Origin of activation of Lattice Oxygen and Synergistic Interaction in Bimetal-Ionic Ce0.89Fe0.1Pd0.01O2-delta Catalyst

Flourite-type nanocrystalline Ce0.9Fe0.1O2-delta and Ce0.89Fe0.1Pd0.01O2-delta solid solutions have been synthesized by solution combustion method,'.which show higher oxygen storage/release property (OSC) compared to CeO2 and Ce0.8Zr0.2O2. Temperature programmed reduction an XPS study reveal that the presence of Pd ion in Ce0.9Fe0.1O2-delta facilitates complete reduction of Fe3+ to Fe2+ state and partial reduction of Ce4+ to Ce3+ state at.temperatures as low as 105 degrees C compared to 400 degrees C for monometal-ionic Ce0.9Fe0.1O2-delta. Fe3+ ion is reduced to Fe2+ and not to Feo due to favorable redox potential for Ce4+ + Fe2+ -> Ce3+ + Fe3+ reaction. Using first-principles density functional theory calculation we determine M-O (M = Pd, Fe, Ce) bond lengths, and find that bond lengths vary from shorter (2.16 angstrom) to longer (2.9 angstrom) bond distances compared to mean Ce-O bond distance of 2.34 angstrom. for CeO2. Using these results in bond valence analysis, we show that oxygen with bond valences as low as -1.55 are created, leading to activation of lattice oxygen in the bimetal ionic catalyst. Temperatures of CO oxidation and NO reduction by CO/H-2 are lower with the bimetalionic Ce0.89Fe0.1Pd0.01O2-delta catalyst compared to monometal-ionic Ce0.9Fe0.1O2-delta and Ce0.99Pd0.01O2-delta catalysts. From XPS studies of Pd impregnated on CeO2 and Fe2O3 oxides, we show that the synergism leading to low temperature activation of lattice oxygen in bimetal-ionic catalyst Ce0.89Fe0.1Pd0.01O2-delta is due to low-temperature reduction of Pd2+ to Pd-0, followed by Pd-0 + 2Fe(3+) -> Pd2+ + 2Fe(2+), Pd-0 + 2Ce(4+) -> Pd2+ + 2Ce(3+) redox reaction.

Structure, dynamics, and interactions of jacalin. Insights from molecular dynamics simulations examined in conjunction with results of X-ray studies

Molecular dynamics simulations have been carried out on all the jacalin-carbohydrate complexes of known structure, models of unliganded molecules derived from the complexes and also models of relevant complexes where X-ray structures are not available. Results of the simulations and the available crystal structures involving jacalin permit delineation of the relatively rigid and flexible regions of the molecule and the dynamical variability of the hydrogen bonds involved in stabilizing the structure. Local flexibility appears to be related to solvent accessibility. Hydrogen bonds involving side chains and water bridges involving buried water molecules appear to be important in the stabilization of loop structures. The lectin-carbohydrate interactions observed in crystal structures, the average parameters pertaining to them derived from simulations, energetic contribution of the stacking residue estimated from quantum mechanical calculations, and the scatter of the locations of carbohydrate and carbohydrate-binding residues are consistent with the known thermodynamic parameters of jacalin-carbohydrate interactions. The simulations, along with X-ray results, provide a fuller picture of carbohydrate binding by jacalin than provided by crystallographic analysis alone. The simulations confirm that in the unliganded structures water molecules tend to occupy the positions occupied by carbohydrate oxygens in the lectin-carbohydrate complexes. Population distributions in simulations of the free lectin, the ligands, and the complexes indicate a combination of conformational selection and induced fit. Proteins 2009; 77:760-777.

Dependence of pH and surfactant effect in the synthesis of magnetite(Fe3O4) nanoparticles and its properties

Nanoparticles of Fe3O4 were synthesized by co-precipitation in an aqueous solution containing ferrous and ferric salts (1:2) at varying pH with ammonia as a base. It was found that the value of pH influences the reaction mechanism for the formation of Fe3O4. Furthermore, the addition of mercaptoethanol significantly reduced the crystalline size of Fe3O4 nanoparticles from 15.03 to 8.02 nm. X-ray diffraction (XRD) spectra revealed that the synthesized nanoparticles were epsilon-Fe2O3 or Fe3O4 phase. To further prove the composition of the product, as-prepared Fe3O4 were examined by X-rayphotoelectron spectroscopy (XPS). Magnetic properties of the obtained particles were determined by vibrating sample magnetometer (VSM). Further analysis of the X-ray studies shows that while maintaining a pH value of 6 and 9 in a solution containing iron salts II and III ions produces epsilon-Fe2O3. Whereas a pH value of 11 produces magnetite (Fe3O4) phase. All of these results show that the pH has a major role in the observed phase formation of (Fe3O4) nanoparticles.

