Supportless PdFe nanorods as highly active electrocatalyst for proton exchange membrane fuel cell

The PdFe nanorods (PdFe-NRs) with tunable length were synthesized by an organic phase reaction of [Pd(acac)₂] and thermal decomposition of [Fe(CO)₅] in a mixture of oleyamine and octadecene at 160 °C. They show a better proton exchange membrane fuel cell (PEMFC) performance than commercial Pt/C in working voltage region of 0.80–0.65 V, due to their high intrinsic activity to oxygen reduction reaction (ORR), reduced cell inner resistance, and improved mass transport.     

Syndiotactic Polystyrene / Fullerene Composites: Elucidation of Structural Aspect

Summary: Syndiotactic polystyrene (sPS), an attractive polymer due to its wide range of application, forms polymer-solvent intercalates with a large variety of solvent molecules ranging from liquids to solids. Recently, it has been realized that sPS intercalate prepared from SPS/naphthalene gel is more promising of making mesoporous materials. Here, the composite of sPS/fullerene have been prepared by taking advantage of sublimation of naphthalene. The different techniques as like XRD, SEM, HRTEM, FT-IR, DSC, TGA etc have been employed to characterized sPS/fullerene composite. XRD investigation shows the presence of δ form sPS in the composite. SEM and HRTEM reveal the fibrillar network with fringe like structure in presence of fullerene only and the average diameter of fibril has increased as compared to pure sPS fibrils. The conductivities of these fibrils have been increased with increasing amount of fullerene.     

The heat of formation of chlorine-isocyanate and the relative stability of isoelectronic molecules: an experimental and theoretical study

Accurate thermochemical data of small molecules are invaluable to the progress of every aspect of chemistry, especially in the atmosphere, combustion and industry. In this work, photofragmentation translational spectroscopy and 1st principles electronic structure theory reveal the literature value of the heat of formation of chlorine-isocyanate to be in error by more than 40 kcalmol. We report a revised experimental value for D0(Cl-NCO) = 51+/-3 kcal/mol which leads to a Delta Hf (ClNCO) = 8.5+/-3 kcal/mol. High level ab initio (CCSD(T)) electronic structure calculations extrapolated to the complete basis set limit give D0(Cl-NCO) = 6.3 kcal/mol, in good agreement with experiment. In light of the present results, the destabilization of azides relative to isoelectronic isocyanates has been evaluated empirically for three pairs of related molecules. It is found to be 90-110 kcal/mol, and has been attributed mainly to the weakening of the N-NN bond relative to the N-CO bond. Electronic structure calculations employing decomposition analysis suggest that, compared to homopolar N2, the (+delta)CO(-delta) pi polarity provides better orbital interaction (charge transfer) and electrostatic attraction and results in a closer encounter and larger stabilization between the fragments and that this is the origin of isoelectronic destabilization of azides relative to the isocyanates.     

Collision-free photochemistry of methylazide: observation of unimolecular decomposition of singlet methylnitrene

Methylazide photolysis at 248 nm has been investigated by ionizing photofragments with synchrotron radiation in a photofragmentation translational spectroscopy study. CH3N and N2 were the only observed primary products. The translational energy release suggests a simple bond rupture mechanism forming singlet methylnitrene, 1CH3N, and N2. Thus, these experiments reveal the unimolecular decomposition of this highly unstable species. We explain our observations through a mechanism which is initiated by the isomerization of 1CH3N to a highly internally excited methanimine H2C=NH isomer, which decomposes by 1,1-H2 elimination forming HNC+H2 as well as sequential H-atom loss (N-H followed by C-H bond cleavage), to form HCN. No evidence for dynamics on the triplet manifold of surfaces is found.     

