Trinuclear and tetranuclear adduct formation between sodium perchlorate and copper(II) complexes of salicylaldimine type ligands: structural characterization and theoretical investigation

The synthesis of two new sodium perchlorate adducts (1:2 and 1:3) with copper(II) "ligand-complexes'' is reported. One adduct is trinuclear [(CuL(1))(2)NaClO(4)] (1) and the other is tetranuclear [(CuL(2))(3)Na]ClO(4)center dot EtOH (2). The ligands are the tetradentate di-Schiff base of 1,3-propanediamines and salicylaldehyde (H(2)L(1)) or 2-hydroxyacetophenone (H(2)L(2)). Both complexes have been characterized by X-ray single crystal structure analyses. In both structures, the sodium cation has a six-coordinate distorted octahedral environment being bonded to four oxygen atoms from two Schiff-base complexes in addition to a chelated perchlorate anion in 1 and to six oxygen atoms from three Schiff-base complexes in 2. We have carried out a DFT theoretical study (RI-B97-D/def2-SVP level of theory) to compute and compare the formation energies of 1:2 and 1:3 adducts. The DFT study reveals that the latter is more stabilized than the former. The X-ray crystal structure of 1 shows that the packing of the trinuclear unit is controlled by unconventional C-H center dot center dot center dot O H-bonds and Cu(2+)-pi non-covalent interactions. These interactions explain the formation of 1 which is a priori disfavored with respect to 2.

Task design and second language performance: the effect of narrative type on learner output

This article reports on a detailed empirical study of the way narrative task design influences the oral performance of second-language (L2) learners. Building on previous research findings, two dimensions of narrative design were chosen for investigation: narrative complexity and inherent narrative structure. Narrative complexity refers to the presence of simultaneous storylines; in this case, we compared single-story narratives with dual-story narratives. Inherent narrative structure refers to the order of events in a narrative; we compared narratives where this was fixed to others where the events could be reordered without loss of coherence. Additionally, we explored the influence of learning context on performance by gathering data from two comparable groups of participants: 60 learners in a foreign language context in Teheran and 40 in an L2 context in London. All participants recounted two of four narratives from cartoon pictures prompts, giving a between-subjects design for narrative complexity and a within-subjects design for inherent narrative structure. The results show clearly that for both groups, L2 performance was affected by the design of the task: Syntactic complexity was supported by narrative storyline complexity and grammatical accuracy was supported by an inherently fixed narrative structure. We reason that the task of recounting simultaneous events leads learners into attempting more hypotactic language, such as subordinate clauses that follow, for example, while, although, at the same time as, etc. We reason also that a tight narrative structure allows learners to achieve greater accuracy in the L2 (within minutes of performing less accurately on a loosely structured narrative) because the tight ordering of events releases attentional resources that would otherwise be spent on finding connections between the pictures. The learning context was shown to have no effect on either accuracy or fluency but an unexpectedly clear effect on syntactic complexity and lexical diversity. The learners in London seem to have benefited from being in the target language environment by developing not more accurate grammar but a more diverse resource of English words and syntactic choices. In a companion article (Foster & Tavakoli, 2009) we compared their performance with native-speaker baseline data and see that, in terms of nativelike selection of vocabulary and phrasing, the learners in London are closing in on native-speaker norms. The study provides empirical evidence that L2 performance is affected by task design in predictable ways. It also shows that living within the target language environment, and presumably using the L2 in a host of everyday tasks outside the classroom, confers a distinct lexical advantage, not a grammatical one.

Hurricane-type vortices in a general circulation model

A very high resolution atmospheric general circulation model, T106-L19, has been used for the simulation of hurricanes in a multi-year numerical experiment. Individual storms as well as their geographical and seasonal distribution agree remarkably well with observations. In spite of the fact that only the thermal and dynamical structure of the storms have been used as criteria of their identification, practically all of them occur in areas where the sea surface temperature is higher or equal to 26 °C. There are considerable variations from year to year in the number of storms in spite of the fact that there are no interannual variations in the SST pattern. It is found that the number of storms in particular areas appear to depend on the intensity of the Hadley-Walker cell. The result is clearly resolution-dependant. At lower horizonal resolution, T42, for example, the intensity of the storms is significantly reduced and their overall structure is less realistic, including their vertical form and extent.

