Anomalous dynamical charges, phonons, and the origin of negative thermal expansion in Y2W3O12

We use a combination of classical model and first-principles density functional theory calculations to study lattice dynamics of Y2W3O12 and identify phonons responsible for its negative thermal expansion (NTE). Born dynamical charges of various atoms are found to deviate anomalously from their nominal values. We find that the phonons with energy from 4 to 10 meV are the primary contributors to its NTE. These phonons involve rotations of the YO6 octahedra and WO4 tetrahedra in mutually opposite sense and collective translational atomic displacements, reflecting a strong mixing between acoustic and optic modes.

Free-volume dependent pressure sensitivity of Zr-based bulk metallic glass

Instrumented indentation experiments on a Zr-based bulk metallic glass (BMG) in as-cast, shot-peened and structurally relaxed conditions were conducted to examine the dependence of plastic deformation on its structural state. Results show significant differences in hardness, H, with structural relaxation increasing it and shot peening markedly reducing it, and slightly changed morphology of shear bands around the indents. This is in contrast to uniaxial compressive yield strength, sigma(y), which remains invariant with the change in the structural state of the alloys investigated. The plastic constraint factor, C = H/sigma(y), of the relaxed BMG increases compared with that of the as-cast glass, indicating enhanced pressure sensitivity upon annealing. In contrast, C of the shot-peened layer was found to be similar to that observed in crystalline metals, indicating that severe plastic deformation could eliminate pressure sensitivity. Microscopic origins for this result, in terms of shear transformation zones and free volume, are discussed.

Geometry-free stochastic analysis of BDS triple frequency signals

The paper presents a geometry-free approach to assess the variation of covariance matrices of undifferenced triple frequency GNSS measurements and its impact on positioning solutions. Four independent geometryfree/ ionosphere-free (GFIF) models formed from original triple-frequency code and phase signals allow for effective computation of variance-covariance matrices using real data. Variance Component Estimation (VCE) algorithms are implemented to obtain the covariance matrices for three pseudorange and three carrier-phase signals epoch-by-epoch. Covariance results from the triple frequency Beidou System (BDS) and GPS data sets demonstrate that the estimated standard deviation varies in consistence with the amplitude of actual GFIF error time series. The single point positioning (SPP) results from BDS ionosphere-free measurements at four MGEX stations demonstrate an improvement of up to about 50% in Up direction relative to the results based on a mean square statistics. Additionally, a more extensive SPP analysis at 95 global MGEX stations based on GPS ionosphere-free measurements shows an average improvement of about 10% relative to the traditional results. This finding provides a preliminary confirmation that adequate consideration of the variation of covariance leads to the improvement of GNSS state solutions.

On the Cubicity of AT-Free Graphs and Circular-Arc Graphs

A unit cube in k dimensions (k-cube) is defined as the Cartesian product R-1 x R-2 x ... x R-k where R-i (for 1 <= i <= k) is a closed interval of the form [a(i), a(i) + 1] on the real line. A graph G on n nodes is said to be representable as the intersection of k-cubes (cube representation in k dimensions) if each vertex of C can be mapped to a k-cube such that two vertices are adjacent in G if and only if their corresponding k-cubes have a non-empty intersection. The cubicity of G denoted as cub(G) is the minimum k for which G can be represented as the intersection of k-cubes. An interesting aspect about cubicity is that many problems known to be NP-complete for general graphs have polynomial time deterministic algorithms or have good approximation ratios in graphs of low cubicity. In most of these algorithms, computing a low dimensional cube representation of the given graph is usually the first step. We give an O(bw . n) algorithm to compute the cube representation of a general graph G in bw + 1 dimensions given a bandwidth ordering of the vertices of G, where bw is the bandwidth of G. As a consequence, we get O(Delta) upper bounds on the cubicity of many well-known graph classes such as AT-free graphs, circular-arc graphs and cocomparability graphs which have O(Delta) bandwidth. Thus we have: 1. cub(G) <= 3 Delta - 1, if G is an AT-free graph. 2. cub(G) <= 2 Delta + 1, if G is a circular-arc graph. 3. cub(G) <= 2 Delta, if G is a cocomparability graph. Also for these graph classes, there axe constant factor approximation algorithms for bandwidth computation that generate orderings of vertices with O(Delta) width. We can thus generate the cube representation of such graphs in O(Delta) dimensions in polynomial time.

