Synthesis and incorporation into cyclic peptides of tolan amino acids and their hydrogenated congeners: construction of an array of A–B-loop mimetics of the Cε3 domain of human IgE

The disruption of the human immunolobulin E–high affinity receptor I (IgE–FcεRI) protein–protein interaction (PPI) is a validated strategy for the development of anti asthma therapeutics. Here, we describe the synthesis of an array of conformationally constrained cyclic peptides based on an epitope of the A–B loop within the Cε3 domain of IgE. The peptides contain various tolan (i.e., 1,2-biarylethyne) amino acids and their fully and partially hydrogenated congeners as conformational constraints. Modest antagonist activity (IC50 660 μM) is displayed by the peptide containing a 2,2′-tolan, which is the one predicted by molecular modeling to best mimic the conformation of the native A–B loop epitope in IgE.

Incorporation of water vapour transfer in the JULES Land Surface Model: implications for key soil variables and land surface fluxes

This study focuses on the mechanisms underlying water and heat transfer in upper soil layers, and their effects on soil physical prognostic variables and the individual components of the energy balance. The skill of the JULES (Joint UK Land Environment Simulator) land surface model (LSM) to simulate key soil variables, such as soil moisture content and surface temperature, and fluxes such as evaporation, is investigated. The Richards equation for soil water transfer, as used in most LSMs, was updated by incorporating isothermal and thermal water vapour transfer. The model was tested for three sites representative of semi-arid and temperate arid climates: the Jornada site (New Mexico, USA), Griffith site (Australia) and Audubon site (Arizona, USA). Water vapour flux was found to contribute significantly to the water and heat transfer in the upper soil layers. This was mainly due to isothermal vapour diffusion; thermal vapour flux also played a role at the Jornada site just after rainfall events. Inclusion of water vapour flux had an effect on the diurnal evolution of evaporation, soil moisture content and surface temperature. The incorporation of additional processes, such as water vapour flux among others, into LSMs may improve the coupling between the upper soil layers and the atmosphere, which in turn could increase the reliability of weather and climate predictions.

Incorporation of a physically based melt pond scheme into the sea ice component of a climate model

The extent and thickness of the Arctic sea ice cover has decreased dramatically in the past few decades with minima in sea ice extent in September 2005 and 2007. These minima have not been predicted in the IPCC AR4 report, suggesting that the sea ice component of climate models should more realistically represent the processes controlling the sea ice mass balance. One of the processes poorly represented in sea ice models is the formation and evolution of melt ponds. Melt ponds accumulate on the surface of sea ice from snow and sea ice melt and their presence reduces the albedo of the ice cover, leading to further melt. Toward the end of the melt season, melt ponds cover up to 50% of the sea ice surface. We have developed a melt pond evolution theory. Here, we have incorporated this melt pond theory into the Los Alamos CICE sea ice model, which has required us to include the refreezing of melt ponds. We present results showing that the presence, or otherwise, of a representation of melt ponds has a significant effect on the predicted sea ice thickness and extent. We also present a sensitivity study to uncertainty in the sea ice permeability, number of thickness categories in the model representation, meltwater redistribution scheme, and pond albedo. We conclude with a recommendation that our melt pond scheme is included in sea ice models, and the number of thickness categories should be increased and concentrated at lower thicknesses.

Movement of newly assimilated 13C carbon in the grass Lolium perenne and its incorporation into rhizosphere microbial DNA

One of the key processes that drives rhizosphere microbial activity is the exudation of soluble organic carbon (C) by plant roots. We describe an experiment designed to determine the impact of defoliation on the partitioning and movement of C in grass (Lolium perenne L.), soil and grass-sterile sand microcosms, using a (13)CO(2) pulse-labelling method. The pulse-derived (13)C in the shoots declined over time, but that of the roots remained stable throughout the experiment. There were peaks in the atom% (13)C of rhizosphere CO(2) in the first few hours after labelling probably due to root respiration, and again at around 100 h. The second peak was only seen in the soil microcosms and not in those with sterilised sand as the growth medium, indicating possible microbial activity. Incorporation of the (13)C label into the microbial biomass increased at 100 h when incorporation into replicating cells, as indicated by the amounts of the label in the microbial DNA, started to increase. These results indicate that the rhizosphere environment is conducive to bacterial growth and replication. The results also show that defoliation had no impact on the pattern of movement of (13)C from plant roots into the microbial population in the rhizosphere.