Simulation of hurricane-type vortices in a general circulation model

A study of intense hurricane-type vortices in the ECMWF operational model is reported. These vortices develop around day 4 in the forecast and occur in the tropical belt in areas and at times where intense tropical cyclones normally occur. The frequency resembles that observed over most tropical regions with a pronounced maximum in the western North Pacific. The life time of the vortices and their 3-dimensional structure agree in some fundamental way with observations although, because of the resolution, the systems are less intense than the observed ones. The general large-scale conditions for active and inactive cyclone periods are discussed. The model cyclones are sensitive to the sea-surface temperature and do not develop with sea surface temperatures lower than 28–29°C. The dynamical conditions favouring cyclone development are characterized by intense large-scale divergence in the upper troposphere. Cyclogenesis appears to take place when these conditions are found outside the equatorial zone and over oceans where the water is sufficiently warm.

Task design and second language performance: the effect of narrative type on learner output

This article presents a study examining how narrative structure and narrative complexity might influence the performance of second language learners. Forty learners of English in London and sixty learners in Teheran were asked to retell cartoon stories from picture prompts. Each performed two of four narrative tasks that had different degrees of narrative structure (loose or tight) and of storyline complexity (with or without background events). Results support the findings of previous research that tight task structure is connected to increased accuracy and that narratives involving background information give rise to more complex syntax. A comparison of the data from the London and Teheran cohorts showed that the learners in London used significantly more complex syntax and diverse vocabulary even though they did not differ from the Teheran learners in other performance dimensions.

Spectroelectrochemical study of complexes [Mo(CO)2(h3-allyl)(adiimine)(NCS)] (a-diimine ¼ bis(2,6-dimethylphenyl)- acenaphthenequinonediimine and 2,20-bipyridine) exhibiting different molecular structure and redox reactivity

The redox properties and reactivity of [Mo(CO)2(η3-allyl)(α-diimine)(NCS)] (α-diimine = bis(2,6-dimethylphenyl)-acenaphthenequinonediimine (2,6-xylyl-BIAN) and 2,2′-bipyridine (bpy)) were studied using cyclic voltammetry and IR/UV–Vis spectroelectrochemistry. [Mo(CO)2(η3-allyl)(2,6-xylyl-BIAN)(NCS)] was shown by X-ray crystallography to have an asymmetric (B-type) conformation. The extended aromatic system of the strong π-acceptor 2,6-xylyl-BIAN ligand stabilises the primary 1e−-reduced radical anion, [Mo(CO)2(η3-allyl)(2,6-xylyl-BIAN•−)(NCS)]−, that can be reduced further to give the solvento anion [Mo(CO)2(η3-allyl)(2,6-xylyl-BIAN)(THF)]−. The initial reduction of [Mo(CO)2(η3-allyl)(bpy)(NCS)] in THF at ambient temperature results in the formation of [Mo(CO)2(η3-allyl)(bpy)]2 by reaction of the remaining parent complex with [Mo(CO)2(η3-allyl)(bpy)]− produced by dissociation of NCS− from [Mo(CO)2(η3-allyl)(bpy•−)(NCS)]−. Further reduction of the dimer [Mo(CO)2(η3-allyl)(bpy)]2 restores [Mo(CO)2(η3-allyl)(bpy)]−. In PrCN at 183 K, [Mo(CO)2(η3-allyl)(2,6-xylyl-BIAN•−)(NCS)]− converts slowly to 2e−-reduced [Mo(CO)2(η3-allyl)(2,6-xylyl-BIAN)(PrCN)]− and free NCS−. At room temperature, the reduction path in PrCN involves mainly the dimer [Mo(CO)2(η3-allyl)(bpy)]2; however, the detailed course of the reduction within the spectroelectrochemical cell is complicated and involves a mixture of several unassigned products. Finally, it has been shown that the five-coordinate anion [Mo(CO)2(η3-allyl)(bpy)]− promotes in THF reduction of CO2 to CO and formate via the formation of the intermediate [Mo(CO)2(η3-allyl)(bpy)(O2CH)] and its subsequent reduction.

