A Synthesis of the Tricyclic Core Structure of FR901483 Featuring an Ugi Four-Component Coupling and a Remarkably Selective Elimination Reaction

Three key reactions, an efficient Ugi four-component coupling, a regiospecific, base-mediated elimination reaction, and an intramolecular nitrone/alkene [3+2] cycloaddition, were used to achieve an effective synthesis of the tricyclic molecular framework of the immunosuppressant FR901483. The outcome of a control experiment supports the idea that an internal deprotonation by an alkoxide ion is the origin of the site selectivity observed in the base-induced elimination of hydroxy mesylate 17.     

Structural characterization of hierarchically porous alumina aerogel and xerogel monoliths

Detailed nanostructures have been investigated for hierarchically porous alumina aerogels and xerogels prepared from ionic precursors via sol–gel reaction. Starting from AlCl₃·6H₂O and poly(ethylene oxide) (PEO) dissolved in a H₂O/EtOH mixed solvent, monolithic wet gels were synthesized using propylene oxide (PO) as a gelation initiator. Hierarchically porous alumina xerogels and aerogels were obtained after evaporative drying and supercritical drying, respectively. Macroporous structures are formed as a result of phase separation, while interstices between the secondary particles in the micrometer-sized gel skeletons work as mesoporous structures. Alumina xerogels exhibit considerable shrinkage during the evaporative drying process, resulting in relatively small mesopores (from 5.4 to 6.2 nm) regardless of the starting composition. For shrinkage-free alumina aerogels, on the other hand, the median mesopore size changes from 13.9 to 33.1 nm depending on the starting composition; the increases in PEO content and H₂O/EtOH volume ratio both contribute to producing smaller mesopores. Small-angle X-ray scattering (SAXS) analysis reveals that variation of median mesopore size can be ascribed to the change in agglomeration state of primary particles. As PEO content and H₂O/EtOH ratio increase, secondary particles become small, which results in relatively small mesopores. The results indicate that the agglomeration state of alumina primary particles is influenced by the presence of weakly interacting phase separation inducers such as PEO.     

Uptake of transition metal ions using liposomes containing dicetylphosphate as a ligand.

The uptake of Cu2+ was investigated using various types of liposomes composed of phosphatidylcholine (PC), cholesterol (Chol) and dicethylphosphate (DCP). DCP played a role as a ligand for Cu2+. Multilamellar vesicles (MLVs) were more effective for the uptake of Cu2+ compared to unilamellar vesicles prepared by the extrusion technique. The uptake efficiency of MLVs for Cu2+ was dependent on the molar ratio of DCP in MLVs. The uptake percent of Cu2+ was 92% using MLVs having a PC:DCP:Chol molar ratio of 4:3:3; 95% of the total vesicle Cu2+ was bound to DCP of the outer membrane surface of the MLVs, and the remaining 5% of the total Cu2+ was distributed into the interior side of the MLVs. MLVs having a PC:DCP:Chol molar ratio of 4:3:3 were also effective as separation media for Mn2+, Co2+, Ni2+ and Zn2+. The uptake efficiency of the MLVs for the transition-metal ions increased in the order Co2+ < Zn2+ < Ni2+ < Mn2+ < Cu2+.     

Algebraic study on the super-KP hierarchy and the ortho-symplectic super-KP hierarchy

Bilinear residue formulas are established for the super-KP hierarchy and the ortho-symplectic super-KP hierarchy. Furthermore, superframes corresponding to the ortho-symplectic super-KP hierarchy are completely characterized. Soliton solutions to the super-KP hierarchy are given.     

Super-Kadomtsev—Petviashvili hierarchy and super-Grassmann manifold

The super-Kadomtsev-Petviashvili (SKP) hierarchy is introduced, and the general solutions are explicitly represented in terms of a superdeterminant. It is proved that the SKP hierarchy can be regarded as a dynamical system on a super-Grassmann manifold of infinite dimensions.     

Energy distribution curves of ultrafast laser-induced field emission and their implications for electron dynamics

Energy distribution curves of laser-induced electron pulses from a tungsten tip have been measured as a function of tip voltage and laser power. Electron emission via tunneling through and/or excitation over the surface barrier from photoexcited nonequilibrium electron distributions are clearly observed. The spectral shapes largely vary with the emission processes and are strongly affected by electron dynamics. Simulations successfully reproduce the spectra, thus allowing direct insight into the involved electron dynamics and revealing the temporal tunability of electron emission via the two experimental parameters. These results should be useful to optimize the pulse characteristics for many applications based on ultrafast laser-induced electron emission.     

Gasification characteristics of woody biomass in the packed bed reactor

Gasification technology is recognized as one of the possibilities for utilizing biomass effectively. This study focused on woody biomass gasification fundamentals, using a bench-scale packed-bed reactor. In this experiment, pellets of black pine were gasified, using air as the oxidizing agent. Gasification tests were carried out under both updraft and downdraft conditions. Temperature distributions and compositions of syngas inside the gasifier were continuously monitored during gasification experiments at several ports on the wall of the reactor. The syngas at the exit of the gasifier was also sampled to estimate the amount of tar. Lower heating values of the syngas under updraft and downdraft conditions were 4.8 and 3.8 MJ/m³N, respectively. It was easier to control the height of the packed bed under the downdraft condition than under the updraft condition. Under the updraft condition, a bridging phenomenon occurred. Tar generation under the downdraft condition was lower than that under the updraft condition. This is because tar passes through a partial combustion zone or higher temperature zone in the downdraft gasifier.     

Noble Metal Sintering Suppression Technology in Three-way Catalyst: Automotive Three-way Catalysts with the Noble Metal Sintering Suppression Technology Based on the Support Anchoring Effect

This paper reviews the progress in our development of the three-way catalyst with a noble metal sintering suppression technology based on the support anchoring effect. The catalytic activity on this catalyst is far superior to the conventional catalyst, but with lower noble metal loading.