Si3N4 single-crystal nanowires grown from silicon micro- and nanoparticles near the threshold of passive oxidation

A simple and most promising oxide-assisted catalyst-free method is used to prepare silicon nitride nanowires that give rise to high yield in a short time. After a brief analysis of the state of the art, we reveal the crucial role played by the oxygen partial pressure: when oxygen partial pressure is slightly below the threshold of passive oxidation, a high yield inhibiting the formation of any silica layer covering the nanowires occurs and thanks to the synthesis temperature one can control nanowire dimensions

Ab initio benchmark study for the oxidative addition of CH4 to Pd: importance of basis-set flexibility and polarization

To obtain a state-of-the-art benchmark potential energy surface (PES) for the archetypal oxidative addition of the methane C-H bond to the palladium atom, we have explored this PES using a hierarchical series of ab initio methods (Hartree-Fock, second-order Møller-Plesset perturbation theory, fourth-order Møller-Plesset perturbation theory with single, double and quadruple excitations, coupled cluster theory with single and double excitations (CCSD), and with triple excitations treated perturbatively [CCSD(T)]) and hybrid density functional theory using the B3LYP functional, in combination with a hierarchical series of ten Gaussian-type basis sets, up to g polarization. Relativistic effects are taken into account either through a relativistic effective core potential for palladium or through a full four-component all-electron approach. Counterpoise corrected relative energies of stationary points are converged to within 0.1-0.2 kcal/mol as a function of the basis-set size. Our best estimate of kinetic and thermodynamic parameters is -8.1 (-8.3) kcal/mol for the formation of the reactant complex, 5.8 (3.1) kcal/mol for the activation energy relative to the separate reactants, and 0.8 (-1.2) kcal/mol for the reaction energy (zero-point vibrational energy-corrected values in parentheses). This agrees well with available experimental data. Our work highlights the importance of sufficient higher angular momentum polarization functions, f and g, for correctly describing metal-d-electron correlation and, thus, for obtaining reliable relative energies. We show that standard basis sets, such as LANL2DZ+ 1f for palladium, are not sufficiently polarized for this purpose and lead to erroneous CCSD(T) results. B3LYP is associated with smaller basis set superposition errors and shows faster convergence with basis-set size but yields relative energies (in particular, a reaction barrier) that are ca. 3.5 kcal/mol higher than the corresponding CCSD(T) values

Spectroscopy of highly excited vibrational states of HCN in its ground electronic state

An experimental technique based on a scheme of vibrationally mediated photodissociation has been developed and applied to the spectroscopic study of highly excited vibrational states in HCN, with energies between 29 000 and 30 000 cm(-1). The technique consists of four sequential steps: in the first one, a high power laser is used to vibrationally excite the sample to an intermediate state, typically (0,0,4), the nu(3) mode being approximately equivalent to the C-H stretching vibration. Then a second laser is used to search for transitions between this intermediate state and highly vibrationally excited states. When one of these transitions is found, HCN molecules are transferred to a highly excited vibrational state. Third, a ultraviolet laser photodissociates the highly excited molecules to produce H and CN radicals in its A (2)Pi electronic state. Finally, a fourth laser (probe) detects the presence of the CN(A) photofragments by means of an A-->B-->X laser induced fluorescence scheme. The spectra obtained with this technique, consisting of several rotationally resolved vibrational bands, have been analyzed. The positions and rotational parameters of the states observed are presented and compared with the results of a state-of-the-art variational calculation. (C) 2004 American Institute of Physics.

Highly excited vibrational states of HCN around 30 000 cm(-1)

This article describes the analysis and interpretation of rovibrational spectra involving highly excited vibrational states in the molecule of HCN. The spectra were obtained by means of the vibrationally mediated photodissociation technique. Analysis of the spectra revealed four bands with Sigma-Sigma structures that, once fitted, provided the energies and rotational constants of four new, highly excited vibrational states in the region of the potential energy surface near and above 30 000 cm(-1). All the states could be identified with the help of a state-of-the-art variational calculation. Together with the states already observed in previous works, eight highly excited states have so far been identified in this region. (c) 2006 American Institute of Physics.

