Space time-index plots for probing dynamical nonstationarity

We propose a simple method to efficiently probe dynamical nonstationarity in observed time series. In a space time-index plot, the density distributions as a function of normalized time-index are V-shaped due to nonstationarity. We show that this method is workable for short data sets and typical examples are illustrated.     

Recent changes in A-level Mathematics: is the availability and uptake of mechanics declining yet more?

In the past 6 years changes have occurred in GCE A-levels. Inparticular, there have been several major changes in A-levelMathematics courses. As engineering students are usually requiredto have studied A-level Mathematics, or its equivalent, thesechanges have had an effect on their prior mathematical knowledge.Moreover, engineering students traditionally obtained a goodgrounding in mechanics as part of their A-level Mathematicsqualification. However, mechanics, which was once included inthe core syllabus, is now optional. This article investigatesthe current availability and uptake of mechanics modules withinA-level Mathematics courses in schools. Comparisons are drawnbetween these results and results of a survey of schools in2004 and surveys of first year engineering students conductedin 2004 and 2005. It is found that there is a decline in theavailability of mechanics modules and the uptake of more thanone mechanics module has also decreased. The implications ofthese findings for engineering educators are discussed.     

Rank-one completions of partial matrices and completely rank-nonincreasing linear functionals

We obtain necessary and sufficient conditions for the existence and the uniqueness of rank-one completions of a partial matrix, and we verify a conjecture of Hadwin and Larson concerning the nature of completely rank-nonincreasing linear functionals defined on pattern subspaces.

     

Density functional theory investigation of the structure of SO2 and SO3 on Cu(1 1 1) and Ni(1 1 1)

Density functional theory (DFT) slab calculations, mainly using the generalised gradient approximation, have been used to investigate the minimum energy structures of molecular SO₂ and SO₃ on Cu(1 1 1) and Ni(1 1 1) surfaces. On Ni(1 1 1) the optimal local adsorption structures are in close agreement with experimental results for both molecular species obtained using the X-ray standing wavefield technique, although for adsorbed SO₂ the energetic difference between two alternative lateral positions of the lying-down molecule on the surface is marginally significant. On Cu(1 1 1) the results for adsorbed SO₂, in particular, were sensitive to the DFT functional used in the calculations, but in all cases failed to reproduce the experimentally-established preference for adsorption with the molecular plane perpendicular to the surface. This result is discussed in the context of previously published DFT results for these species adsorbed on Cu(1 0 0). The optimal geometry found for SO₃ on Cu(1 1 1) is similar to that on Ni(1 1 1), providing agreement with experiment regarding the molecular orientation but not the adsorption site.     

Bioaccumulation and excretion of arsenic compounds by a marine unicellular alga,polyphysa peniculus

Polyphysa peniculus was grown in artificial seawater in the presence of arsenate, arsenite, monomethylarsonate and dimethylarsinic acid. The separation and identification of some of the arsenic species produced in the cells as well as in the growth medium were achieved by using hydride generation–gas chromatography–atomic absorption spectrometry methodology. Arsenite and dimethylarsinate were detected following incubation with arsenate. When the alga was treated with arsenite, dimethylarsinate was the major metabolite in the cells and in the growth medium; trace amounts of monomethylarsonate were also detected in the cells. With monomethylarsonate as a substrate, the metabolite is dimethylarsinate. Polyphysa peniculus did not metabolize dimethylarsinic acid when it was used as a substrate. Significant amounts of more complex arsenic species, such as arsenosungars, were not observed in the cells or medium on the evidence of flow injection–microwave digestion–hydride generation–atomic absorption spectrometry methodology. Transfer of the exposed cells to fresh medium caused release of most cell–associated arsenicals to the surrounding environment.     

O− and OH− chemical ionization of some fatty acid methyl esters and triacylglycerols

O^? and OH^? react with fatty acid methyl esters (FAMES) under chemical ionization conditions both as Bronsted bases to form [M - H]^? and as nucleophiles to form the carboxylate ion RCOO^?. O^? shows a much greater tendency to react as a nucleophile than does OH^?. The [M - H]^? ions fragment by elimination of CH³OH, with unsaturation in certain positions in the fatty acid hydrocarbon chain promoting this elimination for unknown reasons. The reaction of O^? and OH^? with triacylglycerols leads to [M - H]^?, characteristic of the molecular mass, and to carboxylate ions characteristic of the fatty acid(s) present in the lipid. The presence of the three ester functions in the lipids greatly enhances the formation of carboxylate ions compared to the FAMES.     

A phloroglucinol derivative with a new carbon skeleton from Hypericum perforatum (Guttiferae)

Examination of the aerial parts of a Chinese herbal medicine yielded a novel metabolite, perforatumone 1, which is characterized by its unique carbon skeleton. Its structure was determined by detailed spectroscopic analysis.     

Density functional theory investigation of CN on Cu(1 1 1), Ni(1 1 1) and Ni(1 0 0)

The adsorption of CN on Cu(1 1 1), Ni(1 1 1) and Ni(1 0 0) has been investigated using density functional theory (DFT). While experimental studies of CN on Cu(1 1 1) show the molecular axis to be essentially parallel to the surface, the normally-preferred DFT approach using the generalised gradient approximation (GGA) yields a lowest energy configuration with the C-N axis perpendicular to the surface, although calculations using the local density approximation (LDA) do indicate that the experimental geometry is energetically favoured. The same conclusions are found for CN on Ni(1 1 1); on both surfaces bonding through the N atom is always unfavourable, in contrast to some earlier published results of ab initio calculations for Ni(1 1 1)/CN and Ni(1 0 0)/CN. The different predictions of the GGA and LDA approaches may lie in subtly different relative energies of the CN 5σ and 1π orbitals, a situation somewhat similar to that for CO adsorbed on Pt(1 1 1) which has proved challenging for DFT calculations. On Ni(1 0 0) GGA calculations favour a lying-down species in a hollow site in a geometry rather similar to that found experimentally and in GGA calculations for CN on Ni(1 1 0).