An investigation into the unusual linkage isomerization and nitrite reduction activity of a novel tris(2-pyridyl) copper complex

The copper-containing nitrite reductases (CuNIRs) are a class of enzymes that mediate the reduction of nitrite to nitric oxide in biological systems. Metal–ligand complexes that reproduce the salient features of the active site of CuNIRs are therefore of fundamental interest, both for elucidating the possible mode of action of the enzymes and for developing biomimetic catalysts for nitrite reduction. Herein, we describe the synthesis and characterization of a new tris(2-pyridyl) copper complex ([Cu1(NO2)2]) that binds two molecules of nitrite, and displays all three of the common binding modes for NO2−, with one nitrite bound in an asymmetric quasi-bidentate κ2-ONO manner and the other bound in a monodentate fashion with a linkage isomerism between the κ1-ONO and κ1-NO2 binding modes. We use density functional theory to help rationalize the presence of all three of these linkage isomers in one compound, before assessing the redox activity of [Cu1(NO2)2]. These latter studies show that the complex is not a competent nitrite reduction electrocatalyst in non-aqueous solvent, even in the presence of additional proton donors, a finding which may have implications for the design of biomimetic catalysts for nitrite reduction

A hypothalamic channel-system in the inferior lobes of a trigger-fish (Rhinecanthus aculeatus, Balistidae)

In the course of a general investigation of the optic system in some trigger-fishes, a hypothalamic, ventricular channel-system with pores, leading to the outside of the brain, has been discovered in the inferior lobes ofRhinecanthus aculeatus (Balistidae). A description of the morphological relations of the channel-system to the blood-vessel-supply and the cranium suggests that the organ-systems involved form a functional unit. The possibility of a hormone-producing system is discussed in the light of physiological and ecological aspects

Harold Jeffreys's Theory of Probability Revisited

Published exactly seventy years ago, Jeffreys's Theory of Probability (1939) has had a unique impact on the Bayesian community and is now considered to be one of the main classics in Bayesian Statistics as well as the initiator of the objective Bayes school. In particular, its advances on the derivation of noninformative priors as well as on the scaling of Bayes factors have had a lasting impact on the field. However, the book reflects the characteristics of the time, especially in terms of mathematical rigor. In this paper we point out the fundamental aspects of this reference work, especially the thorough coverage of testing problems and the construction of both estimation and testing noninformative priors based on functional divergences. Our major aim here is to help modern readers in navigating in this difficult text and in concentrating on passages that are still relevant today.Comment: This paper commented in: [arXiv:1001.2967], [arXiv:1001.2968], [arXiv:1001.2970], [arXiv:1001.2975], [arXiv:1001.2985], [arXiv:1001.3073]. Rejoinder in [arXiv:0909.1008]. Published in at http://dx.doi.org/10.1214/09-STS284 the Statistical Science (http://www.imstat.org/sts/) by the Institute of Mathematical Statistics (http://www.imstat.org

Low Momentum Scattering in the Dirac Equation

It is shown that the amplitude for reflection of a Dirac particle with arbitrarily low momentum incident on a potential of finite range is -1 and hence the transmission coefficient T=0 in general. If however the potential supports a half-bound state at k=0 this result does not hold. In the case of an asymmetric potential the transmission coefficient T will be non-zero whilst for a symmetric potential T=1.Comment: 12 pages; revised to include additional references; to be published in J Phys

The Woods-Saxon Potential in the Dirac Equation

The two-component approach to the one-dimensional Dirac equation is applied to the Woods-Saxon potential. The scattering and bound state solutions are derived and the conditions for a transmission resonance (when the transmission coefficient is unity) and supercriticality (when the particle bound state is at E=-m) are then derived. The square potential limit is discussed. The recent result that a finite-range symmetric potential barrier will have a transmission resonance of zero-momentum when the corresponding well supports a half-bound state at E=-m is demonstrated.Comment: 8 pages, 4 figures. Submitted to JPhys

Reinforcement learning in populations of spiking neurons

Population coding is widely regarded as a key mechanism for achieving reliable behavioral responses in the face of neuronal variability. But in standard reinforcement learning a flip-side becomes apparent. Learning slows down with increasing population size since the global reinforcement becomes less and less related to the performance of any single neuron. We show that, in contrast, learning speeds up with increasing population size if feedback about the populationresponse modulates synaptic plasticity in addition to global reinforcement. The two feedback signals (reinforcement and population-response signal) can be encoded by ambient neurotransmitter concentrations which vary slowly, yielding a fully online plasticity rule where the learning of a stimulus is interleaved with the processing of the subsequent one. The assumption of a single additional feedback mechanism therefore reconciles biological plausibility with efficient learning

Effect of embryo culture media on birthweight and length in singleton term infants after IVF-ICSI.

QUESTIONS UNDER STUDY: To investigate if two distinct, commercially available embryo culture media have a different effect on birthweight and length of singleton term infants conceived after IVF-ICSI. METHODS: University hospital based cohort study. Between 1 January 2000 and 31 December 2004, patients conceiving through IVF-ICSI at the University Hospital, Lausanne have been allocated to two distinct embryo culture media. Only term singleton pregnancies were analysed (n = 525). Data analysis was performed according to two commercially available culture media: Vitrolife (n = 352) versus Cook (n = 173). Analysis was performed through linear regression adjusted for confounders. Media were considered equivalent if the 95% confidence interval lay between -150 g/+150 g. RESULTS: Length, gestational age and distribution of birthweight percentiles did not differ between groups (for both genders). Analysis of the whole cohort, adjusted for a subset of confounders, resulted in a statistically not different mean birthweight between the two groups (Vitrolife +37 g vs Cook, 95%CI: -46 g to 119 g) suggesting equivalence. Adjustment for an enlarged number of confounders in a subsample of patients (n = 258) also revealed no relevant mean birthweight difference of +71 g (95%CI: -45 g to 187 g) in favour of Vitrolife; however, lacking power to prove equivalence. CONCLUSIONS: Our data suggest that significant differences in birthweight due to these two distinct, commercially available embryo culture media are unlikely

Size Dependence of Metal-Insulator Transition in Stoichiometric Fe3O4 Nanocrystals

Magnetite (Fe3O4) is one of the most actively studied materials with a famous metal-insulator transition (MIT), so-called the Verwey transition at around 123 K. Despite the recent progress in synthesis and characterization of Fe3O4 nanocrystals (NCs), it is still an open question how the Verwey transition changes on a nanometer scale. We herein report the systematic studies on size dependence of the Verwey transition of stoichiometric Fe3O4 NCs. We have successfully synthesized stoichiometric and uniform-sized Fe3O4 NCs with sizes ranging from 5 to 100 nm. These stoichiometric Fe3O4 NCs show the Verwey transition when they are characterized by conductance, magnetization, cryo-XRD, and heat capacity measurements. The Verwey transition is weakly size-dependent and becomes suppressed in NCs smaller than 20 nm before disappearing completely for less than 6 nm, which is a clear, yet highly interesting indication of a size effect of this well-known phenomena. Our current work will shed new light on this ages-old problem of Verwey transition.Comment: 18 pages, 4 figures, Nano Letters (accepted