Hydrogen electrooxidation under conditions of high mass transport in room-temperature ionic liquids and the role of underpotential-deposited hydrogen

The hydrogen oxidation reaction (HOR), an electrocatalytic reaction of fundamental and applied interest, was studied in the protic ionic liquid (PIL) diethylmethylammonium trifluoromethanesulfonate, [dema][TfO], at Pt electrodes using rotating disk electrode (RDE) and ultramicroelectrode (UME) voltammetry. A steady-state HOR current is observed during RDE voltammetry at overpotentials > 50 mV but an additional plateau is observed in the overpotential region 50-200 mV when using UMEs. The difference in voltammetric responses is attributed to higher rate of mass transport to the UME than to the RDE. Three models have been used to fit the experimental data. The first is a dual-pathway model, which assumes that the Tafel-Volmer and Heyrovsky-Volmer pathways are both active over the potential range of interest and no blockage of catalytic sites occurs during the reaction. The second is a dual-pathway model, which assumes that reaction intermediates block access of H2 to catalytic sites. The third is based on the premise that underpotential-deposited hydrogen atoms (Hupd) can block adsorption and electrooxidation of H2 at the Pt surface. While each model fits the polarisation curves reasonably well, detailed analysis suggests that the Hupd- blocking model describes the responses better. To the best of our knowledge, this work is the first to demonstrate the advantages of UME voltammetry over RDE voltammetry for studying electrocatalytic reactions in PILs, and the first to show that Hupd can inhibit an electrocatalytic reactions in an ionic liquid, a factor that may become important as the technological applications of these liquids increase

Open questions in the study of population III star formation

The first stars were key drivers of early cosmic evolution. We review the main physical elements of the current consensus view, positing that the first stars were predominantly very massive. We continue with a discussion of important open questions that confront the standard model. Among them are uncertainties in the atomic and molecular physics of the hydrogen and helium gas, the multiplicity of stars that form in minihalos, and the possible existence of two separate modes of metal-free star formation.Comment: 15 pages, 2 figures. To appear in the conference proceedings for IAU Symposium 255: Low-Metallicity Star Formation: From the First Stars to Dwarf Galaxie

Enhanced and tunable optical quantum efficiencies from plasmon bandwidth engineering in bimetallic CoAg nanoparticles

Plasmonic nanoparticles are amongst the most effective ways to resonantly couple optical energy into and out of nanometer sized volumes. However, controlling and/or tuning the transfer of this incident energy to the surrounding near and far field is one of the most interesting challenges in this area. Due to the dielectric properties of metallic silver (Ag), its nanoparticles have amongst the highest radiative quantum efficiencies (η), i.e., the ability to radiatively transfer the incident energy to the surrounding. Here we report the discovery that bimetallic nanoparticles of Ag made with immiscible and plasmonically weak Co metal can show comparable and/or even higher η values. The enhancement is a result of the narrowing of the plasmon bandwidth from these bimetal systems. The phenomenological explanation of this effect based on the dipolar approximation points to the reduction in radiative losses within the Ag nanoparticles when in contact with cobalt. This is also supported by a model of coupling between poor and good conductors based on the surface to volume ratio. This study presents a new type of bandwidth engineering, one based on using bimetalnanostructures, to tune and/or enhance the quality factor and quantum efficiency for near and far-field plasmonic applications

Theory for the Ultrafast Structural Response of optically excited small clusters: Time-dependence of the Ionization Potential

Combining an electronic theory with molecular dynamics simulations we present results for the ultrafast structural changes in small clusters. We determine the time scale for the change from the linear to a triangular structure after the photodetachment process Ag$_3^- \rightarrow {\rm Ag}_3$. We show that the time-dependent change of the ionization potential reflects in detail the internal degrees of freedom, in particular coherent and incoherent motion, and that it is sensitive to the initial temperature. We compare with experiment and point out the general significance of our results.Comment: 10 pages, Revtex, 3 postscript figure

Three-Dimensionally Engineered Normal Human Lung Tissue-Like Assemblies: Target Tissues for Human Respiratory Viral Infections

