Variation of the mixing state of Saharan dust particles with atmospheric transport

Mineral dust is an important aerosol species in the Earth’s atmosphere and has a major source within North Africa, of which the Sahara forms the major part. Aerosol Time of Flight Mass Spectrometry (ATOFMS) is first used to determine the mixing state of dust particles collected from the land surface in the Saharan region, showing low abundance of species such as nitrate and sulphate internally mixed with the dust mineral matrix. These data are then compared with the ATOFMS single particle mass spectra of Saharan dust particles detected in the marine atmosphere in the vicinity of the Cape Verde islands, which are further compared with those from particles with longer atmospheric residence sampled at a coastal station at Mace Head, Ireland. Saharan dust particles collected near the Cape Verde Islands showed increased internally mixed nitrate but no sulphate, whilst Saharan dust particles collected on the coast of Ireland showed a very high degree of internally mixed secondary species including nitrate, sulphate and methanesulphonate. This uptake of secondary species will change the pH and hygroscopic properties of the aerosol dust and thus can influence the budgets of other reactive gases, as well as influencing the radiative properties of the particles and the availability of metals for dissolution.

A hexadecanuclear copper(I)-copper(II) mixed-valence compound: structure, magnetic properties, intervalence charge transfer, EPR, and NMR

Hexadecanuclear copper mixed-valence complex 2 containing 10 Cu-II, centers and 6 Cu-I centers was isolated with N,O donor ligands. From the X-ray crystal structure, 2 was found to contain a centrosymmetric dimeric cation - each monomeric unit composed of eight copper centers. It displays a very broad and weak intervalence charge-transfer band around 1100 nm at room temperature in the solid state. Variable-temperature magnetic susceptibility measurements indicate an S = 1/2 ground state for half of 2, explicitly, each Cu-8 moiety has a g value around 2.26. Complex 2 was examined by NMR spectroscopy at room temperature in solution and by EPR at low temperature; the data indicates that the valence is delocalized in 2 at room temperature but localized at low temperature. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

Synthesis, structure and solution chemistry of mixed-ligand oxovanadium(IV) and oxovanadium(V) complexes incorporating tridentate ONO donor hydrazone ligands

In the title family, the ONO donor ligands are the acetylhydrazones of salicylaidehyde (H2L1) and 2-hydroxyacetophenone (H2L2) (general abbreviation, H2L). The reaction of bis(acetylacetonato)oxovanadium(IV) with a mixture of tridentate H2L and a bidentate NN donor [e.g., 2,2'-bipyridine(bpy) or 1,10-phenanthroline(phen), hereafter B] ligands in equimolar ratio afforded the tetravalent complexes of the type [(VO)-O-IV(L)(B)]; complexes (1)-(4) whereas, if B is replaced by 8-hydroxyquinoline(Hhq) (which is a bidentate ON donor ligand), the above reaction mixture yielded the pentavalent complexes of the type [(VO)-O-V(L)(hq)]; complexes (5) and (6). Aerial oxygen is most likely the oxidant (for the oxidation of V-IV -> V-V) in the synthesis of pentavalent complexes (5) and (6). [(VO)-O-IV(L)(B)] complexes are one electron paramagnetic and display axial EPR spectra, while the [(VO)-O-V(L)(hq)] complexes are diamagnetic. The X-ray structure of [(VO)-O-V(L-2)(hq)] (6) indicates that H2L2 ligand is bonded with the vanadium meridionally in a tridentate dinegative fashion through its phenolic-O, enolic-O and imine-N atoms. The general bond length order is: oxo < phenolato < enolato. The V-O (enolato) bond is longer than V-O (phenolato) bond by similar to 0.07 angstrom and is identical with V-O (carboxylate) bond. H-1 NMR spectrum of (6) in CDCl3 solution indicates that the binding nature in the solid state is also retained in solution. Complexes (1)(4) display two ligand-field transitions in the visible region near 820 and 480 nm in DMF solution and exhibit irreversible oxidation peak near +0.60 V versus SCE in DMSO solution, while complexes (5) and (6) exhibit only LMCT band near 535 nm and display quasi-reversible one electron reduction peak near -0.10 V versus SCE in CH2Cl2 solution. The VO3+-VO2+ E-1/2 values shift considerably to more negative values when neutral NN donor is replaced by anionic ON donor species and it also provides better VO3+ binding via phenolato oxygen. For a given bidentate ligand, E-1/2 increases in the order: (L-2)(2-) < (L-1)(2-). (c) 2004 Elsevier B.V. All rights reserved.

