Durable electrocatalytic-activity of Pt-Au/C cathode in PEMFCs

Longevity remains as one of the central issues in the successful commercialization of polymer electrolyte membrane fuel cells (PEMFCs) and primarily hinges on the durability of the cathode. Incorporation of gold (Au) to platinum (Pt) is known to ameliorate both the electrocatalytic activity and stability of cathode in relation to pristine Pt-cathodes that are currently being used in PEMFCs. In this study, an accelerated stress test (AST) is conducted to simulate prolonged fuel-cell operating conditions by potential cycling the carbon-supported Pt-Au (Pt-Au/C) cathode. The loss in performance of PEMFC with Pt-Au/C cathode is found to be similar to 10% after 7000 accelerated potential-cycles as against similar to 60% for Pt/C cathode under similar conditions. These data are in conformity with the electrochemical surface-area values. PEMFC with Pt-Au/C cathode can withstand > 10 000 potential cycles with very little effect on its performance. X-ray diffraction and transmission electron microscopy studies on the catalyst before and after AST suggest that incorporating Au with Pt helps mitigate aggregation of Pt particles during prolonged fuel-cell operations while X-ray photoelectron spectroscopy reflects that the metallic nature of Pt is retained in the Pt-Au catalyst during AST in comparison to Pt/C that shows a major portion of Pt to be present as oxidic platinum. Field-emission scanning electron microscopy conducted on the membrane electrode assembly before and after AST suggests that incorporating Au with Pt helps mitigating deformations in the catalyst layer.

Expression of the receptor guanylyl cyclase C and its ligands in reproductive tissues of the rat: A potential role for a novel signaling pathway in the epididymis

Guanylyl cyclase C (GC-C) is a membrane-associated form of guanylyl cyclase and serves as the receptor for the heat-stable enterotoxin (ST) peptide and endogenous ligands guanylin, uroguanylin, and lymphoguanylin. The major site of expression of GC-C is the intestinal epithelial cell, although GC-C is also expressed in extraintestinal tissue such as the kidney, airway epithelium, perinatal liver, stomach, brain, and adrenal glands. Binding of ligands to GC-C leads to accumulation of intracellular cGMP, the activation of protein kinases G and A, and phosphorylation of the cystic fibrosis transmembrane conductance regulator (CFTR), a chloride channel that regulates salt and water secretion. We examined the expression of GC-C and its ligands in various tissues of the reproductive tract of the rat. Using reverse transcriptase and the polymerase chain reaction, we demonstrated the presence of GC-C, uroguanylin, and guanylin mRNA in both male and female reproductive organs. Western blot analysis using a monoclonal antibody to GC-C revealed the presence of differentially glycosylated forms of GC-C in the caput and cauda epididymis. Exogenous addition of uroguanylin to minced epididymal tissue resulted in cGMP accumulation, suggesting an autocrine or endocrine activation of GC-C in this tissue. Immunohistochemical analyses demonstrated expression of GC-C in the tubular epithelial cells of both the caput epididymis and cauda epididymis. Our results suggest that the GC-C signaling pathway could converge on CFTR in the epididymis and perhaps control fluid and ion balance for optimal sperm maturation and storage in this tissue.

Kinetics of hydrogen evolution on submicron size Co, Ni, Pd and CoNi alloy powder electrodes by d.c. polarization and a.c. impedance studies

Submicron size Co, Ni and Co-Ni alloy powders have been synthesized by the polyol method using the corresponding metal malonates and Pd powder by reduction of PdOx in methanol. The kinetics of the hydrogen evolution reaction ( HER) in 6 M KOH electrolyte have been studied on electrodes made from the pressed powders. The d.c. polarization measurements have resulted in a value close to 120 mV decade(-1) for the Tafel slope, suggesting that the HER follows the Volmer-Heyrovsky mechanism. The values of exchange current density (i(o)) are in the range 1-10 mA cm(-2) for electrodes fabricated in the study. The a.c. impedance spectra measured at several potentials in the HER region showed a single semicircle in the Nyquist plots. Exchange current density (i(o)) and energy transfer coefficient (alpha) have been calculated by employing a nonlinear least square-fitting program.

