Estimating the spatial scales of regionalized variables by nested sampling, hierarchical analysis of variance and residual maximum likelihood

The variogram is essential for local estimation and mapping of any variable by kriging. The variogram itself must usually be estimated from sample data. The sampling density is a compromise between precision and cost, but it must be sufficiently dense to encompass the principal spatial sources of variance. A nested, multi-stage, sampling with separating distances increasing in geometric progression from stage to stage will do that. The data may then be analyzed by a hierarchical analysis of variance to estimate the components of variance for every stage, and hence lag. By accumulating the components starting from the shortest lag one obtains a rough variogram for modest effort. For balanced designs the analysis of variance is optimal; for unbalanced ones, however, these estimators are not necessarily the best, and the analysis by residual maximum likelihood (REML) will usually be preferable. The paper summarizes the underlying theory and illustrates its application with data from three surveys, one in which the design had four stages and was balanced and two implemented with unbalanced designs to economize when there were more stages. A Fortran program is available for the analysis of variance, and code for the REML analysis is listed in the paper. (c) 2005 Elsevier Ltd. All rights reserved.

A hexadecanuclear copper(I)-copper(II) mixed-valence compound: structure, magnetic properties, intervalence charge transfer, EPR, and NMR

Hexadecanuclear copper mixed-valence complex 2 containing 10 Cu-II, centers and 6 Cu-I centers was isolated with N,O donor ligands. From the X-ray crystal structure, 2 was found to contain a centrosymmetric dimeric cation - each monomeric unit composed of eight copper centers. It displays a very broad and weak intervalence charge-transfer band around 1100 nm at room temperature in the solid state. Variable-temperature magnetic susceptibility measurements indicate an S = 1/2 ground state for half of 2, explicitly, each Cu-8 moiety has a g value around 2.26. Complex 2 was examined by NMR spectroscopy at room temperature in solution and by EPR at low temperature; the data indicates that the valence is delocalized in 2 at room temperature but localized at low temperature. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

Solvent-induced dynamic single-crystal-to-single-crystal transformation of a synthetic peptide-based cyclic compound

Solvent induced single-crystal-to-single-crystal transformation has been demonstrated indicating the dynamic behavior of one dimensional arrays obtained from a self-assembled new synthetic cyclic peptide.

The Namib Sand Sea digital database of aeolian dunes and key forcing variables

A new digital atlas of the geomorphology of the Namib Sand Sea in southern Africa has been developed. This atlas incorporates a number of databases including a digital elevation model (ASTER and SRTM) and other remote sensing databases that cover climate (ERA-40) and vegetation (PAL and GIMMS). A map of dune types in the Namib Sand Sea has been derived from Landsat and CNES/SPOT imagery. The atlas also includes a collation of geochronometric dates, largely derived from luminescence techniques, and a bibliographic survey of the research literature on the geomorphology of the Namib dune system. Together these databases provide valuable information that can be used as a starting point for tackling important questions about the development of the Namib and other sand seas in the past, present and future.

Using an additive to control the electrospinning of fibres of poly(epsilon-caprolactone)

Electrospinning is a route to polymer fibres with diameters considerably smaller than available from most fibre-producing techniques. We explore the use of a low molecular weight compound as an effective control additive during the electrospinning of poly(epsilon-caprolactone). This approach extends the control variables for the electrospinning of nanoscale fibres from the more usual ones such as the polymer molecular weight, solvent and concentration. We show that through the use of dual solvent systems, we can alter the impact of the additive on the electrospinning process so that finer as well as thicker fibres can be prepared under otherwise identical conditions. As well as the size of the fibres and the number of beads, the use of the additive allows us to alter the level of crystallinity as well as the level of preferred orientation of the poly(epsilon-caprolactone) crystals. This approach, involving the use of a dual solvent and a low molar mass compound, offers considerable potential for application to other polymer systems. (C) 2010 Society of Chemical Industry

Carbonyl compound dependent hydrolysis of mono-condensed Schiff bases: a trinuclear Schiff base complex and a mononuclear mixed-ligand ternary complex of copper(II)

