Cobalt-Catalyzed Intramolecular Hydroacylation Involving Cyclopropane Cleavage

A simple cobalt-diphosphine catalyst has been found to efficiently promote intramolecular cyclization of ortho-cyclopropylvinyl- and cyclopropylidenemethyl-substituted benzaldehydes into benzocyclooctadienone and benzocycloheptadienone derivatives, respectively. This ring-opening hydroacylation likely involves aldehyde C−H oxidative addition, olefin insertion, cyclopropane cleavage by β-carbon elimination, and C−C bond-forming reductive elimination, as was supported by mechanistic experiments and DFT calculations.     

High-pressure and high-temperature generation using diamond/sic composite anvils prepared with hot isostatic pressing

Using a hot isostatic pressing (HIP) technique, we synthesized diamond/SiC composites from diamond and Si powders. At an HIP condition of 1450 °C and 100 MPa, a pressure much lower than that of the diamond stability field, diamond powders react with molten Si to form well-sintered diamond/SiC composites. Cubes of the composites with 15 mm edge length were thereby fabricated, and an application to the second stage anvils in a Kawai-type high-pressure apparatus was attempted. A hybrid anvils system using four cubes of the composites and four of the conventional WC was introduced and heating experiments up to 1600 °C became possible. Because the diamond/SiC composites are transparent to X-rays, the present system is applicable not only to diffraction studies but also to radiographic studies that need a larger window for an X-ray image.     

Fluorobenziodoxole−BF3 Reagent for Iodo(III)etherification of Alkynes in Ethereal Solvent

A combination of fluorobenziodoxole (FBX) and BF₃ ? OEt₂ in cyclopentyl methyl ether promotes regio‐ and stereoselective addition of benziodoxole and methoxy groups to alkynes. This difunctionalization reaction tolerates a variety of functionalized internal and terminal alkynes to afford trans‐β‐alkoxyvinylbenziodoxoles, which represent versatile precursors to stereochemically well‐defined multisubstituted vinyl ethers. The reaction is proposed to involve cleavage of the I?F bond of FBX by BF₃, followed by electrophilic activation of the alkyne by the resulting cationic I^III species that triggers the nucleophilic addition of the ethereal oxygen.     

Some Pharmaceutical Properties of a New Branched Cyclodextrin, 6-O-α-(4-O- α-D-Glucuronyl)-D-glucosylβ-cyclodextrin

Some physicochemical and biological properties of a new branched cyclodextrin, 6-O--(4-O--d-glucuronyl)-d-glucosyl--cyclodextrin GUG--CyD) were investigated. Further, theinteraction of GUG--CyD with several drugs was studied by the solubility and spectroscopic methods, and compared with those of parent -CyD and 6-O--maltosyl--CyD(₂--CyD).The hemolytic activity of GUG--CyD on rabbit erythrocytes was lower than those of -CyD and ₂--CyD. GUG--CyD and ₂--CyD showed negligible cytotoxicity on Caco-2 cells up to at least 0.1 M. The inclusion ability of GUG--CyD to neutral and acidic drugs was comparable to or slightly smaller than those of -CyD and ₂--CyD, probably because of a steric hindrance of the branched sugar. On the other hand, GUG--CyD showed greater affinity for the basic drugs, compared with -CyD and ₂--CyD, owing to the electrostatic interaction of its carboxylate anion with positive charge of basic drugs. Thus GUG--CyD may be useful as a safe solubilizing agent particularly for basic drugs.     

Magnetic moments and GT-type β-decay matrix elements in the fermi gas model

Magnetic moments and GT-type β-decay matrix elements are calculated in the infinitely extended Fermi gas. Relations between various competing mechanisms such as core polarization and exchange-current effects are examined. Some attention is paid to the role of the controversial Δ-hole effect. The results are discussed in comparison with finite nuclei.     

Substituent effect of the coordinated pyridine in a series of pyrazolato bridged dinuclear diiron(II) complexes on the spin-crossover behavior

Two series of pyrazolato bridged dinuclear NCS and NCBH3 diiron(II) complexes with various types of 3- or 4-substituted pyridines, [{Fe(NCS or NCBH3)(X-py)}2(mu-bpypz)2], were prepared and their variable-temperature magnetic susceptibilities were measured. There were found linear correlations of the spin-crossover temperatures Tc not only between the NCS and NCBH3 complexes with the corresponding substituted pyridines, but also between the Tc and the Hammett constants, supporting the electronic substituent effect of the coordinated pyridine rather than a steric effect. The ligand field and the interelectronic repulsion parameters together with the thermodynamic data and/or cooperativity factor were discussed in relation with their spin-crossover behavior.     

Observation of the transient rotator phase of n-hexadecane in emulsified droplets with time-resolved two-dimensional small- and wide-angle X-ray scattering

Crystallization of n-hexadecane in emulsion droplets was studied using time-resolved two-dimensional small- and wide-angle x-ray scattering with differential scanning calorimetry (2D-SAXS-WAXS-in situ DSC) which provides information about both nano- and subnanoscale structural change. n-hexadecane in droplets reproducibly crystallized into the stable triclinic phase via a transient-rotator phase. This is in contrast with previous results that the rotator phase of n-hexadecane was observed only occasionally for bulk samples. Thus we confirmed the existence of rotator phase in n-hexadecane, which is important for the study of crystallization of soft materials. We suggest that the rotator phase at the interface of oil and water plays a precursor role for bulk crystallization. This study demonstrates that 2D-SAXS-WAXS-in situ DSC is a powerful tool for the study of a transient phase.     

X-ray directional dichroism of a polar ferrimagnet

In a polar ferrimagnet GaFeO3, we have found a novel magneto-optical effect, termed x-ray nonreciprocal directional dichroism (XNDD), that the x-ray absorption at around the K edge of an Fe ion depends on whether the x-ray propagation vector is parallel or antiparallel to the outer product of the magnetization and electric-polarization vectors. The XNDD spectroscopy as demonstrated here can be a useful tool to probe the local magnetism in noncentrosymmetric systems such as magnetic interfaces and nanostructures.