Computationally Guided Design of a Readily Assembled Phosphite- Thioether Ligand for a Broad Range of Pd-Catalyzed Asymmetric Allylic Substitutions

A modular approach employing indene as common starting material, has enabled the straightforward preparation in three reaction steps of P-thioether ligands for the Pd-catalyzed asymmetric allylic substitution. The analysis of a starting library of P-thioether ligands based on rational design and theoretical calculations has led to the discovery of an optimized anthracenethiol derivative with excellent behavior in the reaction of choice. Improving most approaches reported to date, this ligand presents a broad substrate and nucleophile scope. Excellent enantioselectivities have been achieved for a range of linear and cyclic allylic substrates using a large number of C-, N-, and O-nucleophiles (40 compounds in total). The species responsible for the catalytic activity have been further investigated by NMR in order to clearly establish the origin of the enantioselectivity. The resulting products have been derivatized by means of ring-closing metathesis or Pauson–Khand reactions to further prove the synthetic versatility of the methodology for preparing enantiopure complex structures

Relationship between Structure, Entropy and Diffusivity in Water and Water-like Liquids

Anomalous behaviour of the excess entropy ($S_e$) and the associated scaling relationship with diffusivity are compared in liquids with very different underlying interactions but similar water-like anomalies: water (SPC/E and TIP3P models), tetrahedral ionic melts (SiO$_2$ and BeF$_2$) and a fluid with core-softened, two-scale ramp (2SRP) interactions. We demonstrate the presence of an excess entropy anomaly in the two water models. Using length and energy scales appropriate for onset of anomalous behaviour, the density range of the excess entropy anomaly is shown to be much narrower in water than in ionic melts or the 2SRP fluid. While the reduced diffusivities ($D^*$) conform to the excess entropy scaling relation, $D^* =A\exp (\alpha S_e)$ for all the systems (Y. Rosenfeld, Phys. Rev. A {\bf 1977}, {\it 15}, 2545), the exponential scaling parameter, $\alpha$, shows a small isochore-dependence in the case of water. Replacing $S_e$ by pair correlation-based approximants accentuates the isochore-dependence of the diffusivity scaling. Isochores with similar diffusivity scaling parameters are shown to have the temperature dependence of the corresponding entropic contribution. The relationship between diffusivity, excess entropy and pair correlation approximants to the excess entropy are very similar in all the tetrahedral liquids.Comment: 24 pages, 4 figures, to be published in Journal of Physical Chemistry

Toward Good Read-Across Practice (GRAP) guidance.

Grouping of substances and utilizing read-across of data within those groups represents an important data gap filling technique for chemical safety assessments. Categories/analogue groups are typically developed based on structural similarity and, increasingly often, also on mechanistic (biological) similarity. While read-across can play a key role in complying with legislations such as the European REACH regulation, the lack of consensus regarding the extent and type of evidence necessary to support it often hampers its successful application and acceptance by regulatory authorities. Despite a potentially broad user community, expertise is still concentrated across a handful of organizations and individuals. In order to facilitate the effective use of read-across, this document aims to summarize the state-of-the-art, summarizes insights learned from reviewing ECHA published decisions as far as the relative successes/pitfalls surrounding read-across under REACH and compile the relevant activities and guidance documents. Special emphasis is given to the available existing tools and approaches, an analysis of ECHA's published final decisions associated with all levels of compliance checks and testing proposals, the consideration and expression of uncertainty, the use of biological support data and the impact of the ECHA Read-Across Assessment Framework (RAAF) published in 2015

Correlation of the ratio of metastatic to non-metastatic cancer cases with the degree of socioeconomic deprivation among Texas counties

<p>Abstract</p> <p>Background</p> <p>Previous studies have demonstrated that cancer registrations and hospital discharge rate are closely correlated with census data-based socioeconomic deprivation indices. We hypothesized that communities with higher degrees of socioeconomic deprivation tend to have a higher ratio of metastatic to non-metastatic cancer cases (lung, breast, prostate, female genital system, colorectal cancers or all types of cancers combined). In this study, we investigate the potential link between this ratio and the Wellbeing Index (WI) among Texas counties.</p> <p>Results</p> <p>Cancer data in 2000 were provided by the Texas Cancer Registry, while data on the ten socioeconomic variables among the 254 Texas counties in 2000 for building the WI were obtained from U.S. Census Bureau. The ten socioeconomic status variables were subjected to the principal component analysis, and the first principal component scores were grouped into deciles for the WI (1 to 10) and the 254 Texas counties were classified into 10 corresponding groups. Weighted linear regression analyses and a Cochran-Armitage trend test were performed to determine the relationship between the ratio of age-adjusted metastatic to non-metastatic cancer incidence cases and WI. The ratios of metastatic to non-metastatic cases of female genital system cancer (<it>r</it>²= 0.84, <it>p </it>= 0.0002), all-type cancers (<it>r</it>²= 0.73, <it>p </it>= 0.0017) and lung cancer (<it>r</it>²= 0.54, <it>p </it>= 0.0156) at diagnosis were positively correlated with WI.</p> <p>Conclusions</p> <p>The ratios of metastatic to non-metastatic cases of all-type, female genital system and lung cancers at diagnosis were statistically correlated with socioeconomic deprivation. Potential mediators for the correlation warrant further investigation in order to reduce health disparities associated with socioeconomic inequality.</p