Two Schiff bases, HL1 and HL2 have been prepared by the condensation of N-methyl-1,3-propanediamine (mpn) with salicylaldehyde and 1-benzoylacetone (Hbn) respectively. HL1 on reaction with Cu(ClO4)(2)center dot 6H(2)O in methanol produced a trinuclear Cu-II complex, [(CuL1)(3)(mu(3)-OH)](ClO4)(2)center dot H2O center dot 0.5CH(2)Cl(2) (1) but HL2 underwent hydrolysis under similar reaction conditions to result in a ternary Cu-II complex, [Cu(bn)(mpn)ClO4]. Both complexes have been characterised by single-crystal X-ray analyses, IR and UV-Vis spectroscopy and electrochemical studies. The partial cubane core [Cu3O4] of 1 consists of a central mu(3)-OH and three peripheral phenoxo bridges from the Schiff base. All three copper atoms of the trinuclear unit are five-coordinate with a distorted square-pyramidal geometry. The ternary complex 2 is mononuclear with the square-pyramidal Cu-II coordinated by a chelating bidentate diamine (mpn) and a benzoylacetonate (bn) moiety in the equatorial plane and one of the oxygen atoms of perchlorate in an axial position. The results show that the Schiff base (HL2) derived from 1-benzoylacetone is more prone to hydrolysis than that from salicylaldehyde (HL1). Magnetic measurements of 1 have been performed in the 1.8-300 K temperature range. The experimental data clearly indicate antiferromagnetism in the complex. The best-fit parameters for complex 1 are g = 2.18(1) and J = -15.4(2) cm(-1).

Correlations of control variables in variational data assimilation

Variational data assimilation systems for numerical weather prediction rely on a transformation of model variables to a set of control variables that are assumed to be uncorrelated. Most implementations of this transformation are based on the assumption that the balanced part of the flow can be represented by the vorticity. However, this assumption is likely to break down in dynamical regimes characterized by low Burger number. It has recently been proposed that a variable transformation based on potential vorticity should lead to control variables that are uncorrelated over a wider range of regimes. In this paper we test the assumption that a transform based on vorticity and one based on potential vorticity produce an uncorrelated set of control variables. Using a shallow-water model we calculate the correlations between the transformed variables in the different methods. We show that the control variables resulting from a vorticity-based transformation may retain large correlations in some dynamical regimes, whereas a potential vorticity based transformation successfully produces a set of uncorrelated control variables. Calculations of spatial correlations show that the benefit of the potential vorticity transformation is linked to its ability to capture more accurately the balanced component of the flow.

N-nitroso compound exposure-associated transcriptomic profiles are indicative of an increased risk for colorectal cancer

Endogenous formation of N-nitroso compounds (NOCs), which are known animal carcinogens, could contribute to human carcinogenesis but definitive evidence is still lacking. To investigate the relevance of NOCs in human colorectal cancer (CRC) development, we analyzed whole genome gene expression modifications in human colon biopsies in relation to fecal NOC exposure. We had a particular interest in patients suffering from intestinal inflammation as this may stimulate endogenous NOC formation, and consequently predispose to CRC risk. Inflammatory bowel disease (IBD) patients diagnosed with ulcerative colitis and irritable bowel syndrome patients without inflammation, serving as controls, were therefore recruited. Fecal NOC were demonstrated in the majority of subjects. By associating gene expression levels of all subjects to fecal NOC levels, we identified a NOC exposure-associated transcriptomic response that suggests that physiological NOC concentrations may potentially induce genotoxic responses and chromatin modifications in human colon tissue, both of which are linked to carcinogenicity. In a network analysis, chromatin modifications were linked to 11 significantly modulated histone genes, pointing towards a possible epigenetic mechanism that may be relevant in comprehending NOC-induced carcinogenesis. In addition, pro-inflammatory transcriptomic modifications were identified in visually non-inflamed regions of the IBD colon. However, fecal NOC levels were slightly but not significantly increased in IBD patients, suggesting that inflammation did not strongly stimulate NOC formation. We conclude that NOC exposure is associated with gene expression modifications in the human colon that may suggest a potential role of these compounds in CRC development.