Thermically and electrochemically induced isomerization of a (bis(ferrocene)-cyclam)copper(II) complex

The new bis(ferrocene)-cyclam macrocycle 1,8-bis(ferrocenylmethyl)-1,4,8,11-tetraazacyclotetradecane, denoted L, has been synthesized. Two Cu(II) complexes with L have been isolated and characterized from X-ray structure determination and electrochemical studies. These two LCu(II) complexes correspond to the type I (ferrocenyl subunits in the same side of the cyclam plane) and type III (ferrocenyl subunits above and below the cyclam plane) isomers. The type I LCu(II) complex was synthesized from L and a Cu(2+) salt, while the type III isomer was obtained by oxidation in air or by comproportionation of the Cu(I) complex. The interconversion between type I and type III LCu(II) complexes is negligible in acetonitrile and slow in dimethyl sulfoxide but fast via an electrochemical reduction-reoxidation cycle. According to UV-vis and electrochemical characterizations, the type III isomer is thermodynamically more stable and the type I isomer is kinetically favored. A type III LNi(II) complex was also isolated and characterized by X-ray diffraction analysis and from electrochemical studies.     

The photochemistry of lipoic acid: photoionization and observation of a triplet excited state of a disulfide.

Under short-wavelength UV irradiation, lipoic acid (LipSS) and its reduced form, dihydrolipoic acid (DHLA), undergo photoionization processes through a bi- or monophotonic pathway. After ionization, the LipSS radical cation (LipSS*+) and radical anion (LipSS*-) are generated. LipSS*- can be converted to equimolar amounts of LipSS and DHLA through second-order decay. Triplet acetone can be quenched by LipSS and DHLA with a rate close to the diffusion-controlled limit. The mechanism was further confirmed by continuous irradiation experiments. When LipSS is directly irradiated with UVA light, the first excited triplet state of LipSS is observed, with a lifetime tau=75 ns. Characteristic reactions include triplet energy transfer to oxygen and beta-carotene and addition to isoprene. The lifetime of triplet LipSS is also shortened by addition of water and methanol.     

Observation of a BCS spectral function in a conventional superconductor by photoelectron spectroscopy

We present high-resolution photoelectron spectra on the A15-type conventional superconductor V 3Si, where-for the first time-both singularities of the BCS density of states can be resolved by photoemission spectroscopy (PES). With a transition temperature of about T(c) approximately 17 K the gap Delta(gap) of this compound has a magnitude of approximately 5 meV. A measurement by PES on this small energy scale requires a very high energy resolution (DeltaE less, similar5 meV) and sample temperatures significantly below T(c).     

Surface-tuned assembly of porphyrin coordination oligomers

Two self-complementary phenanthroline-strapped porphyrins bearing imidazole arms and C 12 or C 18 alkyl chains were synthesized, and their surface self-assembly was investigated by atomic force microscopy (AFM) on mica and highly ordered pyrrolitic graphite (HOPG). Upon zinc(II) complexation, stable porphyrin dimers formed, as confirmed by DOSY (1)H NMR and UV-visible spectroscopy. In solution, the dimers formed J-aggregates. AFM studies of the solutions dip-coated onto mica or drop-casted onto HOPG revealed that the morphologies of the assemblies formed were surface-tuned. On mica, fiber-like assemblies of short stacks of J-aggregates were observed. The strong influence of the mica's epitaxy on the orientation of the fibers suggested a surface-assisted assembly process. On HOPG, interactions between the alkyl chains and the graphite surface resulted in the stabilization and trapping of monomer species followed by their subsequent association into coordination polymers on the surface. Interdigitation of the alkyl chains of separate polymer strands induced lateral association of wires to form islands that grew preferentially upon drop-casting and slow evaporation. Clusters of laterally assembled wires were observed for the more mobile functionalized porphyrins bearing C 12 chains.     

