Structural observations on La2(Ni,Co)O4±δ phases determined from in situ neutron powder diffraction

In situ neutron powder diffraction data have been analysed for a number of compositions in the solid solution series La₂Ni_1−xCo_xO_4±δ over the temperature range 150-650 °C. High-quality Rietveld refinements indicate no major structural transitions have occurred in any of the compositions, although close examination of the Ni/CoO bond distances highlight changes in the coordination environment with increasing temperature. Further, the changes in the coordination can be correlated to changes in both the oxide ion and electronic conductivity indicating a direct link between transport properties, bonding and transition metal valence state in these Co containing layered perovskites.     

Hydrogen bonding definitions and dynamics in liquid water

X-ray and neutron diffractions, vibrational spectroscopy, and x-ray Raman scattering and absorption experiments on water are often interpreted in terms of hydrogen bonding. To this end a number of geometric definitions of hydrogen bonding in water have been developed. While all definitions of hydrogen bonding are to some extent arbitrary, those involving one distance and one angle for a given water dimer are unnecessarily so. In this paper the authors develop a systematic procedure based on two-dimensional potentials of mean force for defining cutoffs for a given pair of distance and angular coordinates. They also develop an electronic structure-based definition of hydrogen bonding in liquid water, related to the electronic occupancy of the antibonding OH orbitals. This definition turns out to be reasonably compatible with one of the distance-angle geometric definitions. These two definitions lead to an estimate of the number of hydrogen bonds per molecule in liquid simple point charge/extended (SPC/E) water of between 3.2 and 3.4. They also used these and other hydrogen-bond definitions to examine the dynamics of local hydrogen-bond number fluctuations, finding an approximate long-time decay constant for SPC/E water of between 0.8 and 0.9 ps, which corresponds to the time scale for local structural relaxation.     

Human and environmental risk assessment of pharmaceuticals: differences,similarities, lessons from toxicology

The presence of human and veterinary pharmaceuticals in the environment has caused increasing concern due their effects on ecological receptors. Improving the risk assessment of these compounds necessitates a quantitative understanding of their metabolism and elimination in the target organism (toxicokinetics), particularly via the ubiquitous cytochrome P-450 (CYP) system and their mechanisms of toxicity (toxicodynamics). This review focuses on a number of pharmaceuticals and veterinary medicines of environmental concern, and the differences and similarities between ecological and human risk assessment. CYP metabolism is discussed with particular reference to its ubiquity in species of ecological relevance. The important issue of pharmaceutical mixtures is discussed to assess how emerging technologies such as ecotoxicogenomics may assist in moving towards a more mechanism-based environmental risk assessment of pharmaceuticals.     

On the Dissection of Rectangles into Right-Angled Isosceles Triangles

We consider the problem of dissecting a rectangle or a square into unequal right-angled isosceles triangles. This is regarded as a generalization of the well-known and much-solved problem of dissecting such figures into unequal squares. There is an analogous “electrical” theory but it is based on digraphs instead of graphs and has an appropriate modification of Kirchhoff's first law. The operation of reversing all edges in the digraph is found to be of great help in the construction of “perfect” dissected squares.     

The electrojet phenomenon

The term ‘electrojet’ is frequently used to describe the intense bands of electric curent which flow at certain times in the earth's ionosphere at an altitude of about 100 km. Two main forms of electrojet current are distinguished; an equatorial electrojet which flows during the daylight hours in a narrow band of latitudes centred on the magnetic equator, and an auroral electrojet which flows during the main phese of magnetic storms in auroral regions. Both are accompanied by abnormally large changes in the geomagnetic field components as measured at the earth's surface. This article reviews the main features of the two forms of electrojet and discusses the present theories for their origin. Ionospheric irregularities are associated with both types of electrojet, and the experimental evidence so far accumulated indicates that these are produced by plane plasma waves generated by a two-stream instability in the plasma and travelling with the acoustic velocity of about 360 m s^?1.     

High frequency induction of CC to TT tandem mutations in DNA repair-proficient mammalian cells

The CC to TT tandem mutation is induced by UV radiation exposure, though at relatively low frequencies when compared with the more commonly induced C to T mutation. Induction of the tandem mutation by UV is enhanced in mammalian cells with certain genetic deficiencies; however, conditions have not been described in which the frequency of this mutation is enhanced in DNA repair-proficient mammalian cells. For this study, an integrated construct that detects C to T and CC to TT mutations at a single codon in mouse Aprt was used to examine UVB mutagenesis under various conditions. Oxidative stress, in the form of intracellular hydrogen peroxide, increased the frequency of UVB-induced CC to TT mutations. Surprisingly, exposure of the cells to two antioxidants (N-acetylcysteine and trolox), either alone or in combination, also enhanced UVB induction of CC to TT tandem mutations. These results demonstrate, for the first time, that the frequency of UVB-induced CC to TT tandem mutations can be enhanced dramatically in DNA repair-proficient mammalian cells, and suggest that the enhancing effect does not require direct damage to DNA.     

