Naresuan University Journal
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    Enantioselective carbolithiation of S-alkenyl-N-aryl thiocarbamates: kinetic and thermodynamic control

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    The addition of n-butyllithium to alkenylthiocarbamates in the presence of (−)-sparteine or the (+)-sparteine surrogate leads to asymmetric carbolithiation, and returns enantiomerically enriched thiocarbamate derivatives of secondary thiols. In THF, with the (+)-sparteine surrogate, in situ aryl migration leads to an enantiomerically enriched tertiary thiol derivative. Remarkably, the two pseudoenantiomeric chiral ligands do not always give enantiomeric products, probably as a result of a complex interplay of kinetic and thermodynamic control. In situ IR and NMR studies of a stable, hindered lithiated thiocarbamate demonstrated its chemical and configurational stability over a period of hours at 0 °C

    Pooled sequencing of 531 genes in inflammatory bowel disease identifies an associated rare variant in BTNL2 and implicates other immune related genes.

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    The contribution of rare coding sequence variants to genetic susceptibility in complex disorders is an important but unresolved question. Most studies thus far have investigated a limited number of genes from regions which contain common disease associated variants. Here we investigate this in inflammatory bowel disease by sequencing the exons and proximal promoters of 531 genes selected from both genome-wide association studies and pathway analysis in pooled DNA panels from 474 cases of Crohn's disease and 480 controls. 80 variants with evidence of association in the sequencing experiment or with potential functional significance were selected for follow up genotyping in 6,507 IBD cases and 3,064 population controls. The top 5 disease associated variants were genotyped in an extension panel of 3,662 IBD cases and 3,639 controls, and tested for association in a combined analysis of 10,147 IBD cases and 7,008 controls. A rare coding variant p.G454C in the BTNL2 gene within the major histocompatibility complex was significantly associated with increased risk for IBD (p = 9.65x10-10, OR = 2.3[95% CI = 1.75-3.04]), but was independent of the known common associated CD and UC variants at this locus. Rare (T) or decreased risk (IL12B p.V298F, and NICN p.H191R) of IBD. These results provide additional insights into the involvement of the inhibition of T cell activation in the development of both sub-phenotypes of inflammatory bowel disease. We suggest that although rare coding variants may make a modest overall contribution to complex disease susceptibility, they can inform our understanding of the molecular pathways that contribute to pathogenesis

    Designing a new measure for cognition after stroke - Easy access report

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    This 15 page document with large text and accessible language is an easy access version of the PhD thesis. It describes the development of a patient centred outcome measure designed to assess impact of cognitive problems after stroke. In August 2015, this report was sent to individuals who supported the PhD work: either as study participants or collaborators

    Programmes for advance distribution of misoprostol to prevent post-partum haemorrhage: a rapid literature review of factors affecting implementation

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    Recent efforts to prevent post-partum haemorrhage (PPH) in low-income countries have focused on providing women with access to oral misoprostol during home birth. The WHO recommends using lay health workers (LHWs) to administer misoprostol in settings where skilled birth attendants are not available. This review synthesizes current knowledge about the barriers and facilitators affecting implementation of advance community distribution of misoprostol to prevent PPH, where misoprostol may be self-administered or administered by an LHW. We searched for and summarized available empirical evidence, and collected primary data from programme stakeholders about their experiences of programme implementation. We present key outcomes and features of advanced distribution programmes that are in operation or have been piloted globally. We categorized factors influencing implementation into those that operate at the health system level, factors related to the community and policy context and those factors more closely connected to the end user. Debates around advance distribution have centred on the potential risks and benefits of making misoprostol available to pregnant women and community members during pregnancy for administration in the home. However, the risks of advance distribution appear manageable and the benefits of self-administration, especially for women who have little chance of expert care for PPH, are considerable

    The Geometry of Moving Bodies

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    The first 4d/4f single-molecule magnet containing a {RuIII2DyIII2} core

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    We report the synthesis, structure and magnetic properties of the first 4d???4f single-molecule magnet. The complex [RuIII2DyIII2(OMe)2(O2CPh)4(mdea)2(NO3)2] displays a butterfly type core, with an anisotropy barrier of 10.7 cm???1. Ab initio and DFT calculations provide insight into the observed magnetic behaviour

    Electrochemically controlled ion exchange: proton ion exchange with sodium zeolite X and A

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    Structural characterisation of proton-exchanged zeolites, prepared using ion-transfer at the liquid–liquid interface, is reported. Specifically, electrochemical exchange of protons for sodium with zeolites X and A is described: the structural integrity of the resultant materials was probed by solid-state NMR spectroscopy and temperature-dependent powder X-ray diffraction. It is shown that replacement of ca. 40 % of the Na+ can be achieved using this approach for both zeolites; however, the results indicate that exchange is accompanied by significant structural degradation in the case of zeolite A, with proton exchange occurring at the amorphous regions of the sample. In contrast, zeolite X retains its structure, and the level of proton exchange is comparable with the highest levels reported using conventional chemical methods, highlighting the utility of the electrochemical approach

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