Entropy production in a two-dimensional reversible Gray-Scott system

The entropy production sigma is calculated in the time evolution processes toward a Turing-like pattern and a chaotic pattern in a two-dimensional reaction-diffusion system. The contributions of reaction and diffusion to the entropy production are evaluated separately. Though its contribution to total sigma is about 5%, the entropy production in diffusion foretells the moving direction of the dots (reaction spots) and the line-shaped patterns. The entropy production of the entire system sigma depicts well the cooperative dynamics and evolution of chaotic dot patterns. It is suggested that sigma can be a scalar measure for quantitative studies of hierarchic pattern dynamics. The relation is also discussed between the bifurcation parameter and the distance from thermodynamic equilibrium.     

Infrared spectroscopic study of polytypic effects on the crystal-growth mechanism of n-hexatriacontane (n-C36H74)

The solution-crystallization mechanism was investigated for two polytypes in the M011 modification of n-hexatriacontane (n-C36H74), single-layered structure Mon, and double-layered one Orth II. The crystal growth under controlled supersaturation was followed with a micro- Fourier-transform-infrared spectrometer equipped with an optical system for oblique transmission measurements. Supersaturation dependence of growth behavior was significantly different between Mon and Orth II. Although the Mon crystal continued growing at a supersaturation of 0.27, the overgrowth of Orth II on the (001) face of the Mon crystal was confirmed at supersaturations below 0.21. Such a polytypic transformation was not observed for the Orth II crystal at any supersaturation below 0.30. The growth rate of Mon showed a quadratic dependence on supersaturation, while that of Orth II was approximately linear, suggesting spiral growth and two-dimensional-nucleation mechanisms for Mon and Orth II, respectively.     

Synthesis of ordered copolyamides by the interfacial polycondensation of the hydrolyzate of bisimidazoline with diacid chloride

Ordered copolyamides were prepared by the interfacial polycondensation of the hydrolyzate of bisimidazoline in the aqueous solution with diacid chloride in chloroform solution; bisimidazolines used were 1,4-bis(imidazoline-2-yl)butane and 1,4-bis(imidazoline-2-yl)-octane; diacid chlorides used were adipoyl chloride, sebacoyl chloride, and terephthaloyl chloride. The aqueous solutions of the hydrolyzates of bisimidazolines were prepared by heating the aqueous solutions of imidazolines at 70°C. It was shown by infrared spectra and paper electrophoresis of the hydrolyzates that bisimidazolines were hydrolyzed to give quantitatively diamines containing amides linkages of the type H₂N(CH₂)₂NH-CORCONH(CH₂)₂NH₂. The regularity in the sequence of the copolyamide of nylon 26 and nylon 2T prepared from the hydrolyzate of 1,4-bis(imidazoline-2-yl)butane and terephthaloyl chloride was studied by NMR spectrometry: it was concluded that the copolyamide was highly ordered.     

Radiation-induced bulk polymerization of maleimide

Radiation-induced bulk polymerization of maleimide in both solid and liquid states was studied. Benzoquinone inhibited the liquid-state polymerization and retarded solid-state polymerization. The results of ESR study showed that solid monomer irradiated at 61°C. gave a spectrum, the concentration of which slowly decreased without changing the shape at 61°C. The radical detected at 61°C. was shown not to be the main propagating species. Overall rate polymerizations in the liquid and solid states were expressed, respectively, by first-order and zero-order rate equations with respect to the concentration of monomer. The overall rate constants in liquid and solid states were proportional to I^0.9 and I^1.0, respectively.     

Formation of ordered mesoscopic polymer arrays by dewetting

It could be shown that by a simple casting process from solution two-dimensionally ordered arrays of mesoscopic (i.e., in the range of submicrometer to micrometer) polymer aggregates on solid substrates can be formed. Patterns were investigated by optical microscopy and atomic force microscopy. The pattern formation was observed in situ by optical and fluorescence microscopy and it was found that a "fingering instability" at the three-phase-line of a solution droplet is the crucial process for pattern formation. (c) 1999 American Institute of Physics.     