Copper and arsenate co-sorption at the mineral-water interfaces of goethite and jarosite

The co-sorption reaction products of arsenate (As(V)) and copper (Cu(II)) on goethite (alpha-FeOOH) and natro-jarosite (Na(3)Fe(3)(SO(4))(2)(OH)(6)) were investigated with extended X-ray absorption fine structure (EXAFS) spectroscopy to determine if Cu(II) and As(V) would form precipitates or compete with each other for surface sites. The reaction products were prepared by mixing 250 microM Cu(SO(4)) with 10, 25, or 50 microM Na(2)HAsO(4) at pH 5.65 and allowing the mixture to react in 10 m(2) L(-1) goethite or jarosite suspensions for 12 days. In addition, EXAFS data of Cu(SO(4)) and As(V) sorbed on goethite and jarosite were collected as control species. All reaction conditions were under-saturated with respect to common copper bearing minerals: tenorite (CuO), brochantite (Cu(4)(OH)(6)SO(4)), and hydrated clinoclase (Cu(3)(AsO(4))(2)2H(2)O). The extents of the As(V) and Cu(II) surface adsorption reactions showed a strong competitive effect from Cu(II) on As(V) adsorption for a nominal Cu:As mole-ratio of 25:1. With increasing nominal As(V) concentration, As(V) sorption on goethite and jarosite increased without diminishing the amount of Cu(II) sorption. In the absence of either co-sorbate, As(V) and Cu(II) formed the expected surface adsorption species, i.e., bidentate binuclear and edge-sharing surface complexes, consistent with previously published results. In each other's presence, the local bonding environments of As(V) and Cu(II) showed that the co-sorbates form a precipitate on the goethite and jarosite surface at nominal concentrations of 10:1 and 5:1. At nominal Cu:As mole-ratios of 25:1, Cu(II) did not form significantly different surface complexes on goethite or jarosite from those in the absence of As(V), however, As K-edge EXAFS results distinctly showed Cu(II) atoms in As(V)'s local bonding environment on the goethite surface. The structures of the two precipitates were different and depended on the anion-layer structure and possibly the presence of structural oxyanions in the case of jarosite. On goethite, the copper-arsenate precipitate was similar to hydrated clinoclase, while on jarosite, a euchroite-like precipitate (Cu(2)[AsO(4)](OH)3H(2)O, P 2(1)2(1)2(1)) had formed. Despite under-saturated solution conditions, the formation of these precipitates may have occurred due to a seed-formation effect from densely surface adsorbed Cu(II) and As(V) for which the "new" saturation index was significantly lower than homogeneous values would otherwise suggest. Synergistic reactions between two co-sorbates of fundamentally different surface adsorption behaviour can thus be achieved if the number of available sites for surface adsorption is limited.     

Vibrational energy relaxation of the bend fundamental of dilute water in liquid chloroform and d-chloroform

The population lifetimes of the bend fundamental of dilute water in liquid chloroform (8.5 ps) and d-chloroform (28.5 ps) display an interesting solvent isotope effect. As the lowest excited vibrational state of the molecule, the water bend fundamental relaxes directly to the ground state with about 1600 cm-1 of energy released to the other degrees of freedom. The strong solvent isotope effect along with the large energy gap indicates the participation of solvent vibrational modes in this vibrational energy relaxation process. We calculate the vibrational energy relaxation rates of the water bend in chloroform and d-chloroform using the Landau-Teller formula with a new potential model developed and parametrized self-consistently to describe the chloroform-water interaction. The computed values are in reasonable agreement with the experimental results, and the trend for the isotope effect is correct. It is found that energy transfer to the solvent vibrations does indeed play an important role. Nevertheless, no single dominant solvent accepting mode can be identified; the relaxation appears to involve both the bend and the C-Cl stretches, and frequency changes of all of these modes upon deuteration contribute to the observed solvent isotope effect.     

Gravity, Twistors and the MHV Formalism

We give a self-contained proof of the formula for the MHV amplitudes for gravity conjectured by Berends, Giele & Kuijf and use the associated twistor generating function to define a twistor action for the MHV diagram approach to gravity. Starting from a background field calculation on a spacetime with anti-self-dual curvature, we obtain a simple spacetime formula for the scattering of a single, positive helicity linearized graviton into one of negative helicity. Re-expressing our integral in terms of twistor data allows us to consider a spacetime that is asymptotic to a superposition of plane waves. Expanding these out perturbatively yields the gravitational MHV amplitudes of Berends, Giele & Kuijf. We go on to take the twistor generating function off-shell at the perturbative level. Combining this with a twistor action for the anti-self-dual background, the generating function provides the MHV vertices for the MHV diagram approach to perturbative gravity. We finish by extending these results to supergravity, in particular N = 4{\mathcal {N} = 4} and N = 8{\mathcal {N} = 8} .