1,2‐Bis(trifluoromethyl)ethene‐1,2‐dicarbonitrile: (2+2) Cycloadditions with Vinyl Ethers

The title compound (short version: BTE) occurs in (E)‐ and (Z)‐isomers (both with b.p. of ca. 100°) which equilibrate with nucleophilic catalysts. Both undergo (2+2) cycloadditions with methyl vinyl ether at 25°. Three stereogenic centers in the cyclobutanes led to four rac‐diastereoisomers, which were obtained in pure and crystalline state. The structures were elucidated by ¹⁹F‐NMR spectroscopy and confirmed by two X‐ray analyses. The cycloadditions were not stereospecific: e.g., (E)‐BTE furnished 73% trans‐adducts (with respect to the CF₃ groups) and 27% cis‐adducts. The loss of stereochemical integrity occurs in the intermediate gauche‐zwitterions which can cyclize or rotate, but not dissociate. Under extreme conditions (2M LiClO₄ in Et₂O, 70°, 3 months), the thermodynamic equilibrium of the four cyclobutanes was achieved. Considerations of Coulombic attraction and conformational strain in the zwitterionic intermediates allow us to rationalize the observed proportions of diastereoisomeric cyclobutanes. Ethyl vinyl ether and butyl vinyl ether furnished cyclobutanes in similar diastereoisomer ratios.     

A microscopic model of annealed vacancies in long-period structures

The axial next-nearest-neighbour Ising (ANNNI) model is a spin model which locks into an infinite number of modulated phases as a function of the interaction parameters and the temperature. In this paper we discuss the effect of allowing this system to contain annealed vacancies. We find that a small concentration of vacancies does not qualitatively affect the structure of the phase diagram and that the vacancies form defect-density waves which mirror the periodicity of the underlying modulated structure.     

The level of cross-linking and the structure of anisotropic magnetorheological elastomers

The influence of the concentration of the magnetic powder on the level of cross-linking of magnetorheological elastomers (MREs) has been studied. Afterwards the structural characterisation of manufactured MREs has been performed by using non-destructive method, specifically the computed tomography. The correlation between internal structures of MREs and the developing of its cross-linking level during the curing was found. It was shown that changes in the concentration of the powder significantly affect morphologies of the sample.     

Chemical bath deposition of SnO2 and Cd2SnO4 thin films

A new approach of chemical bath deposition (CBD) of SnO₂ thin films is reported. Films with a 0.2 μm thickness are obtained using the multi-dip deposition approach with a deposition time as little as 8–10 min for each dip. The possibility of fabricating a transparent conducting oxide layer of Cd₂SnO₄ thin films using CBD is investigated through successive layer deposition of CBD-SnO₂ and CBD-CdO films, followed by annealing at different temperatures. High quality films with transmittance exceeding 80% in the visible region are obtained. Annealed CBD-SnO₂ films are orthorhombic, highly stoichiometric, strongly adhesive, and transparent with an optical band gap of ～4.42 eV. Cd₂SnO₄ films with a band gap as high as 3.08 eV; a carrier density as high as 1.7 × 10²⁰ cm^?3; and a resistivity as low as 1.01 × 10^?2 Ω cm are achieved.     

A first low‐resolution difference Fourier map of phosphorus in a membrane protein from near‐edge anomalous diffraction

Crystal diffraction of three membrane proteins (cytochrome bc₁ complex, sarcoplasmic reticulum Ca²⁺ ATPase, ADP‐ATP carrier) and of one nucleoprotein complex (leucyl tRNA synthetase bound to tRNAleu, leuRS:tRNAleu) was tested at wavelengths near the X‐ray K‐absorption edge of phosphorus using a new set‐up for soft X‐ray diffraction at the beamline ID01 of the ESRF. The best result was obtained from crystals of Ca²⁺ ATPase [adenosin‐5′‐(β,γ‐methylene) triphosphate complex] which diffracted out to 7 Å resolution. Data were recorded at a wavelength at which the real resonant scattering factor of phosphorus reaches the extreme value of ?20 electron units. The positions of the four triphosphates of the monoclinic unit cell of the ATPase have been obtained from a difference Fourier synthesis based on a limited set of anomalous diffraction data.     

