Steam reforming on transition-metal carbides from density-functional theory

A screening study of the steam reforming reaction (CH_4 + H_2O -> CO + 3H_2) on early transition-metal carbides (TMC's) is performed by means of density-functional theory calculations. The set of considered surfaces includes the alpha-Mo_2C(100) surfaces, the low-index (111) and (100) surfaces of TiC, VC, and delta-MoC, and the oxygenated alpha-Mo_2C(100) and TMC(111) surfaces. It is found that carbides provide a wide spectrum of reactivities towards the steam reforming reaction, from too reactive via suitable to too inert. The reactivity is discussed in terms of the electronic structure of the clean surfaces. Two surfaces, the delta-MoC(100) and the oxygen passivated alpha-Mo_2C(100) surfaces, are identified as promising steam reforming catalysts. These findings suggest that carbides provide a playground for reactivity tuning, comparable to the one for pure metals.Comment: 6 pages, 4 figure

Moisture transport by Atlantic tropical cyclones onto the North American continent

Tropical Cyclones (TCs) are an important source of freshwater for the North American continent. Many studies have tried to estimate this contribution by identifying TC-induced precipitation events, but few have explicitly diagnosed the moisture fluxes across continental boundaries. We design a set of attribution schemes to isolate the column-integrated moisture fluxes that are directly associated with TCs and to quantify the flux onto the North American Continent due to TCs. Averaged over the 2004–2012 hurricane seasons and integrated over the western, southern and eastern coasts of North America, the seven schemes attribute 7 to 18 % (mean 14 %) of total net onshore flux to Atlantic TCs. A reduced contribution of 10 % (range 9 to 11 %) was found for the 1980–2003 period, though only two schemes could be applied to this earlier period. Over the whole 1980–2012 period, a further 8 % (range 6 to 9 % from two schemes) was attributed to East Pacific TCs, resulting in a total TC contribution of 19 % (range 17 to 22 %) to the ocean-to-land moisture transport onto the North American continent between May and November. Analysis of the attribution uncertainties suggests that incorporating details of individual TC size and shape adds limited value to a fixed radius approach and TC positional errors in the ERA-Interim reanalysis do not affect the results significantly, but biases in peak wind speeds and TC sizes may lead to underestimates of moisture transport. The interannual variability does not appear to be strongly related to the El Nino-Southern Oscillation phenomenon

Non-Equilibrium Field Dynamics of an Honest Holographic Superconductor

Most holographic models of superconducting systems neglect the effects of dynamical boundary gauge fields during the process of spontaneous symmetry-breaking. Usually a global symmetry gets broken. This yields a superfluid, which then is gauged "weakly" afterwards. In this work we build (and probe the dynamics of) a holographic model in which a local boundary symmetry is spontaneously broken instead. We compute two-point functions of dynamical non-Abelian gauge fields in the normal and in the broken phase, and find non-trivial gapless modes. Our AdS3 gravity dual realizes a p-wave superconductor in (1+1) dimensions. The ground state of this model also breaks (1+1)-dimensional parity spontaneously, while the Hamiltonian is parity-invariant. We discuss possible implications of our results for a wider class of holographic liquids.Comment: 32 pages, 12 figures; v3: string theory derivation of setup added (section 3.1), improved presentation, version accepted by JHEP; v2: paragraph added to discussion, figure added, references added, typos correcte

Structural and magnetic phase diagram of CeFeAsO1-xFx and its relationship to high-temperature superconductivity

We use neutron scattering to study the structural and magnetic phase transitions in the iron pnictides CeFeAsO1-xFx as the system is tuned from a semimetal to a high-transition-temperature (high-Tc) superconductor through Fluorine (F) doping x. In the undoped state, CeFeAsO develops a structural lattice distortion followed by a stripe like commensurate antiferromagnetic order with decreasing temperature. With increasing Fluorine doping, the structural phase transition decreases gradually while the antiferromagnetic order is suppressed before the appearance of superconductivity, resulting an electronic phase diagram remarkably similar to that of the high-Tc copper oxides. Comparison of the structural evolution of CeFeAsO1-xFx with other Fe-based superconductors reveals that the effective electronic band width decreases systematically for materials with higher Tc. The results suggest that electron correlation effects are important for the mechanism of high-Tc superconductivity in these Fe pnictides.Comment: 19 pages, 5 figure

Rudimentary G-Quadruplex-Based Telomere Capping In Saccharomyces Cerevisiae

Telomere capping conceals chromosome ends from exonucleases and checkpoints, but the full range of capping mechanisms is not well defined. Telomeres have the potential to form G-quadruplex (G4) DNA, although evidence for telomere G4 DNA function in vivo is limited. In budding yeast, capping requires the Cdc13 protein and is lost at nonpermissive temperatures in cdc13-1 mutants. Here, we use several independent G4 DNA-stabilizing treatments to suppress cdc13-1 capping defects. These include overexpression of three different G4 DNA binding proteins, loss of the G4 DNA unwinding helicase Sgs1, or treatment with small molecule G4 DNA ligands. In vitro, we show that protein-bound G4 DNA at a 3\u27 overhang inhibits 5\u27-\u3e 3\u27 resection of a paired strand by exonuclease I. These findings demonstrate that, at least in the absence of full natural capping, G4 DNA can play a positive role at telomeres in vivo