Synthesis, structure, solution chemistry and the electronic effect of para substituents on the vanadium center in a family of mixed-ligand [(VO)-O-V(ONO)(ON)] compexes

Four tridentate dibasic ONO donor hydrazone ligands derived from the condensation of benzoylhydrazine with either 2-hydroxyacetophenone or its para substituted derivatives (H2L1-4, general abbreviation H2L) have been used as primary ligands and 8-hydroxyquinoline (Hhq, a bidentate monobasic ON donor species) has been used as auxiliary ligand. The reaction of [(VO)-O-IV(acac)21 with H2L in methanol followed by the addition of Hhq in equimolar ratio under aerobic condition afforded the mixed-ligand oxovanadium(V) complexes of the type [(VO)-O-V(L)(hq)] (1-4) in excellent yield. The X-ray structure of the compound [(VO)-O-V(L-4)(hq)] (4) indicates that the H2L4 ligand is bonded with vanadium meridionally in a tridentate dinegative fashion through its deprotonated phenolic-O, deprotonated enolic-O and imine-N atoms. The V-O bond length order is: oxo < phenolato < enolato. H-1 NMR spectra of 4 in CDCl3 solution indicates that it's solid-state structure is retained in solution. Complexes are diamagnetic and exhibit only ligand to metal charge transfer (LMCT) transition band near 530 nm in CH2Cl2 solution in addition to intra-ligand pi-pi* transition band near 335 rim and they display quasi-reversible one electron reduction peak near -0.10 V versus SCE in CH2Cl2 solution. lambda(max) (for LMCT transition) and the reduction peak potential (E-p(c)) values of the complexes are found to be linearly related with the Hammett (sigma) constants of the substituents in the aryloxy ring of the hydrazone ligands. lambda(max) and E-p(c) values show large dependence d lambda(max)/d sigma = 32.54 nm and dE(p)(c)/d sigma = 0.19 V, respectively, on the Hammett constant. (c) 2006 Elsevier B.V. All rights reserved.

Mixed ligand binuclear copper(I) complexes containing (Cu2N8)-N-I chromophores. Observation of emissions from MLCT excited states involving two different ligands

Using the 1:2 condensate (L) of diethylenetriamine and benzaldehyde as the main ligand, binuclear copper(l) complexes [Cu2L2(4,4'-bipyridine)](CIO4)(2).0.5H(2)O (1a) and [Cu2L2(1,2-bis(4-pyridyl)ethane)](CIO4)(2) (1b) are synthesised. The two metal ions in la are bridged by 4,4'-bipyridine and those in 1b by 1,2-bis(4-pyridyl)ethane, From the X-ray crystal structure of la, each metal ion is found to be bound to three N atoms of L and one of the two N atoms of the bridging ligand in a distorted tetrahedral fashion. The Cu(I)-N bond lengths in la lie in the range of 1.998(5)-2.229(6) Angstrom. Electrochemical studies in dichloromethane (DCM) show that the (Cu2N8)-N-I moieties in la and 1b are composed of two essentially non-interacting (CuN4)-N-I cores with Cu-II/I potential of 0.44 V vs. SCE. While la displays metal induced quenching of the inherent emission of 4,4'-bipyridine in DCM solution, 1b exhibits two weak emission bands in DCM solution at 425 and 477 nm (total quantum yield = 3.59 x 10(-5)) originating from MLCT excited states. With the help of Extended Huckel calculations it is established that the higher energy emission in 1b is from Cu(I) --> bridging-ligand charge transfer excited state and the lower energy one in 1b from Cu(I) --> L charge transfer excited state.

A two-stage continuous culture system to study the effect of supplemental alpha-lactalbumin and glycomacropeptide on mixed cultures of human gut bacteria challenged with enteropathogenic Escherichia coli and Salmonella serotype Typhimurium

