Understanding thio-effects in simple phosphoryl systems : role of solvent effects and nucleophile charge.

Recent experimental work (J. Org. Chem., 2012, 77, 5829) demonstrated pronounced differences in measured thio-effects for the hydrolysis of (thio)phosphodichloridates by water and hydroxide nucleophiles. In the present work, we have performed detailed quantum chemical calculations of these reactions, with the aim of rationalizing the molecular bases for this discrimination. The calculations highlight the interplay between nucleophile charge and transition state solvation in SN2(P) mechanisms as the basis of these differences, rather than a change in mechanism

Predictive learning, prediction errors, and attention: evidence from event-related potentials and eye tracking

Prediction error (‘‘surprise’’) affects the rate of learning: We learn more rapidly about cues for which we initially make incorrect predictions than cues for which our initial predictions are correct. The current studies employ electrophysiological measures to reveal early attentional differentiation of events that differ in their previous involvement in errors of predictive judgment. Error-related events attract more attention, as evidenced by features of event-related scalp potentials previously implicated in selective visual attention (selection negativity, augmented anterior N1). The earliest differences detected occurred around 120 msec after stimulus onset, and distributed source localization (LORETA) indicated that the inferior temporal regions were one source of the earliest differences. In addition, stimuli associated with the production of prediction errors show higher dwell times in an eyetracking procedure. Our data support the view that early attentional processes play a role in human associative learning

Large NcN_c QCD at non-zero chemical potential

The general issue of large $N_c$ QCD at nonzero chemical potential is considered with a focus on understanding the difference between large $N_c$ QCD with an isospin chemical potential and large $N_c$ QCD with a baryon chemical potential. A simple diagrammatic analysis analogous to `t Hooft's analysis at $\mu=0$ implies that the free energy with a given baryon chemical potential is equal to the free energy with an isospin chemical potential of the same value plus $1/N_c$ corrections. Phenomenologically, these two systems behave quite differently. A scenario to explain this difference in light of the diagrammatic analysis is explored. This scenario is based on a phase transition associated with pion condensation when the isospin chemical potential exceeds $m_\pi/2$; associated with this transition there is breakdown of the $1/N_c$ expansion--in the pion condensed phase there is a distinct $1/N_c$ expansion including a larger set of diagrams. While this scenario is natural, there are a number of theoretical issues which at least superficially challenge it. Most of these can be accommodated. However, the behavior of quenched QCD which raises a number of apparently analogous issues cannot be easily understood completely in terms of an analogous scenario. Thus, the overall issue remains open

External and internal noise surveys of London primary schools

Internal and external noise surveys have been carried out around schools in London, UK, to provide information on typical levels and sources to which children are exposed while at school. Noise levels were measured outside 142 schools, in areas away from flightpaths into major airports. 86% of the schools surveyed were exposed to noise from road traffic, the average external noise level outside a school being 57 dB LAeq. Detailed internal noise surveys have been carried out in 140 classrooms in 16 schools, together with classroom observations. It was found that noise levels inside classrooms depend upon the activities in which the children are engaged, with a difference of 20 dB LAeq between the 'quietest' and 'noisiest' activities. The average background noise level in classrooms exceeds the level recommended in current standards. The number of children in the classroom was found to affect noise levels. External noise influenced internal noise levels only when children were engaged in the quietest classroom activities. The effects of the age of the school buildings and types of window upon internal noise were examined but results were inconclusive

Social evolution of toxic metal bioremediation in Pseudomonas aeruginosa

This is the final version. Available on open access from the Royal Society via the DOI in this recordThere is another ORE record for this publication: http://hdl.handle.net/10871/16448Bacteria are often iron-limited, and hence produce extracellular iron-scavenging siderophores. A crucial feature of siderophore production is that it can be an altruistic behaviour (individually costly but benefitting neighbouring cells), thus siderophore producers can be invaded by non-producing social 'cheats'. Recent studies have shown that siderophores can also bind other heavy metals (such as Cu and Zn), but in this case siderophore chelation actually reduces metal uptake by bacteria. These complexes reduce heavy metal toxicity, hence siderophore production may contribute to toxic metal bioremediation. Here, we show that siderophore production in the context of bioremediation is also an altruistic trait and can be exploited by cheating phenotypes in the opportunistic pathogen Pseudomonas aeruginosa. Specifically, we show that in toxic copper concentrations (i) siderophore non-producers evolve de novo and reach high frequencies, and (ii) producing strains are fitter than isogenic non-producing strains in monoculture, and vice versa in co-culture. Moreover, we show that the evolutionary effect copper has on reducing siderophore production is greater than the reduction observed under iron-limited conditions. We discuss the relevance of these results to the evolution of siderophore production in natural communities and heavy metal bioremediation. © 2014 The Authors Published by the Royal Society. All rights reserved.AXANatural Environment Research Council (NERC)University of Exete

Connection between inner jet kinematics and broadband flux variability in the BL Lac object S5 0716+714