Cyclic porphyrin dimers as hosts for coordinating ligands

Bicovalently linked tetraphenylporphyrins bearing dioxypentane groups at the opposite (transoid, H4A) and adjacent (cisoid, H4B) aryl groups have been synthesised. Protonation of the free-base porphyrins leads to fully protonated species H8A4+/H8A4+ accompanied by expansion of cavity size of the bisporphyrins. The electrochemical redox studies of these porphyrins and their Zinc(II) derivatives revealed that the first ring oxidation proceeds through a two-electron process while the second ring oxidation occurs at two distinct one-electron steps indicating unsymmetrical charge distribution in the oxidized intermediate. The axial ligation properties of the Zinc(Il) derivatives of H4A/H4B with DABCO and PMDA investigated by spectroscopic and single crystal X-ray diffraction studies showed predominant existence of 1: I complex. The Zn2A.DABCO complex assumes an interesting eclipsed structure wherein DABCO is located inside the cavity between the two porphyrin planes with Zn-N distances at 2.08 and 2.22 Å. The Zn atoms are pulled into the cavity due to coordination towards nitrogen atoms of DABCO and deviate from the mean porphyrin plane by 0.35 Å. The electrochemical redox potentials of the axially ligated metal derivatives are found to be sensitive function of the relative coordinating ability of the ligands and the conformation of the hosts.

Structural Insights into the acyl-intermediates of plasmodium falciparum fatty acid synthesis pathway; the mechanism of expansion of acyl carrier protein core

Acyl carrier protein (ACP) plays a central role in fatty acid biosynthesis. However, the molecular machinery that mediates its function is not yet fully understood. Therefore, structural studies were carried out on the acyl-ACP intermediates of Plasmodium falciparum using NMR as a spectroscopic probe. Chemical shift perturbation studies put forth a new picture of the interaction of ACP molecule with the acyl chain, namely, the hydrophobic core can protect up to 12 carbon units, and additional carbons protrude out from the top of the hydrophobic cavity. The latter hypothesis stems from chemical shift changes observed in C-alpha and C-beta of Ser-37 in tetradecanoyl-ACP. C-13, N-15-Double-filtered nuclear Overhauser effect (NOE) spectroscopy experiments further substantiate the concept; in octanoyl (C-8)- and dodecanoyl (C-12)-ACP, a long range NOE is observed within the phosphopantetheine arm, suggesting an arch-like conformation. This NOE is nearly invisible in tetradecanoyl (C-14)-ACP, indicating a change in conformation of the prosthetic group. Furthermore, the present study provides insights into the molecular mechanism of ACP expansion, as revealed from a unique side chain-to-backbone hydrogen bond between two fairly conserved residues, Ile-55 HN and Glu-48 O. The backbone amide of Ile-55 HN reports a pK(a) value for the carboxylate, similar to 1.9 pH units higher than model compound value, suggesting strong electrostatic repulsion between helix II and helix III. Charge-charge repulsion between the helices in combination with thrust from inside due to acyl chain would energetically favor the separation of the two helices. Helix III has fewer structural restraints and, hence, undergoes major conformational change without altering the overall-fold of P. falciparum ACP.

Free vibration and wave propagation analysis of uniform and tapered rotating beams using spectrally formulated finite elements

This paper presents a formulation of an approximate spectral element for uniform and tapered rotating Euler-Bernoulli beams. The formulation takes into account the varying centrifugal force, mass and bending stiffness. The dynamic stiffness matrix is constructed using the weak form of the governing differential equation in the frequency domain, where two different interpolating functions for the transverse displacement are used for the element formulation. Both free vibration and wave propagation analysis is performed using the formulated elements. The studies show that the formulated element predicts results, that compare well with the solution available in the literature, at a fraction of the computational effort. In addition, for wave propagation analysis, the element shows superior convergence. (C) 2007 Elsevier Ltd. All rights reserved.

Energy identities in water wave theory for free-surface boundary condition with higher-order derivatives

A modified form of Green's integral theorem is employed to derive the energy identity in any water wave diffraction problem in a single-layer fluid for free-surface boundary condition with higher-order derivatives. For a two-layer fluid with free-surface boundary condition involving higher-order derivatives, two forms of energy identities involving transmission and reflection coefficients for any wave diffraction problem are also derived here by the same method. Based on this modified Green's theorem, hydrodynamic relations such as the energy-conservation principle and modified Haskind–Hanaoka relation are derived for radiation and diffraction problems in a single as well as two-layer fluid.

East Asian audio-visual collaboration and the global expansion of Chinese media

In recent years, many of the world’s leading media producers, screenwriters, technicians and investors, particularly those in the Asia-Pacific region, have been drawn to work in the People's Republic of China (hereafter China or Mainland China). Media projects with a lighter commercial entertainment feel – compared with the heavy propaganda-oriented content of the past – have multiplied, thanks to the Chinese state’s newfound willingness to consider collaboration with foreign partners. This is no more evident than in film. Despite their long-standing reputation for rigorous censorship, state policymakers are now encouraging Chinese media entrepreneurs to generate fresh ideas and to develop products that will revitalise the stagnant domestic production sector. It is hoped that an increase in both the quality and quantity of domestic feature films, stimulated by an infusion of creativity and cutting-edge technology from outside the country, will help reverse China’s ‘cultural trade deficit’ (wenhua maoyi chizi) (Keane 2007).