Relationship between annual rainfall and tree mortality in a tropical dry forest: Results of a 19-year study at Mudumalai, southern India

Variability in rainfall is known to be a major influence on the dynamics of tropical forests, especially rates and patterns of tree mortality. In tropical dry forests a number of contributing factors to tree mortality, including dry season fire and herbivory by large herbivorous mammals, could be related to rainfall patterns, while loss of water potential in trees during the dry season or a wet season drought could also result in enhanced rates of death. While tree mortality as influenced by severe drought has been examined in tropical wet forests there is insufficient understanding of this process in tropical dry forests. We examined these causal factors in relation to inter-annual differences in rainfall in causing tree mortality within a 50-ha Forest Dynamics Plot located in the tropical dry deciduous forests of Mudumalai, southern India, that has been monitored annually since 1988. Over a 19-year period (1988-2007) mean annual mortality rate of all stems >1 cm dbh was 6.9 +/- 4.6% (range = 1.5-17.5%); mortality rates broadly declined from the smaller to the larger size classes with the rates in stems >30 cm dbh being among the lowest recorded in tropical forest globally. Fire was the main agent of mortality in stems 1-5 cm dbh, elephant-herbivory in stems 5-10 cm dbh, and other natural causes in stems > 10 cm dbh. Elephant-related mortality did not show any relationship to rainfall. On the other hand, fire-related mortality was significantly negatively correlated to quantity of rainfall during the preceding year. Mortality due to other causes in the larger stem sizes was significantly negatively correlated to rainfall with a 2-3-year lag, suggesting that water deficit from mild or prolonged drought enhanced the risk of death but only with a time lag that was greater than similar lags in tree mortality observed in other forest types. In this respect, tropical dry forests growing in regions of high rainfall variability may have evolved greater resistance to rainfall deficit as compared to tropical moist or temperate forests but are still vulnerable to drought-related mortality.

Translational fusion of two beta-subunits of human chorionic gonadotropin results in production of a novel antagonist of

The strategy of translationally fusing the alpha-and beta-subunits of human chorionic gonadotropin (hCG) into a single-chain molecule has been used to produce novel analogs of hCG. Previously we reported expression of a biologically active singlechain analog hCG alpha beta expressed using Pichia expression system. Using the same expression system, another analog, in which the alpha-subunit was replaced with the second beta-subunit, was expressed (hCG beta beta) and purified. hCG beta beta could bind to LH receptor with an affinity three times lower than that of hCG but failed to elicit any response. However, it could inhibit response to the hormone in vitro in a dose- dependent manner. Furthermore, it inhibited response to hCG in vivo indicating the antagonistic nature of the analog. However, it was unable inhibit human FSH binding or response to human FSH, indicating the specificity of the effect. Characterization of hCG alpha beta and hCG beta beta using immunological tools showed alterations in the conformation of some of the epitopes, whereas others were unaltered. Unlike hCG, hCG beta beta interacts with two LH receptor molecules. These studies demonstrate that the presence of the second beta-subunit in the single-chain molecule generated a structure that can be recognized by the receptor. However, due to the absence of alpha-subunit, the molecule is unable to elicit response. The strategy of fusing two beta-subunits of glycoprotein hormones can be used to produce antagonists of these hormones.

Aerosol characteristics and radiative impacts over the Arabian Sea during the intermonsoon season: Results from ARMEX field campaign

