Oxygen vacancies as active sites for water dissociation on rutile TiO2(110)

Through an interplay between scanning tunneling microscopy experiments and density functional theory calculations, we determine unambiguously the active surface site responsible for the dissociation of water molecules adsorbed on rutile TiO2(110). Oxygen vacancies in the surface layer are shown to dissociate H2O through the transfer of one proton to a nearby oxygen atom, forming two hydroxyl groups for every vacancy. The amount of water dissociation is limited by the density of oxygen vacancies present on the clean surface exclusively. The dissociation process sets in as soon as molecular water is able to diffuse to the active site.

Bonding of gold nanoclusters to oxygen vacancies on rutile TiO2(110)

Through an interplay between scanning tunneling microscopy (STM) and density functional theory (DFT) calculations, we show that bridging oxygen vacancies are the active nucleation sites for Au clusters on the rutile TiO2(110) surface. We find that a direct correlation exists between a decrease in density of vacancies and the amount of Au deposited. From the DFT calculations we find that the oxygen vacancy is indeed the strongest Au binding site. We show both experimentally and theoretically that a single oxygen vacancy can bind 3 Au atoms on average. In view of the presented results, a new growth model for the TiO2(110) system involving vacancy-cluster complex diffusion is presented.

Probiotic Sonicates Selectively Induce Mucosal Immune Cells Apoptosis Through Ceramide Generation Via Neutral Sphingolyelinase.

Background: Probiotics appear to be beneficial in inflammatory bowel disease, but their mechanism of action is incompletely understood. We investigated whether probiotic-derived sphingomyelinase mediates this beneficial effect. Methodology/Principal Findings: Neutral sphingomyelinase (NSMase) activity was measured in sonicates of the probiotic L.brevis (LB)and S. thermophilus (ST) and the non-probiotic E. coli EC) and E. faecalis (EF). Lamina propria mononuclear cells (LPMC) were obtained from patients with Crohn"s disease (CD) and Ulcerative Colitis (UC), and peripheral blood mononuclear cells (PBMC) from healthy volunteers, analysing LPMC and PBMC apoptosis susceptibility, reactive oxygen species (ROS) generation and JNK activation. In some experiments, sonicates were preincubated with GSH or GW4869, a specific NSMase inhibitor. NSMase activity of LB and ST was 10-fold that of EC and EF sonicates. LB and ST sonicates induced significantly more apoptosis of CD and UC than control LPMC, whereas EC and EF sonicates failed to induce apoptosis. Pre-stimulation with anti-CD3/CD28 induced a significant and time-dependent increase in LB-induced apoptosis of LPMC and PBMC. Exposure to LB sonicates resulted in JNK activation and ROS production by LPMC. NSMase activity of LB sonicates was completely abrogated by GW4869, causing a dose-dependent reduction of LB -induced poptosis. LB and ST selectively induced immune cell apoptosis, an effect dependent on the degree of cell activation and mediated by bacterial NSMase. Conclusions: These results suggest that induction of immune cell apoptosis is a mechanism of action of some probiotics and that NSMase-mediated ceramide generation contributes to the therapeutic effects of probiotics.

Role of PheE15 gate in ligand entry and nitric oxide detoxification function of Mycobacterium tuberculosis truncated hemoglobin N

The truncated hemoglobin N, HbN, of Mycobacterium tuberculosis is endowed with a potent nitric oxide dioxygenase (NOD) activity that allows it to relieve nitrosative stress and enhance in vivo survival of its host. Despite its small size, the protein matrix of HbN hosts a two-branched tunnel, consisting of orthogonal short and long channels, that connects the heme active site to the protein surface. A novel dual-path mechanism has been suggested to drive migration of O(2) and NO to the distal heme cavity. While oxygen migrates mainly by the short path, a ligand-induced conformational change regulates opening of the long tunnel branch for NO, via a phenylalanine (PheE15) residue that acts as a gate. Site-directed mutagenesis and molecular simulations have been used to examine the gating role played by PheE15 in modulating the NOD function of HbN. Mutants carrying replacement of PheE15 with alanine, isoleucine, tyrosine and tryptophan have similar O(2)/CO association kinetics, but display significant reduction in their NOD function. Molecular simulations substantiated that mutation at the PheE15 gate confers significant changes in the long tunnel, and therefore may affect the migration of ligands. These results support the pivotal role of PheE15 gate in modulating the diffusion of NO via the long tunnel branch in the oxygenated protein, and hence the NOD function of HbN.

