Functionalised ionic liquids: synthesis of ionic liquids with tethered basic groups and their use in Heck and Knoevenagel reactions

A simple and efficient synthesis of a novel series of ionic liquids bearing nucleophilic (Me2N) and non-nucleophilic base ((Pr2N)-Pr-i) functionalities is described. The non-nucleophilic base functionality resembles the structure of the Hunig's base (N, N-diisopropylethylamine), which has been used widely in organic synthesis. A qualitative measure of the basicity of these ionic liquids is presented by utilising their interaction with universal indicator. The basicity of these ionic liquids was found to be dependent on the amine tether and choice of linker between the two nitrogen centres. The relative base strength of these ionic liquids was also probed by using them as catalysts in the Heck and Knoevenagel reactions.

Interaction of water, hydrogen and their mixtures with SnO2 based materials: the role of surface hydroxyl groups in detection mechanisms

DRIFTS, TGA and resistance measurements have been used to study the mechanism of water and hydrogen interaction accompanied by a resistance change (sensor signal) of blank and Pd doped SnO2. It was found that a highly hydroxylated surface of blank SnO2 reacts with gases through bridging hydroxyl groups, whereas the Pd doped materials interact with hydrogen and water through bridging oxygen. In the case of blank SnO2 the sensor signal maximum towards H-2 in dry air (R-0/R-g) is observed at similar to 345 degrees C, and towards water, at similar to 180 degrees C, which results in high selectivity to hydrogen in the presence of water vapors (minor humidity effect). In contrast, on doping with Pd the response to hydrogen in dry air and to water occurred in the same temperature region (ca. 140 degrees C) leading to low selectivity with a high effect of humidity. An increase in water concentration in the gas phase changes the hydrogen interaction mechanism of Pd doped materials, while that of blank SnO2 is unchanged. The interaction of hydrogen with the catalyst doped SnO2 occurs predominantly through hydroxyl groups when the volumetric concentration of water in the gas phase is higher than that of H-2 by a factor of 1000.

Dissonances in self-reported health and mortality across denominational groups in Northern Ireland

Measures of self-reported health status are increasingly used in research and health policy. However, the inherent subjectivity of the responses gives rise to lingering concerns about their utility, especially across national and cultural boundaries. In this study we use religious denomination as a proxy for Scottish ancestry within Northern Ireland and demonstrate significant differences in levels of self-reported ill-health that are not fully reflected in mortality risks. These findings mirror the differences between Scotland and Northern Ireland previously shown in ecological studies and provide more definitive evidence that even within the United Kingdom factors other than morbidity levels influence the perception and reporting of health status. Possible explanations for the dissonance between morbidity and mortality levels are discussed and the reasons for a preference for socio-economic rather than cultural factors are described. (C) 2010 Elsevier Ltd. All rights reserved.

Hanging Flower Baskets, Blowing in the Wind? Third Sector Groups, Cross-Border Partnerships and the EU Peace Programmes in Ireland

The EU’s Peace programmes in Ireland have promoted the cross-border activity of Third sector groups. Potentially, such activity gives substantive meaning to regional cross-border governance and helps to ameliorate ethno-national conflict by providing positive sum outcomes for ‘post-conflict’ communities. The paper mobilizes focused research conducted by the authors to explore this potential. It finds that while regional cross-border governance has indeed developed under the Peace programmes, the sustainability of the social partnerships underpinning this governance is uncertain and its significance for conflict resolution is qualified by difficulties in forming a stable power-sharing arrangement at the political elite level.