Addition of the carbonyl oxygen to the ipso- or ortho-carbon atoms of the beta-phenyl ring followed by intersystem crossing and rapid relaxation to the ground-state ketones: a mechanism for beta-phenyl quenching of the first triplet excited states of derivatives of beta-phenylpropiophenone

The first triplet excited states of beta-phenylpropiophenone 1a and derivatives are known to have unusually short triplet lifetimes. On the basis of pronounced substituent and solvent effects observed in the case of 4-methoxy-beta-phenylpropiophenone 1b, a mechanism involving substantial electron transfer has been assumed to be operative. This contribution outlines an alternative mechanism involving addition of the excited carbonyl moiety at the ipso (preferred) or ortho positions of the beta-phenyl ring. The triplet biradicals thus formed may undergo rapid intersystem crossing to the singlet manifold. On the singlet hypersurface, the biradicals are not predicted to be minima, relaxing to the singlet ground-state ketones. Overall, this addition, intersystem crossing, elimination sequence provides a plausible reaction pathway for beta-phenyl quenching. Calculated activation enthalpies and substituent effects are in agreement with experimental data published in the literature.     

Heat conduction and thermal stress induced by an electric current in an infinite thin plate containing an elliptical hole with an edge crack

A uniform electric current at infinity was applied to a thin infinite conductor containing an elliptical hole with an edge crack. The electric current gives rise to two states, i.e., uniform and uneven Joule heat. These two states must be considered to analyze the heat conduction problem. The uneven Joule heat gives rise to uneven temperature and thus to heat flux, and to thermal stress.Using a rational mapping function, problems of the electric current, the Joule heat, the temperature, the heat flux, the thermal stress are analyzed, and each of their solutions is obtained as a closed form. The distributions of the electric current, the Joule heat, the temperature, the heat flux and the stress are shown in figures.The heat conduction problem is solved as a temperature boundary value problem. Solving the thermal stress problem, dislocation and rotation terms appear, which complicates this problem. The solutions of the Joule heat, the temperature, the heat flux and the thermal stress are nonlinear in the direction of the electric current. The crack problems are also analyzed, and the singular intensities at the crack tip of each problem are obtained. Mode II (sliding mode) stress intensity factor (SIF) is produced as well as Mode I (opening mode) SIF, for any direction of the electric current. The relations between the electric current density and the melting temperature and between the electric current density and SIF are investigated for some crack lengths in an aluminum plate.     

An anisotropic viscoelastic soft tissue model at large strains

Soft biological tissues represent complex inhomogeneous, and as a rule multiphase materials subjected to large strains under in vivo mechanical conditions. Apart from a number of other structural-related features they are characterized by a ratedependent material behavior which is attributed to fluid-solid interactions as well as intrinsic viscoelastic properties of the solid matrix. The authors propose to model rate-dependent phenomena of the solid phase of soft biological tissues within the context of a thermodynamically consistent phenomenological material approach resulting from an overstress concept. Due to the presence of directed fibrous constituents soft tissues should be considered as anisotropic materials. Therefore, the viscous overstress model has been completed by a transversely isotropic approach. (© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Solvent-Dependent Growth and Stabilization Mechanisms of Surfactant-Free Colloidal Pt Nanoparticles

Understanding the formation of nanoparticles (NPs) is key to develop materials by sustainable routes. The Co4Cat^TM process is a new synthesis of precious metal NPs in alkaline mono-alcohols well-suited to develop active nanocatalysts. The synthesis is ‘facile’, surfactant-free and performed under mild conditions like low temperature. The reducing properties of the solvent are here shown to strongly influence the formation of Pt NPs. Based on the in situ formation of CO adsorbed on the NP surface by solvent oxidation, a model is proposed that accounts for the different growth and stabilization mechanisms as well as re-dispersion properties of the surfactant-free NPs in different solvents. Using in situ and ex situ characterizations, it is established that in methanol, a slow nucleation with a limited NP growth is achieved. In ethanol, a fast nucleation followed by continuous and pronounced particle sintering occurs.