190 research outputs found

    Some sigmatropic rearrangements of polyfluoroaromatic and heteroaromatic compounds

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    This Thesis describes some [3,3] and [2,3] -sigmatropic rearrangements that can occur in a variety of polyfluoroaromatic and -heteroaromatic compounds. The presence of fluorine on the aromatic moiety precludes the normal rearomatization process. The work is conveniently divided into two parts. Part A concerns the preparation and thermal (Claisen) rearrangement of derivatives of allyl 5-fluoropyrimidin-4-yl ether. These rearrange upon thermolysis to give isomers in which the terminus for the migration of the allyl group is N-3, provided that there is no preceding reaction which localises a double- bond between C-4 and C-5 - in which case C-5 is the migration terminus. Hydrolysis of some of the N-allyl derivatives results in the formation of some new derivatives of 5-fluorouracil. Part B describes the reactions that occur when polyfluor - inated monocyclic, polycyclic and heterocyclic ring systems are treated with dimethylsulphoxide activated by dicyclohexycarbodi-imide or by trifluoroacetic anhydride. Fluorinated phenolic type compounds give products which are the result of a [2,3] sigmatropic rearrangement of the derived sulphoniumylide. Fluorinated anilines and thiophenols behave differently. Dearomatization occurs under very mild conditions. A number of reactions of the fluorinated cyclohexa-2,4-dienone products are described. The preparation and attempted rearrangement of 2,3,4,5,6- pentafluorobenzylmethylsulphoxide is also discussed

    Crystal structures of four indole derivatives as possible cannabinoid allosteric antagonists

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    Acknowledgements We thank the EPSRC National Crystallography Service (University of Southampton) for the data collections and the EPSRC National Mass Spectrometry Service (University of Swansea) for the HRMS data. We thank John Low for carrying out the Cambridge Database survey.Peer reviewedPublisher PD

    Studentsā€™ Perceptions of Choice-based Assessment

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    The traditional teacher-centered approach to assessment places teachers in total control of what, how, and when studentsā€™ learning is assessed. Alternatively, choice-based assessment is a learner-centered approach to assessment that allows students to choose, to some extent, what, how, and/or when their learning is assessed. A case study was designed to expose undergraduate students to a choice-based assessment strategy and subsequently measure the extent to which they agreed, or disagreed, that the strategy influenced their level of engagement and satisfaction with their learning. Students voluntarily shared their perceptions over two survey cycles (n=22 in spring 2017 and n=36 in fall 2017) with an overall response rate of 84 percent. Results clearly demonstrate that most students expressed strong support for this choice-based assessment strategy; it enabled them focus on their strengths and interests, it influenced their level of engagement, it made them feel more responsible for their learning, and it made them feel empowered. However, choice was not motivating for all students; a few students expressed concerns over the potential for procrastination, a lack of experience with choice, and/or too many choices, which were more likely symptoms of the strategyā€™s design rather than choice-based assessment. Overall, this case study clearly demonstrated that students were highly receptive to having a choice in what, how, and when their learning is assessed, which provides further evidence of the untapped potential for choice-based assessment strategies to foster student engagement, improve student satisfaction, and empower students to actively participate in their learning

    Crystal structures of four indole derivatives with a phenyl substituent at the 2-position and a carbonyl group at the 3-position : the C(6) N-Hā‹ÆO chain remains the same, but the weak reinforcing inter-actions are different

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    Acknowledgements We thank the EPSRC National Crystallography Service (University of Southampton) for the data collections and the EPSRC National Mass Spectrometry Service (University of Swansea) for the HRMS data.Peer reviewedPublisher PD

    Weak interactions in the crystal structures of two indole derivatives

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    Acknowledgements We thank the EPSRC National Crystallography Service (University of Southampton) for the data collections and the EPSRC National Mass Spectrometry Service (University of Swansea) for the HRMS data.Peer reviewedPublisher PD