During the second phase of the Arabian Sea Monsoon Experiment (ARMEX-II), extensive measurements of spectral aerosol optical depth, mass concentration, and mass size distribution of ambient aerosols as well as mass concentration of aerosol black carbon (BC) were made onboard a research vessel during the intermonsoon period (i.e., when the monsoon winds are in transition from northeasterlies to westerlies/ southwesterlies) over the Arabian Sea (AS) adjoining the Indian Peninsula. Simultaneous measurements of spectral aerosol optical depths (AODs) were made at different regions over the adjoining Indian landmass. Mean AODs (at 500-nm wavelength) over the ocean (similar to0.44) were comparable to those over the coastal land (similar to0.47), but were lower than the values observed over the plateau regions of central Indian Peninsula (similar to0.61). The aerosol properties were found to respond distinctly with respect to change in the trajectories, with higher optical depths and flatter AOD spectra associated with trajectories indicating advection from west Asia, and northwest and west-coastal India. On average, BC constituted only similar to2.2% to total aerosol mass compared to the climatological values of similar to6% over the coastal land during the same season. These data are used to characterize the physical properties of aerosols and to assess the resulting short-wave direct aerosol forcing. The mean values were similar to27 W m(-2) at the surface and -12 W m(-2) at the top of the atmosphere (TOA), resulting in a net atmospheric forcing of +15 W m(-2). The forcing also depended on the region from where the advection predominates. The surface and atmospheric forcing were in the range -40 to -57 W m(-2) and +27 to +39 W m(-2), respectively, corresponding to advection from the west Asian and western coastal India where they were as low as -19 and +10 W m(-2), respectively, when the advection was mainly from the Bay of Bengal and from central/peninsular India. In all these cases, the net atmospheric forcing (heating) efficiency was lower than the values reported for northern Indian Ocean during northern winter, which is attributed to the reduced BC mass fraction.

Discovering user preferences by using time entries in click-through data to improve search engine results

The search engine log files have been used to gather direct user feedback on the relevancy of the documents presented in the results page. Typically the relative position of the clicks gathered from the log files is used a proxy for the direct user feedback. In this paper we identify reasons for the incompleteness of the relative position of clicks for deciphering the user preferences. Hence, we propose the use of time spent by the user in reading through the document as indicative of user preference for a document with respect to a query. Also, we identify the issues involved in using the time measure and propose means to address them.

Development and transient performance results of a single stage activated carbon - HFC 134a closed cycle adsorption cooling system

A laboratory model of a thermally driven adsorption refrigeration system with activated carbon as the adsorbent and 1,1,1,2-tetrafluoroethane (HFC 134a) as the refrigerant was developed. The single stage compression system has an ensemble of four adsorbers packed with Maxsorb II specimen of activated carbon that provide a near continuous flow which caters to a cooling load of up to 5W in the 5-18 degrees C region. The objective was to utilise the low grade thermal energy to drive a refrigeration system that can be used to cool some critical electronic components. The laboratory model was tested for it performance at various cooling loads with the heat source temperature from 73 to 93 degrees C. The pressure transients during heating and cooling phases were traced. The cyclic steady state and transient performance data are presented. (C) 2010 Elsevier Ltd. All rights reserved.

Electronic structures of electron donor-acceptor complexes: results from ultraviolet photoelectron spectroscopy and molecular orbital calculations

HeI photoelectron spectra of 1:1 electron donor-acceptor complexes are discussed in the light of molecular orbital calculations. The complexes discussed include those formed by BH3, BF3 and SO2. Some systematics have been found in the ionization energy shifts of the complexes compared to the free components and these are related to the strength of the donor-acceptor bond. Hel spectra of hydrogen bonded complexes are discussed in comparison with results from MO calculations. Limitations of such studies as well as scope for further investigations are indicated.

Hardness of approximation results for the problem of finding the stopping distance in Tanner graphs

Tanner Graph representation of linear block codes is widely used by iterative decoding algorithms for recovering data transmitted across a noisy communication channel from errors and erasures introduced by the channel. The stopping distance of a Tanner graph T for a binary linear block code C determines the number of erasures correctable using iterative decoding on the Tanner graph T when data is transmitted across a binary erasure channel using the code C. We show that the problem of finding the stopping distance of a Tanner graph is hard to approximate within any positive constant approximation ratio in polynomial time unless P = NP. It is also shown as a consequence that there can be no approximation algorithm for the problem achieving an approximation ratio of 2(log n)(1-epsilon) for any epsilon > 0 unless NP subset of DTIME(n(poly(log n))).

