A dramatic isotope effect in the reaction of ClSiH with trimethylsilane-1-d: experimental evidence for intermediate complexes in silylene Si-H(D) insertion reactions

A kinetic isotope effect (kD/kH) of 7.4 has been found for the reaction of chlorosilylene with trimethysilane (Me3SiD vs Me3SiH). Such a value can be accounted for by theoretical modelling, but only if an internal rearrangement of the initially form complex is included in the mechanism. This provides the first concrete evidence for such complexes.

Solution-free sets for sums of binary forms

In this paper, we obtain quantitative estimates for the asymptotic density of subsets of the integer lattice Z2 that contain only trivial solutions to an additive equation involving binary forms. In the process we develop an analogue of Vinogradov’s mean value theorem applicable to binary forms.

Historical and idealized climate model experiments: an intercomparison of Earth system models of intermediate complexity

Both historical and idealized climate model experiments are performed with a variety of Earth system models of intermediate complexity (EMICs) as part of a community contribution to the Intergovernmental Panel on Climate Change Fifth Assessment Report. Historical simulations start at 850 CE and continue through to 2005. The standard simulations include changes in forcing from solar luminosity, Earth's orbital configuration, CO2, additional greenhouse gases, land use, and sulphate and volcanic aerosols. In spite of very different modelled pre-industrial global surface air temperatures, overall 20th century trends in surface air temperature and carbon uptake are reasonably well simulated when compared to observed trends. Land carbon fluxes show much more variation between models than ocean carbon fluxes, and recent land fluxes appear to be slightly underestimated. It is possible that recent modelled climate trends or climate–carbon feedbacks are overestimated resulting in too much land carbon loss or that carbon uptake due to CO2 and/or nitrogen fertilization is underestimated. Several one thousand year long, idealized, 2 × and 4 × CO2 experiments are used to quantify standard model characteristics, including transient and equilibrium climate sensitivities, and climate–carbon feedbacks. The values from EMICs generally fall within the range given by general circulation models. Seven additional historical simulations, each including a single specified forcing, are used to assess the contributions of different climate forcings to the overall climate and carbon cycle response. The response of surface air temperature is the linear sum of the individual forcings, while the carbon cycle response shows a non-linear interaction between land-use change and CO2 forcings for some models. Finally, the preindustrial portions of the last millennium simulations are used to assess historical model carbon-climate feedbacks. Given the specified forcing, there is a tendency for the EMICs to underestimate the drop in surface air temperature and CO2 between the Medieval Climate Anomaly and the Little Ice Age estimated from palaeoclimate reconstructions. This in turn could be a result of unforced variability within the climate system, uncertainty in the reconstructions of temperature and CO2, errors in the reconstructions of forcing used to drive the models, or the incomplete representation of certain processes within the models. Given the forcing datasets used in this study, the models calculate significant land-use emissions over the pre-industrial period. This implies that land-use emissions might need to be taken into account, when making estimates of climate–carbon feedbacks from palaeoclimate reconstructions.

Endogenous retailer preferences in intermediate good markets

We model strategic interaction in a differentiated input market as a game among two suppliers and n retailers. Each one of the upstream firms chooses the specification of the input which it will offer.Then, retailers choose their type from a continuum of possibilities. The decisions made in these two first stages affect the degree of compatibility between each retailer's ideal input specification and that of the inputs offered by the two upstream firms. In a third stage, upstream firms compete setting input prices. Equilibrium may be of the two-vendor policy or of the technological monopoly type.

Forms of addresses and terms of reference

This paper examines the relationship between the use of names and other words in address and in reference: how does the way that speaker A addresses B differ from the way that A refers to B, and what are the factors affecting this difference? The study, based on observation and interviews, attempts both to solve a problem in pragmatics and to help historical linguists and others who need to know the extent to which it may be justified to extrapolate from referential to address usage and vice versa.

