The importance of hydrogen's potential-energy surface and the strength of the forming R-H bond in surface hydrogenation reactions

An understanding of surface hydrogenation reactivity is a prevailing issue in chemistry and vital to the rational design of future catalysts. In this density-functional theory study, we address hydrogenation reactivity by examining the reaction pathways for N+H -> NH and NH+H -> NH2 over the close-packed surfaces of the 4d transition metals from Zr-Pd. It is found that the minimum-energy reaction pathway is dictated by the ease with which H can relocate between hollow-site and top-site adsorption geometries. A transition state where H is close to a top site reduces the instability associated with bond sharing of metal atoms by H and N (NH) (bonding competition). However, if the energy difference between hollow-site and top-site adsorption energies (Delta E-H) is large this type of transition state is unfavorable. Thus we have determined that hydrogenation reactivity is primarily controlled by the potential-energy surface of H on the metal, which is approximated by Delta E-H, and that the strength of N (NH) chemisorption energy is of less importance. Delta E-H has also enabled us to make predictions regarding the structure sensitivity of these reactions. Furthermore, we have found that the degree of bonding competition at the transition state is responsible for the trend in reaction barriers (E-a) across the transition series. When this effect is quantified a very good linear correlation is found with E-a. In addition, we find that when considering a particular type of reaction pathway, a good linear correlation is found between the destabilizing effects of bonding competition at the transition state and the strength of the forming N-H (HN-H) bond. (c) 2006 American Institute of Physics.

SiO in G34.26: Outflows and shocks in a high mass star forming region

We have looked for SiO emission as evidence of shocks in the high mass star formation region G34.26+0.15. JCMT, VLA and FCRAO observations show that SiO emission is widespread across the region. The SiO emission highlights a massive, collimated out ow and other regions where stellar winds are interacting with molecular clumps. As in other star forming regions, there is also SiO at ambient velocities which is related to the out ow activity. No strong SiO abundance enhancement was measured in either the out ow or the low velocity gas, though abundances up to 10(-8) are possible if the SiO is locally enhanced in clumps and optically thick. SiO emission is not detected from the hot core itself, indicating either that SiO is not strongly enhanced in the hot core or that column densities in the region where grain mantle evaporation has taken place are low. In line of sight spiral arm clouds, we measure a SiO abundance of 0.4-2 x 10(-10), consistent with previous estimates for quiescent clouds.

Domain Bundle Boundaries in Single Crystal BaTiO3 Lamellae: Searching for Naturally Forming Dipole Flux-Closure / Quadrupole Chains

Naturally occurring boundaries between bundles of 90o stripe domains, which form in BaTiO3 lamellae on cooling through the Curie Temperature, have been characterised using both piezoresponse force microscopy (PFM) and scanning transmission electron microscopy (STEM). Detailed interpretation of the dipole configurations present at these boundaries (using data taken from PFM) shows that, in the vast majority of cases, they are composed of simple zigzag 180° domain walls. Topological information from STEM shows that, occasionally, domain bundle boundaries can support chains of dipole flux closure and quadrupole nanostructures, but these kinds of boundaries are comparatively rare; when such chains do exist, it is notable that singularities at the cores of the dipole structures are avoided. The symmetry of the boundary shows that diads and centres of inversion exist at positions where core singularities should have been expected.

Distribution, extent of inter-annual variability and diet of the bloom-forming jellyfish Rhizostoma in European waters

Jellyfish (Cnidaria: Scyphozoa) are increasingly thought to play a number of important ecosystem roles, but often fundamental knowledge of their distribution, seasonality and inter-annual variability is lacking. Bloom forming species, due to their high densities, can have particularly intense trophic and socio-economic impacts. In northern Europe it is known that one particularly large (up to 30 kg wet weight) bloom forming jellyfish is Rhizostoma spp. Given the potential importance, we set out to review all known records from peer-reviewed and broader public literature of the jellyfish R. octopus (Linnaeus) and R. pulmo (Macri) (Scyphozoa: Rhizostomae) across western Europe. These data revealed distinct hotspots where regular Rhizostoma spp. aggregations appeared to form, with other sites characterized by occasional abundances and a widespread distribution of infrequent observations. Surveys of known R. octopus hotspots around the Irish Sea also revealed marked inter-annual variation with particularly high abundances forming during 2003. The location of such consistent aggregations and inter-annual variances are discussed in relation to physical, climatic and dietary variations.

Tetra-end-linked oligonucleotides forming DNA G-quadruplexes: a new class of aptamers showing anti-HIV activity.

The biophysical and biological properties of unprecedented anti-HIV aptamers are presented. The most active aptamer (1L) shows a significant affinity to the HIV protein gp120.

Ginkgolide B and bilobalide block the pore of the 5-HT3 receptor at a location that overlaps the picrotoxin binding site

Extracts from the Ginkgo biloba tree are widely used as herbal medicines, and include bilobalide (BB) and ginkgolides A and B (GA and GB). Here we examine their effects on human 5-HT(3)A and 5-HT(3)AB receptors, and compare these to the effects of the structurally related compounds picrotin (PTN) and picrotoxinin (PXN), the two components of picrotoxin (PTX), a known channel blocker of 5-HT3, nACh and GABA(A) receptors. The compounds inhibited 5-HT-induced responses of 5-HT3 receptors expressed in Xenopus oocytes, with IC50 values of 470 mu M (BB), 730 mu M (GB), 470 mu M (PTN), 11 mu M (PXN) and > 1 mM (GA) in 5-HT(3)A receptors, and 3.1 mM (BB), 3.9 mM (GB), 2.7 mM (PTN), 62 mu M (PXN) and > 1 mM (GA) in 5-HT(3)AB receptors. Radioligand binding on receptors expressed in HEK 293 cells showed none of the compounds displaced the specific 5-HT3 receptor antagonist [H-3]granisetron, confirming that they do not act at the agonist binding site. Inhibition by GB at 5-HT(3)A receptors is weakly use-dependent, and recovery is activity dependent, indicating channel block. To further probe their site of action at 5-HT(3)A receptors, BB and GB were applied alone or in combination with PXN, and the results fitted to a mathematical model; the data revealed partially overlapping sites of action. We conclude that BB and GB block the channel of the 5-HT(3)A receptor. Thus these compounds have comparable, although less potent, behaviour than at some other Cys-loop receptors, demonstrating their actions are conserved across the family. (C) 2010 Published by Elsevier Ltd.