[1,3‐Bis(di­phenyl­phosphino)prop­ane]­tri­chloro­oxorhenium(V)

Tri­chloro­oxo­[1,3‐prop­ane­diyl­bis­(di­phenyl­phosphine)‐P,P′]rhen­ium(V), [Re­Cl₃­O­(C₂₇­H₂₆P₂)], crystallizes with four formula units per unit cell. The crystal structure consists of neutral complexes of [ReOCl₃(dppp)] [dppp is 1,3‐bis(diphenylphosphino)propane] packed by H?π‐ring interactions. The Re atom is octahedrally coordinated to the oxo anion, three Cl atoms and two P atoms from the dppp ligand. The six‐membered ring formed by the bidentate dppp ligand and the rhenium metal centre is in a chair conformation. The title compound is an intermediate in the synthesis of bis(dppp) complexes of rhenium.     

Functional magnetic resonance imaging: Comparison between activation maps and computation pipelines in a clinical context

In this study new evaluation strategies for comparing different Statistical Parametric Maps computed from fMRI time-series analysis software tools are proposed. The aim of our work is to assess and quantitatively evaluate the statistical agreement of activation maps. Some pre-processing steps are necessary to compare SPMs (Statistical Parametric Maps), including segmentation and co-registration. The study of the statistical agreement is carried out following two ways. The first way considers SPMs as the result of two classification processes and extracts confusion matrix and Cohen's kappa index to assess agreement. Some considerations will be made on the statistical dependence of classes and a new formulation of kappa index will be used for overcoming this problem. The second way considers SPMs as two 3D images, and computes the similarity of SPMs images with a fuzzy formulation of the Jaccard Index. Several experiments were conducted both to assess the performance of the proposed evaluation tools and to compare activation maps computation pipelines from two widely used software tools in a clinical context.     

Electronic Properties of Mono‐Substituted Tetraferrocenyl Porphyrins in Solution and on a Gold Surface: Assessment of the Influencing Factors for Photoelectrochemical Applications

Two unsymmetric meso‐tetraferrocenyl‐containing porphyrins of general formula Fc₃(FcCOR)Por (Fc=ferrocenyl, R=CH₃ or (CH₂)₅Br, Por=porphyrin) were prepared and characterized by a variety of spectroscopic methods, whereas their redox properties were investigated using cyclic voltammetry (CV) and differential pulse voltammetry (DPV) approaches. The mixed‐valence [Fc₃(FcCOR)Por]ⁿ⁺ (n=1,3) were investigated using spectroelectrochemical as well as chemical oxidation methods and corroborated with density functional theory (DFT) calculations. Inter‐valence charge‐transfer (IVCT) transitions in [Fc₃(FcCOR)Por]⁺ were analyzed, and the resulting data matched closely previously reported complexes and were assigned as Robin–Day class II mixed‐valence compounds. Self‐assembled monolayers (SAMs) of a thioacetyl derivative (Fc₃(FcCO(CH₂)₅SCOCH₃)Por) were also prepared and characterized. Photoelectrochemical properties of SAMs in different electrolyte systems were investigated by electrochemical techniques and photocurrent generation experiments, showing that the choice of electrolyte is critical for efficiency of redox‐active SAMs.     

All-carbon detector with buried graphite pillars in CVD diamond

A diamond detector of 3D architecture without any metallization is developed for spectroscopy of ionizing radiation and single particles detection. The carbon electrode system was fabricated using a femtosecond infrared laser ( $\lambda $ = 1,030 nm) to induce graphitization on the surface and inside 4.0  $\times $  4.0  $\times $  0.4 mm $^{3}$ single-crystal chemical vapor deposition diamond slab, resulting in an array of 84 buried graphite pillars of 30  $\upmu $ m diameter formed orthogonally to the surface and connected by surface graphite strips. Sensitivity to ionizing radiation with $^{90}$ Sr $\upbeta $ -source has been measured for the 3D detector and high charge collection efficiency is demonstrated.     

Optical and thermal properties of unsymmetrical liquid crystalline compounds based on isoxazole

The thermal and optical properties of two series of unsymmetrical liquid crystalline compounds based on an isoxazole ring are described. Of these materials, 3–7 and 8–12 displayed strong absorption at 285 nm and a weak blue fluorescence in solution at around 377 nm, even with the presence of a high conjugated core. The fluorescence quantum yields observed varied from low to moderate (Φ _F ?=?1–62%), with large Stokes shifts (60–178 nm). All compounds exhibited liquid crystalline behaviour with a wide mesomorphism temperature range and characteristic phases of calamitic compounds, among them smectic A (SmA), smectic C (SmC) and nematic (N) phases. Their phases were characterised using polarising optical microscopy and differential scanning calorimetry. In addition, with X-ray diffraction experiments, layer spacing of 33.3–40.0 Å were observed for the smectic phases.     

