Metal–Support Interactions in Heterogeneous Catalysis: DFT Calculations on the Interaction of Copper Nanoparticles with Magnesium Oxide

Oxide supports play an important role in enhancing the catalytic properties of transition metal nanoparticles in heterogeneous catalysis. How extensively interactions between the oxide support and the nanoparticles impact the electronic structure as well as the surface properties of the nanoparticles is hence of high interest. In this study, the influence of a magnesium oxide support on the properties of copper nanoparticles with different size, shape, and adsorption sites is investigated using density functional theory (DFT) calculations. By proposing simple models to reduce the cost of the calculations while maintaining the accuracy of the results, we show using the nonreducible oxide support MgO as an example that there is no significant influence of the MgO support on the electronic structure of the copper nanoparticles, with the exception of adsorption directly at the Cu–MgO interface. We also propose a simplified methodology that allows us to reduce the cost of the calculations, while the accuracy of the results is maintained. We demonstrate in addition that the Cu nanowire model corresponds well to the nanoparticle model, which reduces the computational cost even further

The chemistry of C3 & Carbon Chain Molecules in DR21(OH)

(Abridged) We have observed velocity resolved spectra of four ro-vibrational far-infrared transitions of C3 between the vibrational ground state and the low-energy nu2 bending mode at frequencies between 1654--1897 GHz using HIFI on board Herschel, in DR21(OH), a high mass star forming region. Several transitions of CCH and c-C3H2 have also been observed with HIFI and the IRAM 30m telescope. A gas and grain warm-up model was used to identify the primary C3 forming reactions in DR21(OH). We have detected C3 in absorption in four far-infrared transitions, P(4), P(10), Q(2) and Q(4). The continuum sources MM1 and MM2 in DR21(OH) though spatially unresolved, are sufficiently separated in velocity to be identified in the C3 spectra. All C3 transitions are detected from the embedded source MM2 and the surrounding envelope, whereas only Q(4) & P(4) are detected toward the hot core MM1. The abundance of C3 in the envelope and MM2 is \sim6x10^{-10} and \sim3x10^{-9} respectively. For CCH and c-C3H2 we only detect emission from the envelope and MM1. The observed CCH, C3, and c-C3H2 abundances are most consistent with a chemical model with n(H2)\sim5x10^{6} cm^-3 post-warm-up dust temperature, T_max =30 K and a time of \sim0.7-3 Myr. Post warm-up gas phase chemistry of CH4 released from the grain at t\sim 0.2 Myr and lasting for 1 Myr can explain the observed C3 abundance in the envelope of DR21(OH) and no mechanism involving photodestruction of PAH molecules is required. The chemistry in the envelope is similar to the warm carbon chain chemistry (WCCC) found in lukewarm corinos. The observed lower C3 abundance in MM1 as compared to MM2 and the envelope could be indicative of destruction of C3 in the more evolved MM1. The timescale for the chemistry derived for the envelope is consistent with the dynamical timescale of 2 Myr derived for DR21(OH) in other studies.Comment: 11 Pages, 6 figures, accepted for publication in A&

Detection of hydrogen fluoride absorption in diffuse molecular clouds with Herschel/HIFI: a ubiquitous tracer of molecular gas

We discuss the detection of absorption by interstellar hydrogen fluoride (HF) along the sight line to the submillimeter continuum sources W49N and W51. We have used Herschel's HIFI instrument in dual beam switch mode to observe the 1232.4762 GHz J = 1 - 0 HF transition in the upper sideband of the band 5a receiver. We detected foreground absorption by HF toward both sources over a wide range of velocities. Optically thin absorption components were detected on both sight lines, allowing us to measure - as opposed to obtain a lower limit on - the column density of HF for the first time. As in previous observations of HF toward the source G10.6-0.4, the derived HF column density is typically comparable to that of water vapor, even though the elemental abundance of oxygen is greater than that of fluorine by four orders of magnitude. We used the rather uncertain N(CH)-N(H2) relationship derived previously toward diffuse molecular clouds to infer the molecular hydrogen column density in the clouds exhibiting HF absorption. Within the uncertainties, we find that the abundance of HF with respect to H2 is consistent with the theoretical prediction that HF is the main reservoir of gas-phase fluorine for these clouds. Thus, hydrogen fluoride has the potential to become an excellent tracer of molecular hydrogen, and provides a sensitive probe of clouds of small H2 column density. Indeed, the observations of hydrogen fluoride reported here reveal the presence of a low column density diffuse molecular cloud along the W51 sight line, at an LSR velocity of ~ 24kms-1, that had not been identified in molecular absorption line studies prior to the launch of Herschel.Comment: 4 pages, 3 figures, A&A Letter special issue, accepted on 07/13/201

The Principle Of Local Rotational Invariance And The Coexistence Of Magnetism, Charge And Superconductivity

We propose a macroscopic description of the superconducting state in presence of an applied external magnetic field in terms of first order differential equations. They describe a corrugated two-component order parameter intertwined with a spin-charged background, caused by spin correlations and charged dislocations. The first order differential equations are a consequence of a Weitzenb\"ock-Liechnorowitz identity which renders a SUL(2) \otimes UL(1) invariant ground state, based on (L) local rotational and electromagnetic gauge symmetry. The proposal is based on a long ago developed formalism by \'Elie Cartan to investigate curved spaces, viewed as a collection of small Euclidean granules that are translated and rotated with respect to each other. \'Elie Cartan's formalism unveils the principle of local rotational invariance as a gauge symmetry because the global SU(2) invariance of the order parameter is turned local by the interlacement of spin and charge to pairing.Comment: 19 pages, 3 figure

