13,064 research outputs found
Organocatalytic Lewis base functionalisation of carboxylic acids, esters and anhydrides via C1-ammonium or azolium enolates
This tutorial review highlights the organocatalytic Lewis base functionalisation of carboxylic acids, esters and anhydrides via C1-ammonium/azolium enolates. The generation and synthetic utility of these powerful intermediates is highlighted through their application in various methodologies including aldol-lactonisations, Michael-lactonisations/lactamisations and [2,3]-rearrangements.Publisher PDFPeer reviewe
Invited commentary on Stewart and Davis " 'Big data' in mental health research-current status and emerging possibilities"
No abstract available
Modelling the Fluid Mechanics of Cilia and Flagella in Reproduction and Development
Cilia and flagella are actively bending slender organelles, performing
functions such as motility, feeding and embryonic symmetry breaking. We review
the mechanics of viscous-dominated microscale flow, including time-reversal
symmetry, drag anisotropy of slender bodies, and wall effects. We focus on the
fundamental force singularity, higher order multipoles, and the method of
images, providing physical insight and forming a basis for computational
approaches. Two biological problems are then considered in more detail: (1)
left-right symmetry breaking flow in the node, a microscopic structure in
developing vertebrate embryos, and (2) motility of microswimmers through
non-Newtonian fluids. Our model of the embryonic node reveals how particle
transport associated with morphogenesis is modulated by the gradual emergence
of cilium posterior tilt. Our model of swimming makes use of force
distributions within a body-conforming finite element framework, allowing the
solution of nonlinear inertialess Carreau flow. We find that a three-sphere
model swimmer and a model sperm are similarly affected by shear-thinning; in
both cases swimming due to a prescribed beat is enhanced by shear-thinning,
with optimal Deborah number around 0.8. The sperm exhibits an almost perfect
linear relationship between velocity and the logarithm of the ratio of zero to
infinite shear viscosity, with shear-thickening hindering cell progress.Comment: 20 pages, 24 figure
Language Boundaries Driven By Surface Tension
A new model of language evolution assumes that changes in the spatial boundaries between dialects are controlled by a surface tension effect
Stable communication through dynamic language
I use agent-based computational models of inferential language transmission to investigate the relationship between language change and the indeterminacy of meaning. I describe a model of communication and learning based on the inference of meaning through disambiguation across multiple contexts, which is then embedded within an iterated learning model. The dynamic flexibility and uncertainty inherent in the model leads directly to variation between agents, in both their conceptual and lexical structures. Over generations of repeated meaning inference, this variation leads to significant language change. Despite such change, however, the language maintains its utility as a communicative tool within each individual generation
Responsiveness of bovine cumulus-oocyte-complexes (COC) to porcine and recombinant human FSH, and the effect of COC quality on gonadotropin receptor and Cx43 marker gene mRNAs during maturation in vitro
Substantially less development to the blastocyst stage occurs in vitro than in vivo and this may be due to deficiencies in oocyte competence. Although a large proportion of bovine oocytes undergo spontaneous nuclear maturation, less is known about requirements for proper cytoplasmic maturation. Commonly, supraphysiological concentrations of FSH and LH are added to maturation media to improve cumulus expansion, fertilization and embryonic development. Therefore, various concentrations of porcine FSH (pFSH) and recombinant human FSH (rhFSH) were investigated for their effect on bovine cumulus expansion in vitro. Expression of FSHr, LHr and Cx43 mRNAs was determined in cumulus-oocyte complexes to determine whether they would be useful markers of oocyte competence. In serum-free media, only 1000 ng/ml pFSH induced marked cumulus expansion, but the effect of 100 ng/ml pFSH was amplified in the presence of 10% serum. In contrast, cumulus expansion occurred with 1 ng/ml rhFSH in the absence of serum. FSHr mRNA was highest at 0–6 h of maturation, then abundance decreased. Similarly, Cx43 mRNA expression was highest from 0–6 h but decreased by 24 h of maturation. However, the relative abundance of LHr mRNA did not change from 6–24 h of maturation. Decreased levels of FSHr, LHr and Cx43 mRNAs were detected in COCs of poorer quality. In conclusion, expansion of bovine cumulus occurred at low doses of rhFSH in serum-free media. In summary, FSHr, LHr and Cx43 mRNA abundance reflects COC quality and FSHr and Cx43 mRNA expression changes during in vitro maturation; these genes may be useful markers of oocyte developmental competence
Asymmetric synthesis of tri- and tetrasubstituted trifluoromethyl dihydropyranones from alpha-aroyloxyaldehydes via NHC redox catalysis
We thank the Royal Society for a University Research Fellowship (A.D.S.), and the European Research Council under the European Union’s Seventh Framework Programme (FP7/2007-2013) ERC Grant Agreement No. 279850 (A.T.D.).The asymmetric synthesis of tri- and tetrasubstituted trifluoromethyl dihydropyranones via an NHC-catalyzed redox process, introducing methyl, benzyl, and aryl substituents to the C(5) position, is presented. Their substrate-controlled derivatization into δ-lactones and cyclic hemiacetals containing stereogenic trifluoromethyl groups is also described.PostprintPeer reviewe
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