Role of Fe and Co in optical conductivity and electronic structure of TbNi4Fe and TbNi4Co

Optical properties of two intermetallic compounds TbNi₄Fe and TbNi₄Co have been studied employing ellipsometry in a spectral range 0.22–15 μm to reveal their characteristic features in comparison with the parent compound TbNi₅. The electronic structure of TbNi₄Fe and TbNi₄Co was calculated within the LSDA + U method (local spin density approximation with Hubbard U-correction). Based on the calculated electronic structure results, the theoretical optical conductivity was calculated and used to interpret experimental conductivity in the range of interband optical absorption.     

Antitumour effect of Diospyros cordifolia bark on Ehrlich ascites carcinoma-bearing Swiss albino mice

Diospyros cordifolia Roxb. (Ebenaceae), commonly known as Indian ebony, is used traditionally for several medicinal purposes. In this study, the methanol extract of D. cordifolia bark (MEDC) was evaluated for its antitumour effect against Ehrlich ascites carcinoma (EAC)-bearing Swiss albino mice. Twenty-four hours after intraperitoneal inoculation of tumour (EAC) cells in mice, MEDC was administered intraperitoneally at 25 and 50?mg kg?1 bodyweight for 9 consecutive days. On the 10th day, half of the mice were sacrificed to determine the tumour volume, viable and non-viable tumour cell counts, and rest were kept alive for the assessment of median survival time and increase in life span. Haematological profiles were also determined. MEDC exhibited a marked decrease in tumour growth parameters and increased the survival rate of EAC-bearing animals. MEDC normalised the haematological parameters as compared with the EAC control mice. Therefore, this study demonstrated that D. cordifolia bark possessed remarkable antitumour efficacy.     

Supramolecular double helix from capped γ-peptide

The single crystal X-ray diffraction study of capped γ-peptide reveal that the peptide adopts helical conformation which self-assemble to form a supramolecular parallel double helical structure using intermolecular hydrogen bonding as well as π-π stacking interactions in the solid state.     

Unusual room temperature CO(2) uptake in a fluoro-functionalized MOF: insight from Raman spectroscopy and theoretical studies

We herein report an unusual CO(2) adsorption behavior in a fluoro-functionalized MOF {[Zn(SiF(6))(pyz)(2)]·2MeOH}(n) (1) with a 1D channel system, which is made up of pyrazine and SiF(6)(2-) moieties. Surprisingly, desolvated 1 (1') adsorbs higher amounts of CO(2) at 298 K than at 195 K, which is in contrast to the usual trend. Combined Raman spectroscopic and theoretical studies reveal that slanted pyrazine rings in 1' with an angle of 17.2° with respect to the (200) Zn(ii)-Si plane at low temperature block the channel windows and thus reduce the uptake amount.     

Fluxes in "free" and total zinc are essential for progression of intraerythrocytic stages of Plasmodium falciparum

Dynamic fluxes in the concentration of ions and small molecules are fundamental features of cell signaling, differentiation, and development. Similar roles for fluxes in transition metal concentrations are less well established. Here, we show that massive zinc fluxes are essential in the infection cycle of an intracellular eukaryotic parasite. Using single-cell quantitative imaging, we show that growth of the blood-stage Plasmodium falciparum parasite requires acquisition of 30 million zinc atoms per erythrocyte before host cell rupture, corresponding to a 400% increase in total zinc concentration. Zinc accumulates in a freely available form in parasitophorous compartments outside the food vacuole, including mitochondria. Restriction of zinc availability via small molecule treatment causes a drop in mitochondrial membrane potential and severely inhibits parasite growth. Thus, extraordinary zinc acquisition and trafficking are essential for parasite development.     

1,3-Dipolar Cycloadditions VI [1].Structure and Conformation of Cycloadducts from Reactions of C-Aryl-N-phenylnitrones with Substituted Cinnamic Acid Amides

Summary.  Studies on cycloadditions of C,N-diarylnitrones to cinnamic acid amides were carried out. The diastereoisomeric (I, II) and (in some cases) regioisomeric (III) cycloadducts obtained were characterized by spectroscopic and X-ray data. Conformational studies were carried out by molecular modelling. Received February 8, 2000. Accepted February 18, 2000