A new reaction of phosphorylated N-sulfonylimines with hydrophosphoryl agents involving C → N transfer of phosphoryl groups

Hydrophosphoryl nucleophilic agents add to the CN bond of N-sulfonyltrichloroacetimidoylphosphonates to give unstable C,C-diphosphorylated adducts, which undergo competitive 1,2-C → N phosphorotropic rearrangement and dehydrochlorination with the formation of aza-Perkow reaction products, C,N-diphosphorylated dichlorovinylsulfonamides. This is the first reliably identified case of an aza-Perkow transformation for acid phosphites and their initial nucleophilic attack at the C atom of the azomethine bond in the aza-substrates.     

Synthesis of aromatic aldehydes via NiCl2 reduction and hydrolysis of oxazolines

Reduction of 2-aryl-oxazolines with NiCl₂/NaBH₄ followed by hydrolysis gives the corresponding aldehydes in good yields.     

Electronic transport properties of bismuth nanobridges through silicon-nitride membranes

The electronic transport through nanostructured bismuth nanobridges has been investigated at low temperatures (T<2 K) and in magnetic fields B up to 8.5 T. The samples show reproducible resistance fluctuations as a function of B, superimposed on a large magnetoresistance of up to 50%. In addition, time-dependent resistance fluctuations in zero magnetic field demonstrate the presence of bistable scatterers in the constriction region of our samples, which are described by two-level systems. Their dynamics are shown to be sensitive to subtle modifications of the static scatterer configuration in their vicinity, which cannot be detected in the sample magnetofingerprint.     

Structure of solid monolayers and multilayers of n -hexane on graphite

We present all-atom molecular dynamics simulations ofn-hexane on the basal plane of graphite at monolayer and multilayer coverages. In keeping with experimental data, we find the presence of ordered adsorbed layers both at single monolayer coverage and when the adsorbed layer coexists with excess liquid adsorbate. Using a simulation method that does not impose any particular periodicity on the adsorbed layer, we quantitatively compare our results to the results of neutron diffraction experiments and find a structural transition from a uniaxially incommensurate lattice to a fully commensurate structure on increasing the coverage from a monolayer to a multilayer. The zig-zag backbone planes of all the alkane molecules lie parallel to the graphite surface at the multilayer coverage, while a few molecules are observed to attain the perpendicular orientation at monolayer coverage. Dedicated to Professor C N R Rao on his 70th birthday     

Non-isothermal short-range-order kinetics of binary alloys as influenced by solute-vacancy complexes

A model describing the roles of bound and unbound vacancies is proposed in order to predict defect decay and short-range-order kinetics of quenched binary alloys during linear heating experiments. This is an alternative treatment of a previous approach. The model has been applied to the differential scanning calorimetry (DSC) curves of Cu-5 at.% Zn quenched from different temperatures. An expression to calculate the activation energy for migration of solute-vacancy complexes was also developed which make use of DSC trace data. A value of 89.12±0.32 kJ mol^-1 was obtained for the above alloy. The relative contribution of bound and unbound vacancies to partition of effective activation energy corresponding to the ordering process as influenced by quenching temperature was also assessed. This revised version was published online in July 2006 with corrections to the Cover Date.     

Asymptotic expansions for eigenvalues in the presence of small inhomogeneities

We provide a rigorous derivation of an asymptotic formula for perturbations in the eigenvalues caused by the presence of a finite number of inhomogeneities of small diameter with conductivity different from the background conductivity. Copyright © 2003 John Wiley & Sons, Ltd.     

Crystallization and morphology of poly(vinylidene fluoride)/poly(3‐hydroxybutyrate) blends. I. Spherulitic morphology and growth by polarized microscopy

The development of the poly(3‐hydroxybutyrate) (PHB) morphology in the presence of already existent poly(vinylidene fluoride) (PVDF) spherulites was studied by two‐stage solidification with two separate crystallization temperatures. PVDF formed irregular dendrites at lower temperatures and regular, banded spherulites at elevated temperatures. The transition temperature of the spherulitic morphology from dendrites to regular, banded spherulites increased with increasing PVDF content. A remarkable amount of PHB was included in the PVDF dendrites, whereas PHB was rejected into the remaining melt from the banded spherulites. When PVDF crystallized as banded spherulites, PHB could consequently crystallize only around them, if at all. In contrast, PHB crystallized with a common growth front, starting from a defined site in the interfibrillar regions of volume‐filling PVDF dendrites. It formed by itself dendritic spherulites that included a large number of PVDF spherulites. For blends with a PHB content of more than 80 wt %, for which the PVDF dendrites were not volume‐filling, PHB first formed regular spherulites. Their growth started from outside the PVDF dendrites but could later interpenetrate them, and this made their own morphology dendritic. These PHB spherulites melted stepwise because the lamellae inside the PVDF dendrites melted at a lower temperature than those from outside. This reflected the regularity of the two fractions of the lamellae because that of those inside the dendrites of PVDF was controlled by the intraspherulitic order of PVDF, whereas that from outside was only controlled by the temperature and the melt composition. The described morphologies developed without mutual nucleating efficiency of the components. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 873–882, 2003     

Notiz über Parachloraldehyd

Ohne Zusammenfassung