Geometrical isomers of [TEAH][Co(L-Se)(2)]center dot xH(2)O: synthesis, structural, spectroscopic and computational studies

Trans-1, [HNEt3][Co-III(L-Se)(2)]center dot H2O and cis-1, [HNEt3][Co-III(L-Se)(2)]center dot 3H(2)O have been synthesized and characterized by single-crystal X-ray studies. The counter ion Et3NH+ plays a crucial role in the crystal packing leading to the formation of two distinctly different supramolecular assemblies in the two complexes. In trans-1, Co-bisphenolate units and triethylamine molecules are arranged in a linear fashion leading to a supramolecular columnar assembly along the crystallographic a-axis. In this assembly, triethylammonium ions are sandwiched between successive Co-bisphenolate units and act as gluing agents joining Co-bisphenolate units on either side through C-H center dot center dot center dot pi interactions. In sharp contrast to trans-1, Co-bisphenolate units and triethylammonium ions in cis-1 are arranged in a helical supramolecular assembly through similar C-H center dot center dot center dot pi interactions along the crystallographic b-axis. The Se center dot center dot center dot Se van der Waals interactions may be responsible for the predominant occurrence of the cis-isomer. The cyclic voltammetric studies showed quasi-reversible waves for the cobalt(III) -> cobalt(II) reductions with E-1/2 = 0.635 and 0.628 V vs. Ag/AgCl for cis-1 (at similar to 5 degrees C) and trans-1 (at similar to 25 degrees C), respectively. DFT calculations show that the trans-form is the thermodynamic product with higher stability than the cis-one, which is consistent with the variable temperature H-1 NMR studies

Joint modelling of obstacle induced and mesoscale changes: current limits and challenges

Obstacles considerably influence boundary layer processes. Their influences have been included in mesoscale models (MeM) for a long time. Methods used to parameterise obstacle effects in a MeM are summarised in this paper using results of the mesoscale model METRAS as examples. Besides the parameterisation of obstacle influences it is also possible to use a joint modelling approach to describe obstacle induced and mesoscale changes. Three different methods may be used for joint modelling approaches: The first method is a time-slice approach, where steady basic state profiles are used in an obstacle resolving microscale model (MiM, example model MITRAS) and diurnal cycles are derived by joining steady-state MITRAS results. The second joint modelling approach is one-way nesting, where the MeM results are used to initialise the MiM and to drive the boundary values of the MiM dependent on time. The third joint modelling approach is to apply multi-scale models or two-way nesting approaches, which include feedbacks from the MiM to the MeM. The advantages and disadvantages of the different approaches and remaining problems with joint Reynolds-averaged Navier–Stokes modelling approaches are summarised in the paper.

Dielectric relaxation around the nematic-isotropic transition of liquid crystalline polymers

This study is concerned with a series of acrylate based side-chain liquid crystalline (LC) polymers. Previous studies have shown that these LC polymers have a preference for parallel or perpendicular alignment with respect to the polymer chain which depends on the length of the coupling chain joining the mesogenic unit to the polymer backbone. On the other hand, the dielectric relaxation of these side-chain LC polymers shows a strong relaxation associated to the mesogenic unit dynamics. For samples with parallel alignment, it was found that the dielectric relaxation of the nematic is weaker and broader than the relaxation of the isotropic. By contrast, for samples with perpendicular alignment, the isotropic to nematic transition reduces the broadening the relaxation and increases the relaxation strength. These two features are more evident for samples with short coupling units for which the dielectric relaxation observed appears to be strongly coupled with the backbone dynamics.

