Low-temperature partial dissociation of water on Cu(110)

The low-temperature reactivity of water (D2O) adsorbed on clean and oxygen pre-covered Cu(1 1 0) was studied using high resolution X-ray photoelectron spectroscopy (HRXPS) and low energy electron diffraction (LEED). On the clean surface partial dissociation to hydroxyl was observed already at 95 K. Upon annealing to 220 K hydrogen bonded water-hydroxyl chains are formed. Upon further annealing water desorbs leaving behind a layer of hydroxyl, most of which desorbs recombinatively eventually. With pre-adsorbed oxygen water reacts to hydroxyl lifting the added-row reconstruction even below 225 K. Upon annealing this adsorbate layer passes through essentially the same stages as without pre-adsorbed oxygen.

Spectro-electrochemical and DFT studies of a planar Cu(II)–phenolate complex active in the aerobic oxidation of primary alcohols

A square-planar compound [Cu(pyrimol)Cl] (pyrimol = 4-methyl-2-N-(2-pyridylmethylene)aminophenolate) abbreviated as CuL–Cl) is described as a biomimetic model of the enzyme galactose oxidase (GOase). This copper(II) compound is capable of stoichiometric aerobic oxidation of activated primary alcohols in acetonitrile/water to the corresponding aldehydes. It can be obtained either from Hpyrimol (HL) or its reduced/hydrogenated form Hpyramol (4-methyl-2-N-(2-pyridylmethyl)aminophenol; H2L) readily converting to pyrimol (L-) on coordination to the copper(II) ion. Crystalline CuL–Cl and its bromide derivative exhibit a perfect square-planar geometry with Cu–O(phenolate) bond lengths of 1.944(2) and 1.938(2) Å. The cyclic voltammogram of CuL–Cl exhibits an irreversible anodic wave at +0.50 and +0.57 V versus ferrocene/ferrocenium (Fc/Fc+) in dry dichloromethane and acetonitrile, respectively, corresponding to oxidation of the phenolate ligand to the corresponding phenoxyl radical. In the strongly donating acetonitrile the oxidation path involves reversible solvent coordination at the Cu(II) centre. The presence of the dominant CuII–L. chromophore in the electrochemically and chemically oxidised species is evident from a new fairly intense electronic absorption at 400–480 nm ascribed to a several electronic transitions having a mixed pi-pi(L.) intraligand and Cu–Cl -> L. charge transfer character. The EPR signal of CuL–Cl disappears on oxidation due to strong intramolecular antiferromagnetic exchange coupling between the phenoxyl radical ligand (L.) and the copper(II) centre, giving rise to a singlet ground state (S = 0). The key step in the mechanism of the primary alcohol oxidation by CuL–Cl is probably the alpha-hydrogen abstraction from the equatorially bound alcoholate by the phenoxyl moiety in the oxidised pyrimol ligand, Cu–L., through a five-membered cyclic transition state.

A comparison of the relative toxicity of bone meal and other P sources used as remedial treatments to the earthworm Eisenia fetida

It has been suggested that sources of P could be used to remediate metal-contaminated soil. The toxicity of four potential P sources, potassium hydrogen phosphate (PHP), triple superphosphate (TSP), rock phosphate (RP) and raw bone meal (RBM) to Eisenia fetida was determined. The concentration of P that is statistically likely to kill 50% of the population (LC50) for PHP, TSP and RBM was determined in OECD acute toxicity tests. 14 day LC50s expressed as bulk P concentration lay in the range 3319–4272 mg kg−1 for PHP, 3107–3590 mg kg−1 for TSP and 1782–2196 mg kg−1 for RBM (ranges present the 95% confidence intervals). For PHP and TSP mortality was significantly impacted by the electrical conductivity of the treated soils. No consistent relationship existed between mortality and electrical conductivity, soil pH and available (Olsen) P across the PHP, TSP and RBM amendment types. In RP toxicity tests mortality was low and it was not possible to determine a LC50 value. Incineration of bone meal at temperatures between 200 and 300 ◦C, pre-washing the bone meal, co-amendment with 5% green waste compost and delaying introduction of earthworms after bone meal amendments by 21 days or more led to significant reductions in the bone meal toxicity. These results are consistent with the toxicity being associated with the release and/or degradation of a soluble organic component present in raw bone meal. Bone meal can be used as an earthworm-friendly remedial amendment in metal-contaminated soils but initial additions may have a negative effect on any earthworms surviving in the contaminated soil before the organic component in the bone meal degrades in the soil.

