molecular design of novel amphiphatic adducts. After their syntheses and characterizations, we have studied their aggregation properties in aqueous medium. Each of these adducts forms stable suspensions in water. These suspensions have been characterized by dynamic light scattering (DLS) studies and transmission electron microscopy (TEM). The presence of inner aqueous compartments in such aggregates has been demonstrated using dye (methylene blue) entrapment studies. These aggregates have been further characterized using X-ray diffraction (XRD), which indicates the existence of bilayer structures in them. Therefore, the resulting aggregates could be described as vesicles. The temperature-induced order-to-disorder transitions of the vesicular aggregates and the accompanying changes in their packing and hydration have been examined using high-sensitivity differential scanning calorimetry, fluorescence anisotropy, and generalized polarization measurements using appropriate membrane-soluble probe, 1,6-diphenylhexatriene, and Paldan, respectively. The findings of these studies are consistent with each other in terms of the apparent phase transition temperatures. Langmuir monolayer studies confirmed that these click adducts also form stable monolayers on buffered aqueous subphase at the air-water interface.

Anharmonic Effects in Germanium

A precise X-ray investigation is carried out to probe the lowest-order anharmonic contribution of the atomic potential of the germanium atom. A total number of 1052 reflections (h + k + l = 4n and 4n +/- 1) are precisely measured at room temperature using a spherical single crystal of germanium and using a Nonius CAD-4 X-ray diffractometer with crystal monochromatized MoKalpha radiation. A least-square refinement program is used to refine the harmonic and anharmonic thermal parameters of the crystal. The refinement gives beta(Ge) = (-0.749 +/- 1.79) x 10-(16) J nm-3 with B(Ge) = (0.528 +/- 0.004) x 10(-2) nm2. The reliability index (R) amounts to 1.71% for germanium.

Bioinorganic and medicinal chemistry: aspects of gold(I)-protein complexes

Gold(I)-based drugs have been used successfully for the treatment of rheumatoid arthritis (RA) for several years. Although the exact mechanism of action of these gold(I) drugs for RA has not been clearly established, the interaction of these compounds with mammalian enzymes has been extensively studied. In this paper, we describe the interaction of therapeutic gold(I) compounds with mammalian proteins that contain cysteine (Cys) and selenocysteine (Sec) residues. Owing to the higher affinity of gold(I) towards sulfur and selenium, gold(I) drugs rapidly react with the activated cysteine or selenocysteine residues of the enzymes to form protein-gold(I)-thiolate or protein-gold(I)-selenolate complexes. The formation of stable gold(I)-thiolate/selenolate complexes generally lead to inhibition of the enzyme activity. The gold-thiolate/selenolate complexes undergo extensive ligand exchange reactions with other nucleophiles and such ligand exchange reactions alter the inhibitory effects of gold(I) complexes. Therefore, the effect of gold(I) compounds on the enzymatic activity of cysteine-or selenocysteine-containing proteins may play important roles in RA. The interaction of gold(I) compounds with different enzymes and the biochemical mechanism underlying the inhibition of enzymatic activities may have broad medicinal implications for the treatment of RA.

Organometallic chemistry of diphosphazanes. Part IX: Syntheses and spectroscopic studies of molybdenum and tungsten tetracarbonyl complexes of unsymmetrical diphosphazanes

The unsymmetrical diphosphazanes X2PN(Pr(i))PYY'(1a-1h) {X = Ph, YY' = O2 C6H4 (1a) or YY' = O2C12H8 (1b); X = Ph, Y = Ph, Y' = OC6H4Me-4 (1c), OC6H4Br-4 (1d), OC6H3Me2-3,5 (1e), OC5H4N-2 (1f), N2C3HMe2-3,5 (1g) or Cl (1h)} react with [M(CO)4(NHC5H10)2] (M = Mo, W) to yield the cis-chelate complexes [M(CO)4{X2PN(Pr(i)) PYY'}] {M = Mo (2a-2h); M = W (3-f,3-g)}. These complexes have been characterized by H-1, P-31 and C-13 NMR and IR spectroscopic studies.

Soft-chemical routes to synthesis of solid oxide materials

We describe three different families of metal oxides, viz., (i) protonated layered perovskites, (ii) framework phosphates of NASICON and KTiOPO4 (KTP) structures and (iii) layered and three-dimensional oxides in the H-V-W-O system, synthesized by 'soft-chemical' routes involving respectively ion-exchange, redox deinteracalation and acid-leaching from appropriate parent oxides. Oxides of the first family, HyA2B3O10(A = La/Ca; B = Ti/Nb), exhibit variable Bronsted acidity and intercalation behaviour that depend on the interlayer structure. V2(PO4)3 prepared by oxidative deintercalation from Na3V2(PO4)3 is a new host material exhibiting reductive insertion of lithium/hydrogen, while K0.5Nb0.5 M0.5OPO4(M = Ti, V) are novel KTP-like materials exhibiting second harmonic generation of 1064 nm radiation. HxVxW1-xO3 for x = 0.125 and 0.33 possessing alpha-MoO3 and hexagonal WO3 structures, prepared by acid-leaching of LiVWO6, represent functionalized oxide materials exhibiting redox and acid-base intercalation reactivity.

Soft-chemical synthesis of new non-linear optical materials, K0.5M0.5Ti0.5OPO4(M = Nb, Ta),related to KTiOPO4

Soft-chemical oxidation of KTiOPO4-like KM(0.5)(V)Ti(0.5)(III)OPO(4) (M = Nb, Ta) using chlorine in CHCl3 is accompanied by partial deintercalation of potassium, yielding K(0.5)MV(0.5)Ti(0.5)(IV)OPO(4) compounds which are new non-linear optical materials that exhibit efficient second-harmonic generation of 1064 nm radiation, as does KTiOPO4.