On the Methyl-Transfer Reaction in Crystalline Methyl 2-(Methylthio)benzenesulfonate: a Thermally Induced Non-Topochemical Solid-State Reaction

The rearrangement of methyl 2-(methylthio)benzenesulfonate (1) to the zwitterionic 2-(dimethyl-sulfonium)benzenesulfonate (2) is known to proceed in solution by intermolecular Me transfers. The same rearrangement has been observed to occur in crystalline 1, but the crystal structure shows that the molecular packing is not conducive to intermolecular Me transfer. The reaction has been carried out with mixed crystals composed of 1 and deuteriomethylated (D6)-l. By fast-atom-bombardment mass spectroscopy, it has been shown that the product consists of a 1:2:1 mixture of the non-, tri-, and hexadeuterated species, the mixture expected, if the solid-state reaction proceeds by intermolecular Me transfers. From this result, together with the slower rates of conversion in the single crystal compared with the melt, it can be concluded that the reaction must occur not topochemically but rather at defects such as microcavities, surfaces, and other irregularities in the ordered crystal arrangement.

Generation of custom modes in a Nd:YAG laser with a semipassive bimorph adaptive mirror

Custom modes at a wavelength of 1064 nm were generated with a deformable mirror. The required surface deformations of the adaptive mirror were calculated with the Collins integral written in a matrix formalism. The appropriate size and shape of the actuators as well as the needed stroke were determined to ensure that the surface of the controllable mirror matches the phase front of the custom modes. A semipassive bimorph adaptive mirror with five concentric ring-shaped actuators and one defocus actuator was manufactured and characterised. The surface deformation was modelled with the response functions of the adaptive mirror in terms of an expansion with Zernike polynomials. In the experiments the Nd:YAG laser crystal was quasi-CW pumped to avoid thermally induced distortions of the phase front. The adaptive mirror allows to switch between a super-Gaussian mode, a doughnut mode, a Hermite-Gaussian fundamental beam, multi-mode operation or no oscillation in real time during laser operation.

Solder doped polycaprolactone scaffold enables reproducible laser tissue soldering

BACKGROUND AND OBJECTIVES: In this in vitro feasibility study we analyzed tissue fusion using bovine serum albumin (BSA) and Indocyanine green (ICG) doped polycaprolactone (PCL) scaffolds in combination with a diode laser as energy source while focusing on the influence of irradiation power and albumin concentration on the resulting tensile strength and induced tissue damage. MATERIALS AND METHODS: A porous PCL scaffold doped with either 25% or 40% (w/w) of BSA in combination with 0.1% (w/w) ICG was used to fuse rabbit aortas. Soldering energy was delivered through the vessel from the endoluminal side using a continuous wave diode laser at 808 nm via a 400 microm core fiber. Scaffold surface temperatures were analyzed with an infrared camera. Optimum parameters such as irradiation time, radiation power and temperature were determined in view of maximum tensile strength but simultaneously minimum thermally induced tissue damage. Differential scanning calorimetry (DSC) was performed to measure the influence of PCL on the denaturation temperature of BSA. RESULTS: Optimum parameter settings were found to be 60 seconds irradiation time and 1.5 W irradiation power resulting in tensile strengths of around 2,000 mN. Corresponding scaffold surface temperature was 117.4+/- 12 degrees C. Comparison of the two BSA concentration revealed that 40% BSA scaffold resulted in significant higher tensile strength compared to the 25%. At optimum parameter settings, thermal damage was restricted to the adventitia and its interface with the outermost layer of the tunica media. The DSC showed two endothermic peaks in BSA containing samples, both strongly depending on the water content and the presence of PCL and/or ICG. CONCLUSIONS: Diode laser soldering of vascular tissue using BSA-ICG-PCL-scaffolds leads to strong and reproducible tissue bonds, with vessel damage limited to the adventitia. Higher BSA content results in higher tensile strengths. The DSC-measurements showed that BSA denaturation temperature is lowered by addition of water and/or ICG-PCL.

Reconstruction and electrochemical oxidation of Au(110) surface in 0.1 M H2SO4

Variations of the surface structure and composition of the Au(110) electrode during the formation/lifting of the surface reconstruction and during the surface oxidation/reduction in 0.1 M aqueous sulfuric acid were studied by cyclic voltammetry, scanning tunneling microscopy and shell-isolated nanoparticle enhanced Raman spectroscopy. Annealing of the Au(110) electrode leads to a thermally-induced reconstruction formed by intermixed (1×3) and (1×2) phases. In a 0.1 M H2SO4 solution, the decrease of the potential of the atomically smooth Au(110)-(1×1) surface leads to the formation of a range of structures with increasing surface corrugation. The electrochemical oxidation of the Au(110) surface starts by the formation of anisotropic atomic rows of gold oxide. At higher potentials we observed a disordered structure of the surface gold oxide, similar to the one found for the Au(111) surface.

Daily and seasonal thermal stresses in tilings: a field survey combined with numeric modeling

This study investigates thermally induced tensile stresses in ceramic tilings. Daily and seasonal thermal cycles, as well as, rare but extreme events, such as a hail-storm striking a heated terrace tiling, were studied in the field and by numerical modeling investigations. The field surveys delivered temperature– time diagrams and temperature profiles across tiling systems. These data were taken as input parameters for modeling the stress distribution in the tiling system in order to detect potential sites for material failure. Dependent on the thermal scenario (e.g., slow heating of the entire structure during morning and afternoon, or a rapid cooling of the tiles by a rain storm) the modeling indicates specific locations with high tensile stresses. Typically regions along the rim of the tiling field showed stresses, which can become critical with respect to the adhesion strength. Over the years, ongoing cycles of thermal expansion–contraction result in material fatigue promoting the propagation of cracks. However, the installation of flexible waterproofing membranes (applied between substrate and tile adhesive) represents an efficient technical innovation to reduce such crack propagation as confirmed by both numerical modeling results and microstructural studies on real systems.

Interaction of the Trinuclear Triangular Secondary Building Unit [Cu 3 (μ 3 -OH)(μ-pz) 3 ] 2+ with 4,4′-Bipyridine. Structural Characterizations of New Coordination Polymers and Hexanuclear Cu II Clusters. 2°

By reacting 4,4′-bipyridine (bpy) with selected trinuclear triangular CuII complexes, [Cu3(μ3-OH)(μ-pz)3(RCOO)2(LL′)] [pz = pyrazolate anion; R = CH3, CH3CH2, CH2═CH, CH2═C(CH3); L, L′ = Hpz, H2O, MeOH] in MeOH, the substitution of monotopic ligands by ditopic bpy was observed. Depending on the stoichiometric reaction ratios, different compounds were isolated and structurally characterized. One- and two-dimensional coordination polymers (CPs), as well as two hexanuclear CuII clusters were identified. One of the hexanuclear clusters self-assembles into a supramolecular three-dimensional structure, and its crystal packing shows the presence of two intersecting channels, one of which is almost completely occupied by guest bpy, while in the second one guest water molecules are present. This compound also shows a reversible, thermally induced, single-crystal-to-single-crystal transition.