Contrasting effects of dwarfing alleles and nitrogen availability on mineral concentrations in wheat grain

Background and aim Concentrations of essential minerals in plant foods may have declined in modern high-yielding cultivars grown with large applications of nitrogen fertilizer (N). We investigated the effect of dwarfing alleles and N rate on mineral concentrations in wheat. Methods Gibberellin (GA)-insensitive reduced height (Rht) alleles were compared in near isogenic wheat lines. Two field experiments comprised factorial combinations of wheat variety backgrounds, alleles at the Rht-B1 locus (rht-B1a, Rht-B1b, Rht-B1c), and different N rates. A glasshouse experiment also included Rht-D1b and Rht-B1b+D1b in one background. Results In the field, depending on season, Rht-B1b increased crop biomass, dry matter (DM) harvest index, grain yield, and the economically-optimal N rate (Nopt). Rht-B1b did not increase uptake of Cu, Fe, Mg or Zn so these minerals were diluted in grain. Nitrogen increased DM yield and mineral uptake so grain concentrations were increased (Fe in both seasons; Cu, Mg and Zn in one season). Rht-B1b reduced mineral concentrations at Nopt in the most N responsive season. In the glasshouse experiment, grain yield was reduced, and mineral concentrations increased, with Rht allele addition. Conclusion Effects of Rht alleles on Fe, Zn, Cu and Mg concentrations in wheat grain are mostly due to their effects on DM, rather than of GA-insensitivity on Nopt or mineral uptake. Increased N requirement in semi-dwarf varieties partly offsets this dilution effect.

Identification of critical residues in the active site of porcine membrane-bound aminopeptidase P

The membrane-bound form of mammalian aminopeptidase P (AP-P; EC 3.4. 11.9) is a mono-zinc-containing enzyme that lacks any of the typical metal binding motifs found in other zinc metalloproteases. To identify residues involved in metal binding and catalysis, sequence and structural information was used to align the sequence of porcine membrane-bound AP-P with other members of the peptidase clan MG, including Escherichia coli AP-P and methionyl aminopeptidases. Residues predicted to be critical for activity were mutated and the resultant proteins were expressed in COS-1 cells. Immunoelectrophoretic blot analysis was used to compare the levels of expression of the mutant proteins, and their ability to hydrolyze bradykinin and Gly-Pro-hydroxyPro was assessed. Asp449, Asp460, His523, Glu554, and Glu568 are predicted to serve as metal ion ligands in the active site, and mutagenesis of these residues resulted in fully glycosylated proteins that were catalytically inactive. Mutation of His429 and His532 also resulted in catalytically inactive proteins, and these residues, by analogy with E. coli AP-P, are likely to play a role in shuttling protons during catalysis. These studies indicate that mammalian membrane-bound AP-P has an active-site configuration similar to that of other members of the peptidase clan MG, which is compatible with either a dual metal ion model or a single metal ion in the active site. The latter model is consistent, however, with the known metal stoichiometry of both the membrane-bound and cytosolic forms of AP-P and with a recently proposed model for methionyl aminopeptidase.

Facile in situ copper(ii) mediated C–S bond activation transforming dithiocarbimate to carbamate and thiocarbamate generating Cu(ii) and Cu(i) complexes

Facile in situ Cu(II) mediated transformation of p-tolylsulfonyldithiocarbimate in conjunction with polypyridyl or phosphine ligands into corresponding carbamate and thiocarbamate led to the formation of new copper complexes with varying nuclearities and geometries, via C-S bond activation of the ligand within identical reaction systems.

A very rare self-assembled ribbon of fused cyclic water pentamers encapsulated in a Cu-II based metal-organic framework

A metal organic framework of Cu-II, tartarate (tar) and 2,2'-bipyridyl (2,2'-bipy)], {[Cu(tar)(2,2'-bipy)]center dot 5H(2)O}(n)} (1) has been synthesized at the mild ambient condition and characterized by single crystal X-ray crystallography. In the compound, the Cu(2,2'-bipy) entities are bridged by tartarate ions which are coordinated to Cu-II by both hydroxyl and monodentate carboxylate oxygen to form a one-dimensional chain. The non-coordinated water molecules form ID water chains by edge-sharing cyclic water pentamers along with dangling water dimers. It shows reversible water expulsion upon heating. The water chains join the ID coordination polymeric chains to a 31) network through hydrogen-bond interactions.

