Physico-geometric kinetics of solid-state reactions by thermal analyses

The physico-geometric kinetics for the solid-state reactions by thermoanalytical (TA) measurements were reexamined by focusing some fundamental aspects: (1) the fundamental kinetic equation, (2) the kinetic model function, (3) the fractional reaction , and (4) the apparent kinetic parameters. It was pointed out that some pitfalls in the practical kinetic study are originated by the disagreement between the kinetic information from the TA measurements and the theory of the physico-geometric kinetics. In order to increase the degree of coordination between the theory and practice, several attempts were made from both the theoretical and experimental points of views. The significance of the apparent kinetic parameters was discussed with a possible orientation for obtaining the reliable kinetic parameters.I would like to thank to Profs H. Tanaka, J. esták, J. M. Criado, A. K. Galwey and Dr. J. Malek for their kind supports.     

Excess partial molar enthalpies,entropies, Gibbs energies,and volumes in aqueous dimethylsulfoxide

The excess partial molar enthalpies, the vapor pressures, and the densities of dimethylsulfoxide (DMSO)–H₂O mixtures were measured and the excess partial molar Gibbs energies and the partial molar volumes were calculated for DMSO and for H₂O. The values of the excess partial molar Gibbs energies for both DMSO and H₂O are negative over the entire composition range. The results for the water-rich region indicated that the presence of DMSO enhances the hydrogen bond network of H₂O. Unlike monohydric alcohols, however, the solute-solute interaction is repulsive in terms of the Gibbs energy. This was a result of the fact that the repulsion among solutes in terms of enthalpy surpassed the attraction in terms of entropy. The data in the DMSO-rich region suggest that DMSO molecules form clusters which protect H₂O molecules from exposure to the nonpolar alkyl groups of DMSO.     

Preparation and Thermal Decomposition of Synthetic Bayerite

The formation process of bayerite, from an aqueous solution of sodium aluminate through enforced decomposition of aluminate ions by introducing CO₂ gas and aging with mechanical stirring, was investigated by pH measurements of the mother solution during preparation reaction and characterization of precipitates obtained at various stages of preparation. An amorphous precipitate, produced initially by the reaction of introduced CO₂, transformed to bayerite via pseudoboehmite during aging. It was found that the crystalline particle size and morphology of the crystallized bayerite change depending systematically on the preparation conditions. The reaction pathway of the thermal decomposition of the synthesized bayerite was investigated by using thermoanalytical techniques. This revised version was published online in July 2006 with corrections to the Cover Date.     

Formation of ice nanotube with hydrophobic guests inside carbon nanotube

A composite ice nanotube inside a carbon nanotube has been explored by molecular-dynamics and grand canonical Monte Carlo simulations. It is made from an octagonal ice nanotube whose hollow space contains hydrophobic guest molecules such as neon, argon, and methane. It is shown that the attractive interaction of the guest molecules stabilizes the ice nanotube. The guest occupancy of the hollow space is calculated by the same method as applied to clathrate hydrates.     

Synthesis of calix[4]arene library substituted with peptides at the upper rim

A fluorescence-labeled calix[4]arene library substituted with peptides at the upper rim was synthesized. Screening of the library for binding a dye-labeled oligopeptide indicated that some peptidocalix[4]arenes selectively bind the oligopeptide. The chemosensitivity of the library members for a target peptide was also investigated.     

Drag reduction in spatially developing turbulent boundary layers by spatially intermittent blowing at constant mass-flux

A series of large-eddy simulations of spatially developing turbulent boundary layers with uniform blowing at moderate Reynolds numbers (based on free-stream velocity, U_∞, and momentum thickness, θ) up to Re_θ ≈ 2500 were performed with the special focus on the effect of intermittent (separated in streamwise direction) blowing sections. The number of blowing sections, N, investigated is set to be 3, 6, 20, 30 and compared to N = 1, which constitutes the reference case, while the total wall-mass flux is constrained to be the same for all considered cases, corresponding to a blowing amplitude of 0.1% of U_∞ for the reference case. Results indicate that the reference case provides a net-energy saving rate of around 18%, which initially decreases at most 2% points for N = 3 but recovers with increasing N, where the initial reduction of the drag reduction is found to be related to the shorter streamwise length of the intermittent blowing sections. The physical decomposition of the skin friction drag through the Fukagata-Iwamoto-Kasagi (FIK) identity shows that the distribution of all components over each blowing section has similar trends, resulting in similar averaged values over the whole control region.     

A synthesis of lumazine derivatives

Treatment of 6-amino-1,3-dimethyl-5-nitrosouracil (Ia) with dimethyl acetylenedicarboxylate (DMAD) in dimethylformamide (DMF) afforded 6,7-bis(dimethoxycarbonyl)-1,3-dimethyllumazine (II). Similarly, the reaction of 6-amino-1,3-dimethyl-5-phenylazouracil with DMAD gave also II. Hydrolysis of II with hydrochloric acid gave 1,3-dimethyllumazine-6-carboxylic acid (III). III was chlorinated with thionyl chloride and then aminated with ethanolic ammonia to give rise to 6-carbamoyl-1,3-dimethyllumazine (V). V was alternatively synthesized by the treatment of Ia with propiolamide in DMF.     

Novel isomerization of dibenzocyclooctadiene lignan lactone —first synthesis of (±)-stegane—

(±)-Isostegane isomerized into (+-)-isopicrostegane, (±)-picrostegane, and (±)-stegane, the parent compound o steganacin-type dibenzocyclooctadiene lignan lactones.     

Rheological properties of physical gel formed by hydrophobically modified urethane ethoxylate (HEUR) associative polymers in methanol–water mixtures

We investigated the effects of methanol on the two rheological properties, dynamic modulus and flow behaviour, for an aqueous solution of hydrophobically ethoxylated urethane (HEUR). When the added methanol constitutes 0–10 mol% of the sample, the gel relaxation time shortens; when it constitutes 20 mol% of the sample, the distribution of relaxation times broadens. Relaxation of the physical gel formed by a transient network is directly related to the lifetime of the crosslink points, i.e. flower micelles. We speculate that methanol addition shortens the relaxation time by changing the hydrophobic interactions in the flower micelles. The changed hydrophobic interactions then affect not only the relaxation time but also the shape of the HEUR-chain molecular associating structures which in turn affects the mechanical spectrum. Under constant shear flow, shear thickening increases with increasing methanol concentration, and the increase in stress under constant shear flow shows unusual behaviour. A possible contributing factor to this behaviour may be the non-cosolvency of methanol with polyethyleneoxide (PEO). At some critical concentration, methanol in PEO aqueous solution becomes a poor solvent, which then affects the properties of the PEO chains in the transient networks of HEUR aqueous solution. The rheological properties of the transient networks clearly affect the properties of both the crosslink points and the chains. In short, methanol addition induces complicated changes in gel mechanical properties.