Molecular dynamics of electrosprayed water nanodroplets containing sodium bis(2‐ethylhexyl)sulfosuccinate

The behavior of aqueous solutions of sodium bis(2‐ethylhexyl)sulfosuccinate (AOTNa) subject to electrospray ionization (ESI) has been investigated by molecular dynamics (MD) simulations at three temperatures (350, 500 and 800 K). We consider several types of water nanodroplets containing AOTNa molecules and composed of a fixed number of water molecules (1000), N⁰_AOT AOT^? anions (N⁰_AOT = 0, 5, 10) and N⁰_Na sodium ions (N⁰_Na = 0, 5, 10, 15, 20): in a short time scale (less than 1 ns), the AOTNa molecules, initially forming direct micelles in the interior of the water nanodroplets, are observed in all cases to diffuse nearby the nanodroplet surface, so that the hydrophilic heads and sodium ions become surrounded by water molecules, whereas the alkyl chains lay at the droplet surface. Meanwhile, evaporation of water molecules and of solvated sodium ions occurs, leading to a decrease of the droplet size and charge. At 350 K, no ejection of neutral or charged surfactant molecules is observed, whereas at 500 K, some fragmentation occurs, and at 800 K, this event becomes more frequent. The interplay of all these processes, which depend on the values of temperature, N⁰_AOT and N⁰_Na eventually leads to anhydrous charged surfactant aggregates with prevalence of monocharged ones, in agreement with experimental results of ESI mass spectrometry. The quantitative analysis of the MD trajectories allows to evidence molecular details potentially useful in designing future ESI experimental conditions. Copyright © 2013 John Wiley & Sons, Ltd.     

The Computer Simulation of Partnership Formation

This paper is intended to present and apply a formal dependence model to a simulation study of partnership formation. Although the emergence and evolution of coalitions is an issue of major concern in the study of organisations, a number of questions are still laid open. How do coalitions emerge? Which processes and mechanisms are responsible for their evolution? The agents&;#x2018; informal communications, commitments and negotiations are considered as &;#x201C;given&;#x201D;, and none or poor effort is done to ground them upon the agents&;#x2018; self-interests. The philosophy underlying this paper is that the objective relationships of dependence among heterogeneous agents provide a fundamental ground for the emergence of spontaneous coalitions. As long as agents are endowed with different goals and heterogeneous competencies, a structure of social relationships, namely dependence relations, is likely to occur among them. A formal model of dynamic dependence relationships based on the agents&;#x2018; individual properties will be used to derive a further agents&;#x2018; property, namely their negotiation powers. Through computer simulation, this property will be used to predict how likely each agent in a population will form rewarding partnerships.     

Apertureless near-field vibrational imaging of block-copolymer nanostructures with ultrahigh spatial resolution.

Nanodomains formed by microphase separation in thin films of the diblock copolymers poly(styrene-b-2-vinylpyridine) (PS-b-P2VP) and poly(styrene-b-ethyleneoxide) (PS-b-PEO) were imaged by means of infrared scattering-type near-field microscopy. When probing at 3.39 mum (2950 cm(-1)), contrast is obtained due to spectral differences between the C--H stretching vibrational resonances of the respective polymer constituents. An all-optical spatial resolution better than 10 nm was achieved, which corresponds to a sensitivity of just several thousand C--H groups facilitated by the local-field enhancement at the sharp metallic probe tips. The results demonstrate that infrared spectroscopy with access to intramolecular dimensions is within reach.     

Dependence Graphs: Dependence Within and Between Groups

This paper applies the two-party dependence theory (Castelfranchi, Cesta and Miceli, 1992, in Y. Demazeau and E. Werner (Eds.) Decentralized AI-3, Elsevier, North Holland) to modelling multiagent and group dependence. These have theoretical potentialities for the study of emerging groups and collective structures, and more generally for understanding social and organisational complexity, and practical utility for both social-organisational and agent systems purposes. In the paper, the dependence theory is extended to describe multiagent links, with a special reference to group and collective phenomena, and is proposed as a framework for the study of emerging social structures, such as groups and collectives. In order to do so, we propose to extend the notion of dependence networks (applied to a single agent) to dependence graphs (applied to an agency). In its present version, the dependence theory is argued to provide (a) a theoretical instrument for the study of social complexity, and (b) a computational system for managing the negotiation process in competitive contexts and for monitoring complexity in organisational and other cooperative contexts.