D3h‐Symmetric Porphyrin‐Based Rigid Macrocyclic Ligands for Multicofacial Multinuclear Complexes in a One‐Nanometer‐Sized Cavity

The one‐step synthesis of D_3h‐symmetric cyclic porphyrin trimers 1 composed of three 2,2′‐[4,4′‐bis(methoxycarbonyl)]bipyridyl moieties and three porphyrinatozinc moieties was achieved from a nickel‐mediated reductive coupling of meso‐5,15‐bis(6‐chloro‐4‐methoxycarbonylpyrid‐2‐yl)porphyrinatozinc. Although cyclic trimers 1 were obtained as a mixture that included other cyclic and acyclic porphyrin oligomers, an extremely specific separation was observed only for cyclic trimers 1 when using columns of silica gel modified with pyrenylethyl, cyanopropyl, and other groups. Structural analysis of cyclic trimers 1 was carried out by means of NMR spectroscopy and X‐ray crystallography. Treatment of an η³‐allylpalladium complex with a cyclic trimer gave a tris(palladium) complex containing three η³‐allylpalladium groups inside the space, which indicated that the bipyridyl moieties inside the ring could work as bidentate metalloligands.     

Positive photosensitive polyimides with cyclobutane structure

A new family of positive photosensitive polyimide (PPI) systems composed of solvent soluble polyimides (Pls) with cyclobutane (CBDA) structures and diazonaphthoquinone compounds (DNQ) has been prepared. Heat and catalytic imidizations were carried out to obtain CBDA Pls; the former was better than the latter in controlling the molecular weight of the Pl. The ? OH groups in the Pls were easily acetylated during catalytic imidization, so ? COOH groups were selected as weak acidic groups in the Pls. The ? COOH groups were also effective in giving the Pls an alkaline solubility. Therefore, Pls having ? COOH groups were superior to those having ? OH groups for PPI systems. The photosensitive properties of various PPl systems containing ? COOH were found to vary with the fraction of ? COOH groups in the Pls, the content of DNQ in the systems, and the molecular weight of the Pls.     

Status of heavy element research using a gas-filled recoil separator at RIKEN

A gas-filled type of recoil separator for heavy element research was installed at an experimental hall of RIKEN Linear Accelerator facility to realize getting higher intensity of primary beam and long beam time. Performance of the separator was studied using target recoils and various nuclear reactions. The results show the high performance of the separator for heave element research. As an application of the GARIS, production and identification of an isotope of the 110th element ²⁷¹[110] have been performed using the ²⁰⁸Pb(⁶⁴Ni,1n)²⁷¹[110] reaction. Three decay chains coincide well both in decay times and energies with the ones reported by the group of SHIP experiment at GSI, Germany. Our results provide a confirmation of the synthesis of an isotope ²⁷¹[110] of element 110.     

Charge density study under high pressure

The experimental and analytical method of the high-pressure powder experiment at BL10XU, SPring-8, is described. There is no doubt that BL10XU must be one of the most appropriate beam lines for high pressure X-ray diffraction experiment taking advantage of third generation synchrotron source. As an example of the advanced charge density study under high pressure, the structural change of Cs₂Au₂Br₆ by applying pressure is studied by Rietveld/MEM analysis. It reveals that the structural change of Cs₂Au₂Br₆ by applying pressure occurs basically at electron level, such as valence state change and chemical bonding, which may be called the electronic phase transition.     

Preparation and evaluation of oral dosage form using acylglycerols. II. Effect of food ingestion on dissolution and absorption of aspirin from the granules prepared by acylglycerols in human subjects.