Expression of epitope-tagged LMW glutenin subunits in the starchy endosperm of transgenic wheat and their incorporation into glutenin polymers

The low-molecular-weight (LMW) glutenin subunits are components of the highly cross-linked glutenin polymers that confer viscoelastic properties to gluten and dough. They have both quantitative and qualitative effects on dough quality that may relate to differences in their ability to form the inter-chain disulphide bonds that stabilise the polymers. In order to determine the relationship between dough quality and the amounts and properties of the LMW subunits, we have transformed the pasta wheat cultivars Svevo and Ofanto with three genes encoding proteins, which differ in their numbers or positions of cysteine residues. The transgenes were delivered under control of the high-molecular-weight (HMW) subunit 1Dx5 gene promoter and terminator regions, and the encoded proteins were C-terminally tagged by the introduction of the c-myc epitope. Stable transformants were obtained with both cultivars, and the use of a specific antibody to the c-myc epitope tag allowed the transgene products to be readily detected in the complex mixture of LMW subunits. A range of transgene expression levels was observed. The addition of the epitope tag did not compromise the correct folding of the trangenic subunits and their incorporation into the glutenin polymers. Our results demonstrate that the ability to specifically epitope-tag LMW glutenin transgenes can greatly assist in the elucidation of their individual contributions to the functionality of the complex gluten system.

Environmental and ecological economics in the 21st century: an age adjusted citation analysis of the influential articles, journals, authors and institutions

We investigate the influence of articles, authors, journals and institutions in the field of environmental and ecological economics. We depart from studies that investigated the literature until 2001 and include a time period that has witnessed an enormous increase of importance in the field. We adjust for the age effect given the huge impact of the year of an article's publication on its influence and we show that this adjustment does make a substantial difference — especially for disaggregated units of analysis with diverse age characteristics such as articles or authors. We analyse 6597 studies on environmental and ecological economics published between 2000 and 2009. We provide rankings of the influential articles, authors, journals and institutions and find that Ecological Economics, Energy Economics and the Journal of Environmental Economics and Management have the most influential articles, they publish very influential authors and their articles are cited most. The University of Maryland, Resources for the Future, the University of East Anglia and the World Bank appear to be the most influential institutions in the field of environmental and ecological economics.

Production and on-line comprehension of definite articles and clitic pronouns by Greek sequential bilingual children and monolingual children with specific language impairment

The present study compared production and on-line comprehension of definite articles and third person direct object clitic pronouns in Greek-speaking typically developing, sequential bilingual (L2-TD) children and monolingual children with specific language impairment (L1-SLI). Twenty Turkish Greek L2-TD children, 16 Greek L1-SLI children, and 31 L1-TD Greek children participated in a production task examining definite articles and clitic pronouns and, in an on-line comprehension task, involving grammatical sentences with definite articles and clitics and sentences with grammatical violations induced by omitted articles and clitics. The results showed that the L2-TD children were sensitive to the grammatical violations despite low production. In contrast, the children with SLI were not sensitive to clitic omission in the on-line task, despite high production. These results support a dissociation between production and on-line comprehension in L2 children and for impaired grammatical representations and lack of automaticity in children with SLI. They also suggest that on-line comprehension tasks may complement production tasks by differentiating between the language profiles of L2-TD children and children with SLI.