Reactivity switching and selective activation of C-1 or C-3 in 2,3-unsaturated thioglycosides

Reactivity switching and selective activation of C-1 or C-3 in 2,3-unsaturated thioglycosides, namely, 2,3-dideoxy-1-thio-D-hex-2-enopyranosides are reported. The reactivity switching allowed activation of either C-1 or C-3, with the use of either N-iodosuccinimide (NIS)/triflic acid (TfOH) or TfOH alone. C-1 glycosylation with alcohol acceptors occurred in the presence of NIS/TfOH, without the acceptors reacting at C-3. On the other hand, reaction of 2,3-unsaturated thioglycosides with alcohols mediated by triflic acid led to transposition of C-1 ethylthio-moiety to C-3 intramolecularly, to form 3-ethylthio-glycals. Resulting glycals underwent glycosylation with alcohols to afford 3-ethylthio-2-deoxy glycosides. However, when thiol was used as an acceptor, only a stereoselective addition at C-3 resulted, so as to form C-1, C-3 dithio-substituted 2-deoxypyranosides. (C) 2011 Elsevier Ltd. All rights reserved.

A study of Al2O3:C films on Si(100) grown by low pressure MOCVD

We report the characterization of carbonaceous aluminium oxide, Al2O3:C, films grown on Si(100) by metalorganic chemical vapor deposition. The focus is on the study of the effects of carbon on the dielectric properties of aluminium oxide in a qualitative manner. The carbon present in the aluminium oxide film derives from aluminium acetylacetonate used as the source of aluminium. As-grown films comprise nanometer-sized grains of alumina (∼ 20–50 nm) in an amorphous carbonaceous matrix, as examined by X-ray diffractometry (XRD) and transmission electron microscopy (TEM). The films are shiny; they are smooth as observed by scanning electron microscopy (SEM). An attempt has been made to explore the defects (viz., oxide charge density) in the aluminium oxide films using room temperature high frequency capacitance – voltage (C-V) and current–voltage (I-V) measurements. The hysteresis and stretch-out in the high frequency C-V plots is indicative of charge trapping. The role of heteroatoms, as characterized by X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared (FTIR) spectroscopy, in the transport of charge in Al2O3:C films is discussed.

Effect of Post-Metallization Hydrogen Annealing on C-V Characteristic of Zirconia Grown Using Atomic Layer Deposition

Substantial amount of fixed charge present in most of the alternative gate dielectrics gives rise to large shifts in the flat-band voltage (VFB) and charge trapping and de-trapping causes hysterectic changes on voltage cycling. Both phenomena affect stable and reliable transistor operation. In this paper we have studied for the first time the effect of post-metallization hydrogen annealing on the C-V curve of MOS capacitors employing zirconia, one of the most promising gate dielectric. Samples were annealed in hydrogen ambient for up to 30 minutes at different temperatures ranging from room temperature to 400°C. C-V measurements were done after annealing at each temperature and the hysteresis width was calculated from the C-V curves. A minimum hysteresis width of ∼35 mV was observed on annealing the sample at 200°C confirming the excellent suitability of this dielectric

Interface states of laser ablated BaTiO3 and Ba0.9Ca0.1TiO3 thin films in MFS structure determined by DLTS and C – V technique

BaTiO3 and Ba0.9Ca0.1TiO3 thin films were deposited on the p – type Si substrate by pulsed excimer laser ablation technique. The Capacitance – Voltage (C-V) measurement measured at 1 MHz exhibited a clockwise rotating hysteresis loop with a wide memory window for the Metal – Ferroelectric – Semiconductor (MFS) capacitor confirming the ferroelectric nature. The low frequency C – V measurements exhibited the response of the minority carriers in the inversion region while at 1 MHz the C – V is of a high frequency type with minimum capacitance in the inversion region. The interface states of both the MFS structures were calculated from the Castagne – Vaipaille method (High – low frequency C – V curve). Deep Level Transient Spectroscopy (DLTS) was used to analyze the interface traps and capture cross section present in the MFS capacitor. There were distinct peaks present in the DLTS spectrum and these peaks were attributed to the presence of the discrete interface states present at the semiconductor – ferroelectric interface. The distribution of calculated interface states were mapped with the silicon energy band gap for both the undoped and Ca doped BaTiO3 thin films using both the C – V and DLTS method. The interface states of the Ca doped BaTiO3 thin films were found to be higher than the pure BaTiO3 thin films.