Functional diversity of macrophyte communities within and between Pyrenean lakes

Submersed vegetation is a common feature in about 70% Pyrene an high mountain (>1500 m a.s.l.) lakes. Isoetids and soft-water elodeids are common elements of this underw ater flora and can form distinct vegetation units (i.e. patches of vegetation dominated by different species) within complex mosaics of vegetation in shallow waters (<7 m). Since is oetids exert a strong influence on sediment biogeochemistry due to high radial oxygen loss, we examined the small scale characteristics of the lake environment (water and sediment) associated to vegetation patches in order to ascertain potential functional differences among them. To do so, we characterised the species composition and biomass of the main vegetation units from 11 lakes, defined plant communities based on biomass data, and then related each community with sediment properties (redox and dissolved nutrient concentration in the pore water) and water nutrient concentration within plant canopy. We also characterised lake water and sediment in areas without vegetation as a reference. A total of twenty-one vegetation units were identified, ranging from one to five per lake. A cluster analysis on biomass species composition suggested seven different macrophyte communities that were named after the most dominant species:Nitella sp.,Potamogeton praelongus, Myriophyllum alterniflorum, Sparganium angustifolium , Isoetes echinospora,Isoetes lacustris and Carex rostrata . Coupling between macrophyte communities and their immediate environment (overlying water and sediment) was manifested mainly as variation in sediment redox conditions and the dominant form of inorganic nitrogen in pore-water. These effects depended on the specific compositi on of the community, and on the allocation between above- and belowground biomass, and could be predicted with a model relating the average and standard deviation of sediment redox potential from 0 down to -20 cm, across macrophyte communities. Differences in pore-water total dissolved phosphorus were related to the trophic state of the lakes. There was no correlation between sediment and water column dissolved nutrients. However, nitrate concentrations tended to be lower in the water overlaying isoetid communities, in apparent contradiction to the patterns of dissolved nitrates in the pore-water. These tendencies were robust even when comparing the water over laying communities within the same lake, thus pointing towards a potential effect of isoetids in reducing dissolved nitrogen in the lakes.

Operational Cost Reduction in WDM Networks using Lighttours

Wavelength division multiplexing (WDM) networks have been adopted as a near-future solution for the broadband Internet. In previous work we proposed a new architecture, named enhanced grooming (G+), that extends the capabilities of traditional optical routes (lightpaths). In this paper, we compare the operational expenditures incurred by routing a set of demands using lightpaths with that of lighttours. The comparison is done by solving an integer linear programming (ILP) problem based on a path formulation. Results show that, under the assumption of single-hop routing, almost 15% of the operational cost can be reduced with our architecture. In multi-hop routing the operation cost is reduced in 7.1% and at the same time the ratio of operational cost to number of optical-electro-optical conversions is reduced for our architecture. This means that ISPs could provide the same satisfaction in terms of delay to the end-user with a lower investment in the network architecture

Reduction of the Ant Mandible Gap Range After Biotic Homogenization Caused by an Ant Invasion (Hymenoptera: Formicidae)

After most of the native ant species are displaced by the Argentine ant invasion, it is probable that some ecological processes carried out by natives are not replaced. In some cases this could be due to a morphological difference between the Argentine ant and the displaced native ants. The significant decrease in ant richness after the invasion (only two species detected in the invaded zones vs. 25 species in surrounding non-invaded zones) implies a drastic reduction in the ant mandible gap range (the mandible gap spectra of all the ant species in a community) in the invaded zones. This reduction could explain why some roles that were previously carried out by the displaced native species are not performed by the invasive species. This could be due to a functional inability to carry out these activities. The mandible gap waspositively correlated with the ant body mass in the 26 ant species considered. The functional inability hypothesis could be applied to other invasive ants as well as to the Argentine ant