Impact of variation in structure of condensed tannins from sainfoin (Onobrychis viciifolia) on in vitro ruminal methan production and fermentation characteristics

Our study investigated the effects of condensed tannins (CT) on rumen in vitro methane (CH4) production and fermentation characteristics by incubating lucerne in buffered rumen fluid in combination with different CT extracts at 0 (control), 40, 80 and 120 g CT/kg of substrate DM. Condensed tannins were extracted from four sainfoin accessions: Rees ‘A’, CPI63763, Cotswold Common and CPI63767. Gas production (GP) was measured using a fully automated GP apparatus with CH4 measured at distinct time points. Condensed tannins differed substantially in terms of polymer size and varied from 13 (Rees ‘A’) to 73 (CPI63767) mean degree of polymerization, but had relatively similar characteristics in terms of CT content, procyanidin: prodelphinidin (PC: PD) and cis:trans ratios. Compared to control, addition of CT from CPI63767 and CPI63763 at 80 and 120 g CT/kg of substrate DM reduced CH4 by 43% and 65%, and by 23% and 57%, respectively, after 24-h incubation. Similarly, CT from Rees ‘A’ and Cotswold Common reduced CH4 by 26% and 46%, and by 28% and 46% respectively. Addition of increasing level of CT linearly reduced the maximum rates of GP and CH4 production, and the estimated in vitro organic matter digestibility. There was a negative linear and quadratic (p < 0.01) relation between CT concentration and total volatile fatty acid (VFA) production. Inclusion of 80 and 120 g CT/kg of substrate DM reduced (p < 0.001) branched-chain VFA production and acetate: propionate ratio and was lowest for CPI63767. A decrease in proteolytic activity as indirectly shown by a change in VFA composition favouring a shift towards propionate and reduction in branched-chain VFA production varied with type of CT and was highest for CPI63767. In conclusion, these results suggest that tannin polymer size is an important factor affecting in vitro CH4 production which may be linked to the CT interaction with dietary substrate or microbial cells.

Structure-based energetics of protein interfaces guides foot-and-mouth disease virus vaccine design

Virus capsids are primed for disassembly, yet capsid integrity is key to generating a protective immune response. Foot-and-mouth disease virus (FMDV) capsids comprise identical pentameric protein subunits held together by tenuous noncovalent interactions and are often unstable. Chemically inactivated or recombinant empty capsids, which could form the basis of future vaccines, are even less stable than live virus. Here we devised a computational method to assess the relative stability of protein-protein interfaces and used it to design improved candidate vaccines for two poorly stable, but globally important, serotypes of FMDV: O and SAT2. We used a restrained molecular dynamics strategy to rank mutations predicted to strengthen the pentamer interfaces and applied the results to produce stabilized capsids. Structural analyses and stability assays confirmed the predictions, and vaccinated animals generated improved neutralizing-antibody responses to stabilized particles compared to parental viruses and wild-type capsids.

Activation of glycoprotein VI (GPVI) and C-type lectin-like receptor-2 (CLEC-2) underlies platelet activation by diesel exhaust particles and other charged/hydrophobic ligands

Platelets are activated by a range of stimuli that share little or no resemblance in structure to each other or to recognized ligands, including diesel exhaust particles (DEP), small peptides [4N1-1, Champs (computed helical anti-membrane proteins), LSARLAF (Leu-Ser-Ala-Arg-Leu-Ala-Phe)], proteins (histones) and large polysaccharides (fucoidan, dextran sulfate). This miscellaneous group stimulate aggregation of human and mouse platelets through the glycoprotein VI (GPVI)-FcR γ-chain complex and/or C-type lectin-like receptor-2 (CLEC-2) as shown using platelets from mice deficient in either or both of these receptors. In addition, all of these ligands stimulate tyrosine phosphorylation in GPVI/CLEC-2-double-deficient platelets, indicating that they bind to additional surface receptors, although only in the case of dextran sulfate does this lead to activation. DEP, fucoidan and dextran sulfate, but not the other agonists, activate GPVI and CLEC-2 in transfected cell lines as shown using a sensitive reporter assay confirming a direct interaction with the two receptors. We conclude that this miscellaneous group of ligands bind to multiple proteins on the cell surface including GPVI and/or CLEC-2, inducing activation. These results have pathophysiological significance in a variety of conditions that involve exposure to activating charged/hydrophobic agents.