Symmetry-break in Voronoi tessellations

We analyse in a common framework the properties of the Voronoi tessellations resulting from regular 2D and 3D crystals and those of tessellations generated by Poisson distributions of points, thus joining on symmetry breaking processes and the approach to uniform random distributions of seeds. We perturb crystalline structures in 2D and 3D with a spatial Gaussian noise whose adimensional strength is α and analyse the statistical properties of the cells of the resulting Voronoi tessellations using an ensemble approach. In 2D we consider triangular, square and hexagonal regular lattices, resulting into hexagonal, square and triangular tessellations, respectively. In 3D we consider the simple cubic (SC), body-centred cubic (BCC), and face-centred cubic (FCC) crystals, whose corresponding Voronoi cells are the cube, the truncated octahedron, and the rhombic dodecahedron, respectively. In 2D, for all values α>0, hexagons constitute the most common class of cells. Noise destroys the triangular and square tessellations, which are structurally unstable, as their topological properties are discontinuous in α=0. On the contrary, the honeycomb hexagonal tessellation is topologically stable and, experimentally, all Voronoi cells are hexagonal for small but finite noise with α<0.12. Basically, the same happens in the 3D case, where only the tessellation of the BCC crystal is topologically stable even against noise of small but finite intensity. In both 2D and 3D cases, already for a moderate amount of Gaussian noise (α>0.5), memory of the specific initial unperturbed state is lost, because the statistical properties of the three perturbed regular tessellations are indistinguishable. When α>2, results converge to those of Poisson-Voronoi tessellations. In 2D, while the isoperimetric ratio increases with noise for the perturbed hexagonal tessellation, for the perturbed triangular and square tessellations it is optimised for specific value of noise intensity. The same applies in 3D, where noise degrades the isoperimetric ratio for perturbed FCC and BCC lattices, whereas the opposite holds for perturbed SCC lattices. This allows for formulating a weaker form of the Kelvin conjecture. By analysing jointly the statistical properties of the area and of the volume of the cells, we discover that also the cells shape heavily fluctuates when noise is introduced in the system. In 2D, the geometrical properties of n-sided cells change with α until the Poisson-Voronoi limit is reached for α>2; in this limit the Desch law for perimeters is shown to be not valid and a square root dependence on n is established, which agrees with exact asymptotic results. Anomalous scaling relations are observed between the perimeter and the area in the 2D and between the areas and the volumes of the cells in 3D: except for the hexagonal (2D) and FCC structure (3D), this applies also for infinitesimal noise. In the Poisson-Voronoi limit, the anomalous exponent is about 0.17 in both the 2D and 3D case. A positive anomaly in the scaling indicates that large cells preferentially feature large isoperimetric quotients. As the number of faces is strongly correlated with the sphericity (cells with more faces are bulkier), in 3D it is shown that the anomalous scaling is heavily reduced when we perform power law fits separately on cells with a specific number of faces.

The Climate-G testbed: towards large scale distributed data management for climate change

Climate-G is a large scale distributed testbed devoted to climate change research. It is an unfunded effort started in 2008 and involving a wide community both in Europe and US. The testbed is an interdisciplinary effort involving partners from several institutions and joining expertise in the field of climate change and computational science. Its main goal is to allow scientists carrying out geographical and cross-institutional data discovery, access, analysis, visualization and sharing of climate data. It represents an attempt to address, in a real environment, challenging data and metadata management issues. This paper presents a complete overview about the Climate-G testbed highlighting the most important results that have been achieved since the beginning of this project.

Synthesis, crystal structures and magnetic properties of a phenoxo-bridged dinuclear Cu(II) complex and a dicyanamide bridged novel molecular rectangle based on it

The phenoxo-bridged dinuclear Cu-II complex [Cu2L2-(NCNCN)(2)] (1) and the dicyanamide-bridged molecular rectangle [Cu4L4{mu(1,5)-(NCNCN)(2)}]center dot(ClO4)(2)(H2O)(2) (2) were synthesized using the tridentate reduced Schiff-base ligand HL {2-[(2-dimethylamino-ethylamino) methyl] phenol}. The complexes were characterized by X-ray structural analyses and variable-temperature magnetic susceptibility measurements. Complex 2 was formed through the joining of the phenoxo-bridged dinuclear Cu2O2 cores of 1 via the mu(1,5)-bridging mode of dicyanamide. The structural properties of the Cu2O2 cores in two complexes are significantly different. The geometry of the copper ions is distorted trigonal bipyramid in 1 but is nearly square-pyramidal in 2. These differences have a marked effect on the magnetic properties of two compounds. Although both are antiferromagnetically coupled, the coupling constants (J = -185.2 and -500.9 cm(-1) for 1 and 2, respectively) differ considerably.

Adobe Bickham Script Greek typeface

Design support for typeface design: collaborative work commissioned by Adobe, Inc. Published 2011. The original Bickham typeface was based on the hands of the 18th century writing master George Bickham. The ornate script represented the apogee of the art of formal writing with a steel nib, and defined the visual style for decorated, formal documents. In 2010 Adobe revised and extended the typeface, with the express purpose of making it a showcase for OpenType technology, demonstrating the visual importance of using different glyph forms in different contexts, employing contextual substitution rules. Although Bickham had published a single example of a Greek style, it was a standalone exercise, never intended to match the Latin. The key challenge was to identify historical records for appropriate Greek writing, preferably by writers familiar with the language, adapt them for digital typography and the particularities of contextual substitution, in a manner that would not make the Greek a ‘second-class citizen’. Research involved uncovering and analysing appropriate contemporary and later writing examples to identify both the range of writing styles of the period, and the manner of joining letters in written Greek with both pointed pens and broad nibs. This work was essential to make up for the comparative lack of relevant material by Bickham, as well as investigating the possible range of stylistic variants that were approved for the final typeface, which attempted to emulate a written texture through complex substitutions. This aspect of the work is highly original for implementing a substantial number of contextual alternates and ligatures. These were reviewed in the context of use, bringing together an analysis of occurring letter combinations and patterns, and the design of stylistic alternates to imitate natural handwriting.

