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.     

Iron-Catalyzed Biomimetic Dimerization of Tryptophan-Containing Peptides

Biomimetic oxidative dimerization of tryptophan derivatives in aqueous media with oxygen as a bulk oxidant catalyzed by an iron octacarboxy phthalocyanine complex was established. The discovery of the extremely active iron catalyst enables aerobic enzyme-mimetic oxidation to be performed in a flask. This method was applicable to the oxidative dimerization of a wide range of tryptophan derivatives, including various dipeptides and oligopeptides, with remarkable functional-group tolerance without the protection of the amino acid residues. Furthermore, oxidative dimerization of tryptophan derivatives bearing dioxopiperazine units enabled the convergent total synthesis of five natural pyrroloindole compounds and unnatural congeners. The established chemical method provides facile access to a broad range of dimerized peptides with a unique scaffold to link two turn structures, which will serve as a powerful tool to create new small- and medium-sized-molecules as drug candidates.     

3-Oxo-4,4,4-trifluorobutyronitriles as building blocks of trifluoromethyl substituted heterocycles 2. Heterocyclization to 3-aryl-4-trifluoromethyl-2H-1-benzopyran-2-ones under hoesch reaction conditions

Resorcinol and 5-methylresorcinol, respectively, react with 3-oxo-2-aryl-4,4,4-trifluorobutyronitrile using zinc chloride as a catalyst in dibutyl ether under the Hoesch reaction conditions to give a low yield of 3-aryl-7-hydoxy-4-trifluoromethyl- or 3-aryl-5-hydroxy-7-methyl-4-trifluoromethyl-2H-l-benzopyran-2-ones. However, the related reaction with m-methoxyphenol was found to produce poor yields of 3-aryl-7-methoxy-4-trifluoromethyl-2H-1-benzopyran-2-one and its 3,4-dihydro-4-hydroxy derivative.     

Microbubble formations in MEMS-fabricated rectangular channels: A high-speed observation

A microfluidic device that consists of MEMS-fabricated rectangular channels is developed for stable and sequential production of monodispersed microbubbles. The central inlet for gas phase is located between two inlets for liquid phases, where the device works as a two-fluid atomizer. The interfacial flow mechanism of microbubble formation at the junction of the inlets in the device is investigated using a high-speed visualization technique and digital image processing. The periodic formation process is successfully realized by the consideration of the wettability between the microbubble and the channel wall. The produced microbubbles are relatively uniform in size, and the size is controlled from 113 to 153 μm by changing the flow rates of the liquid and gas phases. Furthermore, a simple theoretical model to predict the equivalent diameter of microbubbles is developed by considering the mass balance of the gas phase in the formation process, where the experimental and theoretical results are in reasonable agreement.