Data mining approach identifies research priorities and data requirements for resolving the red algal tree of life

Background. The assembly of the tree of life has seen significant progress in recent years but algae and protists have been largely overlooked in this effort. Many groups of algae and protists have ancient roots and it is unclear how much data will be required to resolve their phylogenetic relationships for incorporation in the tree of life. The red algae, a group of primary photosynthetic eukaryotes of more than a billion years old, provide the earliest fossil evidence for eukaryotic multicellularity and sexual reproduction. Despite this evolutionary significance, their phylogenetic relationships are understudied. This study aims to infer a comprehensive red algal tree of life at the family level from a supermatrix containing data mined from GenBank. We aim to locate remaining regions of low support in the topology, evaluate their causes and estimate the amount of data required to resolve them. Results. Phylogenetic analysis of a supermatrix of 14 loci and 98 red algal families yielded the most complete red algal tree of life to date. Visualization of statistical support showed the presence of five poorly supported regions. Causes for low support were identified with statistics about the age of the region, data availability and node density, showing that poor support has different origins in different parts of the tree. Parametric simulation experiments yielded optimistic estimates of how much data will be needed to resolve the poorly supported regions (ca. 103 to ca. 104 nucleotides for the different regions). Nonparametric simulations gave a markedly more pessimistic image, some regions requiring more than 2.8 105 nucleotides or not achieving the desired level of support at all. The discrepancies between parametric and nonparametric simulations are discussed in light of our dataset and known attributes of both approaches. Conclusions. Our study takes the red algae one step closer to meaningful inclusion in the tree of life. In addition to the recovery of stable relationships, the recognition of five regions in need of further study is a significant outcome of this work. Based on our analyses of current availability and future requirements of data, we make clear recommendations for forthcoming research.

First record of a chiton from the Palaeocene of Denmark (Polyplacophora : Leptochitonidae) and its phylogenetic affinities

Anew species of fossil polyplacophoran from the Danian (Lower Palaeocene) of Denmark is described from over 450 individual disarticulated plates. The polyplacophorans originate from the 'nose-chalk' in the classical Danish locality of Fakse Quarry, an unconsolidated coral limestone in which aragonitic mollusc shells are preserved through transformation into calcite. In plate architecture and sculpture, the new Danish material is similar to Recent Leptochiton spp., but differs in its underdeveloped apophyses and high dorsal elevation (height/width ca. 0.54). Cladistic analysis of 55 original shell characters coded for more than loo Recent and fossil species in the order Lepiclopleurida shows very high resolution of interspecific relationships, but does not consistently recover traditional genera or subgenera. Inter-relationships within the suborder Lepidopleurina are of particular interest as it is often considered the most 'basal' neoloricate lineage. In a local context, the presence of chitons in the faunal assemblage of Fakse contributes evidence of shallow depositional depth for at least some elements of this Palaeocene seabed, a well-studied formation of azooxanthellic coral limestones. This new record for Denmark represents a well-dated and ecologically well-understood fossil chiton with potential value for understanding the radiation of the Neotoricata.

Deep molluscan phylogeny: synthesis of palaeontological and neontological data

The position of the earliest-derived living molluscs, the Polyplacophora ( chitons) and shell-less vermiform Aplacophora, remains highly contentious despite many morphological, developmental and molecular studies of extant organisms. These two groups are thought to represent either a basal molluscan grade or a clade (Aculifera) sister to the 'higher' molluscs (Conchifera). These incompatible hypotheses result in very different predictions about the earliest molluscs. A new cladistic analysis incorporating both Palaeozoic and extant molluscs is presented here. Our results support the monophyly of Aculifera and suggest that extant aplacophorans and polyplacophorans both derive from a disparate group of multivalved molluscs in two major clades. Reanalysis of the critical Ordovician taxon 'Helminthochiton' thraivensis shows that this animal lacks a true foot despite bearing polyplacophoran-like valves. Its position within our phylogenetic reconstruction indicates that many fossil 'polyplacophorans' in the order Palaeoloricata are likely to represent footless stem-group aplacophorans. 'H.' thraivensis and similar forms such as Acaenoplax may be morphological stepping stones between chitons and the shell-less aplacophorans. Our results imply that crown-group molluscan synapomorphies include serial repetition, the presence of a foot, a mineralized scleritome and a creeping rather than worm-like mode of life.

