Enantioselective formal total synthesis of the Dendrobatidae frog toxin, (+)-pumiliotoxin B, via O-directed alkyne free radical hydrostannation

Herein we describe our application of the O-directed free radical hydrostannation of disubstituted alkyl-acetylenes (with Ph3SnH and Et3B) to the (+)-pumiliotoxin B total synthesis problem. Specifically, we report on the use of this method in the synthesis of the Overman alkyne 8, and thereby demonstrate the great utility of this process in a complex natural product total synthesis setting for the very first time. We also report here on a new, stereocontrolled, and highly practical enantioselective pathway to Overman's pyrrolidine epoxide partner 9 for 8, which overcomes the previous requirement for use of preparative HPLC to separate the 1:1 mixture of diastereomeric epoxides that was obtained in the original synthesis of 9.

Development and validation of a method for the confirmation of nicarbazin in chicken liver and eggs using LC-electrospray MS-MS according to the revised EU criteria for veterinary drug residue analysis

A method is described for the quantitative confirmation of 4,4'-dinitrocarbanilide (DNC), the marker residue for nicarbazin in chicken liver and eggs. The method is based on LC coupled to negative ion electrospray MS-MS of tissue extracts prepared by liquid-liquid extraction. The [M-H](-) ion at m/z 301 is monitored along with two transition ions at m/z 137 and 107 for DNC and the [M-H](-) ion at m/z 309 for the internal standard, d(8)-DNC. The method has been validated according to the new EU criteria for the analysis of veterinary drug residues at 100, 200 and 300 mug kg(-1) in liver and at 10, 30 and 100 mug kg(-1) in eggs. Difficulties concerning the application of the new analytical limits, namely the decision limit (CC) and the detection capability (CC) to the determination of DNC in both liver and eggs are discussed.

Design criteria for a barrier-based gas-liquid flow distributor for parallel microchannels

This paper presents criteria for the design of a flow distributor for even distribution of gas and liquid flows over parallel microchannels. The design criteria are illustrated for the case of a nitrogen-water Taylor flow (1

Chemoenzymatic formal synthesis of (-)- and (+)-epibatidine

The cis-dihydrocatechol, derived from enzymatic cis-dihydroxylation of bromobenzene using the microorganism Pseudomonas putida UV4, was converted into (-)-epibatidine in eleven steps with complete stereocontrol. In addition, an unprecedented palladium-catalysed disproportionation reaction gave the (+)-enantiomer of an advanced key intermediate employed in a previous synthesis of epibatidine.

British Constructions with Constitutions:The Formal and Informal Nature of 'Island' Relations on Montserrat and Gibraltar

This article explores social, economic and political relations on two British Dependent Territories (BDTs) -- Montserrat and Gibraltar. This article notes that though BDTs are British colonial constructions, created, sustained and modelled upon and by Britain, they differ from Britain in that they have political constitutions. They also exhibit an ambiguous dependence and independence upon and with Britain. This article goes on to look at social and economic relations on Montserrat and Gibraltar before comparing and contrasting the political climates on each BDT. Throughout this article, it is suggested that there is a dynamic tension between formal and informal aspects to managing life. Finally, this article concludes with a discussion about the suitability of the split between Executive and Legislative Councils in these two BDTs.

The role of formal structure in liking for popular music

The effect of restructuring the form of three unfamiliar pop/rock songs was investigated in two experiments. In the first experiment, listeners' judgements of the likely location of sections of novel popular songs were explored by requiring participants to place the eight sections (Intro - Verse 1 - Chorus 1 - Verse 2 - Chorus 2 - Bridge (solo) - Chorus 3 - Extro) of the songs into the locations they thought them most likely to occur within the song. Results revealed that participants were able to place the sections in approximately the right location with some accuracy, though they were unable to differentiate between choruses. In Experiment 2, three versions of each of the songs were presented in three different structures: intact (original form), medium restructured (the sections in a moderately changed order), and highly restructured (more severe restructuring). The results show that listeners' judgments of predictability and liking were largely uninfluenced by the restructuring of the songs, in line with findings for classical music. Moment-by-moment liking judgements of the songs demonstrated a change in liking judgements with repeated exposure, though the trend was downwards with repeated exposure rather than upwards. Detailed analysis of moment-by-moment judgements at the ends and beginnings of sections showed that listeners were able to respond quickly to intact songs, but not to restructured songs. The results suggest that concatenism prevails in listening to popular song at the expense of paying attention to larger structural features. © 2012 by the regents of the university of california all rights reserved.