An examination of climate sensitivity for idealised climate change experiments in an intermediate general circulation model

Radiative forcing and climate sensitivity have been widely used as concepts to understand climate change. This work performs climate change experiments with an intermediate general circulation model (IGCM) to examine the robustness of the radiative forcing concept for carbon dioxide and solar constant changes. This IGCM has been specifically developed as a computationally fast model, but one that allows an interaction between physical processes and large-scale dynamics; the model allows many long integrations to be performed relatively quickly. It employs a fast and accurate radiative transfer scheme, as well as simple convection and surface schemes, and a slab ocean, to model the effects of climate change mechanisms on the atmospheric temperatures and dynamics with a reasonable degree of complexity. The climatology of the IGCM run at T-21 resolution with 22 levels is compared to European Centre for Medium Range Weather Forecasting Reanalysis data. The response of the model to changes in carbon dioxide and solar output are examined when these changes are applied globally and when constrained geographically (e.g. over land only). The CO2 experiments have a roughly 17% higher climate sensitivity than the solar experiments. It is also found that a forcing at high latitudes causes a 40% higher climate sensitivity than a forcing only applied at low latitudes. It is found that, despite differences in the model feedbacks, climate sensitivity is roughly constant over a range of distributions of CO2 and solar forcings. Hence, in the IGCM at least, the radiative forcing concept is capable of predicting global surface temperature changes to within 30%, for the perturbations described here. It is concluded that radiative forcing remains a useful tool for assessing the natural and anthropogenic impact of climate change mechanisms on surface temperature.

Molecular forms of porphobilinogen deaminase in acute intermittent porphyria. A study by Western immunoblotting

Acute intermittent porphyria is an inborn error of haem synthesis which is transmitted as a dominant character with variable phenotypic expression. The disorder is caused by a partial deficiency of porphobilinogen deaminase in all tissues so far studied. The nature of the enzymatic deficiency of porphobilinogen deaminase in haemolysates from patients with acute intermittent porphyria was examined by the use of monospecific antibody probes. In affected heterozygotes from three British pedigrees of diverse ancestry, the catalytic deficiency of porphobilinogen deaminase was accompanied by diminished enzyme protein, as determined by radial immunodiffusion. No evidence of functionally attenuated enzyme was demonstrable by kinetic studies. The molecular forms of the residual enzyme were investigated in red cell extracts and in lysed preparations of reticulocytes by a sensitive Western blotting procedure. This revealed the presence of reduced amounts of porphobilinogen deaminase polypeptide co-migrating with wild type enzyme (Mr approximately 40,000), and no evidence of variant forms in situ. The studies show that porphobilinogen deaminase deficiency in acute intermittent porphyria is commonly associated with a CRM-phenotype. The residual activity under these circumstances is thus related to expression of a single normal allele, since sensitive techniques detected neither aberrant nor degraded forms of the enzyme in erythroid tissues.

The dermomyotome ventrolateral lip is essential for the hypaxial myotome formation

Background The myotome is the primitive skeletal muscle that forms within the embryonic metameric body wall. It can be subdivided into an epaxial and hypaxial domain. It has been shown that the formation of the epaxial myotome requires the dorsomedial lip of the dermomyotome (DML). Although the ventrolateral lip (VLL) of the dermomyotome is believed to be required for the formation of the hypaxial myotome, experimentally evidence for this statement still needs to be provided. Provision of such data would enable the resolution of a debate regarding the formation of the hypaxial dermomyotome. Two mechanisms have been proposed for this tissue. The first proposes that the intermediate dermomyotome undergoes cellular expansion thereby pushing the ventral lateral lip in a lateral direction (translocation). In contrast, the alternative view holds that the ventral lateral lip grows laterally. Results Using time lapse confocal microscopy, we observed that the GFP-labelled ventrolateral lip (VLL) of the dermomyotome grows rather than translocates in a lateral direction. The necessity of the VLL for lateral extension of the myotome was addressed by ablation studies. We found that the hypaxial myotome did not form after VLL ablation. In contrast, the removal of an intermediate portion of the dermomyotome had very little effect of the hypaxial myotome. These results demonstrate that the VLL is required for the formation of the hypaxial myotome. Conclusion Our study demonstrates that the dermomyotome ventrolateral lip is essential for the hypaxial myotome formation and supports the lip extension model. Therefore, despite being under independent signalling controls, both the dorsomedial and ventrolateral lip fulfil the same function, i.e. they extend into adjacent regions permitting the growth of the myotome.

