Substituent control of hydrogen bonding in palladium(II)-pyrazole complexes

Inter- and intramolecular hydrogen bonding of an N-H group in pyrazole complexes was studied using ligands with two different groups at pyrazole C-3 and C-5. At C-5, groups such as methyl, i-propyl, phenyl, or tert-butyl were present. At C-3, side chains L-CH(2)- and L-CH(2)CH(2)- (L = thioether or phosphine) ensured formation of chelates to a cis-dichloropalladium(II) fragment through side-chain atom L and the pyrazole nitrogen closest to the side chain. The significance of the ligands is that by placing a ligating side chain on a ring carbon (C-3), rather than on a ring nitrogen, the ring nitrogen not bound to the metal and its attached proton are available for hydrogen bonding. As desired, seven chelate complexes examined by X-ray diffraction all showed intramolecular hydrogen bonding between the pyrazole N-H and a chloride ligand in the cis position. In addition, however, intermolecular hydrogen bonding could be controlled by the substituent at C-5: complexes with either a methyl at C-5 or no substituent there showed significant intermolecular hydrogen bonding interactions, which were completely avoided by placing a tert-butyl group at C-5. The acidity of two complexes in acetonitrile solutions was estimated to be closer to that of pyridinium ion than those of imidazolium or triethylammonium ions.     

Diastereoselective synthesis of cularine alkaloids via enium ions and an easy entry to isoquinolines by aza-Wittig electrocyclic ring closure

In preliminary communications, we reported the diastereoselective synthesis of cularine and sarcocapnine via the intramolecular ring closure of nitrenium and oxenium ions, a new highly diastereoselective reductive methylation with (+)-8-phenylmenthyl chloroacetate followed by reduction with sodium borohydride, and a facile entry to the isoquinoline precursors by aza-Wittig electrocyclic ring closure. We now report the full details of the syntheses of (+)-O-demethylcularine, (+)-cularine, (+)-sarcocapnidine, (+)-sarcocapnine, and (+)-crassifoline and describe different methods of synthesis of their precursors.     

Synergic effect in electrical conductivity using a combination of two fillers in PVDF hybrids composites

The objective of this work was to prepare novel conductive blends of poly(vinylidene fluoride) (PVDF) with polypyrrole (PPy) and to compare their performance with PVDF/multiwall carbon nanotube (MWCNT) composites and novel PVDF/PPy/MWCNT hybrid systems. All the compositions were prepared by melt mixing using a miniature mixer. The mixtures were characterized by Fourier transformed infrared (FTIR), wide angle X-ray diffraction (WAXD), thermogravimetric analyses (TGA), scanning and transmission electron microscopy (SEM and TEM, respectively) and volume electrical resistivity. For the binary PVDF/PPy and PVDF/MWCNT systems, percolation thresholds of 10 and 0.3 wt%, respectively, were found. In the hybrid systems, however, the percolation threshold for each filler was lower than in the binary systems, but the electrical conductivities were always much higher at all concentrations than the conductivities of the binary systems. Therefore, the addition of both fillers had a synergistic effect on the hybrid system conductivity, which was attributed to its morphology: the PPy increased the homogeneity of the MWCNT distribution and decreased the available free volume for the MWCNT; as a result the MWCNT rolled around the PPy particles bridging them through the PVDF matrix, increasing the quantum tunneling effect and thus, the electrical conductivity of the system.     

White-light imaging with fractal zone plates

We report the achievement of the first images to our knowledge obtained with a fractal zone plates (FraZPs). FraZPs are diffractive lenses characterized by the fractal structure of their foci. This property predicts an improved performance of FraZPs as image forming devices with an extended depth of field and predicts a reduced chromatic aberration under white-light illumination. These theoretical predictions are confirmed experimentally in this work. We show that the polychromatic modulation transfer function of a FraZP affected by defocus is about two times better than one corresponding to a Fresnel zone plate.     

Nonlinear weighted best simultaneous approximation in Banach spaces

The present paper is concerned with the problem of weighted best simultaneous approximations in Banach spaces. The weighted best simultaneous approximations to sequences from S- and BS-suns in the Banach space are characterized in view of the Kolmogorov conditions. Applications are provided for weighted best simultaneous approximations from RS-sets and strict RS-sets. Our results obtained in the present paper extend and improve all earlier known results in this direction.     

The Schauder fixed point theorem in geodesic spaces

We give a direct proof of Schauder's fixed point theorem in the setting of geodesic metric spaces, generalizing the classical Schauder's theorem and improving a recent version of this theorem in CAT(κ)$\mathrm{CAT}(\kappa )$ spaces. As an application we prove an existence result for a variational inequality in the setting of CAT(κ)$\mathrm{CAT}(\kappa )$ spaces.     

The Kneser Property for the Second Order Functional Abstract Cauchy Problem

In this work we establish existence of mild solutions for a class of abstract semi-linear functional differential equations of second order and we prove that the set consisting of the mild solutions for these problems is connected.     

Block Transformation of Hybrid Cellular Automata

By introducing a sequence-block transformation and vector-block transformation, we explore the dynamical properties of hybrid cellular automation (HCA) and hybrid cellular automation with memory (HCAM) in the framework of symbolic dynamics. As the local evolution rules of HCA and HCAM are not-uniform, the new uniform cellular automata (CAs) with multiple states are constructed by specifical the block transformations. Furthermore, because the new CA rules are topologically conjugate with the originals, the complex dynamics of the HCA and HCAM rules can be investigated via the new CA rules.     

X-ray studies of the structure of thermotropic copolyesters

This paper describes x-ray analysis of the structure of a group of wholly aromatic thermotropic liquid crystalline copolyesters, focusing on two systems: condensation copolymers of 4-hydroxy-benzoic acid (HBA) and 2-hydroxy–6-naphthoic acid; and of HBA, 2,6-dihydroxy-naphthalene, and terephthalic acid. The fiber diagrams of these copolymers contain a series of aperiodic meridional maxima that shift in position with the monomer ratio. We have shown that these characteristics are predicted by a structure consisting of an array of chains of completely random monomer sequence. The positions of the maxima are predicted by a simple model in which the monomers are represented by points, separated from their neighbors by the appropriate monomer lengths. Use of atomic models for the monomers leads to prediction of both the positions and the intensities of the maxima. Calculations for nonrandom sequence distribution show that all but minimal blockiness can be ruled out. From the breath of the meridional maximum at d = 2.1 Å it is possible to estimate the correlation or persistence length for the stiff chain conformation in the solid state.