Herbal medicine: the science of the art

In the last 50 years science has provided new perspectives on the ancient art of herbal medicine. The present article discusses ways in which the evidence base for the professional use of 'Western' herbal medicine, as therapy to treat disease, known as phytotherapy, can be strengthened and developed. The evidence base for phytotherapy is small and lags behind that for the nutritional sciences, mainly because phytochemicals are ingested as complex mixtures that are incompletely characterised and have only relatively recently been subject to scientific scrutiny. While some methodologies developed for the nutritional sciences can inform phytotherapy research, opportunities for observational studies are more limited, although greater use could be made of patient case notes. Randomised clinical trials of single-herb interventions are relatively easy to undertake and increasing numbers of such studies are being published. Indeed, enough data are available on three herbs (ginkgo (Ginkgo biloba), St John's wort (Hypericum perforatum) and saw palmetto (Serenoa repens)) for meta-analyses to have been undertaken. However, phytotherapy is holistic therapy, using lifestyle advice, nutrition and individually-prescribed mixtures of herbs aimed at reinstating homeostasis. While clinical experience shows that this approach is applicable to a wide range of conditions, including chronic disease, evidence of its efficacy is scarce. Strategies for investigating the full holistic approach of phytotherapy and its main elements are discussed and illustrated through the author's studies at the University of Reading.

How difficult is it to recover from dangerous levels of global warming?

Climate models provide compelling evidence that if greenhouse gas emissions continue at present rates, then key global temperature thresholds (such as the European Union limit of two degrees of warming since pre-industrial times) are very likely to be crossed in the next few decades. However, there is relatively little attention paid to whether, should a dangerous temperature level be exceeded, it is feasible for the global temperature to then return to safer levels in a usefully short time. We focus on the timescales needed to reduce atmospheric greenhouse gases and associated temperatures back below potentially dangerous thresholds, using a state-of-the-art general circulation model. This analysis is extended with a simple climate model to provide uncertainty bounds. We find that even for very large reductions in emissions, temperature reduction is likely to occur at a low rate. Policy-makers need to consider such very long recovery timescales implicit in the Earth system when formulating future emission pathways that have the potential to 'overshoot' particular atmospheric concentrations of greenhouse gases and, more importantly, related temperature levels that might be considered dangerous.

Tiny objects writ large: the private world of ice age art made public

Ice Age Art: Arrival of the Modern Mind was an exhibition at the British Museum from 27 February to 2 June 2013 exhibiting sculptures and engravings from the Ice Age of Europe and Eurasia, 40,000–10,000 years ago. It was accompanied by a lavishly illustrated book by Jill Cook with the same title, published by the British Museum Press. The exhibition was a sell-out, attracting considerable coverage in the press. Here I reflect critically on some aspects of the exhibition, exploring what such a display might tell us about ice age life, the modern mind and our present-day approach to displaying such objects.

An evaluation of decadal probability forecasts from state-of-the-art climate models

While state-of-the-art models of Earth's climate system have improved tremendously over the last 20 years, nontrivial structural flaws still hinder their ability to forecast the decadal dynamics of the Earth system realistically. Contrasting the skill of these models not only with each other but also with empirical models can reveal the space and time scales on which simulation models exploit their physical basis effectively and quantify their ability to add information to operational forecasts. The skill of decadal probabilistic hindcasts for annual global-mean and regional-mean temperatures from the EU Ensemble-Based Predictions of Climate Changes and Their Impacts (ENSEMBLES) project is contrasted with several empirical models. Both the ENSEMBLES models and a “dynamic climatology” empirical model show probabilistic skill above that of a static climatology for global-mean temperature. The dynamic climatology model, however, often outperforms the ENSEMBLES models. The fact that empirical models display skill similar to that of today's state-of-the-art simulation models suggests that empirical forecasts can improve decadal forecasts for climate services, just as in weather, medium-range, and seasonal forecasting. It is suggested that the direct comparison of simulation models with empirical models becomes a regular component of large model forecast evaluations. Doing so would clarify the extent to which state-of-the-art simulation models provide information beyond that available from simpler empirical models and clarify current limitations in using simulation forecasting for decision support. Ultimately, the skill of simulation models based on physical principles is expected to surpass that of empirical models in a changing climate; their direct comparison provides information on progress toward that goal, which is not available in model–model intercomparisons.