Chemoproteomics reveals Toll-like receptor fatty acylation

Partial funding for Open Access provided by The Ohio State University Open Access Fund.Background: Palmitoylation is a 16-carbon lipid post-translational modification that increases protein hydrophobicity. This form of protein fatty acylation is emerging as a critical regulatory modification for multiple aspects of cellular interactions and signaling. Despite recent advances in the development of chemical tools for the rapid identification and visualization of palmitoylated proteins, the palmitoyl proteome has not been fully defined. Here we sought to identify and compare the palmitoylated proteins in murine fibroblasts and dendritic cells. Results: A total of 563 putative palmitoylation substrates were identified, more than 200 of which have not been previously suggested to be palmitoylated in past proteomic studies. Here we validate the palmitoylation of several new proteins including Toll-like receptors (TLRs) 2, 5 and 10, CD80, CD86, and NEDD4. Palmitoylation of TLR2, which was uniquely identified in dendritic cells, was mapped to a transmembrane domain-proximal cysteine. Inhibition of TLR2 S-palmitoylation pharmacologically or by cysteine mutagenesis led to decreased cell surface expression and a decreased inflammatory response to microbial ligands. Conclusions: This work identifies many fatty acylated proteins involved in fundamental cellular processes as well as cell type-specific functions, highlighting the value of examining the palmitoyl proteomes of multiple cell types. Spalmitoylation of TLR2 is a previously unknown immunoregulatory mechanism that represents an entirely novel avenue for modulation of TLR2 inflammatory activity.This work was supported by funding from the NIH/NIAID (grant R00AI095348 to J.S.Y.), the NIH/NIGMS (R01GM087544 to HCH), and the Ohio State University Public Health Preparedness for Infectious Diseases (PHPID) program. NMC is supported by the Ohio State University Systems and Integrative Biology Training Program (NIH/NIGMS grant T32GM068412). BWZ is a fellow of the National Science Foundation Graduate Research Fellowship Program (DGE-0937362)

Control of intestinal stem cell function and proliferation by mitochondrial pyruvate metabolism.

Most differentiated cells convert glucose to pyruvate in the cytosol through glycolysis, followed by pyruvate oxidation in the mitochondria. These processes are linked by the mitochondrial pyruvate carrier (MPC), which is required for efficient mitochondrial pyruvate uptake. In contrast, proliferative cells, including many cancer and stem cells, perform glycolysis robustly but limit fractional mitochondrial pyruvate oxidation. We sought to understand the role this transition from glycolysis to pyruvate oxidation plays in stem cell maintenance and differentiation. Loss of the MPC in Lgr5-EGFP-positive stem cells, or treatment of intestinal organoids with an MPC inhibitor, increases proliferation and expands the stem cell compartment. Similarly, genetic deletion of the MPC in Drosophila intestinal stem cells also increases proliferation, whereas MPC overexpression suppresses stem cell proliferation. These data demonstrate that limiting mitochondrial pyruvate metabolism is necessary and sufficient to maintain the proliferation of intestinal stem cells

Electronic Origin of High Temperature Superconductivity in Single-Layer FeSe Superconductor

The latest discovery of high temperature superconductivity signature in single-layer FeSe is significant because it is possible to break the superconducting critical temperature ceiling (maximum Tc~55 K) that has been stagnant since the discovery of Fe-based superconductivity in 2008. It also blows the superconductivity community by surprise because such a high Tc is unexpected in FeSe system with the bulk FeSe exhibiting a Tc at only 8 K at ambient pressure which can be enhanced to 38 K under high pressure. The Tc is still unusually high even considering the newly-discovered intercalated FeSe system A_xFe_{2-y}Se_2 (A=K, Cs, Rb and Tl) with a Tc at 32 K at ambient pressure and possible Tc near 48 K under high pressure. Particularly interesting is that such a high temperature superconductivity occurs in a single-layer FeSe system that is considered as a key building block of the Fe-based superconductors. Understanding the origin of high temperature superconductivity in such a strictly two-dimensional FeSe system is crucial to understanding the superconductivity mechanism in Fe-based superconductors in particular, and providing key insights on how to achieve high temperature superconductivity in general. Here we report distinct electronic structure associated with the single-layer FeSe superconductor. Its Fermi surface topology is different from other Fe-based superconductors; it consists only of electron pockets near the zone corner without indication of any Fermi surface around the zone center. Our observation of large and nearly isotropic superconducting gap in this strictly two-dimensional system rules out existence of node in the superconducting gap. These results have provided an unambiguous case that such a unique electronic structure is favorable for realizing high temperature superconductivity

Controlling Cherenkov angles with resonance transition radiation

Cherenkov radiation provides a valuable way to identify high energy particles in a wide momentum range, through the relation between the particle velocity and the Cherenkov angle. However, since the Cherenkov angle depends only on material's permittivity, the material unavoidably sets a fundamental limit to the momentum coverage and sensitivity of Cherenkov detectors. For example, Ring Imaging Cherenkov detectors must employ materials transparent to the frequency of interest as well as possessing permittivities close to unity to identify particles in the multi GeV range, and thus are often limited to large gas chambers. It would be extremely important albeit challenging to lift this fundamental limit and control Cherenkov angles as preferred. Here we propose a new mechanism that uses constructive interference of resonance transition radiation from photonic crystals to generate both forward and backward Cherenkov radiation. This mechanism can control Cherenkov angles in a flexible way with high sensitivity to any desired range of velocities. Photonic crystals thus overcome the severe material limit for Cherenkov detectors, enabling the use of transparent materials with arbitrary values of permittivity, and provide a promising option suited for identification of particles at high energy with enhanced sensitivity.Comment: There are 16 pages and 4 figures for the manuscript. Supplementary information with 18 pages and 5 figures, appended at the end of the file with the manuscript. Source files in Word format converted to PDF. Submitted to Nature Physic