Towards integrated operation of membrane bioreactors : effects of aeration on biological and filtration performance

Two experimental studies evaluated the effect of aerobic and membrane aeration changes on sludge properties, biological nutrient removal and filtration processes in a pilot plant membrane bioreactor. The optimal operating conditions were found at an aerobic dissolved oxygen set-point (DO) of 0.5mgO2L-1 and a membrane specific aeration demand (SADm) of 1mh-1, where membrane aeration can be used for nitrification. Under these conditions, a total flow reduction of 42% was achieved (75% energy reduction) without compromising nutrient removal efficiencies, maintaining sludge characteristics and controlled filtration. Below these optimal operating conditions, the nutrient removal efficiency was reduced, increasing 20% for soluble microbial products, 14% for capillarity suction time and reducing a 15% for filterability. Below this DO set-point, fouling increased with a transmembrane pressure 75% higher. SADm below 1mh-1 doubled the values of transmembrane pressure, without recovery after achieving the initial conditions

Mitochondrial fatty acid oxidation in obesity

Significance: Current lifestyles with high-energy diets and little exercise are triggering an alarming growth in obesity. Excess of adiposity is leading to severe increases in associated pathologies, such as insulin resistance, type 2 diabetes, atherosclerosis, cancer, arthritis, asthma, and hypertension. This, together with the lack of efficient obesity drugs, is the driving force behind much research. Recent Advances: Traditional anti-obesity strategies focused on reducing food intake and increasing physical activity. However, recent results suggest that enhancing cellular energy expenditure may be an attractive alternative therapy. Critical Issues: This review evaluates recent discoveries regarding mitochondrial fatty acid oxidation (FAO) and its potential as a therapy for obesity. We focus on the still controversial beneficial effects of increased FAO in liver and muscle, recent studies on how to potentiate adipose tissue energy expenditure, and the different hypotheses involving FAO and the reactive oxygen species production in the hypothalamic control of food intake. Future Directions: The present review aims to provide an overview of novel anti-obesity strategies that target mitochondrial FAO and that will definitively be of high interest in the future research to fight against obesity-related disorders.

Comparative performance of the stable isotope signatures of carbon, nitrogen and oxygen in assessing early vigour and grain yield in durum wheat

The present paper studied the performance of the stable isotope signatures of carbon (δ13C), nitrogen (δ15N) and oxygen (δ18O) in plants when used to assess early vigour and grain yield (GY) in durum wheat growing under mild and moderate Mediterranean stress conditions. A collection of 114 recombinant inbred lines was grown under rainfed (RF) and supplementary irrigation (IR) conditions. Broad sense heritabilities (H2) for GY and harvest index (HI) were higher under RF conditions than under IR. Broad sense heritabilities for δ13C were always above 0·60, regardless of the plant part studied, with similar values for IR and RF trials. Some of the largest genetic correlations with GY were those shown by the δ13C content of the flag leaf blade and mature grains. Under both water treatments, mature grains showed the highest negative correlations between δ13C and GY across genotypes. Flag leaf δ13C was negatively correlated with GY only under RF conditions. The δ13C in seedlings was negatively correlated, under IR conditions only, with GY but also with early vigour. The sources of variation in early vigour were studied by stepwise analysis using the stable isotope signatures measured in seedlings. The δ13C was able to explain almost 0·20 of this variation under RF, but up to 0·30 under IR. In addition, nitrogen concentration in seedlings accounted for another 0·05 of variation, increasing the amount explained to 0·35. The sources of variation in GY were also studied through stable isotope signatures and biomass of different plant parts: δ13C was always the first parameter to appear in the models for both water conditions, explaining c. 0·20 of the variation. The second parameter (δ15N or N concentration of grain, or biomass at maturity) depended on the water conditions and the plant tissue being analysed. Oxygen isotope composition (δ18O) was only able to explain a small amount of the variation in GY. In this regard, despite the known and previously described value of δ13C as a tool in breeding, δ15N is confirmed as an additional tool in the present study. Oxygen isotope composition does not seem to offer any potential, at least under the conditions of the present study.