Absorption spectra of human skin in vivo in the ultraviolet wavelength range measured by optoacoustics

Knowledge of the optical properties of human skin in the ultraviolet range is fundamental for photobiologic research. However, optical properties of human skin in the ultraviolet spectral range have so far mainly been measured ex vivo . We have determined the absorption spectra of human skin in vivo in the wavelength range from 290 to 341 nm in 3 nm steps using laser optoacoustics. In this technique, optical properties are derived from the pressure profile generated by absorbed light energy in the sample. In a study on 20 subjects belonging to phototypes I–IV, we studied the optical properties at the volar and dorsal aspect of the forearm as well as on the thenar. Analysis of the measured absorption spectra shows that comparable skin areas—like different sides of the forearm—have qualitatively similar optical characteristics. Still, the optical properties may vary substantially within the same area, probably due to the skin structure and inhomogeneities. Comparison of the spectra from different skin sites indicates that the spectral characteristics of the stratum corneum and its chromophores play an important role for the optical properties of human skin in vivo in the ultraviolet B range.     

Fulvalenediyl-bridged heterobimetallic complexes consisting of sandwich and half-sandwich compounds with early-late transition metals

A straightforward synthesis methodology for the preparation of heterobimetallic [(η⁵-C₅H₅)(η⁵-C₅H₄-C₅Me₄)M] (3a, M = Fe; 3b, M = Ru) and [(η⁵-C₅H₅)((μ-η⁵:η⁵-C₅H₄-C₅Me₄)TiCl₃)M] (4a, M = Fe; 4b, M = Ru) in which early and late transition metals are connected by a fulvalenediyl bridge is reported.The structures of molecules 3b and 4a in the solid state are discussed. Most noteworthy in 4a is the exo arrangement of the iron and titanium atoms coordinated by the fulvalenediyl unit which itself is twisted with a dihedral angle between the joined cyclopentadienyl rings of 19.33(9)°. Electrochemical, UV/Vis/NIR spectroscopic and spectroelectrochemical experiments on 4a and Cp∗TiCl₃, for comparison, provide evidence for some transfer of electronic information between the conjoined ferrocene and half-sandwich titanocene trichloride subunits of 4a. Evidence comes from systematic potential shifts and the presence of a fairly intense Fe → Ti charge-transfer absorption band that vanishes upon oxidation and reduction of 4a.     

A spin-selective approach for surface states at Co nanoislands

During recent years the surface electronic states of cobalt nanoislands grown on Cu(111) and Au(111) have been extensively studied and still yield fascinating results. Among magnetic surfaces, cobalt islands are particularly appealing because of their spin-polarized electronic states near the Fermi energy, involving localized d states of minority character, as well as free-like s–p states of majority character. We show here that these states are a sensitive probe to minute changes of structural details such as strain and stacking, and therefore constitute an ideal playground to study the interplay between structural and spin-related properties. Due to their size, cobalt islands on Cu(111) offer the additional opportunity to host single-magnetic adsorbates suitable for spin-polarized scanning tunneling microscopy and spectroscopy (SP-STM and SP-STS). We establish here that, in an energy interval just below the Fermi level, the spin-polarization of a transition-metal atom is governed by surface-induced states opposite in sign compared to the island, while the spin-polarization of Co-Phthalocyanine molecules is governed by molecular states. This opens up interesting perspectives for controlling and engineering spin-polarized phenomena at the nanoscale.     

Influence of liquid layers on energy absorption during particle impact

The influence of the thickness of a covering liquid layer and its viscosity as well as the impact velocity on energy loss during the normal impact on a flat steel wall of spherical granules with a liquid layer was studied. Free-fall experiments were performed to obtain the restitution coefficient of elastic-plastic γ- Al2O3 granules by impact on the liquid layer, using aqueous solutions of hydroxypropyl methylcellulose with different concentrations for variation of viscosity （1-300 mPa s）, In the presence of a liquid layer, increase of liquid viscosity decreases the restitution coefficient and the minimum thickness of the liquid layer at which the granule sticks to the wall. The measured restitution coefficients were compared with experiments performed without liquid layer. In contrast to the dry restitution coefficient, due to viscous losses at lower impact velocity, higher energy dissipation was obtained, A rational explanation for the effects obtained was given by results of numerically solved force and energy balances for a granule impact on a liquid layer on the wall. The model takes into account forces acting on the granule including viscous, surface tension, capillary, contact, drag, buoyancy and gravitational forces. Good agreement between simulations and experiments has been achieved.     

Observation of surface solitons in chirped waveguide arrays

We report the observation of surface solitons in chirped semi-infinite waveguide arrays whose waveguides exhibit exponentially decreasing refractive indices. We show that the power threshold for surface wave formation decreases with an increase of the array chirp and that for sufficiently large chirp values linear surface modes are supported.