Silica templating of a self-assembling peptide amphiphile that forms nanotapes

The peptide amphiphile C16-KTTKS templates silica polymerization, enabling the production of silica nanotape structures, imaged via electron microscopy (TEM and SEM). X-ray scattering shows that the nanotapes comprise stacked layers, as for the parent peptide amphiphile, but with a substantially increased layer spacing resulting from silica polymerization.

Conceptualising public-private partnerships: a critical appraisal of approaches to meanings and forms

Purpose – The purpose of this article is to survey various meanings attached to a public-private partnership (PPP) and related aspects in Western literature, and identify commonalities and differences between them. Additionally, the article intends to critically assess conflicting and overlapping views on contractual and institutional PPPs, their forms and models, and draw insights for transitional economies. Design/methodology/approach – The article contrasts and compares views on PPP meanings, forms and models within Western PPP literature, and also draws comparisons with understanding of partnership aspects in the Russian language sources. The article examines theories underpinning PPPs, builds connections to PPP advantages and drawbacks, and provides critical assessment of net benefits that PPPs may bring along to the society. Findings – The article concludes that future PPP research in transitional countries such as Kazakhstan and Russia, particularly in the area of organisational and power arrangements in partnerships, may delineate new concepts such as government as a guarantor of a PPP project, social significance of a PPP project, and risk management in a country's contextual environment. Practical implications – In transitional countries, in which PPPs are in their infancy, clarification of theoretical positions, and identification of commonalities and differences between meanings attached to the PPP terminology may enable better decisions by researchers and practitioners in their selection and further development of partnerships and related concepts. Originality/value – Research in the field of PPPs in transitional countries such as Russia and Kazakhstan is in its infancy. The paper intends to contribute to the body of knowledge about PPPs by providing detailed account and categorisation of their principal meanings, forms, models, underpinning theories, and drawing insights for future research in transitional countries.

Effects of land management on different forms of soil carbon in olive groves in Mediterranean areas

This study analyses soil organic carbon (SOC) and hot-water extractable carbon (HWC), both measures of soil quality, under different land management: (1) conventional tillage (CT); (2) CT plus the addition of oil mill waste alperujo (A); (3) CT plus the addition of oil mill waste olive leaves (L); (4) no tillage with chipped pruned branches (NT1); and (5) no tillage with chipped pruned branches and weeds (NT2); in a typical Mediterranean agricultural area; the olive groves of Andalucía, southern Spain. SOC values in CT, A, NT1 and NT2 decreased with depth, but in NT2 the surface horizon (0-5 cm) had higher values than the other treatments, 47% more than the average values in the other three soils. In L, SOC also decreased with depth, although there was an increase of 88.5% from the first (0-10 cm) to the second horizon (10-16 cm). Total SOC stock values were very similar under A (101.9 Mg ha−1), CT (101.7 Mg ha−1), NT1 (105.8 Mg ha−1) and NT2 (111.3 Mg ha−1, if we consider the same depth of the others). However, SOC under L was significantly higher (p < 0.05) at 250.2 Mg ha−1. HWC decreased with depth in A, CT and NT1. NT2 and L followed the same pattern as the other management types but with a higher value in the surface horizon (2.3 and 4.9 mg g−1 respectively). Overall, our results indicate that application of oil mill waste olive leaves under CT (L) is a good management practice to improve SOC and reduce waste.