The variational theory and rate equation method with applications to relaxation near the instability point

The variational principle of Glansdorff and Prigogine is formulated for stochastic processes and the relation between this method and the rate equation method is discussed in a certain frame-work of variational functions. An application is given to the Fokker-Planck equation to describe the formation process of macroscopic order and to obtain the onset time.     

Monte Carlo simulations of the two-dimensional quantal and classical spin systems — A new type of phase transition with vortices

A new type of phase transition has been found in the two-dimensional XY-model using Monte Carlo simulations, which show a divergence of susceptibility, but no divergence of specific heat. Vortices appear below T_c as was predicted by Kosterlitz and Thouless.     

Colloidal Quantum Dot Arrangement Assisted by Perylene Bisimide Self-Assembly

Colloidal semiconductor nanocrystals, so-called quantum dots (QDs), are attractive as molecular-like smart nanomaterials, and their emission and optoelectronic properties in the dispersed state have been actively studied. The construction of supramolecular structures composed of multiple QDs, however, is still challenging. Here, a new strategy to form supramolecular QD structures via self-assembly of perylene bisimide (PBI) dyes is demonstrated. In a mixed solution, QDs and PBI undergo time-dependent fusion to form an isolated colloidal QD-PBI complex or a unique QD-PBI co-aggregate composed of QDs arranged along a sheet-like PBI nanostructure, and these dramatically different supramolecular structures can be controlled by the solvent polarity.     

Theoretical calculation of N.M.R. spectral line shapes

The line shape of a multiplet proton resonance changes greatly as the rate of relaxation of a nuclear spin I to which the proton is coupled increases. In order to show that such complex line shapes are generally accessible to theoretical analysis, examples of line contours are calculated and shown graphically for I = 1, 3/2, 2, 5/2 and 3.     

Irreversibility and entropy production in transport phenomena,III—Principle of minimum integrated entropy production including nonlinear responses

A new variational principle of steady states is found by introducing an integrated type of energy dissipation (or entropy production) instead of instantaneous energy dissipation. This new principle is valid both in linear and nonlinear transport phenomena. Prigogine’s dream has now been realized by this new general principle of minimum “integrated” entropy production (or energy dissipation). This new principle does not contradict with the Onsager–Prigogine principle of minimum instantaneous entropy production in the linear regime, but it is conceptually different from the latter which does not hold in the nonlinear regime. Applications of this theory to electric conduction, heat conduction, particle diffusion and chemical reactions are presented.     

Synthesis of pentacene-, tetracene- and anthracene bisimides using double-cyclization reaction mediated by bismuth(III) triflate

Novel bisimide-fused acenes were synthesized via bismuth triflate mediated double-cyclization reaction of acid chlorides and isocyanates. Their optical and electrical properties revealed significantly smaller HOMO-LUMO gaps compared with those of their parent acenes. Fabricated OFET based on tetracene bisimide showed n-type OFET outputs.     

Design and synthesis of novel 7-[(N-substituted-thioureidopiperazinyl)-methyl]-camptothecin derivatives as potential cytotoxic agents

Abstract

As part of continuing our research on diverse C-7 derivatives of camptothecin (CPT), 16 CPT derivatives bearing piperazinyl-thiourea chemical scaffold and different substituent groups have been designed, synthesized and evaluated in vitro for cytotoxicity against five tumor cell lines (A-549, MDA-MB-231, MCF-7, KB and KBvin). As a result, all the synthesized compounds showed promising in vitro cytotoxic activity against the five tumor cell lines tested, and were more potent than irinotecan. Importantly, compounds 13?g (IC₅₀ = 0.514?μM) and 13o (IC₅₀ = 0.275?μM) possessed similar or better antiproliferative activity against the multidrug-resistant (MDR) KBvin subline than that of topotecan (IC₅₀ = 0.511?μM) and merit further development as anticancer candidates for clinical trail. With these results in hand, we have a reason to conclude that incorporating piperazinyl-thiourea motifs into position-7 of camptothecin confers well cytotoxic activity against cancer cell lines, probably resulting in new anticancer drugs.     

Mössbauer studies of Jarosite, Mikasaite and Yavapaiite, and implication to their Martian counterparts

In order to confirm Mössbauer spectra of Jarosite, unidentified Fe³⁺ species (Fe3D3) and Fe₂O₃ found on Martian surface, some Jarosite specimens produced on Earth were characterized by ⁵⁷Fe Mössbauer spectroscopy. For comparison, anhydrous ferric sulfate minerals, Mikasaite (Fe³⁺ _1.56Al_0.44)(SO₄)₃, and Yavapaiite, KFe (SO₄)₂ were also measured. The thermal decomposition products of Jarosite and their hydration products were also traced by scattering Mössbauer spectra (CEMS and XMS). These data are useful for the identification of hydrous and anhydrous ferric sulfate phases on Mars, including Fe3D3.     

Interaction of Near-Field Light with Ordered Polystyrene Spheres: Experimental Studies

We have experimentally observed the interaction of near-field light excited in a total internal reflection geometry with a periodic two-dimensional array of polystyrene spheres. The angular- and frequencyscanned attenuated-total-reflection (ATR) method was employed to observe the interaction. ATR spectra indicate that there is an easy axis and a difficult axis for the light propagation. When light is incident toward the easy axis, resonant dips appear in the ATR spectra. The experimental results were compared with those obtained by finite-difference time-domain analysis. The numerical results obtained by this method are able to explain a part of the experimental ones. Parts of the dips in the ATR spectra were considered to stem from propagating and whispering-gallery (WG) modes. That is, the propagation of the WG-modes over several spheres may enhance the coupling between the spheres and the incident light, and consequently may induce resonant structures in the ATR spectra.This paper was originally presented at the 5th International Conference on NEAR FIELD OPTICS and RELATED TECHNOLOGIES (NFO-5), which was held on December 6–10, 1998 at Coganoi Bay Hotel, Shirahama, Japan, in cooperation with the Japan Society of Applied Physics and Mombusho Grant-in Aid for Scientific Research on Priority Areas “Nearfield Nano-optics” Project, sponsored by Japan Society for the Promotion of Science.     

Regioselective oxidative polymerization of 1,5-dihydroxynaphthalene catalyzed by bilirubin oxidase in a water–organic solvent mixed solution

Bilirubin oxidase (EC1.11.1.7) was used to catalyze the oxidative polymerization of 1,5-dihydroxynaphthalene to its polymer in a mixed solvent composed of dioxane, ethyl acetate, and acetate buffer. In an aqueous solution, the enzymatic oxidative polymerization hardly occurred and resulted in negligible yield mainly due to the poor solubility of 1,5-dihydroxynaphthalene. In the mixed solvent the conversion proceeded with a yield of ca. 70%. The polymer yield was studied with respect to reaction time and solvent components. Elemental analysis, UV-visible, fluorescent, and FT-IR spectroscopic analyses, proton NMR and electrochemical studies, and solubility in various organic solvents revealed that 1,5-dihydroxynaphthalene is polymerized by the C? C coupling. The molecular weight of the polymeric products solubilized with DMF varied from low molecular weight product to high molecular weight polymer. From the chromatographic studies, the organic solvent–insoluble residue was suggested to be highly polymerized material. Based on these findings a possible mechanism for enzymatic polymerization of 1,5-dihydroxynaphthalene is presented: less stable intermediates produced enzymatically from 1,5-dihydroxynaphthalene undergo coupling and polymerization to ortho-1,5-dihydroxynaphthalene polymer, thereby resulting in a regioselective polymerization of 1,5-dihydroxynaphthalene. © 1993 John Wiley & Sons, Inc.