In vitro three-dimensional (3D) human lung epithelio-mesenchymal tissue-like assemblies (3D hLEM TLAs) from this point forward referred to as TLAs were engineered in Rotating Wall Vessel (RWV) technology to mimic the characteristics of in vivo tissues thus providing a tool to study human respiratory viruses and host cell interactions. The TLAs were bioengineered onto collagen-coated cyclodextran microcarriers using primary human mesenchymal bronchial-tracheal cells (HBTC) as the foundation matrix and an adult human bronchial epithelial immortalized cell line (BEAS-2B) as the overlying component. The resulting TLAs share significant characteristics with in vivo human respiratory epithelium including polarization, tight junctions, desmosomes, and microvilli. The presence of tissue-like differentiation markers including villin, keratins, and specific lung epithelium markers, as well as the production of tissue mucin, further confirm these TLAs differentiated into tissues functionally similar to in vivo tissues. Increasing virus titers for human respiratory syncytial virus (wtRSVA2) and the detection of membrane bound glycoproteins over time confirm productive infection with the virus. Therefore, we assert TLAs mimic aspects of the human respiratory epithelium and provide a unique capability to study the interactions of respiratory viruses and their primary target tissue independent of the host s immune system

Branching ratios for the beta decay of 21Na

We have measured the beta-decay branching ratio for the transition from 21Na to the first excited state of 21Ne. A recently published test of the standard model, which was based on a measurement of the beta-nu correlation in the decay of 21Na, depended on this branching ratio. However, until now only relatively imprecise (and, in some cases, contradictory) values existed for it. Our new result, 4.74(4)%, reduces but does not remove the reported discrepancy with the standard model.Comment: Revtex4, 2 fig

Nonlinear software sensor for monitoring genetic regulation processes with noise and modeling errors

Nonlinear control techniques by means of a software sensor that are commonly used in chemical engineering could be also applied to genetic regulation processes. We provide here a realistic formulation of this procedure by introducing an additive white Gaussian noise, which is usually found in experimental data. Besides, we include model errors, meaning that we assume we do not know the nonlinear regulation function of the process. In order to illustrate this procedure, we employ the Goodwin dynamics of the concentrations [B.C. Goodwin, Temporal Oscillations in Cells, (Academic Press, New York, 1963)] in the simple form recently applied to single gene systems and some operon cases [H. De Jong, J. Comp. Biol. 9, 67 (2002)], which involves the dynamics of the mRNA, given protein, and metabolite concentrations. Further, we present results for a three gene case in co-regulated sets of transcription units as they occur in prokaryotes. However, instead of considering their full dynamics, we use only the data of the metabolites and a designed software sensor. We also show, more generally, that it is possible to rebuild the complete set of nonmeasured concentrations despite the uncertainties in the regulation function or, even more, in the case of not knowing the mRNA dynamics. In addition, the rebuilding of concentrations is not affected by the perturbation due to the additive white Gaussian noise and also we managed to filter the noisy output of the biological systemComment: 21 pages, 7 figures; also selected in vjbio of August 2005; this version corrects a misorder in the last three references of the published versio

Sites of Biosynthesis of Outer and Inner Membrane Proteins of Neurospora crassa Mitochondria

Outer and inner membranes of Neurospora crassa mitochondria were separated by the combined swelling, shrinking, sonication procedure. Membranes were characterized by electron microscopy and by marker enzyme activities. A red carotenoid pigment was found to be concentrated in the outer membrane. The inner mitochondrial membrane was resolved into about 20 protein bands on polyacrylamide gel electrophoresis, whereas the outer membrane shows essentially one single protein band. Only negligible incorporation of radioactive amino acids occurs into outer membrane when isolated mitochondria are synthesizing polypeptide chains. In agreement with this observation labeling of outer membrane protein is almost entirely blocked, when whole Neurospora cells are incubated with radioactive amino acids in the presence of cycloheximide, an inhibitor of cytoplasmic protein synthesis. Finally, the essential electrophoretic protein band from outer membrane does not become labeled when mitochondria are incubated with radioactive amino acids either in vitro or in vivo in the presence of cycloheximide. It is concluded that the vast majority, if not all, of the outer membrane protein is synthesized by the cytoplasmic system and that polypeptide chains formed by the mitochondrial ribosomes are integrated into the inner mitochondrial membrane

Diffusion of hydrogen in crystalline silicon

The coefficient of diffusion of hydrogen in crystalline silicon is calculated using tight-binding molecular dynamics. Our results are in good quantitative agreement with an earlier study by Panzarini and Colombo [Phys. Rev. Lett. 73, 1636 (1994)]. However, while our calculations indicate that long jumps dominate over single hops at high temperatures, no abrupt change in the diffusion coefficient can be observed with decreasing temperature. The (classical) Arrhenius diffusion parameters, as a consequence, should extrapolate to low temperatures.Comment: 4 pages, including 5 postscript figures; submitted to Phys. Rev. B Brief Repor