Identifying the Azobenzene/Aniline reaction intermediate on TiO2-(110) : a DFT Study

Density functional theory (DFT) calculations, both with and without dispersion corrections, have been performed to investigate the nature of the common surface reaction intermediate that has been shown to exist on TiO2(110) as a result of exposure to either azobenzene (C6H5N═NC6H5) or aniline (C6H5NH2). Our results confirm the results of a previous DFT study that dissociation of azobenzene into two adsorbed phenyl imide (C6H5N) fragments, as was originally proposed, is not energetically favorable. We also find that deprotonation of aniline to produce this surface species is even more strongly energetically disfavored. A range of alternative surface species has been considered, and while dissociation of azobenzene to form surface C6H4NH species is energetically favored, the same surface species cannot form from adsorbed aniline. On the contrary, adsorbed aniline is much the most stable surface species. Comparisons with experimental determinations of the local adsorption site, the Ti–N bond length, the molecular orientation, and the associated C 1s and N 1s photoelectron core level shifts are all consistent with the DFT results for adsorbed aniline and are inconsistent with other adsorbed species considered. Possible mechanisms for the hydrogenation of azobenzene required to produce this surface species are discussed

Jamming and percolation in the random sequential adsorption of a binary mixture on the square lattice

We study the competitive irreversible adsorption of a binary mixture of monomers and square-shaped particles of linear size $R$ on the square lattice. With the random sequential adsorption model, we investigate how the jamming coverage and percolation properties depend on the size ratio $R$ and relative flux $F$. We find that the onset of percolation of monomers is always lower for the binary mixture than in the case with only monomers ($R=1$). Moreover, for values $F$ below a critical value, the higher is the flux or size of the largest species, the lower is the value of the percolation threshold for monomers.Comment: Submitted to a special issue of Journal of Physics A: Mathematical and Theoretical to mark the 70th Birthday of Robert M. Zif

Atividade de extrato aquoso de folhas de nim (Azadirachta indica) sobre Spodoptera frugiperda.

A lagarta-do-cartucho do milho (Spodoptera frugiperda (J. E. Smith)) tem sido controlada com inseticidas sintéticos. Uma das caracteristicas do nim (Azadirachta indica A. Juss) é sua atividade inseticida contra pragas, como sucedâneo aos sintéticos. O objetivo deste trabalho foi avaliar a atividade inseticida do extrato aquoso das folhas do nim sobre a lagarta-do-cartucho do milho, em laboratório. Bioensaios com diferentes concentrações de extrato em dieta artificial, tendo o inseticida chlorpyrifos como testemunha, revelaram, 15 dias após infestação com larvas, eficiência equivalente entre as concentrações 3,60 a 10,00 mg mL-'. A análise de Probit mostrou CL50 = 2,67 mg mL-'; o extrato aquoso das folhas de nim apresenta, portanto, efeito inseticida sobre a lagarta-do-cartucho do milho

Differential mesenteric fat deposition in bovines fed on silage or concentrate is independent of glycerol membrane permeability

© The Animal Consortium 2011In the meat industry, the manipulation of fat deposition in cattle is of pivotal importance to improve production efficiency, carcass composition and ultimately meat quality. There is an increasing interest in the identification of key factors and molecular mechanisms responsible for the development of specific fat depots. This study aimed at elucidating the influence of breed and diet on adipose tissue membrane permeability and fluidity and their interplay on fat deposition in bovines. Two Portuguese autochthonous breeds, Alentejana and Barrosã, recognized as late- and early-maturing breeds, respectively, were chosen to examine the effects of breed and diet on fat deposition and on adipose membrane composition and permeability. Twenty-four male bovines from these breeds were fed on silage-based or concentrate-based diets for 11 months. Animals were slaughtered to determine their live slaughter and hot carcass weights, as well as weights of subcutaneous and visceral adipose depots. Mesenteric fat depots were excised and used to isolate adipocyte membrane vesicles where cholesterol content, fatty acid profile as well as permeability and fluidity were determined. Total accumulation of neither subcutaneous nor visceral fat was influenced by breed. In contrast, mesenteric and omental fat depots weights were higher in concentrate-fed bulls relative to silage-fed animals. Membrane fluidity and permeability to water and glycerol in mesenteric adipose tissue were found to be independent of breed and diet. Moreover, the deposition of cholesterol and unsaturated fatty acids, which may influence membrane properties, were unchanged among experimental groups. Adipose membrane lipids from the mesenteric fat depot of ruminants were rich in saturated fatty acids, and unaffected by polyunsaturated fatty acids dietary levels. Our results provide evidence against the involvement of cellular membrane permeability to glycerol on fat accumulation in mesenteric fat tissue of concentrate-fed bovines, which is consistent with the unchanged membrane lipid profile found among experimental groups.This study was supported by Fundação para a Ciência e a Tecnologia (FCT) through grant PTDC/CVT/2006/66114 and individual fellowships to Ana P. Martins (SFRH/BD/2009/65046), Ana S. H. Costa (SFRH/BD/2009/61068) and Susana V. Martins (SFRH/BPD/2009/63019). Paula A. Lopes is a researcher from the program ‘‘Ciência 2008’’ from FC