We present a high-frequency very long baseline interferometry (VLBI) kinematical study of the BL Lac object S5 0716+714 over the time period of September 2008 to October 2010. The aim of the study is to investigate the relation of the jet kinematics to the observed broadband flux variability. We find significant non-radial motions in the jet outflow of the source. In the radial direction, the highest measured apparent speed is \sim37 c, which is exceptionally high, especially for a BL Lac object. Patterns in the jet flow reveal a roughly stationary feature \sim0.15 mas downstream of the core. The long-term fits to the component trajectories reveal acceleration in the sub-mas region of the jet. The measured brightness temperature, T_{B}, follows a continuous trend of decline with distance, T_B \propto r_{jet}^{-(2.36\pm0.41)}, which suggests a gradient in Doppler factor along the jet axis. Our analysis suggest that a moving disturbance (or a shock wave) from the base of the jet produces the high-energy (optical to \gamma-ray) variations upstream of the 7 mm core, and then later causes an outburst in the core. Repetitive optical/\gamma-ray flares and the curved trajectories of the associated components suggest that the shock front propagates along a bent trajectory or helical path. Sharper \gamma-ray flares could be related to the passage of moving disturbances through the stationary feature. Our analysis suggests that the \gamma-ray and radio emission regions have different Doppler factors.Comment: 12 pages, 8 figures, accepted for publication in A&

'The heart of what we do': policies on teaching, learning and assessment in the learning and skills sector

One of the stated aims of government policy in England is to put teaching, training,and learning at the heart of the learning and skills system. This paper provides a critical review of policies on teaching, learning and assessment in the learning and skills sector over the past five years. It draws upon data collected and analysed in the early stages of an ESRC-funded Teaching and Learning Research Programme project. Using evidence from policy sources, we argue that despite policy rhetoric about devolution of responsibility to the 'front line', the dominant 'images' that government has of putting teaching, learning and assessment at the heart of the Learning and Skills Sector involves a narrow concept of learning and skills; an idealisation of learner agency lacking an appreciation of the pivotal role of the learner/tutor relationship and a top-down view of change in which central government agencies are relied on to secure education standards

Sperm morphology in five species of cicadettine cicadas (Hemiptera: Cicadomorpha: Cicadidae)

Mature spermatozoa from five species of cicadas of the subfamily Cicadettinae (Quintilia wealei, Melampsalta leucoptera, Stagira simplex, Xosopsaltria thunbergi and Monomatapa matoposa) were examined by light and electron microscopy. In each species sperm are elongate, aggregated into organized bundles with their heads embedded in a homogenous matrix to form spermatodesmata, and exhibit polymegaly. The head of the sperm consist of an anteriorly positioned conical acrosome that has a tubular substructure and a deep, posterior invagination that forms the subacrosomal space (eccentrically positioned anteriorly). The acrosome is flattened anteriorly; posteriorly it extends along either side of the nucleus as two tubular processes that gradually decrease in diameter. The filiform nucleus tapers anteriorly and intrudes into the subscrosomal space. Posteriorly the nucleus has a lateral invagination that houses material of the so-called centriolar adjunct. Posterior to the centriolar adjuct and the nucleus are two crystalline mitochondrial derivatives and a centriole, respectively, the latter giving rise to the axoneme, which has a 9 + 9 + 2 arrangement of microtubules. In these respects the sperm are similar to those of platypleurine cicadas. However, some features seem unique to cicadettines, including the structural organization of an enlarged centriolar adjunct and the dimensions of the tails. The enlarged centriolar adjunct has a lamella-like substructure and can be considered a synapomorphic character in the Cicadettinae. It is, therefore, potentially useful in the separation of this subfamily from the Cicadinae. In addition, the great length of the sperm nucleus of long-headed sperm in M. matoposa could be a synapomorphy of this genus and related taphurine and cicadettine species

Sperm morphology in four species of African platypleurine cicadas (Hemiptera: Cicadomorpha: Cicadidae)

Mature spermatozoa from four species of platypleurine cicadas (Albanycada albigera, Azanicada zuluensis, Platypleura capensis and P. hirtipennis) were examined by light and electron microscopy. The filiform sperm have a similar ultrastructure in all species but notable variations were found in sperm dimensions. All species produce more than one discrete length of nucleated, motile sperm, a form of polymorphism termed polymegaly. Polymegaly is expressed in two ways: sperm have bi- or trimodal head and tail lengths. The anterior parts of sperm heads are embedded in an elongate homogenous matrix forming a spermatodesm. The conical acrosome is deeply invaginated posteriorly, and sits on top of the nucleus. The acrosomal contents are differentiated internally with an electron-lucent central medulla and a denser cortex. The homogenously electron-dense nucleus is pointed anteriorly and is generally cylindrical, although posteriorly there is a lateral invagination that extends part-way along the nucleus. This invagination houses fine granular material of the centriolar adjunct. Vesicle-like elements that are associated with both the posterior nucleus and the centriolar adjunct are also found within the invagination. Immediately posterior of and adjoining the centriolar adjunct is a pair of mitochondrial derivatives that are elongated and extend for almost the entire length of the tail. The absence of accessory bodies in cicada sperm suggests that within the Cicadomorpha, the families Cicadidae and Cercopidae are closely affiliated