Nature and strength of C-H center dot center dot center dot O interactions involving formyl hydrogen atoms: computational and experimental studies of small aldehydes

Structural and electronic properties of C-H center dot center dot center dot O contacts in compounds containing a formyl group are investigated from the perspective of both hydrogen bonding and dipole-dipole interactions, in a systematic and graded approach. The effects of a-substitution and self-association on the nature of the formyl H-atom are studied with the NBO and AIM methodologies. The relative dipole-dipole contributions in formyl C-H center dot center dot center dot O interactions are obtained for aldehyde dimers. The stabilities and energies of aldehyde clusters (dimer through octamer) have been examined computationally. Such studies have an implication in crystallization mechanisms. Experimental X-ray crystal structures of formaldehyde, acrolein and N-methylformamide have been determined in order to ascertain the role of C-H center dot center dot center dot O interactions in the crystal packing of formyl compounds.

Microwave spectroscopic and theoretical studies on the phenylacetylene center dot center dot center dot H(2)O complex: C-H center dot center dot center dot O and O-H center dot center dot center dot pi hydrogen bonds as equal partners

Rotational spectra of five isotopologues of the title complex, C(6)H(5)CCH center dot center dot center dot H(2)O, C(6)H(5)CCH center dot center dot center dot HOD, C(6)H(5)CCH center dot center dot center dot D(2)O, C(6)H(5)CCH center dot center dot center dot H(2)(18)O and C(6)H(5)CCD center dot center dot center dot H(2)O, were measured and analyzed. The parent isotopologue is an asymmetric top with kappa = -0.73. The complex is effectively planar (ab inertial plane) and both `a' and `b' dipole transitions have been observed but no c dipole transition could be seen. All the transitions of the parent complex are split into two resulting from an internal motion interchanging the two H atoms in H(2)O. This is confirmed by the absence of such doubling for the C(6)H(5)CCH center dot center dot center dot HOD complex and a significant reduction in the splitting for the D(2)O analog. The rotational spectra, unambiguously, reveal a structure in which H(2)O has both O-H center dot center dot center dot pi (pi cloud of acetylene moiety) and C-H center dot center dot center dot O (ortho C-H group of phenylacetylene) interactions. This is in agreement with the structure deduced by IR-UV double resonance studies (Singh et al., J. Phys. Chem. A, 2008, 112, 3360) and also with the global minimum predicted by advanced electronic structure theory calculations (Sedlack et al., J. Phys. Chem. A, 2009, 113, 6620). Atoms in Molecule (AIM) theoretical analysis of the complex reveals the presence of both O-H center dot center dot center dot pi and C-H center dot center dot center dot O hydrogen bonds. More interestingly, based on the electron densities at the bond critical points, this analysis suggests that both these interactions are equally strong. Moreover, the presence of both these interactions leads to significant deviation from linearity of both hydrogen bonds.

Indium Nitride Nanometric-Objects on c-Sapphire Grown by Plasma-Assisted Molecular Beam Epitaxy

The indium nitride (InN)-based nanometric-objects were grown directly on a c-sapphire substrate by using plasma-assisted molecular beam epitaxy (PAMBE) at different substrate temperatures. High resolution X-ray diffraction (HRXRD) reveals the InN (0002) reflection and full width at half maximum (FWHM) found to be decreased with increasing the growth temperature. The size, height and density of the grown nanometric-objects studied by scanning electron microscopy (SEM) has remarkable differences, evidencing the decisive role of substrate temperature. Photoluminescence (PL) studies revealed that the emission energy is shifted towards the higher side from the bulk value, i.e., a blue shift in the PL spectra was observed. The temperature dependence of the PL peak position shows an ``S-shaped'' emission energy shift, which can be attributed to the localization of carriers in the nanometric-objects.