Trusting Groups in Coalition Formation using Social Distance

In environments where distributed team formation is key, and defections are possible, the use of trust as social capital allows social norms to be defied and compared. An agent can use this information, when invited to join a group or collation, to decide whether or not its utility will be increased by joining. In this work a social network approach is used to define and reason about the relationships contained in the agent community. Previous baseline work is extended with two decision making mechanisms. These are compared by simulating an abstract grid-like environment, and preliminary results are reported.

Analysis of transduction in wastewater bacterial populations by targeting the phage-derived 16S rRNA gene sequences

Bacterial 16S rRNA genes transduced by bacteriophages were identified and analyzed in order to estimate the extent of the bacteriophage-mediated horizontal gene transfer in the wastewater environment. For this purpose, phage and bacterial DNA was isolated from the oxidation tank of a municipal wastewater treatment plant. Phylogenetic analysis of the 16S rRNA gene sequences cloned from a phage metagenome revealed that bacteriophages transduce genetic material in several major groups of bacteria. The groups identified were as follows: Betaproteobacteria, Gammaproteobacteria, Alphaproteobacteria, Actinomycetales and Firmicutes. Analysis of the 16S rRNA gene sequences in the total bacterial DNA from the same sample revealed that several bacterial groups found in the oxidation tank were not present in the phage metagenome (e.g. Deltaproteobacteria, Nitrospira, Planctomycetes and many Actinobacteria genera). These results suggest that transduction in a wastewater environment occurs in several bacterial groups; however, not all species are equally involved into this process. The data also showed that a number of distinctive bacterial strains participate in transduction-mediated gene transfer within identified bacterial groupings. Denaturing gradient gel electrophoresis analysis confirmed that profiles of the transduced 16S rRNA gene sequences and those present in the whole microbial community show significant differences.

Contextualism as an important facet of individualism-collectivism: personhood beliefs across 37 national groups

Beliefs about personhood are understood to be a defining feature of individualism-collectivism (I-C), but they have been insufficiently explored, given the emphasis of research on values and self-construals. We propose the construct of contextualism, referring to beliefs about the importance of context in understanding people, as a facet of cultural collectivism. A brief measure was developed and refined across 19 nations (Study 1: N = 5,241), showing good psychometric properties for cross-cultural use and correlating well at the nation level with other supposed facets and indicators of I-C. In Study 2 (N = 7,623), nation-level contextualism predicted ingroup favoritism, corruption and differential trust of ingroup and outgroup members, while controlling for other facets of I-C, across 34 nations. We conclude that contextualism is an important part of cultural collectivism. This highlights the importance of beliefs alongside values and self-representations, and contributes to a wider understanding of cultural processes.

Molecular characterization and phylogenetic analysis of quinolone resistance-determining regions (QRDRs) of gyrA, gyrB, parC and parE gene loci in viridans group streptococci isolated from adult patients with cystic fibrosis

This study demonstrated key resistance genes to fluroquinilones in Streptococcci isolated from sputum of people with CF. This suggests that other bacteria which are sometimes considered commensal may be a resovoir for resistance. Jse designed the study with Moore.

Second-order NMR spectra at high field of common organic functional groups

The proton NMR spectra of aryl n-propyl sulfides gave rise to what may appear to be first-order proton NMR spectra. Upon oxidation to the corresponding sulfone, the spectra changed appearance dramatically and were clearly second-order. A detailed analysis of these second-order spectra, in the sulfone series, provided vicinal coupling constants which indicated that these compounds had a moderate preference for the anti-conformer, reflecting the much greater size of the sulfone over the sulfide. It also emerged, from this study, that the criterion for observing large second-order effects in the proton NMR spectra of 1,2-disubstituted ethanes was that the difference in vicinal coupling constants must be large and the difference in geminal coupling constants must be small. n-Propyl triphenylphosphonium bromide and 2-trimethylsilylethanesulfonyl chloride, and derivatives thereof, also exhibited second-order spectra, again due to the bulky substituents. Since these spectra are second-order due to magnetic nonequivalence of the nuclei in question, not chemical shifts, the proton spectra are perpetually second-order and can never be rendered first-order by using higher field NMR spectrometers.