T-20 and T-1249 HIV fusion inhibitors’ structure and conformational behavior in solution: a molecular dynamics study

Fusion of the HIV envelope with the target cell membrane is a critical step of HIV entry into the target cell. Several peptides based on the C-region of HIV gp41 have been used in clinical trials as possible HIV fusion inhibitors. Among these are T-1249 and T-20 (also known as enfurvitide; see fig. 1). Despite recent works, a detailed molecular picture of the inhibitory mechanism of these molecules is still lacking. These peptides are usually depicted as α-helices by analogy with the structure of the sequence of the gp41 protein with which they are homologous. However, structures like these would not explain the ability that the two fusion inhibitors have to both become solvated by water and interact effectively with cell membranes. This led us to study the structure and conformational behavior of all these peptides. To this effect, extensive molecular dynamics simulations (total time 400 ns) with explicit solvent (SPC water) were carried out to investigate the structure and conformational behavior of T-1249 and T-20, as well as shorter homologous peptides CTP and 3f5 (see fig. 1), which show no inhibitory action. The monitored parameters include mean square displacement relative to the initial conformation (α-helix structures in all cases), secondary structure, solvent accessible surface and radius of gyration. We found that the studied peptides have no stable structure in solution in the time scale studied. Additionally, the solvent accessible area varies significantly during the simulation. Our findings suggest that these peptides may assume not only one but several possible sets of structures in solution, some of which more adequate to interact with the solvent, whereas others might be better suited to interact with cell membranes

Geodetic implications on block formation and geodynamic domains in the South Shetland Islands, Antarctic Peninsula

The South Shetland Islands archipelago is dynamically complex due to its tectonic surroundings. Most islands are part of a formerly active volcanic arc, although Deception, Penguin and Bridgeman Islands, as well as several submarine volcanoes, are characterized by active back-arc volcanism. Geodetic benchmarks were deployed and the movement of the lithosphere to which they were fixed measured to provide geodynamic insight for the South Shetland Islands, Bransfield Basin and Antarctic Peninsula area based on surface deformation. These benchmarks' data add spatial and temporal coverage to previous results. The results reveal two different geodynamic patterns, each confined to a distinct part of the South Shetland Islands archipelago. The inferred absolute horizontal velocity vectors for the benchmarks in the northeastern part of the archipelago are consistent with the opening of the Bransfield Basin, while benchmark vectors in the southwestern part of the archipelago are similar to those of the benchmarks on the Antarctic Peninsula. In between, Snow, Deception and Livingston Islands represent a transition zone. In this area, the horizontal velocity vectors relative to the Antarctic plate shift northeastwards from N to NW. Furthermore, the South Shetland Islands benchmarks, except for that at Gibbs (Elephant) Islands, indicate subsidence, which might be a consequence of the slab roll-back at the South Shetland Trench. In contrast, the uplift revealed by the Antarctic Peninsula benchmarks suggests glacial isostatic adjustment after the Larson B ice-shelf breakup. (C) 2015 Elsevier B.V. All rights reserved