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.

Stability of dobutamine 500 mg in 50 ml syringes prepared using a Central Intravenous Additive Service

Objectives A pharmacy Central Intravenous Additives Service (CIVAS) provides ready to use injectable medicines. However, manipulation of a licensed injectable medicine may significantly alter the stability of drug(s) in the final product. The aim of this study was to develop a stability indicating assay for CIVAS produced dobutamine 500 mg in 50 ml dextrose 1% (w/v) prefilled syringes, and to allocate a suitable shelf life. Methods A stability indicating high performance liquid chromatography (HPLC) assay was established for dobutamine. The stability of dobutamine prefilled syringes was evaluated under storage conditions of 4°C (protected from light), room temperature (protected from light), room temperature (exposed to light) and 40°C (protected from light) at various time points (up to 42 days). Results An HPLC method employing a Hypersil column, mobile phase (pH=4.0) consisting of 82:12:6 (v/v/v) 0.05 M KH2PO4:acetonitrile:methanol plus 0.3% (v/v) triethylamine with UV detection at λ=280 nm was specific for dobutamine. Under different storage conditions only samples stored at 40°C showed greater than 5% degradation (5.08%) at 42 days and had the shortest T95% based on this criterion (44.6 days compared with 111.4 days for 4°C). Exposure to light also reduced dobutamine stability. Discolouration on storage was the limiting factor in shelf life allocation, even when dobutamine remained within 5% of the initial concentration. Conclusions A stability indicating HPLC assay for dobutamine was developed. The shelf life recommended for the CIVAS product was 42 days at 4°C and 35 days at room temperature when protected from light.

Surface chemistry of alanine on Cu{111}: Adsorption geometry and temperature dependence

Adsorption of l-alanine on the Cu{111} single crystal surface was investigated as a model system for interactions between small chiral modifier molecules and close-packed metal surfaces. Synchrotron-based X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy are used to determine the chemical state, bond coordination and out-of-plane orientation of the molecule on the surface. Alanine adsorbs in its anionic form at room temperature, whilst at low temperature the overlayer consists of anionic and zwitterionic molecules. NEXAFS spectra exhibit a strong angular dependence of the π ⁎ resonance associated with the carboxylate group, which allows determining the tilt angle of this group with respect to the surface plane (48° ± 2°) at room temperature. Low-energy electron diffraction (LEED) shows a p(2√13x2√13)R13° superstructure with only one domain, which breaks the mirror symmetry of the substrate and, thus, induces global chirality to the surface. Temperature-programmed XPS (TP-XPS) and temperature-programmed desorption (TPD) experiments indicate that the zwitterionic form converts into the anionic species (alaninate) at 293 K. The latter desorbs/decomposes between 435 K and 445 K.

Weak intermolecular interactions in an ionically bound molecular adsorbate: cyclopentadienyl=Cu(111)

The dissociative adsorption of cyclopentadiene (C5H6) on Cu(111) yields a cyclopentadienyl (Cp) species with strongly anionic characteristics. The Cp potential energy surface and frictional coupling to the substrate are determined from measurements of dynamics of the molecule together with density functional calculations. The molecule is shown to occupy degenerate threefold adsorption sites and molecular motion is characterized by a low diffusional energy barrier of 40 +/- 3 meV with strong frictional dissipation. Repulsive dipole-dipole interactions are not detected despite charge transfer from substrate to adsorbate.

Putting the P in Ptilotus: a phosphorus accumulating herb native to Australia

Background and Aims Ptilotus polystachyus (green mulla mulla; ptilotus) is a short-lived perennial herb that occurs widely in Australia in arid and semi-arid regions with nutrient poor soils. As this species shows potential for domestication, its response to addition of phosphorus (P) and nitrogen (N) was compared to a variety of the domesticated exotic perennial pasture herb Cichorium intybus (chicory), ‘Puna’. Methods Pots were filled with 3 kg of an extremely nutrient-deficient sterilized field soil that contained 3 mg kg−1 mineral N and 2 mg kg−1 bicarbonate-extractable P. The growth and P and N accumulation of ptilotus and chicory in response to seven rates of readily available phosphorus (0–300 mg P pot−1) and nitrogen (N) (0–270 mg N pot−1) was examined. Key Results Ptilotus grew extremely well under low P conditions: shoot dry weights were 23, 6 and 1·7 times greater than for chicory at the three lowest levels of P addition, 0, 15 and 30 mg P pot−1, respectively. Ptilotus could not downregulate P uptake. Concentrations of P in shoots approached 4 % of dry weight and cryo-scanning electron microscopy and X-ray microanalysis showed 35–196 mm of P in cell vacuoles in a range of tissues from young leaves. Ptilotus had a remarkable tolerance of high P concentrations in shoots. While chicory exhibited symptoms of P toxicity at the highest rate of P addition (300 mg P pot−1), no symptoms were present for ptilotus. The two species responded in a similar manner to addition of N. Conclusions In comparison to chicory, ptilotus demonstrated an impressive ability to grow well under conditions of low and high P availability. Further study of the mechanisms of P uptake and tolerance in ptilotus is warranted.