Nitrogen hydrides in interstellar gas: Herschel/HIFI observations towards G10.6-0.4 (W31C)

The HIFI instrument on board the Herschel Space Observatory has been used to observe interstellar nitrogen hydrides along the sight-line towards G10.6-0.4 in order to improve our understanding of the interstellar chemistry of nitrogen. We report observations of absorption in NH N=1-0, J=2-1 and ortho-NH2 1_1,1-0_0,0. We also observed ortho-NH3 1_0-0_0, and 2_0-1_0, para-NH3 2_1-1_1, and searched unsuccessfully for NH+. All detections show emission and absorption associated directly with the hot-core source itself as well as absorption by foreground material over a wide range of velocities. All spectra show similar, non-saturated, absorption features, which we attribute to diffuse molecular gas. Total column densities over the velocity range 11-54 km/s are estimated. The similar profiles suggest fairly uniform abundances relative to hydrogen, approximately 6*10^-9, 3*10^-9, and 3*10^-9 for NH, NH2, and NH3, respectively. These abundances are discussed with reference to models of gas-phase and surface chemistry.Comment: 5 pages, 3 figures, 2 online pages with 2 figures. Accepted for publication in A&A July 6 (Herschel/HIFI special issue

Excitation and Abundance of C3 in star forming cores:Herschel/HIFI observations of the sight-lines to W31C and W49N

We present spectrally resolved observations of triatomic carbon (C3) in several ro-vibrational transitions between the vibrational ground state and the low-energy nu2 bending mode at frequencies between 1654-1897 GHz along the sight-lines to the submillimeter continuum sources W31C and W49N, using Herschel's HIFI instrument. We detect C3 in absorption arising from the warm envelope surrounding the hot core, as indicated by the velocity peak position and shape of the line profile. The sensitivity does not allow to detect C3 absorption due to diffuse foreground clouds. From the column densities of the rotational levels in the vibrational ground state probed by the absorption we derive a rotation temperature (T_rot) of ~50--70 K, which is a good measure of the kinetic temperature of the absorbing gas, as radiative transitions within the vibrational ground state are forbidden. It is also in good agreement with the dust temperatures for W31C and W49N. Applying the partition function correction based on the derived T_rot, we get column densities N(C3) ~7-9x10^{14} cm^{-2} and abundance x(C3)~10^{-8} with respect to H2. For W31C, using a radiative transfer model including far-infrared pumping by the dust continuum and a temperature gradient within the source along the line of sight we find that a model with x(C3)=10^{-8}, T_kin=30-50 K, N(C3)=1.5 10^{15} cm^{-2} fits the observations reasonably well and provides parameters in very good agreement with the simple excitation analysis.Comment: Accepted for publication in Astronomy and Astrophysics (HIFI first results issue

Cell cycle-dependent phosphorylation of pRb-like protein in root meristem cells of Vicia faba

The retinoblastoma tumor suppressor protein (pRb) regulates cell cycle progression by controlling the G1-to-S phase transition. As evidenced in mammals, pRb has three functionally distinct binding domains and interacts with a number of proteins including the E2F family of transcription factors, proteins with a conserved LxCxE motif (D-type cyclin), and c-Abl tyrosine kinase. CDK-mediated phosphorylation of pRb inhibits its ability to bind target proteins, thus enabling further progression of the cell cycle. As yet, the roles of pRb and pRb-binding factors have not been well characterized in plants. By using antibody which specifically recognizes phosphorylated serines (S807/811) in the c-Abl tyrosine kinase binding C-domain of human pRb, we provide evidence for the cell cycle-dependent changes in pRb-like proteins in root meristems cells of Vicia faba. An increased phosphorylation of this protein has been found correlated with the G1-to-S phase transition

Gene expression meta-analysis of Parkinson’s disease and its relationship with Alzheimer’s disease

Abstract Parkinson’s disease (PD) and Alzheimer’s disease (AD) are the most common neurodegenerative diseases and have been suggested to share common pathological and physiological links. Understanding the cross-talk between them could reveal potentials for the development of new strategies for early diagnosis and therapeutic intervention thus improving the quality of life of those affected. Here we have conducted a novel meta-analysis to identify differentially expressed genes (DEGs) in PD microarray datasets comprising 69 PD and 57 control brain samples which is the biggest cohort for such studies to date. Using identified DEGs, we performed pathway, upstream and protein-protein interaction analysis. We identified 1046 DEGs, of which a majority (739/1046) were downregulated in PD. YWHAZ and other genes coding 14–3-3 proteins are identified as important DEGs in signaling pathways and in protein-protein interaction networks (PPIN). Perturbed pathways also include mitochondrial dysfunction and oxidative stress. There was a significant overlap in DEGs between PD and AD, and over 99% of these were differentially expressed in the same up or down direction across the diseases. REST was identified as an upstream regulator in both diseases. Our study demonstrates that PD and AD share significant common DEGs and pathways, and identifies novel genes, pathways and upstream regulators which may be important targets for therapy in both diseases