Free software and the law. Out of the frying pan and into the fire: How shaking up intellectual property suits competition law just fine

Free software is viewed as a revolutionary and subversive practice, and in particular has dealt a strong blow to the traditional conception of intellectual property law (although in its current form could be considered a 'hack' of IP rights). However, other (capitalist) areas of law have been swift to embrace free software, or at least incorporate it into its own tenets. One area in particular is that of competition (antitrust) law, which itself has long been in theoretical conflict with intellectual property, due to the restriction on competition inherent in the grant of ‘monopoly’ rights by copyrights, patents and trademarks. This contribution will examine how competition law has approached free software by examining instances in which courts have had to deal with such initiatives, for instance in the Oracle Sun Systems merger, and the implications that these decisions have on free software initiatives. The presence or absence of corporate involvement in initiatives will be an important factor in this investigation, with it being posited that true instances of ‘commons-based peer production’ can still subvert the capitalist system, including perplexing its laws beyond intellectual property.

Internet privatization, WikiLeaks, and free expression

In late 2010, the online nonprofit media organization WikiLeaks published classified documents detailing correspondence between the U.S. State Department and its diplomatic missions around the world, numbering around 250,000 cables. These diplomatic cables contained classified information with comments on world leaders, foreign states, and various international and domestic issues. Negative reactions to the publication of these cables came from both the U.S. political class (which was generally condemnatory of WikiLeaks, invoking national security concerns and the jeopardizing of U.S. interests abroad) and the corporate world, with various companies ceasing to continue to provide services to WikiLeaks despite no legal measure (e.g., a court injunction) forcing them to do so. This article focuses on the legal remedies available to WikiLeaks against this corporate suppression of its speech in the U.S. and Europe since these are the two principle arenas in which the actors concerned are operating. The transatlantic legal protection of free expression will be considered, yet, as will be explained in greater detail, the legal conception of this constitutional and fundamental right comes from a time when the state posed the greater threat to freedom. As a result, it is not generally enforceable against private, non-state entities interfering with speech and expression which is the case here. Other areas of law, namely antitrust/competition, contract and tort will then be examined to determine whether WikiLeaks and its partners can attempt to enforce their right indirectly through these other means. Finally, there will be some concluding thoughts about the implications of the corporate response to the WikiLeaks embassy cables leak for freedom of expression online.

Dynamics of free-running, pump-modulated and coupled semiconductor and solid-state lasers

The output of a laser is a high frequency propagating electromagnetic field with superior coherence and brightness compared to that emitted by thermal sources. A multitude of different types of lasers exist, which also translates into large differences in the properties of their output. Moreover, the characteristics of the electromagnetic field emitted by a laser can be influenced from the outside, e.g., by injecting an external optical field or by optical feedback. In the case of free-running solitary class-B lasers, such as semiconductor and Nd:YVO4 solid-state lasers, the phase space is two-dimensional, the dynamical variables being the population inversion and the amplitude of the electromagnetic field. The two-dimensional structure of the phase space means that no complex dynamics can be found. If a class-B laser is perturbed from its steady state, then the steady state is restored after a short transient. However, as discussed in part (i) of this Thesis, the static properties of class-B lasers, as well as their artificially or noise induced dynamics around the steady state, can be experimentally studied in order to gain insight on laser behaviour, and to determine model parameters that are not known ab initio. In this Thesis particular attention is given to the linewidth enhancement factor, which describes the coupling between the gain and the refractive index in the active material. A highly desirable attribute of an oscillator is stability, both in frequency and amplitude. Nowadays, however, instabilities in coupled lasers have become an active area of research motivated not only by the interesting complex nonlinear dynamics but also by potential applications. In part (ii) of this Thesis the complex dynamics of unidirectionally coupled, i.e., optically injected, class-B lasers is investigated. An injected optical field increases the dimensionality of the phase space to three by turning the phase of the electromagnetic field into an important variable. This has a radical effect on laser behaviour, since very complex dynamics, including chaos, can be found in a nonlinear system with three degrees of freedom. The output of the injected laser can be controlled in experiments by varying the injection rate and the frequency of the injected light. In this Thesis the dynamics of unidirectionally coupled semiconductor and Nd:YVO4 solid-state lasers is studied numerically and experimentally.

Specific Small-Molecule Activator of Aurora Kinase A Induces Autophosphorylation in a Cell-Free System

Aurora kinases are essential for chromosomal segregation and cell division and thereby important for maintaining the proper genomic integrity. There are three classes of aurora kinases in humans: A, B, and C. Aurora kinase A is frequently overexpressed in various cancers. The link of the overexpression and tumorigenesis is yet to be understood. By employing virtual screening, we have found that anacardic acid, a pentadecane aliphatic chain containing hydroxylcarboxylic acid, from cashew nut shell liquid could be docked in Aurora kinases A and B. Remarkably, we found that anacardic acid could potently activate the Aurora kinase A mediated phosphorylation of histone H3, but at a similar concentration the activity of aurora kinase B remained unaffected in vitro. Mechanistically, anacardic acid induces the structural changes and also the autophosphorylation of the aurora kinase A to enhance the enzyme activity. This data thus indicate anacardic acid as the first small-molecule activator of Aurora kinase, which could be highly useful for probing the function of hyperactive (overexpressed) Aurora kinase A.