Pt-Au/C cathode with enhanced oxygen-reduction activity in PEFCs

Carbon-supported Pt-Au (Pt-Au/C) catalyst is prepared separately by impregnation, colloidal and micro-emulsion methods, and characterized by physical and electrochemical methods. Highest catalytic activity towards oxygen-reduction reaction (ORR) is exhibited by Pt-Au/C catalyst prepared by colloidal method. The optimum atomic ratio of Pt to Au in Pt-Au/C catalyst prepared by colloidal method is determined using linear-sweep and cyclic voltammetry in conjunction with cell-polarization studies. Among 3:1, 2:1 and 1:1 Pt-Au/C catalysts, (3:1) Pt-Au/C exhibits maximum electrochemical activity towards ORR. Powder X-ray diffraction pattern and transmission electron micrograph suggest Pt-Au alloy nanoparticles to be well dispersed onto the carbon-support. Energy dispersive X-ray analysis and inductively coupled plasma-optical emission spectroscopy data suggest that the atomic ratios of the alloying elements match well with the expected values. A polymer electrolyte fuel cell (PEFC) operating at 0 center dot 6 V with (3:1) Pt-Au/C cathode delivers a maximum power-density of 0 center dot 65 W/cm (2) in relation to 0 center dot 53 W/cm (2) delivered by the PEFC with pristine carbon-supported Pt cathode.

A System-C based Micro architectural Exploration Framework for Latency, Power and Performance Trade-offs of On-Chip Interconnection

We describe a System-C based framework we are developing, to explore the impact of various architectural and microarchitectural level parameters of the on-chip interconnection network elements on its power and performance. The framework enables one to choose from a variety of architectural options like topology, routing policy, etc., as well as allows experimentation with various microarchitectural options for the individual links like length, wire width, pitch, pipelining, supply voltage and frequency. The framework also supports a flexible traffic generation and communication model. We provide preliminary results of using this framework to study the power, latency and throughput of a 4x4 multi-core processing array using mesh, torus and folded torus, for two different communication patterns of dense and sparse linear algebra. The traffic consists of both Request-Response messages (mimicing cache accesses)and One-Way messages. We find that the average latency can be reduced by increasing the pipeline depth, as it enables higher link frequencies. We also find that there exists an optimum degree of pipelining which minimizes energy-delay product.

Synergy between the N-terminal and C-terminal domains of Mycobacterium tuberculosis HupB is essential for high-affinity binding, DNA supercoiling and inhibition of RecA-promoted strand exchange

The occurrence of DNA architectural proteins containing two functional domains derived from two different architectural proteins is an interesting emerging research theme in the field of nucleoid structure and function. Mycobacterium tuberculosis HupB, unlike Escherichia coli HU, is a two-domain protein that, in the N-terminal region, shows broad sequence homology with bacterial HU. The long C-terminal extension, on the other hand, contains seven PAKK/KAAK motifs, which are characteristic of the histone H1/H5 family of proteins. In this article, we describe several aspects of HupB function, in comparison with its truncated derivatives lacking either the C-terminus or N-terminus. We found that HupB binds a variety of DNA repair and replication intermediates with K(d) values in the nanomolar range. By contrast, the N-terminal fragment of M. tuberculosis HupB (HupB(MtbN)) showed diminished DNA-binding activity, with K(d) values in the micromolar range, and the C-terminal domain was completely devoid of DNA-binding activity. Unlike HupB(MtbN), HupB was able to constrain DNA in negative supercoils and introduce negative superhelical turns into relaxed DNA. Similarly, HupB exerted a robust inhibitory effect on DNA strand exchange promoted by cognate and noncognate RecA proteins, whereas HupB(MtbN), even at a 50-fold molar excess, had no inhibitory effect. Considered together, these results suggest that synergy between the N-terminal and C-terminal domains of HupB is essential for its DNA-binding ability, and to modulate the topological features of DNA, which has implications for processes such as DNA compaction, gene regulation, homologous recombination, and DNA repair.