Theoretical insight into the rearrangement of sulfur atoms on the Ni- and Cu-doped MoS2 S-edge induced by hydrogen adsorption under HDS reaction conditions.

Density functional theory (DFT) calculations and an atomistic thermodynamic approach were used to study the geometric rearrangement of sulfur atoms on the Ni- and Cu-doped MoS2 S-edge upon hydrogen adsorption. Under HDS conditions, thermodynamically stable hydrogenated structures were identified as SH groups on the undoped S-edge with 100% sulfur coverage, on the Ni-doped S-edge with 50% sulfur coverage and on the Cu-doped S-edge with 25% sulfur coverage. It was found that the rearrangement of the S atoms is essential to reach the most stable state at the edge for the undoped and Ni-doped S-edge. Hydrogen adsorption on the Ni-doped S-edge leads to the greatest amount of S rearrangement (ΔERearrang = 0.93 eV/H2). Our results suggest that under the reaction conditions, the H2 dissociative adsorption process is strongly coupled to the rearrangement of the sulfur atoms. By examining the differential hydrogen adsorption energy on the most stable edge structures, we found a plausible explanation for the trend in the hydrogenation activity of the doped edges. Our results suggest that Ni enhances the hydrogenation activity of the S-edge by decreasing the S-H bond strength, while Cu poisons it by increasing the S-H bond strength.

The relative importance of biological and environmental factors on the trophodynamics of a pelagic marine predator, the blue shark (Prionace glauca).

Marine ecosystems have been significantly altered by the cumulative impacts of human activities. Pelagic sharks have become vulnerable to increases in mortality rates caused by fishing. The decrease in number of these top predators could have substantial cascading effects on wider marine communities. Concerns about these potential impacts, and the critical need for effective management, have led to an increased interest in assessing the trophic ecology of sharks. While stable isotope analyses have been used to provide relevant insights about the trophic ecology of sharks, the causal factors leading to trophic variation between individuals has been largely overlooked. Here, we investigated the relative effect of biological factors, geographic location, and environmental factors on the spatial trophodynamics of the blue shark (Prionace glauca). Specifically, stable isotope values of δ15N and δ13C, and the estimated trophic position (TP) were analysed for 180 blue sharks collected from south of the Canary Islands in the Atlantic Ocean, to the north-western Mediterranean Sea. The results showed that models which included combined variables explained the variation in δ15N, TP and δ13C values better than models which considered only stand-alone predictors. The independent contributions of environmental variables and biological factors seemed to be more important than geographic location for δ15N and TP. δ15N and TP increased in a curvilinear fashion with body size, and TP was higher for females. In the case of δ13C values, only an effect from sex was observed. Among environmental variables, chlorophyll-a, pelagic productivity, and sea-surface temperature proved to be reliable predictors, particularly for δ15N and TP, most likely due to their relationship with productivity and prey availability. This study provides new information on ranking the factors that influence the trophodynamics of the blue shark, namely the environment, the geographic location, and the biological factors of the species.

CD69 Plays a Beneficial Role in Ischemic Stroke by Dampening Endothelial Activation.

RATIONALE: CD69 is an immunomodulatory molecule induced during lymphocyte activation. Following stroke, T-lymphocytes upregulate CD69 but its function is unknown. OBJECTIVE: We investigated whether CD69 was involved in brain damage following an ischemic stroke. METHODS AND RESULTS: We used adult male mice on the C57BL/6 or BALB/c backgrounds, including wild-type mice and CD69-/- mice, and CD69+/+ and CD69-/- lymphocyte-deficient Rag2-/- mice, and generated chimeric mice. We induced ischemia by transient or permanent middle cerebral artery occlusion. We measured infarct volume, assessed neurological function, and studied CD69 expression, as well as platelet function, fibrin(ogen) deposition, and VWF (von Willebrand factor) expression in brain vessels and VWF content and activity in plasma, and performed the tail-vein bleeding test and the carotid artery ferric chloride-induced thrombosis model. We also performed primary glial cell cultures and sorted brain CD45-CD11b-CD31+ endothelial cells for mRNA expression studies. We blocked VWF by intravenous administration of anti-VWF antibodies. CD69-/- mice showed larger infarct volumes and worse neurological deficits than the wild-type mice after ischemia. This worsening effect was not attributable to lymphocytes or other hematopoietic cells. CD69 deficiency lowered the time to thrombosis in the carotid artery despite platelet function not being affected. Ischemia upregulated Cd69 mRNA expression in brain endothelial cells. CD69-deficiency increased fibrin(ogen) accumulation in the ischemic tissue, and plasma VWF content and activity, and VWF expression in brain vessels. Blocking VWF reduced infarct volume and reverted the detrimental effect of CD69-/- deficiency. CONCLUSIONS: CD69 deficiency promotes a prothrombotic phenotype characterized by increased VWF and worse brain damage after ischemic stroke. The results suggest that CD69 acts as a downregulator of endothelial activation.

The bending machine: CO2 activation and hydrogenation on δ-MoC(001) and ß-Mo2C(001) surfaces.