Aims: Certain milk factors may promote the growth of a gastrointestinal microflora predominated by bifidobacteria and may aid in overcoming enteric infections. This may explain why breast-fed infants experience fewer intestinal infections than their formula-fed counterparts. The effect of formula supplementation with two such factors was investigated in this study. Methods and Results: Infant faecal specimens were used to ferment formulae supplemented with glycomacropeptide (GMP) and alpha-lactalbumin (alpha-la) in a two-stage compound continuous culture model. At steady state, all fermenter vessels were inoculated with 5 ml of 0.1 M phosphate-buffered saline (pH 7.2) containing 10(8) CFU ml(-1) of either enteropathogenic Escherichia coli 2348/69 (O127:H6) or Salmonella serotype Typhimurium (DSMZ 5569). Bacteriology was determined by independent fluorescence in situ hybridization. Vessels that contained breast milk (BM), as well as alpha-la and GMP supplemented formula had stable total counts of bifidobacteria while lactobacilli increased significantly only in vessels with breast milk. Bacteroides, clostridia and E. coli decreased significantly in all three groups prior to pathogen addition. Escherichia coli counts decreased in vessels containing BM and alpha-la while Salmonella decreased significantly in all vessels containing BM, alpha-la and GMP. Acetate was the predominant acid. Significance and Impact of the Study: Supplementation of infant formulae with appropriate milk proteins may be useful in mimicking the beneficial bacteriological effects of breast milk.

Conformational studies of mixed-ligand copper(II) chelates. Crystal and molecular structure of (N,N-dimethyl-N′-ethyl-1,2-diaminoethane-(1-phenyl-1,3,-butanedionato)copper(II) perchlorate

The IR and ligand field spectra and the structure of the mixed-ligand compound [N,N-dimethyl-N′-ethyl-1,2-diaminoethane(1-phenyl-1,3-butanedionato)(perchlorato)copper(II)]), [Cu(dmeen)bzac(OClO3)], are reported. The structure was determined by single crystal X-ray diffraction analysis (triclinic, space group ). The structure is square pyramidal with the apical position occupied by one oxygen of the tetrahedral perchlorato group (distance from copper 2.452(5) Å). The plane of the phenyl ring is tilted forming an angle of 16.72(14)° with the plane of the β-dionato moiety. The nitrogenous base adopts the gauche conformation with torsional angle of 108.72(14)°. The ethyl group is cis oriented relative to the phenyl group, occupying the equatorial position with the vector of the carbon-nitrogen bond forming an angle of 143.9(3)° with the CuNN plane. The interactions of the adjacent axial hydrogen with an oxygen of the perchlorato group result in hydrogen bond formation. The IR spectra reveal that in the solid state the Br− or Cl− displace easily the ClO4− group. The shifts in the ligand field spectra indicate that polar solvents participate in donor-acceptor interactions with the metal centre along an axis perpendicular to the CuN2O2 plane.

Simultaneous bridge-localized and mixed-valence character in diruthenium radical cations featuring diethynylaromatic bridging ligands

A series of bimetallic ruthenium complexes [{Ru(dppe)Cp*}2(μ-C≡CArC≡C)] featuring diethynylaromatic bridging ligands (Ar = 1,4-phenylene, 1,4-naphthylene, 9,10-anthrylene) have been prepared and some representative molecular structures determined. A combination of UV–vis–NIR and IR spectroelectrochemical methods and density functional theory (DFT) have been used to demonstrate that one-electron oxidation of compounds [{Ru(dppe)Cp*}2(μ-C≡CArC≡C)](HC≡CArC≡CH = 1,4-diethynylbenzene; 1,4-diethynyl-2,5-dimethoxybenzene; 1,4-diethynylnaphthalene; 9,10-diethynylanthracene) yields solutions containing radical cations that exhibit characteristics of both oxidation of the diethynylaromatic portion of the bridge, and a mixed-valence state. The simultaneous population of bridge-oxidized and mixed-valence states is likely related to a number of factors, including orientation of the plane of the aromatic portion of the bridging ligand with respect to the metal d-orbitals of appropriate π-symmetry.

Mapping evidence gaps in anti-corruption: assessing the state of the operationally relevant evidence on donors' actions and approaches to reducing corruption

This paper charts the current evidence on effectiveness of different anti-corruption reforms, and identifies significant evidence gaps. Despite a substantial amount of literature on corruption, this review found very few studies focusing on anti-corruption reforms, and even fewer that credibly assess issues of effectiveness and impact. The evidence was strong for only two types of interventions: public financial management (PFM) reforms and supreme audit institutions (SAIs). For PFM, the evidence in general showed positive results, whereas the effectiveness was mixed for SAIs. No strong evidence indicates that any of the interventions pursued have been ineffective, but there is fair evidence that anti-corruption authorities, civil service reforms and the use of corruption conditionality in aid allocation decisions in general have not been effective. The paper advocates more operationally-relevant research and rigorous evaluations to build up the missing evidence base, particularly in conflict-afflicted states, in regards to the private sector, and on the interactions and interdependencies between different anti-corruption interventions.