Cobalt incorporation in calcite: Thermochemistry of (Ca,Co)CO3 solid solutions from density functional theory simulations

The incorporation of cobalt in mixed metal carbonates is a possible route to the immobilization of this toxic element in the environment. However, the thermodynamics of (Ca,Co)CO3 solid solutions are still unclear due to conflicting data from experiment and from the observation of natural ocurrences. We report here the results of a computer simulation study of the mixing of calcite (CaCO3) and spherocobaltite (CoCO3), using density functional theory calculations. Our simulations suggest that previously proposed thermodynamic models, based only on the range of observed compositions, significantly overestimate the solubility between the two solids and therefore underestimate the extension of the miscibility gap under ambient conditions. The enthalpy of mixing of the disordered solid solution is strongly positive and moderately asymmetric: calcium incorporation in spherocobaltite is more endothermic than cobalt incorporation in calcite. Ordering of the impurities in (0001) layers is energetically favourable with respect to the disordered solid solution at low temperatures and intermediate compositions, but the ordered phase is still unstable to demixing. We calculate the solvus and spinodal lines in the phase diagram using a sub-regular solution model, and conclude that many Ca1-xCoxCO3 mineral solid solutions (with observed compositions of up to x=0.027, and above x=0.93) are metastable with respect to phase separation. We also calculate solid/aqueous distribution coefficients to evaluate the effect of the strong non-ideality of mixing on the equilibrium with aqueous solution, showing that the thermodynamically-driven incorporation of cobalt in calcite (and of calcium in spherocobaltite) is always very low, regardless of the Co/Ca ratio of the aqueous environment.

Efficient incorporation of channel cross-section geometry uncertainty into regional and global scale flood inundation models

This paper investigates the challenge of representing structural differences in river channel cross-section geometry for regional to global scale river hydraulic models and the effect this can have on simulations of wave dynamics. Classically, channel geometry is defined using data, yet at larger scales the necessary information and model structures do not exist to take this approach. We therefore propose a fundamentally different approach where the structural uncertainty in channel geometry is represented using a simple parameterization, which could then be estimated through calibration or data assimilation. This paper first outlines the development of a computationally efficient numerical scheme to represent generalised channel shapes using a single parameter, which is then validated using a simple straight channel test case and shown to predict wetted perimeter to within 2% for the channels tested. An application to the River Severn, UK is also presented, along with an analysis of model sensitivity to channel shape, depth and friction. The channel shape parameter was shown to improve model simulations of river level, particularly for more physically plausible channel roughness and depth parameter ranges. Calibrating channel Manning’s coefficient in a rectangular channel provided similar water level simulation accuracy in terms of Nash-Sutcliffe efficiency to a model where friction and shape or depth were calibrated. However, the calibrated Manning coefficient in the rectangular channel model was ~2/3 greater than the likely physically realistic value for this reach and this erroneously slowed wave propagation times through the reach by several hours. Therefore, for large scale models applied in data sparse areas, calibrating channel depth and/or shape may be preferable to assuming a rectangular geometry and calibrating friction alone.

Production of definite and indefinite articles in typically developing English-speaking children and children with SLI

The present paper examines the production of definite and indefinite articles in English-speaking typically developing (TD) children and children with Specific Language Impairment (SLI). Twenty four English-speaking children with SLI (mean age: 7;5), twenty nine TD age-matched (TD-AM) children (mean age: 7;5) and eleven younger (mean age: 5;5) TD vocabulary-matched (TD-VM) children participated in a production task involving short stories without picture props based on Schafer and de Villiers (2000). Article production was examined in two different semantic contexts for the definite article, namely in the anaphoric and the bridging context. In the anaphoric condition, definiteness is established via linguistic means, whereas in the bridging condition via shared world knowledge. Indefinite article production was examined in the referential specific, non-referential predicational, and non-referential instrumental contexts. The referential specific context involves [+speaker, −hearer] knowledge and the non-referential predicational and instrumental [−speaker, −hearer] knowledge. Results showed that in the definite article contexts, all three groups performed better on the bridging compared with the anaphoric condition; in the indefinite article contexts, they had better performance on the non-referential predicational vs. the referential specific and the non-referential instrumental conditions. In terms of errors, the TD-VM children and the children with SLI produced significantly more substitutions than the TD-AM children in the definite article contexts. In the indefinite article contexts, the three groups did not differ in terms of accuracy or error patterns. The present results point towards problems in the discourse integration of entities that are part of the speaker's and hearer's knowledge in children with SLI and TD-VM controls, especially in definite articles. These problems are accentuated in the children with SLI due to their grammatical impairment and suggest that children with SLI exhibit a delayed acquisition profile.