Elimination of cross-talk in diffuse optical tomographic reconstructions through a weighted update procedure: results of simulation study - art. no. 61640S

Reconstructions in optical tomography involve obtaining the images of absorption and reduced scattering coefficients. The integrated intensity data has greater sensitivity to absorption coefficient variations than scattering coefficient. However, the sensitivity of intensity data to scattering coefficient is not zero. We considered an object with two inhomogeneities (one in absorption and the other in scattering coefficient). The standard iterative reconstruction techniques produced results, which were plagued by cross talk, i.e., the absorption coefficient reconstruction has a false positive corresponding to the location of scattering inhomogeneity, and vice-versa. We present a method to remove cross talk in the reconstruction, by generating a weight matrix and weighting the update vector during the iteration. The weight matrix is created by the following method: we first perform a simple backprojection of the difference between the experimental and corresponding homogeneous intensity data. The built up image has greater weightage towards absorption inhomogeneity than the scattering inhomogeneity and its appropriate inverse is weighted towards the scattering inhomogeneity. These two weight matrices are used as multiplication factors in the update vectors, normalized backprojected image of difference intensity for absorption inhomogeneity and the inverse of the above for the scattering inhomogeneity, during the image reconstruction procedure. We demonstrate through numerical simulations, that cross-talk is fully eliminated through this modified reconstruction procedure.

As-deposited near-single crystalline high Tc and Jc superconducting thin films by a pulsed lased deposition process

As-deposited high Tc superconducting Y1Ba2Cu3O7−x films with zero resistance temperatures of similar, equals89 K and critical current densities about 0.7×106 A/cm2 at 77 K have been reproducibly fabricated at a substrate holder temperature at 650°C, using pulsed laser deposition, without post-annealing. One key to these results is the injection of gaseous oxygen into laser produced plume just in front of the target. In this way, the correct amount of oxygen is incorporated into the as-grown film so that post-deposition treatment becomes unnecessary. Axial ion channeling in these as-deposit high Tc superconducting films on (100) SrTiO3 and X-ray photoelectron spectroscopy (XPS) on the film surfaces were performed. Angular yield profile near the film surface for Ba, and the surface peak intensity were measured using 3 MeV He ions. For channeling normal to the substrate a minimum yield of 7%, compared to similar, equals3% for single crystals, was obtained. The results of ion channeling and XPS studies indicate that the as-deposited films have good crystallinity as well as toichiometry to within similar, equals1 nm of the film surface. The in-situ growth of such high Tc and Jc films is an important step in the use of the laser deposition technique to fabricate multilayer structures and the surface perfection is of importance in tunneling devices such as Josephson junctions.

Information Theoretic Results for Three-User Cognitive Channels

In this paper, we introduce the three-user cognitive radio channels with asymmetric transmitter cooperation, and derive achievable rate regions under several scenarios depending on the type of cooperation and decoding capability at the receivers. Two of the most natural cooperation mechanisms for the three-user channel are considered here: cumulative message sharing (CMS) and primary-only message sharing (PMS). In addition to the message sharing mechanism, the achievable rate region is critically dependent on the decoding capability at the receivers. Here, we consider two scenarios for the decoding capability, and derive an achievable rate region for each one of them by employing a combination of superposition and Gel'fand-Pinsker coding techniques. Finally, to provide a numerical example, we consider the Gaussian channel model to plot the rate regions. In terms of achievable rates, CMS turns out to be a better scheme than PMS. However, the practical aspects of implementing such message-sharing schemes remain to be investigated.

Diesel Engine Driven Stand-Alone Variable Speed Constant Frequency Slip Ring Induction Generator - Theory and Experimental Results

The operation of a stand-alone, as opposed to grid connected generation system, using a slip-ring induction machine as the electrical generator, is considered. In contrast to an alternator, a slip-ring induction machine can run at variable speed and still deliver constant frequency power to loads. This feature enables optimization of the system when the prime mover is inherently variable speed in nature eg. wind turbines, as well as diesel driven systems, where there is scope for economizing on fuel consumption. Experimental results from a system driven by a 44 bhp diesel engine are presented. Operation at subsynchronous as well as super-synchronous speeds is examined. The measurement facilitates the understanding of the system as well as its design.

XPS evidence for molecular charge-transfer doping of graphene

By employing X-ray photoelectron spectroscopy (XPS), we have been able to establish the occurrence of charge-transfer doping in few-layer graphene covered with electron acceptor (TCNE) and donor (TTF) molecules. We have performed quantitative estimates of the extent of charge transfer in these complexes and elucidated the origin of unusual shifts of their Raman G-bands and explained the differences in the dependence of conductivity on n- and p-doping. The study unravels the cause of the apparent difference between the charge-transfer doping and electrochemical doping. (C) 2010 Elsevier B.V. All rights reserved.