The adsorption and activation of a CO2 molecule on cubic δ-MoC(001) and orthorhombic ß-Mo2C(001) surfaces have been investigated by means of periodic density functional theory based calculations using the Perdew-Burke-Ernzerhof exchange-correlation functional and explicitly accounting for (or neglecting) the dispersive force term description as proposed by Grimme. The DFT results indicate that an orthorhombic ß-Mo2C(001) Mo-terminated polar surface provokes the spontaneous cleavage of a C-O bond in CO2 and carbon monoxide formation, whereas on a ß-Mo2C(001) C-terminated polar surface or on a δ-MoC(001) nonpolar surface the CO2 molecule is activated yet the C-O bond prevails. Experimental tests showed that Mo-terminated ß-Mo2C(001) easily adsorbs and decomposes the CO2 molecule. This surface is an active catalyst for the hydrogenation of CO2 to methanol and methane. Although MoC does not dissociate C-O bonds on its own, it binds CO2 better than transition metal surfaces and is an active and selective catalyst for the CO2 + 3H2 → CH3OH + H2O reaction. Our theoretical and experimental results illustrate the tremendous impact that the carbon/metal ratio has on the chemical and catalytic properties of molybdenum carbides. This ratio must be taken into consideration when designing catalysts for the activation and conversion of CO2.

Assisted deprotonation of formic acid on Cu(111) and self-assembly of 1D chains.

Formic acid (HCOOH) deprotonates on the open surfaces of Cu(110) and Cu(100) when exposed at 300 K. However, this does not occur on the close-packed surface of clean Cu(111). In this study, we show that the deprotonation of formic acid on atomically flat Cu(111) surfaces can be induced by pre-adsorbing polymeric formic acid clusters at low temperatures, and then annealing the system to break the acidic O-H bond of HCOOH adsorbed on the edges of the polymeric clusters. The thermal activation of HCOOH to bidentate formate was studied using a combination of infrared reflection absorption spectroscopy, scanning tunneling microscopy, X-ray photoelectron spectroscopy, and near edge X-ray absorption fine structure spectroscopy. Extended 1D formate structures self-assemble due to a templating effect introduced by the formation of long α-polymeric formic acid chains commensurate with the substrate.

Density functional study of water-gas shift reaction on M3O(3x)/Cu(111).

Density functional theory (DFT) was employed to study the water dissociation and water-gas shift (WGS) reaction on a series of inverse model catalysts, M(3)O(3x)/Cu(111) (M = Mg, Ti, Zr, Mo, W; x = 1, 2, 3). It has been found that the WGS reaction on Cu can be facilitated by introducing various oxides to lower the barrier of water dissociation. Accordingly, the calculated reaction energy for water dissociation was used as a scaling descriptor to screen the WGS activity of oxide-Cu model catalysts. Our calculations show that the activity towards water dissociation decreases in a sequence: Mg(3)O(3)/Cu(111) > Zr(3)O(6)/Cu(111) > Ti(3)O(6)/Cu(111) > W(3)O(9)/Cu(111), Mo(3)O(9)/Cu(111). It seems that Mg(3)O(3)/Cu(111) is the best WGS catalyst among the systems studied here, being able to dissociate water with no barrier. During the process, both Cu and oxides participate in the reaction directly. The strong M(3)O(3x)-Cu interaction is able to tune the electronic structure of M(3)O(3x) and therefore the activity towards water dissociation. Further studies of the overall WGS reaction on Mg(3)O(3)/Cu(111) show that water dissociation may not be the key step to control the WGS reaction on Mg(3)O(3)/Cu(111) and the removal of H from Mg(3)O(3) can be problematic. The strong interaction between H and O from Mg(3)O(3) blocks the O sites for further water dissociation and therefore the WGS reaction. Our study observes a very different behavior of oxide clusters in such small size from the bigger ones supported on Cu(111) and provides new insight into the rational design of the WGS catalysts.

CO2 Activation and Methanol Synthesis on Novel Au/TiC and Cu/TiC Catalysts.

Small Cu and Au particles in contact with a TiC(001) surface undergo a charge polarization that makes them very active for CO2 activation and the catalytic synthesis of methanol. The binding energy of CO2 on these systems is in the range of 0.6 to 1.1 eV, much larger than those observed on surfaces or nanoparticles of Cu and Au. Thus, in spite of the poor CO2 hydrogenation performance of Cu(111) and Au(111), the Cu/TiC(001) and Au/TiC(001) systems display a catalytic activity for methanol synthesis substantially higher than that of conventional Cu/ZnO catalysts. The turnover frequencies for methanol production on Cu/TiC(001) are 170-500 times much larger than on Cu(111). The present study moves away from the typical approach of using metal/oxide catalysts for the synthesis of methanol via CO2 hydrogenation. This work shows that metal carbides can be excellent supports for enhancing the ability of noble metals to bond and activate CO2.

First-principles study of low Miller index Ni3S2 surfaces in hydrotreating conditions.

Density functional theory (DFT) calculations combined with surface thermodynamic arguments and the Gibbs-Curie-Wulff equilibrium morphology formalism have been employed to explore the effect of the reaction conditions, temperature (T), and gas-phase partial pressures (PH2 and PH2S) on the stability of nickel sulfide (Ni3S2) surfaces. Furthermore, the strength and nature of chemical bonds for selected Ni3S2 surface cuts were investigated with the quantum theory of atoms in molecules methodology. A particular analysis of the electrostatic potential within this theoretical framework is performed to study the potential activity of nickel sulfide nanoparticles as hydrodesulfurization (HDS) catalysts. The calculated thermodynamic surface stabilities and the resulting equilibrium morphology model suggest that unsupported Ni3S2 nanoparticles mainly expose (111) and (111) type surface faces in HDS conditions. Analysis of the electrostatic potential mapped onto a selected electron density isocontour (0.001 au) on those expose surface reveals a poor potential reactivity toward electron-donating reagents (i.e., low Lewis acidity). Consequently, a very low attraction between coordinatively unsaturated active sites (Lewis sites) exposed at the catalytic particles and the S atoms coming from reagent polluting molecules does inactive these kinds of particles for HDS.