Synergetic effects of the Cu/Pt{110} surface alloy: enhanced reactivity of water and carbon monoxide

We have used synchrotron-based high-resolution X-ray photoelectron spectroscopy in combination with ab initio density functional theory calculations to investigate the characteristics of water and CO adsorption on the bimetallic Cu/Pt{110}-(2 x 1) surface at a Cu coverage near 0.5 ML. Cu fills the troughs of the reconstructed clean surface forming nanowires, which are stable up to 830 K. Their presence dramatically influences the adsorption of water and CO. Water adsorption changes from intact to partially dissociated while the desorption temperature of CO on this surface increases by up to 27 K with respect to the clean Pt{110} surface. Ab initio calculations and experimental valence band spectra reveal that the Cu 3d-band is narrowed and shifted upward with respect to bulk Cu surfaces. This and electron donation to surface Pt atoms cause the increase in the bond strength between CO and the Pt surface atoms. The pathway for water dissociation occurs via Cu surface atoms. The heat of adsorption of water bonding to Cu surface atoms was calculated to be 0.82 eV, which is significantly higher than on the clean Pt{110} surface; the activation energy for partial dissociation is 0.53 eV (not corrected for zero point energy).

Ultra-thin porous silica coated silver-platinum alloy nano-particle as a new catalyst precursor

Templated sol-gel encapsulation of surfactant-stabilised micelles containing metal precursor(s) with ultra-thin porous silica coating allows solvent extraction of organic based stabiliser from the composites in colloidal state hence a new method of preparing supported alloy catalysts using the inorganic silica-stabilised nano-sized, homogenously mixed, silver - platinum (Ag-Pt) colloidal particles is reported.

Synthesis and X-ray crystal structure of the triethylammonium magnesium β-octamolybdate(VI)salt[Et3NH]2[Mg(H2O)6Mo8O26]·2H2O

[Et3NH]4[Mo8O26] reacted with MgCl2 giving the triethylammonum magnesium β-octamolybdate(VI) salt [Et3NH]2[Mg(H2O)6Mo8O26]·2H2O (3) and the triethylammonium hydronium β-octaamolybdate(VI) salt [Et3NH]3[(H3O)Mo8O26·2H2O (4), respectively. A small amount of [Et3NH]2[Mo6O269] was formed as a by-product. The salts 3 and 4 were characterized by X-ray crystallography. The [Mg(H2O)6Mo8O26]2− moiety in 3 is polymeric, with each octahedral [Mg(H2O)6]2+ ion sandwiched between two β[Mo8O26]4− ions, being hydrogen bonded to three terminal MOO oxygen atoms on one face of each β[Mo8O26]4− ion. The X-ray crystal structure of 4 corresponds to the reported previously. IR and conductivity data are given for 3 and 4.

Shoot calcium and magnesium concentrations differ between subtaxa, are highly heritable, and associate with potentially pleiotropic loci in Brassica oleracea

Calcium (Ca) and magnesium (Mg) are the most abundant group II elements in both plants and animals. Genetic variation in shoot Ca and shoot Mg concentration (shoot Ca and Mg) in plants can be exploited to biofortify food crops and thereby increase dietary Ca and Mg intake for humans and livestock. We present a comprehensive analysis of within-species genetic variation for shoot Ca and Mg, demonstrating that shoot mineral concentration differs significantly between subtaxa (varietas). We established a structured diversity foundation set of 376 accessions to capture a high proportion of species-wide allelic diversity within domesticated Brassica oleracea, including representation of wild relatives (C genome, 1n = 9) from natural populations. These accessions and 74 modern F-1 hybrid cultivars were grown in glasshouse and field environments. Shoot Ca and Mg varied 2- and 2.3-fold, respectively, and was typically not inversely correlated with shoot biomass, within most subtaxa. The closely related capitata (cabbage) and sabauda (Savoy cabbage) subtaxa consistently had the highest mean shoot Ca and Mg. Shoot Ca and Mg in glasshouse-grown plants was highly correlated with data from the field. To understand and dissect the genetic basis of variation in shoot Ca and Mg, we studied homozygous lines from a segregating B. oleracea mapping population. Shoot Ca and Mg was highly heritable (up to 40). Quantitative trait loci (QTL) for shoot Ca and Mg were detected on chromosomes C2, C6, C7, C8, and, in particular, C9, where QTL accounted for 14 to 55 of the total genetic variance. The presence of QTL on C9 was substantiated by scoring recurrent backcross substitution lines, derived from the same parents. This also greatly increased the map resolution, with strong evidence that a 4-cM region on C9 influences shoot Ca. This region corresponds to a 0.41-Mb region on Arabidopsis (Arabidopsis thaliana) chromosome 5 that includes 106 genes. There is also evidence that pleiotropic loci on C8 and C9 affect shoot Ca and Mg. Map-based cloning of these loci will reveal how shoot-level phenotypes relate to Ca 21 and Mg 21 uptake and homeostasis at the molecular level.

