Regioselectivity and stereoselectivity of dioxygenase catalysed cis-dihydroxylation of mono- and tri-cyclic azaarene substrates

cis-Dihydrodiol metabolites were obtained from dioxygenase-catalysed asymmetric dihydroxylations of. five monocyclic (azabiphenyl) and four tricyclic (azaphenanthrene) azaarene substrates. Enantiopurity values and absolute configuration assignments were determined using a combination of stereochemical correlation, X-ray crystallography and spectroscopy methods. The degree of regioselectivity found during cis-dihydroxylation of monocyclic azaarenes (2,3 bond >> 3,4 bond) and of tricyclic azaarenes (bay region > non-bay region bonds) was dependent on the type of dioxygenase used. The cis-dihydrodiol metabolite from an azaarene (3-phenylpyridine) was utilised in the chemoenzymatic synthesis of the corresponding trans-dihydrodiol.

Do All Flares Have White-Light Emission?

High-cadence, multiwavelength optical observations of a solar active region (NOAA AR 10969), obtained with the Swedish Solar Telescope, are presented. Difference imaging of white light continuum data reveals a white-light brightening, 2 minutes in duration, linked to a cotemporal and cospatial C2.0 flare event. The flare kernel observed in the white-light images has a diameter of 300 km, thus rendering it below the resolution limit of most space-based telescopes. Continuum emission is present only during the impulsive stage of the flare, with the effects of chromospheric emission subsequently delayed by approximate to 2 minutes. The localized flare emission peaks at 300% above the quiescent flux. This large, yet tightly confined, increase in emission is only resolvable due to the high spatial resolution of the Swedish Solar Telescope. An investigation of the line-of-sight magnetic field derived from simultaneous MDI data shows that the continuum brightening is located very close to a magnetic polarity inversion line. In addition, an Ha flare ribbon is directed along a region of rapid magnetic energy change, with the footpoints of the ribbon remaining cospatial with the observed white-light brightening throughout the duration of the flare. The observed flare parameters are compared with current observations and theoretical models for M- and X-class events and we determine the observed white-light emission is caused by radiative back-warming. We suggest that the creation of white-light emission is a common feature of all solar flares.

Adaptive data echo cancellation using cost function adaptation

For a digital echo canceller it is desirable to reduce the adaptation time, during which the transmission of useful data is not possible. LMS is a non-optimal algorithm in this case as the signals involved are statistically non-Gaussian. Walach and Widrow (IEEE Trans. Inform. Theory 30 (2) (March 1984) 275-283) investigated the use of a power of 4, while other research established algorithms with arbitrary integer (Pei and Tseng, IEEE J. Selected Areas Commun. 12(9)(December 1994) 1540-1547) or non-quadratic power (Shah and Cowan, IEE.Proc.-Vis. Image Signal Process. 142 (3) (June 1995) 187-191). This paper suggests that continuous and automatic, adaptation of the error exponent gives a more satisfactory result. The family of cost function adaptation (CFA) stochastic gradient algorithm proposed allows an increase in convergence rate and, an improvement of residual error. As special case the staircase CFA algorithm is first presented, then the smooth CFA is developed. Details of implementations are also discussed. Results of simulation are provided to show the properties of the proposed family of algorithms. (C) 2000 Elsevier Science B.V. All rights reserved.

The relationship between counterfactual thinking and emotional reactions to event outcomes: Does one account fit all?

By enabling a comparison between what is and what might have been, counterfactual thoughts amplify our emotional responses to bad outcomes. Well-known demonstrations such as the action effect (the tendency to attribute most regret to a character whose actions brought about a bad outcome) and the temporal order effect (the tendency to undo the last in a series of events leading up to a bad outcome) are often explained in this way. An important difference between these effects is that outcomes are due to decisions in the action effect, whereas in the temporal order effect outcomes are achieved by chance. In Experiment 1, we showed that imposing time pressure leads to a significant reduction in the action but not in the temporal order effect. In Experiment 2, we found that asking participants to evaluate the protagonists (

When some is actually all: Scalar inferences in face-threatening contexts

Accounts of the scalar inference from 'some X-ed' to 'not all X-ed' are central to the debate between contemporary theories of conversational pragmatics. An important contribution to this debate is to identify contexts that decrease the endorsement rate of the inference. We suggest that the inference is endorsed less often in face-threatening contexts, i.e., when X implies a loss of face for the listener. This claim is successfully tested in Experiment 1. Experiment 2 rules out a possible confound between face-threatening contexts and lower-bound contexts. Experiment 3 shows that whilst saying 'some X-ed' when one knew for a fact that all X-ed is always perceived as an underinformative utterance, it is also seen as a nice and polite thing to do when X threatens the face of the listener. These findings are considered from the perspective of Relevance Theory as well as that of the Generalized Conversational Inference approach. (C) 2009 Elsevier B.V. All rights reserved.

When all you have is a hammer ...: RCTs and hegemony in science

People diagnosed with autism spectrum disorder (ASD) deserve the same respect as any other person and should be free to benefit from scientific research that can help them achieve skills which enable them to reach their full potential. Over the past 40 years Applied Behaviour Analysis (ABA) has utilised inductive, natural science methods to investigate techniques for the analysis and augmentation of socially significant behaviours. Unfortunately, many individuals with ASD in the UK cannot avail of these techniques because of an obdurate reliance on randomised controlled trials (RCTs) as the single most respectable measure of effectiveness of interventions. In this paper we focus on how the debate about RCTs is played out in the ‘autism wars’.