Formal Analysis of MPI-based Parallel Programs

Most parallel computing applications in highperformance computing use the Message Passing Interface (MPI) API. Given the fundamental importance of parallel computing to science and engineering research, application correctness is paramount. MPI was originally developed around 1993 by the MPI Forum, a group of vendors, parallel programming researchers, and computational scientists. However, the document defining the standard is not issued by an official standards organization but has become a de facto standard © 2011 ACM.

A strategy to identify critical appraisal criteria for primary mixed-method studies

The practice of mixed-methods research has increased considerably over the last 10 years. While these studies have been criticized for violating quantitative and qualitative paradigmatic assumptions, the methodological quality of mixed-method studies has not been addressed. The purpose of this paper is to identify criteria to critically appraise the quality of mixed-method studies in the health literature. Criteria for critically appraising quantitative and qualitative studies were generated from a review of the literature. These criteria were organized according to a cross-paradigm framework. We recommend that these criteria be applied to a sample of mixed-method studies which are judged to be exemplary. With the consultation of critical appraisal experts and experienced qualitative, quantitative, and mixed-method researchers, further efforts are required to revise and prioritize the criteria according to importance.

Modified Information Criteria and Selection of Long Memory Time Series Models

The problem of model selection of a univariate long memory time series is investigated once a semi parametric estimator for the long memory parameter has been used. Standard information criteria are not consistent in this case. A Modified Information Criterion (MIC) that overcomes these difficulties is introduced and proofs that show its asymptotic validity are provided. The results are general and cover a wide range of short memory processes. Simulation evidence compares the new and existing methodologies and empirical applications in monthly inflation and daily realized volatility are presented.

Diagnosing diabetes mellitus - Do we need new criteria?

The current classification and diagnostic criteria for diabetes mellitus were introduced by the United States National Data Group in 1979 and endorsed by the World Health Organization in 1980, with modifications in 1985 and 1994. The criteria, chosen to reflect the risk of complications, were the synthesis of considerable thought and expertise and represented a consensus which, it was hoped, would prove helpful to all those involved with diabetes practising clinician, research scientist and epidemiologist alike. The inconvenience, variability and nonphysiological nature of the oral glucose tolerance test (OGTT) are well-recognised. In spite of these limitations the 2-h post-load plasma glucose has remained the standard against which all other tests have been evaluated. This article reviews the original justification for the OGTT, and in the light of more recent epidemiological research seeks to place the current diagnostic criteria for diabetes into a pathophysiological, diagnostic and prognostic perspective.

Improving Patient Safety Through Formal and Informal Learning Networks

This paper explores a novel perspective on patient safety improvements, which draws on
contemporary social network and learning theories. A case study was conducted at a Portuguese
acute university hospital. Data collection followed a staged approach, whereby 46 interviews
were conducted involving 49 respondents from a broad array of departments and professional
backgrounds. This case study highlights the importance of two major interlinked factors in
contributing to patient safety improvements. The first of these is the crucial role of formal and
informal, internal and external social networks. The second is the importance and the possible
advantage of combining formal and informal learning. The analysis suggests that initiatives
rooted in formal learning approaches alone do not necessarily lead to the creation of long-term
grounded internal safety networks, and that patient safety improvements can crucially depend on
bottom-up initiatives of communities of practice and informal learning. Traditional research on
patient safety places a strong emphasis on top-down and managerialist approaches and is often
based on the assumption that „safety? learning is primarily formal and context-independent. This
paper suggests that bottom-up initiatives and a combination of formal and informal learning can
make a major contribute to patient safety improvements.