Distribution of calcium (Ca) and magnesium (Mg) in the leaves of Brassica rapa under varying exogenous Ca and Mg supply

Background and Aims Leafy vegetable Brassica crops are an important source of dietary calcium (Ca) and magnesium (Mg) and represent potential targets for increasing leaf Ca and Mg concentrations through agronomy or breeding. Although the internal distribution of Ca and Mg within leaves affects the accumulation of these elements, such data are not available for Brassica. The aim of this study was to characterize the internal distribution of Ca and Mg in the leaves of a vegetable Brassica and to determine the effects of altered exogenous Ca and Mg supply on this distribution. Methods Brassica rapa ssp. trilocularis ‘R-o-18’ was grown at four different Ca:Mg treatments for 21 d in a controlled environment. Concentrations of Ca and Mg were determined in fully expanded leaves using inductively coupled plasma-mass spectrometry (ICP-MS). Internal distributions of Ca and Mg were determined in transverse leaf sections at the base and apex of leaves using energy-dispersive X-ray spectroscopy (EDS) with cryo-scanning electron microscopy (cryo-SEM). Key Results Leaf Ca and Mg concentrations were greatest in palisade and spongy mesophyll cells, respectively, although this was dependent on exogenous supply. Calcium accumulation in palisade mesophyll cells was enhanced slightly under high Mg supply; in contrast, Mg accumulation in spongy mesophyll cells was not affected by Ca supply. Conclusions The results are consistent with Arabidopsis thaliana and other Brassicaceae, providing phenotypic evidence that conserved mechanisms regulate leaf Ca and Mg distribution at a cellular scale. The future study of Arabidopsis gene orthologues in mutants of this reference B. rapa genotype will improve our understanding of Ca and Mg homeostasis in plants and may provide a model-to-crop translation pathway for targeted breeding.

Dopant-vacancy binding effects in Li-doped magnesium hydride

We use a combination of ab initio calculations and statistical mechanics to investigate the substitution of Li+ for Mg2+ in magnesium hydride (MgH2) accompanied by the formation of hydrogen vacancies with positive charge (with respect to the original ion at the site). We show that the binding energy between dopants and vacancy defects leads to a significant fraction of trapped vacancies and therefore a dramatic reduction in the number of free vacancies available for diffusion. The concentration of free vacancies initially increases with dopant concentration but reaches a maximum at around 1 mol % Li doping and slowly decreases with further doping. At the optimal level of doping, the corresponding concentration of free vacancies is much higher than the equilibrium concentrations of charged and neutral vacancies in pure MgH2 at typical hydrogen storage conditions. We also show that Li-doped MgH2 is thermodynamically metastable with respect to phase separation into pure magnesium and lithium hydrides at any significant Li concentration, even after considering the stabilization provided by dopant-vacancy interactions and configurational entropic effects. Our results suggest that lithium doping may enhance hydrogen diffusion hydride but only to a limited extent determined by an optimal dopant concentration and conditioned to the stability of the doped phase.