Photoisomerisation in Aminoazobenzene‐Substituted Ruthenium(II) Tris(bipyridine) Complexes: Influence of the Conjugation Pathway

Transition‐metal complexes containing stimuli‐responsive systems are attractive for applications in optical devices, photonic memory, photosensing, as well as luminescence imaging. Amongst them, photochromic metal complexes offer the possibility of combining the specific properties of the metal centre and the optical response of the photochromic group. The synthesis, the electrochemical properties and the photophysical characterisation of a series of donor–acceptor azobenzene derivatives that possess bipyridine groups connected to a 4‐dialkylaminoazobenzene moiety through various linkers are presented. DFT and TD‐DFT calculations were performed to complement the experimental findings and contribute to their interpretation. The position and nature of the linker (ethynyl, triazolyl, none) were engineered and shown to induce different electronic coupling between donor and acceptor in ligands and complexes. This in turn led to strong modulations in terms of photoisomerisation of the ligands and complexes.     

Electronic structure and topography of annealed SrTiO3(1 1 1) surfaces studied with MIES and STM

Perovskites of ABO₃ type like strontium titanate (SrTiO₃) are of great practical concern as materials for oxygen sensors operating at high temperatures. It is well known that the surface layer shows different properties compared to the bulk. Numerous studies exist for the SrTiO₃(1 0 0) and (1 1 0) surfaces which have investigated the changes in the electronic structure and topography as a function of the preparation conditions. They have indicated a rather complex behaviour of the surface and the near surface region of SrTiO₃ at elevated temperatures. Up to now, the behaviour of the SrTiO₃(1 1 1) surfaces under thermal treatment is not sufficiently known. This contribution is intended to work out the relation between alteration of the surface topography with respect to the preparation conditions and the simultaneous changes of the electronic structure. We applied scanning tunneling microscopy (STM) to investigate the surface topography and, additionally, metastable impact electron spectroscopy (MIES) to study the surface electronic structure of reconstructed SrTiO₃(1 1 1) surfaces. The crystals were heated up to 1000 °C under reducing and oxidizing conditions. Both preparation conditions cause strong changes of the surface topography and electronic structure. A microfaceting of the topmost layers is found.     

Scattering from infinite rough tubular surfaces

We study the Helmholtz equation in the exterior of an infinite perturbed cylinder with a Dirichlet boundary condition. Existence and uniqueness of solutions are established using the variational technique introduced (SIAM J. Math. Anal. 2005; 37 (2):598–618). We also provide stability estimates with explicit dependence of the constants in terms of the frequency and the perturbed cylinder thickness. Copyright © 2006 John Wiley & Sons, Ltd.     

2- and 2,7-Substituted para-N-Methylpyridinium Pyrenes: Syntheses,Molecular and Electronic Structures,Photophysical, Electrochemical,and Spectroelectrochemical Properties and Binding to Double-Stranded (ds) DNA

Two N-methylpyridinium compounds and analogous N-protonated salts of 2- and 2,7-substituted 4-pyridyl-pyrene compounds were synthesised and their crystal structures, photophysical properties both in solution and in the solid state, electrochemical and spectroelectrochemical properties were studied. Upon methylation or protonation, the emission maxima are significantly bathochromically shifted compared to the neutral compounds, although the absorption maxima remain almost unchanged. As a result, the cationic compounds show very large apparent Stokes shifts of up to 7200 cm⁻¹. The N-methylpyridinium compounds have a single reduction at ca. −1.5 V vs. Fc/Fc⁺ in MeCN. While the reduction process was reversible for the 2,7-disubstituted compound, it was irreversible for the mono-substituted one. Experimental findings are complemented by DFT and TD-DFT calculations. Furthermore, the N-methylpyridinium compounds show strong interactions with calf thymus (ct)-DNA, presumably by intercalation, which paves the way for further applications of these multi-functional compounds as potential DNA-bioactive agents.     