Generalized CRF-structures

A generalized F-structure is a complex, isotropic subbundle E of \({T_cM \oplus T^*_cM}\) (\(T_cM = TM \otimes_{{\mathbb{R}}} {\mathbb{C}}\) and the metric is defined by pairing) such that \(E \cap \bar{E}^{\perp} = 0\). If E is also closed by the Courant bracket, E is a generalized CRF-structure. We show that a generalized F-structure is equivalent with a skew-symmetric endomorphism Φ of \(TM \oplus T^*M\) that satisfies the condition Φ³ +  Φ =  0 and we express the CRF-condition by means of the Courant-Nijenhuis torsion of Φ. The structures that we consider are generalizations of the F-structures defined by Yano and of the CR (Cauchy-Riemann) structures. We construct generalized CRF-structures from: a classical F-structure, a pair \(({\mathcal{V}}, \sigma)\) where \({\mathcal{V}}\) is an integrable subbundle of TM and σ is a 2-form on M, a generalized, normal, almost contact structure of codimension h. We show that a generalized complex structure on a manifold M? induces generalized CRF-structures into some submanifolds \(M \subseteq \tilde{M}\) . Finally, we consider compatible, generalized, Riemannian metrics and we define generalized CRFK-structures that extend the generalized Kähler structures and are equivalent with quadruples (γ, F ₊, F _?, ψ), where (γ, F _±) are classical, metric CRF-structures, ψ is a 2-form and some conditions expressible in terms of the exterior differential d ψ and the γ-Levi-Civita covariant derivatives ? F _± hold. If d ψ =  0, the conditions reduce to the existence of two partially Kähler reductions of the metric γ. The paper ends by an Appendix where we define and characterize generalized Sasakian structures.     

Asymmetric Total Synthesis of Cytotrienin A: Late-Stage Installation of C11 Side Chain onto the Macrolactam Scaffold

Cytotrienin A, an ansamycin-class antibiotic, exhibits potent apoptosis-inducing activity and has attracted much attention as a lead compound for anticancer drugs. Herein, we report a new asymmetric synthetic route to cytotrienin A, employing an unexplored approach involving the late-stage installation of a C11 side chain onto the macrolactam core. In this strategy, we utilized the redox properties of hydroquinone and installed a side chain on the sterically hindered C11 hydroxy group by the traceless Staudinger reaction. This study also demonstrated that the boron-Wittig/iterative Suzuki–Miyaura cross-coupling sequence was effective for the concise and selective construction of the (E,E,E)-conjugated triene moiety. The developed route opens new opportunities for the structure–activity relationship studies of the side chains of these ansamycin antibiotics and the preparation of other synthetic analogs and chemical probes for further biological studies.     

Electron microscopy investigations of the organization of cerium oxide nanocrystallites and polymers developed in polyvinylpyrrolidone-assisted polyol synthesis process

The microstructures and the organization mechanism of cerium oxide (ceria) nanospheres were investigated by transmission electron microscopy. The ceria nanospheres with the diameter of 50–150 nm were produced by the polyol synthesis method with cerium nitrate precursor and with polyvinylpyrrolidone (PVP) used as a protecting agent. Dose-limited observations performed by energy-filtering transmission electron microscopy revealed that the ceria nanospheres were the aggregated products consisting of ceria nanocrystallites ~3 nm in size and PVP-derived polymer products. It was found that the ceria nanocrystallites were oriented within the nanospheres by high-resolution transmission electron microscopy and selected-area electron diffraction. Selective adsorption of PVP on the crystal facets of the ceria nanocrystallites was suggested, and the aggregation of the PVP-adsorbed ceria through cross-linking reaction of PVP causes the crystal orientation.     

Binary organogelators which show light and temperature responsiveness

The gelation ability of 10 alkylammonium (CnH(2n+1)NH3+ where n=4-11, 12 and 16) anthracene-9-carboxylates (1n) has been evaluated. In cyclohexane, 1(4), 1(5), 1(6) and 1(7) only provided precipitates whereas 1(11), 1(12) and 1(16) provided very viscous solutions. In contrast, 1(8) 1(9) and 1(10) resulted in gels. The critical gelation concentration of 1(10) was very low (5.0 x 10(-4) mol dm(-3)). SEM observations showed that in the gel phase the morphology changes from straight fibrils to frizzy fibrils with the increase in n, whereas in the sol phase the formation of the sheet-like, two-dimensional aggregate is recognized. When the cyclohexane 1(10) gel was photoirradiated (lambda > 300 nm), the UV-VIS absorption bands assignable to monomeric anthracene were decreased and the gel was changed into the sol. It was confirmed by dark-field optical microscopy that the fibrillar bundles supporting the gel formation gradually disappear with photoirradiation time. When this sol was warmed at 30 degrees C in the dark, the gel was not regenerated but the precipitation of 1(10) resulted. When this sol was heated once at the bp of cyclohexane and cooled to 15 degrees C, the solution was changed into the gel again. This finding indicates that the fibrillar structure required for the gel formation is not reconstructed at 30 degrees C but obtained only when the hot cyclohexane solution is cooled.