Environmental and ecological economics in the 21st century: an age adjusted citation analysis of the most influential articles, journals, authors and institutions

We investigate the influence of articles, authors, journals and institutions in the field of environmental and ecological economics. We depart from studies that investigated the literature until 2001 and include a time period that has witnessed an enormous increase of importance in the field. We adjust for the age effect given the huge impact of the year of an article's publication on its influence and we show that this adjustment does make a substantial difference — especially for disaggregated units of analysis with diverse age characteristics such as articles or authors. We analyse 6597 studies on environmental and ecological economics published between 2000 and 2009. We provide rankings of the influential articles, authors, journals and institutions and find that Ecological Economics, Energy Economics and the Journal of Environmental Economics and Management have the most influential articles, they publish very influential authors and their articles are cited most. The University of Maryland, Resources for the Future, the University of East Anglia and the World Bank appear to be the most influential institutions in the field of environmental and ecological economics.

Incorporation of different and changing client interests in the course of a project

There is a widespread assumption that clients’ expectations should be accommodated during a building project. However, there may be conflicting expectations within a client organization and these may change over time in the course of a project. Actor-Network Theory (ANT) is used to study the incorporation of client expectations into the on-going development of a building project. To illustrate this, negotiations over a particular decision, namely the location of a building on one university campus was analysed. Negotiations went through a number of stages, involving a master plan architect, members of the public, campus maps and the Vice Chancellor. An ANT analysis helped to trace diverse actors' interests in a series of discussions and how these interests conflict with each other as one option was chosen over another. The analysis revealed new client interests in each negotiation process. Also, the prioritisation of client interests changed over time. The documentation of diverse and dynamic client interests especially contributes to the understanding of how some client interests fail to be incorporated in decision-making processes

Improvement in the Reduction Behavior of Novel ZrO(2)-CeO(2) Solid Solutions with a Tubular Nanostructure by Incorporation of Pd

In this work, 1 wt % Pd/ZrO(2)-CeO(2) mixed oxide nanotubes with 90 mol % CeO(2) were synthesized following a very simple, high-yield procedure and their properties were characterized by synchrotron radiation X-ray diffraction, X-ray absorption near-edge spectroscopy (XANES), and scanning and high-resolution transmission electron microscopy (SEM and HRTEM). In situ XANES experiments were carried out under reducing conditions to investigate the reduction behavior of these novel nanotube materials. The Pd/CeO(2)-based nanotubes exhibited the cubic phase (Fm3m space group). The nanotube walls were composed of nanoparticles with an average crystallite size of about 7 nm, and the nanotubes exhibited a large specific surface area (85 m(2).g(-1)). SEM and HRTEM studies showed that individual nanotubes were composed of a curved sheet of these nanoparticles. Elemental analysis showed that the Ce:Zr:Pd ratios appeared to be approximately constant across space, suggesting compositional homogeneity in the samples. XANES results indicated that the extent of reduction of these materials is low and that the Ce(4+) state is in the majority over the reduced Ce(3+) state. The results suggest that Pd cations-most likely Pd(2+)-form a Pd-Ce-Zr oxide solid solution and that the Pd(2+) is stabilized against reduction in this phase. However, incorporation of the Pd (1 wt %) into the crystal lattice of the nanotubes also appeared to destabilize Ce(4+) against reduction to Ce(3+) and caused a significant increase in its reducibility.