Global Ocean Sediment Composition and Burial Flux in the Deep Sea

Quantitative knowledge about the burial of sedimentary components at the seafloor has wide-ranging implications in ocean science, from global climate to continental weathering. The use of 230Th-normalized fluxes reduces uncertainties that many prior studies faced by accounting for the effects of sediment redistribution by bottom currents and minimizing the impact of age model uncertainty. Here we employ a recently compiled global data set of 230Th-normalized fluxes with an updated database of seafloor surface sediment composition to derive atlases of the deep-sea burial flux of calcium carbonate, biogenic opal, total organic carbon (TOC), nonbiogenic material, iron, mercury, and excess barium (Baxs). The spatial patterns of major component burial are mainly consistent with prior work, but the new quantitative estimates allow evaluations of deep-sea budgets. Our integrated deep-sea burial fluxes are 136 Tg C/yr CaCO3, 153 Tg Si/yr opal, 20Tg C/yr TOC, 220 Mg Hg/yr, and 2.6 Tg Baxs/yr. This opal flux is roughly a factor of 2 increase over previous estimates, with important implications for the global Si cycle. Sedimentary Fe fluxes reflect a mixture of sources including lithogenic material, hydrothermal inputs and authigenic phases. The fluxes of some commonly used paleo-productivity proxies (TOC, biogenic opal, and Baxs) are not well-correlated geographically with satellite-based productivity estimates. Our new compilation of sedimentary fluxes provides detailed regional and global information, which will help refine the understanding of sediment preservation

Globally invariant metabolism but density-diversity mismatch in springtails.

Soil life supports the functioning and biodiversity of terrestrial ecosystems. Springtails (Collembola) are among the most abundant soil arthropods regulating soil fertility and flow of energy through above- and belowground food webs. However, the global distribution of springtail diversity and density, and how these relate to energy fluxes remains unknown. Here, using a global dataset representing 2470 sites, we estimate the total soil springtail biomass at 27.5 megatons carbon, which is threefold higher than wild terrestrial vertebrates, and record peak densities up to 2 million individuals per square meter in the tundra. Despite a 20-fold biomass difference between the tundra and the tropics, springtail energy use (community metabolism) remains similar across the latitudinal gradient, owing to the changes in temperature with latitude. Neither springtail density nor community metabolism is predicted by local species richness, which is high in the tropics, but comparably high in some temperate forests and even tundra. Changes in springtail activity may emerge from latitudinal gradients in temperature, predation and resource limitation in soil communities. Contrasting relationships of biomass, diversity and activity of springtail communities with temperature suggest that climate warming will alter fundamental soil biodiversity metrics in different directions, potentially restructuring terrestrial food webs and affecting soil functioning

Learning from Poverty: Why Business Schools Should Address Poverty, and How They Can Go About It.

In the past few years, business schools have begun to address poverty issues in their teaching, learning and curricula. While this is a positive development, the arguments for reconfiguring educational programs to address such matters remain undeveloped, with much of the impetus for such endeavors rooted in calls for social responsibility in the United Nations Millennium Development Goals, the Social Compact, the Principles for Responsible Management Education and benchmarks such as ISO 26000. This article seeks to clarify the pedagogical grounds for integrating poverty issues in management education by examining the intellectual and personal development benefits of doing so. By critically examining four modes of business involvement in poverty reduction, the article shows how such initiatives can be used as intellectual lenses through which to view the complex and often paradoxical interconnections between socioeconomic and environmental systems. It is thus concluded that a consideration of poverty issues is not a marginal matter, but is key to grasping the 21st century complexities of global business and management

Ionic Liquid Crystals in Tribology

The present work intends to provide a brief account of the most recent advances in the use of ionic liquid crystals (ILCs) in the field of tribology, that is, the development of new lubricants with the ability to reduce the coefficients of friction and the wear rates of materials under sliding conditions. After a definition of ILCs and their relationship with neutral liquid crystals (LCs) and ionic liquids (ILs), the review will be focused on the influence of molecular structure and composition on the tribological performance, the combination with base oils, surfactants or water, and the different sliding configuration and potential applications. The main mechanisms proposed in order to justify the lubricating ability of ILCs will be analyzed. Special emphasis will be made for recent results obtained for fatty acid derivatives due to their renewable and environmentally friendly nature