A comparison between elastohydrodynamic and dry hertzian line contacts with regard to their nonlinear vibration behaviour

The nonlinear dynamic behaviour of a simple system employing two different types of contact is compared: elastohydrodynamic line contact and Hertzian line contact with appropriate damping. The elastohydrodynamic problem is solved with finite elements. For the Hertzian line contact problem an analytical solution is known. It is found that for highly loaded cases Hertzian and elastohydrodynamic contacts lead to very similar frequency response curves. This means that instead of solving the computational expensive elastohydrodynamic problem the Hertzian contact can be used. However, considering weakly loaded contacts the two types of contact show very different behaviour. In particular the natural frequencies are different and the elastohydrodynamic contact exhibits rich nonlinear dynamic behaviour including jump phenomena as well as sub- and superharmonic bifurcations. (© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

A constitutive model for shape memory alloy fibres and its applicability to prestressed composites

This contribution is concerned with a constitutive model for shape memory fibres. The 1D-constitutive model accounts for the pseudoplastic and shape memory effect (SME). The macroscopic answer of the material is determined by the evolution from a twinned martensitic lattice into a deformed and detwinned one. On the macroscopic scale these effects are responsible for the upper boundary of the hysteresis which is situated around the origin of the stress-strain-diagram. During the phase transition process inelastic strains arise. When the lattice is fully detwinned, a linear elastic branch at the end of the hysteresis is observed. The initial state of the material is recovered by unloading and heating the material subsequently. The constitutive model is derived from the Helmholtz' free energy and fulfils the 2nd law of thermodynamics. For the present model five internal state variables are employed. Two of them are used to describe the inelastic strain and a backstress. The others represent the martensitic volume fraction and are necessary to describe the SME. The latter variables are depending on the deformation state as well as on temperature. A change on temperature goes along with a reduction of the inelastic strain. The model is incorporated in a fibre matrix discretization to prestress the surrounding structure. The boundary value problem is solved for a truss element applying the finite element method. Examples will demonstrate the applicability in engineering structures. (© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Isolation and structure elucidation of two new cytotoxic metabolites from red yeast rice

In this study, 10 already described secondary metabolites and 2 unknown metabolites were identified in an extract of Monascus purpureus by high-performance liquid chromatography-diode array detection. The unknown metabolites were isolated and their chemical structures were elucidated. The new metabolites possess the molecular formulas C(21)H(27)NO(4) and C(23)H(31)NO(4). They were named monascopyridines E and F due to their pyridine backbone. The cytotoxicity of the new compounds was studied using immortalised human kidney epithelial cells displaying IC(50) values in the micromolar range.     

Photochemical synthesis of a ladder diborole: a new boron-containing conjugate material

Climbing the ladder: Reductive cyclization of alkynyl haloboranes lead to the bis-benzocycloborabutylidene rather than the expected ladder diborole, despite the former being much less thermodynamically favored. Photochemical conversion to the ladder diborole was, however, quite facile upon irradiation at 254?nm.     

A high-spin iron(IV)-oxo complex supported by a trigonal nonheme pyrrolide platform

We report the generation and characterization of a new high-spin iron(IV)-oxo complex supported by a trigonal nonheme pyrrolide platform. Oxygen-atom transfer to [(tpa(Mes))Fe(II)](-) (tpa(Ar) = tris(5-arylpyrrol-2-ylmethyl)amine) in acetonitrile solution affords the Fe(III)-alkoxide product [(tpa(Mes2MesO))Fe(III)](-) resulting from intramolecular C-H oxidation with no observable ferryl intermediates. In contrast, treatment of the phenyl derivative [(tpa(Ph))Fe(II)](-) with trimethylamine N-oxide in acetonitrile solution produces the iron(IV)-oxo complex [(tpa(Ph))Fe(IV)(O)](-) that has been characterized by a suite of techniques, including mass spectrometry as well as UV-vis, FTIR, M?ssbauer, XAS, and parallel-mode EPR spectroscopies. Mass spectral, FTIR, and optical absorption studies provide signatures for the iron-oxo chromophore, and M?ssbauer and XAS measurements establish the presence of an Fe(IV) center. Moreover, the Fe(IV)-oxo species gives parallel-mode EPR features indicative of a high-spin, S = 2 system. Preliminary reactivity studies show that the high-spin ferryl tpa(Ph) complex is capable of mediating intermolecular C-H oxidation as well as oxygen-atom transfer chemistry.     

The axiom of real Blackwell determinacy

The theory of infinite games with slightly imperfect information has been developed for games with finitely and countably many moves. In this paper, we shift the discussion to games with uncountably many possible moves, introducing the axiom of real Blackwell determinacy ${\mathsf{Bl-AD}_\mathbb{R}}$ (as an analogue of the axiom of real determinacy ${\mathsf{AD}_\mathbb{R}}$ ). We prove that the consistency strength of ${\mathsf{Bl-AD}_\mathbb{R}}$ is strictly greater than that of AD.     

Fluorescence-based active site probes for profiling deubiquitinating enzymes

Novel ubiquitin-based active site probes including a fluorescent tag have been developed and evaluated. A new, functionalizable electrophilic trap is utilized allowing for late stage diversification of the probe. Attachment of fluorescent dyes allowed direct detection of endogenous deubiquitinating enzyme (DUB) activities in cell extracts by in-gel fluorescence imaging.     

Nonlinear, electrocatalytic swimming in the presence of salt

A small, bimetallic particle in a hydrogen peroxide solution can propel itself by means of an electrocatalytic reaction. The swimming is driven by a flux of ions around the particle. We model this process for the presence of a monovalent salt, where reaction-driven proton currents induce salt ion currents. A theory for thin diffuse layers is employed, which yields nonlinear, coupled transport equations. The boundary conditions include a compact Stern layer of adsorbed ions. Electrochemical processes on the particle surface are modeled with a first order reaction of the Butler-Volmer type. The equations are solved numerically for the swimming speed. An analytical approximation is derived under the assumption that the decomposition of hydrogen peroxide occurs mainly without inducing an electric current. We find that the swimming speed increases linearly with hydrogen peroxide concentration for small concentrations. The influence of ion diffusion on the reaction rate can lead to a concave shape of the function of speed vs. hydrogen peroxide concentration. The compact layer of ions on the particle diminishes the reaction rate and consequently reduces the speed. Our results are consistent with published experimental data.