The timing of anthropogenic emergence in simulated climate extremes

Determining the time of emergence of climates altered from their natural state by anthropogenic influences can help inform the development of adaptation and mitigation strategies to climate change. Previous studies have examined the time of emergence of climate averages. However, at the global scale, the emergence of changes in extreme events, which have the greatest societal impacts, has not been investigated before. Based on state-of-the-art climate models, we show that temperature extremes generally emerge slightly later from their quasi-natural climate state than seasonal means, due to greater variability in extremes. Nevertheless, according to model evidence, both hot and cold extremes have already emerged across many areas. Remarkably, even precipitation extremes that have very large variability are projected to emerge in the coming decades in Northern Hemisphere winters associated with a wettening trend. Based on our findings we expect local temperature and precipitation extremes to already differ significantly from their previous quasi-natural state at many locations or to do so in the near future. Our findings have implications for climate impacts and detection and attribution studies assessing observed changes in regional climate extremes by showing whether they will likely find a fingerprint of anthropogenic climate change.

Future, Fortune, and the graphic design of information

This is a study of graphic information designed for Future Books/Future magazine (UK) and Fortune magazine (USA) in the years immediately after the Second World War. It highlights work made by the Isotype Institute for Future, which is then situated against contributions by Abram Games and F. H. K. Henrion. Similar work in Fortune under the art editorship of Will Burtin is discussed in a parallel account, drawing on examples by him and by others including György Kepes, Matthew Liebowitz, Alex Steinweiss and Ladislav Sutnar. Attention is drawn to links and relationships between to the two periodicals and the graphic information published in both. Further comparisons are made between underlying editorial and design strategies pursued by Otto Neurath (Isotype Institute) and Will Burtin. An argument is made for recognising the little-known innovations of Future alongside the long-acknowledged innovations of Fortune.

Baseline and stress-induced plasma corticosterone concentrations of mice selectively bred for high voluntary wheel running

The hypothalamic-pituitary-adrenal (HPA) axis is important in regulating energy metabolism and in mediating responses to stressors, including increasing energy availability during physical exercise. In addition, glucocorticoids act directly on the central nervous system and influence behavior, including locomotor activity. To explore potential changes in the HPA axis as animals evolve higher voluntary activity levels, we characterized plasma corticosterone (CORT) concentrations and adrenal mass in four replicate lines of house mice that had been selectively bred for high voluntary wheel running (HR lines) for 34 generations and in four nonselected control (C) lines. We determined CORT concentrations under baseline conditions and immediately after exposure to a novel stressor (40 min of physical restraint) in mice that were housed without access to wheels. Resting daytime CORT concentrations were approximately twice as high in HR as in C mice for both sexes. Physical restraint increased CORT to similar concentrations in HR and C mice; consequently, the proportional response to restraint was smaller in HR than in C animals. Adrenal mass did not significantly differ between HR and C mice. Females had significantly higher baseline and postrestraint CORT concentrations and significantly larger adrenal glands than males in both HR and C lines. Replicate lines showed significant variation in body mass, length, baseline CORT concentrations, and postrestraint CORT concentrations in one or both sexes. Among lines, both body mass and length were significantly negatively correlated with baseline CORT concentrations, suggesting that CORT suppresses growth. Our results suggest that selection for increased locomotor activity has caused correlated changes in the HPA axis, resulting in higher baseline CORT concentrations and, possibly, reduced stress responsiveness and a lower growth rate. © 2007 by The University of Chicago. All rights reserved.

Clinical evaluation of multiple-surface ART restorations: three-year follow-up

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Identifique-se: Exposição de Mail Art, uma poética compartilhada

This work refers to a cut of my artistic creation path with some reflections on the subject other. Mail Art has been an alternative trend of art / avant-garde, where communication between artists networks is the goal to be achieved, therefore, from this statement, was approached some historical and particular aspects regarding the post and its contingencies in the art / forefront. Share this moment of academic completion with a postcard exhibition that will take place through the agency of other participating artists. To do so, were invited artists from the theme IDENTIFY UP to send work in postcard size with the exclusive use of the Post Office. The exhibition event will take place in the Gallery of the Art Institute. Participant of other similar projects, I believe I experienced a new role: who calls, organizes and rules.

Identifique-se: Exposição de Mail Art, uma poética compartilhada

This work refers to a cut of my artistic creation path with some reflections on the subject other. Mail Art has been an alternative trend of art / avant-garde, where communication between artists networks is the goal to be achieved, therefore, from this statement, was approached some historical and particular aspects regarding the post and its contingencies in the art / forefront. Share this moment of academic completion with a postcard exhibition that will take place through the agency of other participating artists. To do so, were invited artists from the theme IDENTIFY UP to send work in postcard size with the exclusive use of the Post Office. The exhibition event will take place in the Gallery of the Art Institute. Participant of other similar projects, I believe I experienced a new role: who calls, organizes and rules.