Syk and Src family kinases regulate C-type lectin receptor 2 (CLEC-2)-mediated clustering of podoplanin and platelet adhesion to lymphatic endothelial cells

The interaction of C-type lectin receptor 2 (CLEC-2) on platelets with Podoplanin on lymphatic endothelial cells initiates platelet signaling events that are necessary for prevention of blood-lymph mixing during development. In the present study, we show that CLEC-2 signaling via Src family and Syk tyrosine kinases promotes platelet adhesion to primary mouse lymphatic endothelial cells at low shear. Using supported lipid bilayers containing mobile Podoplanin, we further show that activation of Src and Syk in platelets promotes clustering of CLEC-2 and Podoplanin. Clusters of CLEC-2-bound Podoplanin migrate rapidly to the center of the platelet to form a single structure. Fluorescence lifetime imaging demonstrates that molecules within these clusters are within 10 nm of one another and that the clusters are disrupted by inhibition of Src and Syk family kinases. CLEC-2 clusters are also seen in platelets adhered to immobilized Podoplanin using direct stochastic optical reconstruction microscopy. These findings provide mechanistic insight by which CLEC-2 signaling promotes adhesion to Podoplanin and regulation of Podoplanin signaling, thereby contributing to lymphatic vasculature development.

Structure and electrical transport properties of the ordered skutterudites MGe1.5S1.5 (M = Co, Rh, Ir)

High-resolution powder neutron diffraction data collected for the skutterudites MGe1.5S1.5 (M=Co, Rh, Ir) reveal that these materials adopt an ordered skutterudite structure (space group R3¯), in which the anions are ordered in layers perpendicular to the [111] direction. In this ordered structure, the anions form two-crystallographically distinct four-membered rings, with stoichiometry Ge2S2, in which the Ge and S atoms are trans to each other. The transport properties of these materials, which are p-type semiconductors, are discussed in the light of the structural results. The effect of iron substitution in CoGe1.5S1.5 has been investigated. While doping of CoGe1.5S1.5 has a marked effect on both the electrical resistivity and the Seebeck coefficient, these ternary skutterudites exhibit significantly higher electrical resistivities than their binary counterparts.

The atomic structure of low-index surfaces of the intermetallic compound InPd

The intermetallic compound InPd (CsCl type of crystal structure with a broad compositional range) is considered as a candidate catalyst for the steam reforming of methanol. Single crystals of this phase have been grown to study the structure of its three low-index surfaces under ultra-high vacuum conditions, using low energy electron diffraction (LEED), X-ray photoemission spectroscopy (XPS), and scanning tunneling microscopy (STM). During surface preparation, preferential sputtering leads to a depletion of In within the top few layers for all three surfaces. The near-surface regions remain slightly Pd-rich until annealing to ∼580 K. A transition occurs between 580 and 660 K where In segregates towards the surface and the near-surface regions become slightly In-rich above ∼660 K. This transition is accompanied by a sharpening of LEED patterns and formation of flat step-terrace morphology, as observed by STM. Several superstructures have been identified for the different surfaces associated with this process. Annealing to higher temperatures (≥750 K) leads to faceting via thermal etching as shown for the (110) surface, with a bulk In composition close to the In-rich limit of the existence domain of the cubic phase. The Pd-rich InPd(111) is found to be consistent with a Pd-terminated bulk truncation model as shown by dynamical LEED analysis while, after annealing at higher temperature, the In-rich InPd(111) is consistent with an In-terminated bulk truncation, in agreement with density functional theory (DFT) calculations of the relative surface energies. More complex surface structures are observed for the (100) surface. Additionally, individual grains of a polycrystalline sample are characterized by micro-spot XPS and LEED as well as low-energy electron microscopy. Results from both individual grains and “global” measurements are interpreted based on comparison to our single crystals findings, DFT calculations and previous literature.

