Identification of geometrical isomers using vibrational circular dichroism spectroscopy: a series of mixed-ligand complexes of diamagnetic Co(III) ions

Vibrational circular dichroism (VCD) spectra were measured on the chloroform solutions of a series of mixed-ligand diamagnetic Co(III) complexes, [Co(tfac)(n)(acac)(3-n)] (n = 0-3, tfac = 1,1,1-trifluoro-2,4-pentanedionato; acac = acetylacetonato). Distinct differences were observed in the VCD spectra among the geometrical isomers of the same ligand composition. Such differentiation was hardly possible by their infra-red spectra alone. The structural identification of these isomers was performed in conjunction with DFT calculations.     

Dicationic ((−)-sparteine)palladium-catalyzed enantioselective aldol reaction of aldehydes with 1-phenyl-1-trimethylsilyloxyethene, proceeding via a palladium enolate

A dicationic ((−)-sparteine)palladium complex underwent a superior catalytic enantioselective aldol reaction of aldehydes with 1-phenyl-1-trimethylsilyloxyethene performing satisfactorily, starting with ((−)-sparteine)PdCl₂ and AgSbF₆ as catalyst precursors (1 mol % loading) in the presence of 3 Å molecular sieves over the reaction.     

Effective synthesis of diiodinated picene and dibenzo[a,h]anthracene by AuCl-catalyzed double cyclization

6,13-Diiododibenzo[a,h]anthracene and 5,8-diiodopicene were synthesized by AuCl-catalyzed double cyclization. The highly selective reaction yielded a new class of peri-halogenated fused aromatics.     

A modular approach to a new class of phosphinohydrazones and their use in asymmetric allylic alkylation reactions

A group of five phosphino hydrazones with a pendant binaphthyl unit as a chiral modifier has been synthesized from non-racemic 2,2′-bis(bromomethyl)-1,1′-binaphthyl and 3,3′-diiodo-2,2′-bis(bromomethyl)-1,1′-binaphthyl as the key intermediates. Their efficiency as chiral ligands in palladium-catalyzed allylic alkylation reactions has been investigated showing up to 95% ee under optimized conditions. X-ray diffraction structures of mono- and dimeric Pd complexes are also reported.     

Layered silicate‐polyamide‐6 nanocomposites: Influence of silicate species on morphology and properties

The effect of two different species of layered silicates on the morphology, mechanical properties, and methanol vapor barrier properties of polyamide‐6 (PA6) nanocomposites was examined using identical experimental conditions for both species. The layered silicate species used were natural montmorillonite (MMT) and synthetic expandable fluoro‐mica (FM), the chemical compositions of which were Na_0.43(Al_1.56Mg_0.31Fe²⁺ _0.09)(Si_3.95Al_0.05)O₁₀(OH)₂ and Na_0.66Mg_2.68(Si_3.98Al_0.02)O₁₀F₂, respectively. The layered silicates were modified with a dodecylammonium salt (DDA) using an ion‐exchange method. The resulting organically modified layered silicates were melt‐kneaded with PA6 in a twin‐screw kneader at 260 °C. By quantitative analysis of the silicate layers dispersed in the PA6, the number‐average aspect ratio was estimated to be 76 for DDAMMT‐PA6 and 85 for DDAFM‐PA6. This confirmed that the primary particle size of the initial silicate did affect the aspect ratio. The rigidity and gas barrier properties of the nanocomposites appeared to depend upon the morphology of the nanocomposite. On the other hand, the elongation at break of the nanocomposites decreased as the amount of silicate increased. This reduction in ductility was ascribed to the difference in morphology of the nanocomposites, that is, distribution of silicate nanolayers in the polymer matrix. The homogeneity of the particle fraction of exfoliated nanolayers was clearly an important factor affecting the properties of the nanocomposites. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 583–595, 2009     

Synthesis and antiulcer activity of the metabolites of 2-(4-ethyl-1-piperazinyl)-4-phenylquinoline dimaleate (AS-2646), a novel gastric antisecretory and antiulcer agent

The metabolites 3 and 4 of 2-(4-ethyl-1-piperazinyl)-4-phenylquinoline dimaleate (AS-2646, 1), a candidate as a gastric antisecretory and antiulcer drug, were synthesized to confirm the proposed structures. The effects of the metabolites 2-4 on ulcer induced by stress were determined.     

Aberration correction and its automatic control in scanning electron microscopes

An automatic aberration correction method has been implemented in scanning electron microscopes (SEM). Necessity of the automatic aberration correction is discussed. The procedure of the automatic aberration correction is explained in detail, where deconvolution techniques are used in order to extract probe information from SEM images. Due to the precise digitization and the usage of proper combinations of correction fields, linearity has been found between the amplitude of each aberration and the corresponding field strength. Experimental results are shown which demonstrate that the aberrations are corrected automatically by a linear feedback control method. After the automatic aberration correction, the image quality has been improved drastically.