Advanced source apportionment of size-resolved trace elements at multiple sites in London during winter

Trace element measurements in PM10–2.5, PM2.5–1.0 and PM1.0–0.3 aerosol were performed with 2 h time resolution at kerbside, urban background and rural sites during the ClearfLo winter 2012 campaign in London. The environment-dependent variability of emissions was characterized using the Multilinear Engine implementation of the positive matrix factorization model, conducted on data sets comprising all three sites but segregated by size. Combining the sites enabled separation of sources with high temporal covariance but significant spatial variability. Separation of sizes improved source resolution by preventing sources occurring in only a single size fraction from having too small a contribution for the model to resolve. Anchor profiles were retrieved internally by analysing data subsets, and these profiles were used in the analyses of the complete data sets of all sites for enhanced source apportionment. A total of nine different factors were resolved (notable elements in brackets): in PM10–2.5, brake wear (Cu, Zr, Sb, Ba), other traffic-related (Fe), resuspended dust (Si, Ca), sea/road salt (Cl), aged sea salt (Na, Mg) and industrial (Cr, Ni); in PM2.5–1.0, brake wear, other traffic-related, resuspended dust, sea/road salt, aged sea salt and S-rich (S); and in PM1.0–0.3, traffic-related (Fe, Cu, Zr, Sb, Ba), resuspended dust, sea/road salt, aged sea salt, reacted Cl (Cl), S-rich and solid fuel (K, Pb). Human activities enhance the kerb-to-rural concentration gradients of coarse aged sea salt, typically considered to have a natural source, by 1.7–2.2. These site-dependent concentration differences reflect the effect of local resuspension processes in London. The anthropogenically influenced factors traffic (brake wear and other traffic-related processes), dust and sea/road salt provide further kerb-to-rural concentration enhancements by direct source emissions by a factor of 3.5–12.7. The traffic and dust factors are mainly emitted in PM10–2.5 and show strong diurnal variations with concentrations up to 4 times higher during rush hour than during night-time. Regionally influenced S-rich and solid fuel factors, occurring primarily in PM1.0–0.3, have negligible resuspension influences, and concentrations are similar throughout the day and across the regions.

Socio-economic variables influence the prevalence of inadequate nutrient intake in Brazilian adolescents: results from a population-based survey

Objective: To estimate the prevalence of inadequate nutrient intake among adolescents and the association between socio-economic variables and nutritional status. Design: Cross-sectional study with a population-based sample. Settings: The usual nutrient intake distribution was estimated using the Iowa State University method. The Estimated Average Requirement cut-off point method was used to determine the proportion of adolescents with inadequate intake for each nutrient, according to sex, income, parental educational level and nutritional status. Subjects: Twenty-four-hour dietary recalls were applied in 525 male and female Brazilian adolescents aged 14-18 years. Results: The highest prevalence of inadequate nutrient intake was observed for vitamin E (99% in both sexes). For male and female adolescents, the prevalence of inadequate intake was: Mg, 89% and 84%; vitamin A, 78% and 71 %; vitamin C, 79% and 53%; and vitamin B(6), 21% and 33%, respectively. The prevalence of inadequate intake for niacin, thiamin, riboflavin, Se, Cu and vitamin B(12) was <15 %. Individuals in the lower income and lower parental educational level strata had the highest risk of having inadequate intake for P, riboflavin and vitamins A, B(6) and B(12). Compared with non-overweight individuals, overweight individuals had a higher risk of inadequate intake for Mg, vitamin A, P, thiamin and riboflavin. Conclusions: The present study found a high prevalence of inadequate intake of nutrients that are recognised as being protective against chronic diseases. Adolescents in the lower income and lower parental educational level strata were less likely to have their nutrient intake requirements met.