    Transition Experiences of Former Collegiate Womenā€™s Soccer Athletes

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    Athlete transition from American collegiate sport participation, to non-sport careers or professional sport, has been a topic of contemporary sport science research but it is still not well understood, especially in female athlete populations. Informed by extant transition theory, the current study purpose was to describe the transition experiences of former womenā€™s collegiate soccer athletes, including both positive and negative contributing factors. Using a deductive conceptual content analysis, results showcase both positive (i.e., social support, career goals, recreational sport play) and negative (i.e., lack of a team/support, lack of soccer/competition, lack of direction) contributors to the post-collegiate sport transition for female soccer athletes sampled. The importance of athletic identity and potential transition resources were identified. Specifically, participants endorsed career guidance, physical activity/exercise, mentorship programming, and mental health resources as potentially helpful to future athletes. Study findings expanded upon relevant transition theory and former female athlete research. Our study results may inform future research and program development efforts aimed at former female collegiate athletes from soccer and other sports

    Different Nā€”HĀ·Ā·Ā·Ļ€ interactions in two indole derivatives

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    Acknowledgements We thank the EPSRC National Crystallography Service (University of Southampton) for the data collections and the EPSRC National Mass Spectrometry Service (University of Swansea) for the HRMS dataPeer reviewedPublisher PD

    The changing health impact of vaccines in the COVID-19 pandemic: a modeling study

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    Much of the worldā€™s population had already been infected with COVID-19 by the time the Omicron variant emerged at the end of 2021, but the scale of the Omicron wave was larger than any that had come before or has happened since, and it left a global imprinting of immunity that changed the COVID-19 landscape. In this study, we simulate a South African population and demonstrate how population-level vaccine effectiveness and efficiency changed over the course of the first 2 years of the pandemic. We then introduce three hypothetical variants and evaluate the impact of vaccines with different properties. We find that variant-chasing vaccines have a narrow window of dominating pre-existing vaccines but that a variant-chasing vaccine strategy may have global utility, depending on the rate of spread from setting to setting. Next-generation vaccines might be able to overcome uncertainty in pace and degree of viral evolution

    A New Family of DNA Viruses Causing Disease in Crustaceans from Diverse Aquatic Biomes

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    Recent genomic and metagenomic studies have led to a dramatic expansion of the known diversity of nucleocytoplasmic large DNA viruses (NCLDVs) of eukaryotes, which include giant viruses of protists and important pathogens of vertebrates, such as poxviruses. However, the characterization of viruses from nonmodel hosts still lags behind. We sequenced the complete genomes of three viruses infecting crustaceans, the Caribbean spiny lobster, demon shrimp, and European shore crab. These viruses have the smallest genomes among the known NCLDVs, with losses of many core genes, some of which are shared with iridoviruses. The deterioration of the transcription apparatus is compatible with microscopic and ultrastructural observations indicating that these viruses replicate in the nucleus of infected cells rather than in the cytoplasm. Phylogenomic analysis indicates that these viruses are sufficiently distinct from all other NCLDVs to justify the creation of a separate family, for which we propose the name ā€œMininucleoviridaeā€ (i.e., small viruses reproducing in the cell nucleus).Panulirus argus virus 1 (PaV1) is the only known virus infecting the Caribbean spiny lobster (Panulirus argus) from the Caribbean Sea. Recently, related viruses, Dikerogammarus haemobaphes virus 1 (DhV1) and Carcinus maenas virus 1 (CmV1), have been detected in the demon shrimp (Dikerogammarus haemobaphes) and the European shore crab (Carcinus maenas), respectively, from sites in the United Kingdom. The virion morphology of these crustacean viruses is similar to that of iridoviruses. However, unlike iridoviruses and other nucleocytoplasmic large DNA viruses (NCLDVs), these viruses complete their morphogenesis in the host cell nucleus rather than in the cytoplasm. To date, these crustacean viruses have remained unclassified due to a lack of genomic data. Using an Illumina MiSeq sequencer, we sequenced the complete genomes of PaV1, CmV1, and DhV1. Comparative genome analysis shows that these crustacean virus genomes encode the 10 hallmark proteins previously described for the NCLDVs of eukaryotes, strongly suggesting that they are members of this group. With a size range of 70 to 74 kb, these are the smallest NCLDV genomes identified to date. Extensive gene loss, divergence of gene sequences, and the accumulation of low-complexity sequences reflect the extreme degradation of the genomes of these ā€œminimalā€ NCLDVs rather than any direct relationship with the NCLDV ancestor. Phylogenomic analysis supports the classification of these crustacean viruses as a distinct family, ā€œMininucleoviridae,ā€ within the pitho-irido-Marseille branch of the NCLDVs
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