A Novel Serine Metallokeratinase from a Newly Isolated <Emphasis Type="BoldItalic">Bacillus pumilus</Emphasis> A1 Grown on Chicken Feather Meal: Biochemical and Molecular Characterization

A keratinolytic enzyme (KerA1) secreted by a newly isolated Bacillus pumilus strain A1 cultivated in medium containing chicken feather meal was purified and characterized, and the gene was isolated and sequenced. The molecular mass of the purified enzyme was estimated to be 34,000 Da by sodium dodecyl sulfate (SDS) polyacrylamide gel electrophoresis and gel filtration. The optimum pH and temperature for the purified keratinase were 9.0 and 60 °C, respectively, using keratin as a substrate. KerA1 showed a high stability towards nonionic surfactants. It was found to be relatively stable toward the strong anionic surfactant (SDS). The deduced amino acid sequence of the keratinase KerA1 differs from both the organic solvent tolerant protease of B. pumilus 115b and the dehairing protease of B. pumilus UN-31-C-42 by one and nine amino acids, respectively. These results suggest that this keratinase may be a useful alternative and ecofriendly route for handling the abundant amount of waste feathers and for applications in detergent formulations.     

Finite element method for the stress analysis of isotropic cylindrical helical spring

This paper presents an efficient two nodes finite element with six degrees of freedom per node, capable to model the total behaviour of a helical spring. The formulation, which includes the shear deformation effects, is based on the assumed forces hybrid approach. The resultant forces approximation verifies exactly the resultant equilibrium equations. The developed model proves its accuracy compared with other elements. This element permits to get the distribution of different stresses along the spring and through the wire surface by only one element.     

Influence of thermal aging on tensile and creep behavior of thermoplastic polyurethane

Changes in mechanical and physical properties of polyurethane thermoplastic during aging at 70 °C and 90 °C were investigated. The loss weight response was analyzed by gravimetric measurements under these temperatures. Changes in appearance and morphology of TPU after thermal aging were revealed by optical microscopy. The prolongation of the thermal exposure time, up to 270 days, leads to a progressive increase in tensile strength. In fact, elastic modulus and stress at 200% of strain were increased with thermal exposure time. These results can be explained by the increase of thermal stability due to the increase of material rigidity and the decrease in chain mobility. The evolution of the mechanical properties from tensile tests seems to be well correlated to the creep behavior. Finally, Scanning Electron Microscopy (SEM) revealed the modification of TPU morphology fracture surface after thermal aging.     

Efficient solution of a wave equation with fractional-order dissipative terms

We consider a wave equation with fractional-order dissipative terms modeling visco-thermal losses on the lateral walls of a duct, namely the Webster-Lokshin model. Diffusive representations of fractional derivatives are used, first to prove existence and uniqueness results, then to design a numerical scheme which avoids the storage of the entire history of past data. Two schemes are proposed depending on the choice of a quadrature rule in the Laplace domain. The first one mimics the continuous energy balance but suffers from a loss of accuracy in long time simulation. The second one provides uniform control of the accuracy. However, even though the latter is more efficient and numerically stable under the standard CFL condition, no discrete energy balance has been yet found for it. Numerical results of comparisons with a closed-form solution are provided.     

An improved time domain linear sampling method for Robin and Neumann obstacles

We consider inverse obstacle scattering problems for the wave equation with Robin or Neumann boundary conditions. The problem of reconstructing the geometry of such obstacles from measurements of scattered waves in the time domain is tackled using a time domain linear sampling method. This imaging technique yields a picture of the scatterer by solving a linear operator equation involving the measured data for many right-hand sides given by singular solutions to the wave equation. We analyse this algorithm for causal and smooth impulse shapes, we discuss the effect of different choices of the singular solutions used in the algorithm, and finally we propose a fast FFT-based implementation.     

Simulating the dynamic behavior of planetary gearbox based on improved Hanning function

Planetary gearboxes are widely used in industrial machines. They usually work in harsh environments giving rise to damages and high maintenance costs. Condition monitoring is a key action allowing one to detect the presence of such damage ensuring healthy running conditions. The knowledge of the dynamic behavior of such a gearbox can be achieved using modeling tools as a primary step before conditioning the monitoring subject. In addition, modeling a gear set can help in the stage of design in order to optimize physical and geometric parameters of the system. Therefore, in this work, a two-dimensional lumped parameter model is adopted to build all vibration sources. The time-varying mesh stiffness is approximated as a square wave form. A novel mathematical formulation is proposed to model the amplitude modulation phenomenon due to the rotational motion of the planets around the center of the gearbox. Finally, the overall vibration signal is concluded as a summation of all vibration components influenced by the modulation function.