The dissolution behavior of the aspirin enteric granule prepared using acylglycerols, glyceryl monostearate (GMS) and glyceryl trilaurate (GTL), was investigated in vitro and in human subjects in a fasting or non-fasting state. Aspirin was slowly released from the granule in vitro at pH 1.2. No acceleration of the aspirin dissolution rate in the medium without lipase and cholic acid was observed when the pH level of the medium increased to a neutral region (pH 6.4). However, the dissolution of aspirin was significantly increased by increasing the concentrations of lipase and cholic acid in the medium. Lipase appears to play an essential role in the dissolution process of aspirin granules. In human subjects, the average levels of the cumulative amount of total salicylate excreted in a urine-time curve, and the mean residence time (MRT) obtained after oral administration of a granule in the fasting state were markedly delayed in comparison with the results observed using an aqueous solution and a crystalline form of aspirin. In comparing the fasting condition with the non-fasting condition (after food ingestion), no significant difference was recognized in the total amount of salicylate excreted in urine to an infinite time (Ae(infinity)), whether the MRT was obtained by granule, crystalline form or aqueous solution. It can be concluded that aspirin granule prepared by GMS and GTL has a property of pancreatic lipase-sensitive dissolution, and its bioavailability is unaffected by food intake.     

Copolymers containing a spiro orthoester moiety that undergo no shrinkage during cationic crosslinking

A spiro orthoester with an exomethylene group (exoSOE) was radically copolymerized with acrylonitrile or vinyl acetate at several feed ratios to obtain the corresponding copolymers having spiro orthoester moieties in the side chain. The obtained copolymers could be crosslinked via the double ring‐opening polymerization of the spiro orthoester moieties in their side chain by a treatment with BF₃OEt₂. The volume changes upon the crosslinking of the copolymers were evaluated by density measurements with a micromeritics gas pycnometer. The copolymers experienced less than 1% volume expansion instead of volume shrinkage during typical cationic crosslinking, regardless of the copolymer compositions. Negligible shrinkage was observed during the thermal cationic crosslinking of a film cast from a nitrobenzene solution of the copolymers containing a benzylthiophenium salt as a thermally latent cationic initiator. The constantly low volume changes during the crosslinking of the copolymers from exoSOE probably depended on the almost zero volume change during the cationic polymerizations of spiro orthoester derivatives. This indicates that exoSOE is an effective monomer for crosslinkable polymers without volume changes. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3666–3673, 2006     

Preparation and properties of isobutylene–isoprene rubber–clay nanocomposites

Isobutylene isoprene rubber (IIR)‐clay nanocomposites have been prepared successfully by melt intercalation with maleic anhydride‐grafted IIR (Ma‐g‐IIR) and organophilic clay. In IIR‐clay nanocomposites, the silicate layers of the clay were exfoliated and dispersed into the monolayer. The nanocomposites exhibited greater gas barrier properties compared with those of Ma‐g‐IIR. When 15 phr clay was added, gas barrier properties were 2.5 times greater than those of Ma‐g‐IIR. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1182–1188, 2006     

Synthesis of copolymers containing a spiro orthocarbonate moiety and evaluation of the volume change during their cationic crosslinking

Spiro orthocarbonate (SOC) monomers having either an exomethylene group {3,3‐dimethyl‐9‐methylene‐1,5,7,11‐tetraoxaspiro[5.5]undecane (ExoSOC)} or an allyl group {9‐allyl‐3,3‐dimethyl‐1,5,7,11‐tetraoxaspiro[5.5]undecane (AllylSOC)} were radically copolymerized with vinyl monomers at several feed ratios to obtain the corresponding copolymers having SOC moieties in the side chain. The obtained copolymers were crosslinked via the double ring‐opening polymerization of the SOC moieties by a treatment with boron trifluoride etherate. The volume changes during the crosslinking of the copolymers were evaluated by density measurements with a gas pycnometer. As the SOC moiety composition increased, the volume shrinkage during the crosslinking was suppressed, and that finally changed into volume expansion. The volume changes during the crosslinking of the copolymers from AllylSOC were slightly larger than those of the copolymers from ExoSOC. The higher volume expansions in the crosslinking of AllylSOC‐based copolymers were ascribable to the lower steric hindrance around the SOC moieties. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 7040–7053, 2006