The performance effects of composition changes on sector specific stock indices: The case of European listed real estate

This paper examines the impact of changes in the composition of real estate stock indices, considering companies both joining and leaving the indices. Stocks that are newly included not only see a short-term increase in their share price, but trading volumes increase in a permanent fashion following the event. This highlights the importance of indices in not only a benchmarking context but also in enhancing investor awareness and aiding liquidity. By contrast, as anticipated, the share prices of firms removed from indices fall around the time of the index change. The fact that the changes in share prices, either upwards for index inclusions or downwards for deletions, are generally not reversed, would indicate that the movements are not purely due to price pressure, but rather are more consistent with the information content hypothesis. There is no evidence, however, that index changes significantly affect the volatility of price changes or their operating performances as measured by their earnings per share.

Educating integrated catalysts: transforming business schools toward ethics and sustainability

Joining the sharpening critique of conventional University-based business school education, we argue that educating integrated catalysts is necessary to meet current sustainability challenges. The key feature of moving toward the integration required at the individual level is focusing on developing students' capacity for moral and cognitive maturity. Practically, this makes the practice of genuine dialogue focal as core interpersonal method for educating management students. In supporting such education, business schools must however first transform themselves. Acting as transformative social enterprises, they can demonstrate being a part in critically questioning and improving the impact and relevance of management on the flourishing of wider society and the practice of an ethically oriented economy. We offer practical suggestions and implications for future business education reform.

Barabas's Fall

Early modern play-texts present numerous puzzles for scholars interested in ascertaining how plays were (or may have been) staged. the principal evidence of course for a notional "reconstruction" of practices is the apparatus of stage directions, augmented by indications in the dialogue. in conjunction a joining-of-the-dots is often possible, at least in broad-brush terms. But as is well known, the problem is that stage directions tend to be incomplete, imprecise, inaccurate ­ or missing altogether; more significantly, even when present they offer only slight and indirect evidence of actual stagecraft. Some stage directions are rather more "literary" than "theatrical" in provenance, and in any case to the extent that they do serve the reader (early modern or modern) they cannot be regarded as providing a record of stage practice. After all, words can be no more than imperfect substitutes for (and of another order from) the things they represent. For the most part directions serve as a guide that provides the basis for reasonable interpretation informed by our knowledge of theatre architecture, technology, and comparable play-situations, rather than concrete evidence of actual practice. Quite how some stage business was carried out remains uncertain, leaving the scholar little option but to hypothesize solutions. One such conundrum arises in christopher Marlowe's The Jew of Malta. the scenario in question is hardly an obscure one, but it has not been examined in detail, even by modern editors. the purpose of this essay is to explore what sense might be made of the surviving textual evidence, in combination with our knowledge of theatre architecture and playmaking culture in the late sixteenth century.

A proof of van Aubel's theorem using orthogonal vectors

We show how two linearly independent vectors can be used to construct two orthogonal vectors of equal magnitude in a simple way. The proof that the constructed vectors are orthogonal and of equal magnitude is a good exercise for students studying properties of scalar and vector triple products. We then show how this result can be used to prove van Aubel's theorem that relates the two line segments joining the centres of squares on opposite sides of a plane quadrilateral.

It’s not the size, it’s the relationship: from ‘small states’ to asymmetry

Debate about the definition of “small state” has produced more fragmentation than consensus, even as the literature has demonstrated its subjects’ roles in joining international organizations propagating norms, executing creative diplomacy, influencing allies, avoiding and joining conflicts, and building peace. However, work on small states has struggled to identify commonalities in these states’ international relations, to cumulate knowledge, or to impact broader IR theory. This paper advocates a changed conceptual and definitional framework. Analysis of “small states” should pivot to examine the dynamics of the asymmetrical relationships in which these states are engaged. Instead of seeking an overall metric for size as the relevant variable—falling victim in a different way Dahl’s “lump-of-power fallacy,” we can recognize the multifaceted, variegated nature of power, whether in war or peacetime.