Hepatitis C virus NS5A inhibits mixed lineage kinase 3 to block apoptosis

Hepatitis C virus (HCV) infection results in the activation of numerous stress responses including oxidative stress, with the potential to induce an apoptotic state. Previously we have shown that HCV attenuates the stress-induced, p38MAPK-mediated up-regulation of the K+ channel Kv2.1, to maintain the survival of infected cells in the face of cellular stress. We demonstrated that this effect was mediated by HCV non-structural 5A (NS5A) protein, which impaired p38MAPK activity through a polyproline motif dependent interaction, resulting in reduction of phosphorylation activation of Kv2.1. In this study, we investigated the host cell proteins targeted by NS5A in order to mediate Kv2.1 inhibition. We screened a phage-display library expressing the entire complement of human SH3 domains for novel NS5A-host cell interactions. This analysis identified mixed lineage kinase 3 (MLK3) as a putative NS5A interacting partner. MLK3 is a serine/threonine protein kinase that is a member of the MAPK kinase kinase (MAP3K) family and activates p38MAPK. An NS5A-MLK3 interaction was confirmed by co-immunoprecipitation and western blot analysis. We further demonstrate a novel role of MLK3 in the modulation of Kv2.1 activity, whereby MLK3 overexpression leads to the up-regulation of channel activity. Accordingly, coexpression of NS5A suppressed this stimulation. Additionally we demonstrate that overexpression of MLK3 induced apoptosis which was also counteracted by NS5A. We conclude that NS5A targets MLK3 with multiple downstream consequences for both apoptosis and K+ homeostasis.

MetUM-GOML: a near-globally coupled atmosphere–ocean-mixed-layer model

Well-resolved air–sea interactions are simulated in a new ocean mixed-layer, coupled configuration of the Met Office Unified Model (MetUM-GOML), comprising the MetUM coupled to the Multi-Column K Profile Parameterization ocean (MC-KPP). This is the first globally coupled system which provides a vertically resolved, high near-surface resolution ocean at comparable computational cost to running in atmosphere-only mode. As well as being computationally inexpensive, this modelling framework is adaptable– the independent MC-KPP columns can be applied selectively in space and time – and controllable – by using temperature and salinity corrections the model can be constrained to any ocean state. The framework provides a powerful research tool for process-based studies of the impact of air–sea interactions in the global climate system. MetUM simulations have been performed which separate the impact of introducing inter- annual variability in sea surface temperatures (SSTs) from the impact of having atmosphere–ocean feedbacks. The representation of key aspects of tropical and extratropical variability are used to assess the performance of these simulations. Coupling the MetUM to MC-KPP is shown, for example, to reduce tropical precipitation biases, improve the propagation of, and spectral power associated with, the Madden–Julian Oscillation and produce closer-to-observed patterns of springtime blocking activity over the Euro-Atlantic region.

Ionothermal synthesis of the mixed-anion material, Ba3Cl4CO3

A low-temperature ionothermal method for the facile synthesis of the halide carbonate, Ba3Cl4CO3, in single-crystalline form has been developed. This has enabled the first determination of the crystal structure of this material to be carried out. Analysis of single-crystal X-ray diffraction data indicates that barium chloride carbonate crystallises in the orthorhombic space group Pnma (Z=4), with a=8.4074(11), b=9.5886(12), c=12.4833(15) Å (Rw=0.0392). It exhibits a complex structure in which a three-dimensional network is formed from cross-linking of chains of anion-centred octahedra that share faces.

Processes controlling surface, bottom and lateral melt of Arctic sea ice in a state of the art sea ice model

We present a modelling study of processes controlling the summer melt of the Arctic sea ice cover. We perform a sensitivity study and focus our interest on the thermodynamics at the ice–atmosphere and ice–ocean interfaces. We use the Los Alamos community sea ice model CICE, and additionally implement and test three new parametrization schemes: (i) a prognostic mixed layer; (ii) a three equation boundary condition for the salt and heat flux at the ice–ocean interface; and (iii) a new lateral melt parametrization. Recent additions to the CICE model are also tested, including explicit melt ponds, a form drag parametrization and a halodynamic brine drainage scheme. The various sea ice parametrizations tested in this sensitivity study introduce a wide spread in the simulated sea ice characteristics. For each simulation, the total melt is decomposed into its surface, bottom and lateral melt components to assess the processes driving melt and how this varies regionally and temporally. Because this study quantifies the relative importance of several processes in driving the summer melt of sea ice, this work can serve as a guide for future research priorities.