Extending N-heterocyclic carbene ligands into the third dimension: a new type of hybrid phosphazane/NHC system

A simple, “click” synthetic approach to a new type of hybrid phosph(III)azane/NHC system is described. The presence of the phosphazane P₂N₂ ring unit, with P atoms flanking the NCN fragment and with this ring perpendicular to the binding site of the NHC, provides unique opportunities for modifying the electronic and steric character of these carbenes.     

Compressing strongly connected subgroups in social networks: An entropy-based approach

To detect and study cohesive subgroups of actors is a main objective in social network analysis. What are the respective relations inside such groups and what separates them from the outside. Entropy-based analysis of network structures is an up-and-coming approach. It turns out to be a powerful instrument to detect certain forms of cohesive subgroups and to compress them to superactors without loss of information about their embeddedness in the net: Compressing strongly connected subgroups leaves the whole net’s and the (super-)actors’ information theoretical indices unchanged; i.e., such compression is information-invariant. The actual article relates on the reduction of networks with hundreds of actors. All entropy-based calculations are realized in an expert system shell.     

Theories with an additive gauge group

This paper investigates the structure of theories that obtain from variational statements that are invariant under the action of a gauge group. Partial differential equations are obtained for the gauge group and for the infinitesimal generators of the gauge group. These are used to derive partial differential equations whose solutions give Lagrangian functions that result in action functionals that are strongly invariant under the gauge group. Properties of the Euler equations for such theories are analyzed, where it is shown that it is always possible to add a gauge condition to such theories when the data is of Neumann type. The results are illustrated by theories for the interaction of a vector 4-potential with a finite number of matter fields. The current and the charge-current potentials are shown to be determined from knowledge of the Lagrangian function and of the infinitesimal generators of the gauge transformations of the matter fields.     

Robust Damping in Self-Excited Mechanical Systems

A technique to optimize the stability of a general mechanical system is outlined. The method relies on decomposing the damping matrix into several component matrices, which may have some special structure or physical relevance. An optimization problem can then be formulated where the ratio of these are varied to either stabilize or make more stable the equilibrium state subject to sensible constraints. For the purpose of this study, we define a system to be more stable if its eigenvalue with largest real part is as negative as possible. The technique is demonstrated by applying it to an introduced non-dimensionalized variant of a known minimal wobbling disc brake model. In this case, it is shown to be beneficial to shift some damping from the disc to the pins for a system optimized for stability. (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Computational Homogenisation using Reduced-Order Modelling applied to Hyperelasticity

Within this study nonlinear reduced-order modelling for hyperelastic material is applied for the boundary value problem on the micro-scale which arises in the context of computational homogenisation. This involves the Proper Orthogonal Decomposition and the Discrete Empirical Interpolation Method for the nonlinear term. Considered error measures are the errors of the displacement field, the averaged stresses and the effective elasticity tensor. (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Neptunium(III) application in extraction chromatography

This paper describes a novel strategy for actinide separation by extraction chromatography with Np(III) valence adjustment. Neptunium(IV) was reduced to Np(III) using Cr(II) and then selectively separated from uranium (IV) on a TEVA resin. After elution, Np(III) was retained on a DGA resin in order to remove any detrimental chromium impurities. Neptunium(III) formation was demonstrated by the complete and selective elution of Np from TEVA resin (99 ± 7%) in less than 12 mL of 9 M HCl from U(IV) (0.7 ± 0.7%). It was determined by UV–visible and kinetic studies that Cr(II) was the only species responsible for the elution of Np(IV) as Np(III) and that the Cr(II) solution could be prepared from 2 to 30 min before its use without the need of complex degassing systems to prevent the oxidation of Np(III) by oxygen. The methodology proposed here with TEVA/DGA resins provides removal of Cr(III) impurities produced at high decontamination factors (2.8 × 10³ and 7.3 × 10⁴ respectively).     

A nonstandard finite difference scheme for contaminant transport with kinetic langmuir sorption

This study focuses on a contaminant transport model with Langmuir sorption under nonequilibrium conditions. The numerical instabilities of the standard finite difference schemes including the upwind method are investigated. By using the nonstandard finite difference method, a better finite difference model is constructed. The numerical simulation on a specific system configuration proves the advantages of the new finite difference model. © 2009 Wiley Periodicals, Inc. Numer Methods Partial Differential Eq 27: 767–785, 2011     

Tunneling currents that increase with molecular elongation

We present a model molecular system with an unintuitive transport-extension behavior in which the tunneling current increases with forced molecular elongation. The molecule consists of two complementary aromatic units (1,4-anthracenedione and 1,4-anthracenediol) hinged via two ether chains and attached to gold electrodes through thiol-terminated alkenes. The transport properties of the molecule as it is mechanically elongated in a single-molecule pulling setting are computationally investigated using a combination of equilibrium molecular dynamics simulations of the pulling with gDFTB computations of the transport properties in the Landauer limit. Contrary to the usual exponential decay of tunneling currents with increasing molecular length, the simulations indicate that upon elongation electronic transport along the molecule increases 10-fold. The structural origin of this inverted trend in the transport is elucidated via a local current analysis that reveals the dual role played by H-bonds in both stabilizing π-stacking for selected extensions and introducing additional electronic couplings between the complementary aromatic rings that also enhance tunneling currents across the molecule. The simulations illustrate an inverted electromechanical single-molecule switch that is based on a novel class of transport-extension behavior that can be achieved via mechanical manipulation and highlight the remarkable sensitivity of conductance measurements to the molecular conformation.