Impact of chemical structure of flavanol monomers and condensed tannins on in vitro anthelmintic activity against bovine nematodes

Plants containing condensed tannins (CT) may have potential to control gastrointestinal nematodes (GIN) of cattle. The aim was to investigate the anthelmintic activities of four flavan-3-ols, two galloyl derivatives and 14 purified CT fractions, and to define which structural features of CT determine the anti-parasitic effects against the main cattle nematodes. We used in vitro tests targeting L1 larvae (feeding inhibition assay) and adults (motility assay) of Ostertagia ostertagi and Cooperia oncophora. In the larval feeding inhibition assay, O. ostertagi L1 were significantly more susceptible to all CT fractions than C. oncophora L1. The mean degree of polymerization of CT (i.e. average size) was the most important structural parameter: large CT reduced larval feeding more than small CT. The flavan-3-ols of prodelphinidin (PD)-type tannins had a stronger negative influence on parasite activity than the stereochemistry, i.e. cis- vs trans-configurations, or the presence of a gallate group. In contrast, for C. oncophora high reductions in the motility of larvae and adult worms were strongly related with a higher percentage of PDs within the CT fractions while there was no effect of size. Overall, the size and the percentage of PDs within CT seemed to be the most important parameters that influence anti-parasitic activity.

STRUCTURE OF THE SHRUB-ARBOREAL COMPONENT OF AN ATLANTIC FOREST FRAGMENT ON A HILLOCK IN THE CENTRAL LOWLAND OF RIO DE JANEIRO, BRAZIL

The present study describes and evaluates the horizontal and vertical structures of a lowland forest fragment on a hillock in the municipality of Silva Jardim, Rio de Janeiro State, Brazil (22 degrees 31`56 `` S and 42 degrees 20`46 `` W). Twenty plots (10x2m) totaling 0.5ha were laid out following the slope grade using DBH >= 5cm as the inclusion criterion. A total of 734 individuals were encountered, yielding a total density of 1468 ind./ha and a total basal area of 10783m(2). The richness values (129 species/41 families), Shannon-Wiener diversity (4.22) and equitability (0.87) indices indicated an accentuated floristic heterogeneity and low ecological dominance. Lauraceae, Myrtaceae, Fabaceae and Euphorbiaceae showed the greatest species richness, corroborating other studies that indicated these species as the most representative of Atlantic Forest areas in southeastern Brazil. The species with the greatest importance values (VI) were Aparisthmium cordatum, Guapira opposita, Lacistema pubescens, Xylopia sericea, Tapirira guianensis and Piptocarpha macropoda. The high diversity observed was influenced by earlier anthropogenic actions and by the current successional stage. The forest fragment studied demonstrated closer floristic similarity to areas inventoried in a close-by biological reserve than to fragments dispersed throughout the coastal plain. Similarities in soil type, degree of soil saturation and use-history of forest resources all support these relationships. The fragmented physiognomy of the central lowland in this region and the use-history of the landscape make these small remnant forest areas important in terms of establishing strategies for landscape restoration and species conservation.

Two new species of Pamphobeteus Pocock 1901 (Araneae : Mygalomorphae : Theraphosidae) from Brazil, with a new type of stridulatory organ

Two new species of Pamphobeteus Pocock 1901 are described from Brazil: Pamphobeteus crassifemur sp. nov. and Pamphobeteus grandis sp. nov.; Pamphobeteus nigricolor, formerly described from Colombia, Ecuador and Bolivia, is recorded from Brazil and its distribution in Ecuador and Bolivia is questioned. A new type of stridulatory organ is described from legs III and IV of P. crassifemur sp. nov. The structure consists of spiniform setae. Stridulation occurs when the spider moves the legs III and IV, sometimes while shedding urticating hairs.