Novel pattern formation in the collapse process of floating monolayer at the air-water interface

We have observed a remarkable two-armed spiral in the collapse process of a floating monolayer at the air-water interface by phase contrast microscopy. This demonstrates that the floating monolayer as a form of soft condensed matter reorganizes itself due to a certain kind of macroscopic or collective behavior of molecules as it collapses. This pattern formation is caused by the breakdown of a critical dynamical balance between the deformation of solid domain and the applied surface pressure. The fragility as well as the flexibility of the floating monolayer can be associated with the observed pattern growth. There are also observed interesting, periodically arranged collections of molecules in numerous collapsed regions. Received: 8 July 1997 / Accepted: 4 November 1997     

Conformation and Atropisomeric Properties of Indometacin Derivatives

The stereochemistry around the N‐benzoylated indole moiety of indometacin was studied by restricting the rotation about the N? C7′ and/or C7′? C1′ bond. In the 2′,6′‐disubstituted ones, an atropisomeric property was found and the atropoisomers were separated and isolated as stable forms. Their biological abilities to inhibit cyclooxygenase‐1 (COX‐1) and cyclooxygenase‐2 (COX‐2) were examined. Only the aR‐isomer showed specific inhibition of COX‐1, and COX‐2 was not inhibited by either atropisomer. Conformational analysis in NMR studies and X‐ray crystallography, and CD spectra in combination with calculations were utilized to elucidate the bioactive conformations.     

Self‐Replication and Amplification of Enantiomeric Excess of Chiral Multifunctionalized Large Molecules by Asymmetric Autocatalysis

Self‐replication of large chiral molecular architectures is one of the great challenges and interests in synthetic, systems, and prebiotic chemistry. Described herein is a new chemical system in which large chiral multifunctionalized molecules possess asymmetric autocatalytic self‐replicating and self‐improving abilities, that is, improvement of their enantioenrichment in addition to the diastereomeric ratio. The large chiral multifunctionalized molecules catalyze the production of themselves with the same structure, including the chirality of newly formed asymmetric carbon atoms, in the reaction of the corresponding achiral aldehydes and reagent. The chirality of the large multifunctionalized molecules controlled the enantioselectivity of the reaction in a highly selective manner to construct multiple asymmetric stereogenic centers in a single reaction.     

A variational principle for the Navier-Stokes equation

Motivated from Arnold's variational characterization of the Euler equation in terms of geodesic families of diffeomorphisms, a variational principle for the motion of incompressible viscous fluids is presented. A volume preserving diffusion process with drift velocity field subject to the Navier-Stokes equation is shown to extremize the energy functional of the fluid under a certain class of stochastic variations.     

Stochastic quantization: A review

The present status of the work on the application of the stochastic quantization procedure is reviewed. A compact mathematical introduction to the basic notions of random processes such as Markov processes, Martingales and Fokker-Planck equations is presented. The stochastic quantization procedure is explained in much detail and it is found to possess remarkable features which can not be achieved within the conventional framework of quantum theory. This admits us to give systematic analyses of irreversible quantum dynamics of dissipative systems and the vacuum tunneling phenomena in non-Abelian gauge theory     

Thermal mechanics: A quantum mechanical analogue of nonequilibrium statistical thermodynamics

A formal but not conventional equivalence between stochastic processes in nonequilibrium statistical thermodynamics and Schrödinger dynamics in quantum mechanics is shown. It is found, for each stochastic process described by a stochastic differential equation of Itô type, there exists a Schrödinger-like dynamics in which the absolute square of a wavefunction gives us the same probability distribution as the original stochastic process. In utilizing this equivalence between them, that is, rewriting the stochastic differential equation by an equivalent Schrödinger equation, it is possible to obtain the notion of deterministic limit of the stochastic process as a semi-classical limit of the “Schrödinger” equation. The deterministic limit thus obtained improves the conventional deterministic approximation in the sense of Onsager-Machlup. The present approach is valid for a general class of stochastic equations where local drifts and diffusion coefficients depend on the position. Two concrete examples are given. It should be noticed that the approach in the present form has nothing to do with the conventional one where only a formal similarity between the Fokker-Planck equation and the Schrödinger equation is considered.     

Periodic knolls and valleys: coexistence of solid and liquid states in granular suspensions

We report the spontaneous emergence of a doubly periodic train of sedimented knolls in a dense suspension. These solidified knolls rise out of, and coexist alongside, a sea of freely flowing liquid in a slowly rotating horizontal bottle. We apply a variable viscosity model that permits simultaneous analysis of fluidlike and solidlike behaviors that are ubiquitous in a variety of sedimenting flows. The model generates qualitative agreement with experiments, and produces new insights into mechanisms by which sedimented structures form.     

Rod-like liquid crystals of organic transition metal complexes. I. Reversible transformation between blue smectogen and red nematogen

Two novel types of transition-metal-containing liquid crystals, bis(p-n-koxydithiobenzoato)nickel(II) (abbreviated as (C_nO-DTB)₂Ni), and (p-n-alkoxydithiobenzoato)(p-n-alkoxyperthiobenzoato)nickel(II) (abbreviated as (C_nO-DTB)(C_nO-PTB)Ni), were synthesized. It was found that the (C_nO-DTB)₂Ni complex for n = 8 has smectic H and C mesophases, and that the (C_nO-DTB)₂Ni complexes for n = 4 and 8 easily transform into the corresponding monoperthio complexes, _nO-PTB)Ni, by heating at temperatures between 230°C and 285°C. It was confirmed that the transformation originates from an intermolecular reaction between the (C_nO-DTB)₂Ni complexes at high temperatures, and that the origin of the extra sulphurs in the resulting (C_nO-DTB)(C_nO-PTB)Ni complexes is the neighbouring (C_nO-DTB)₂Ni complexes. Interestingly, each of the (C_nO-DTB)(C_nO-PTB)Ni complexes (n = 4 and 8), has nematic mesophase and exhibits a unique double melting behaviour via the nematic phase, which is the first example in liquid crystals. The reversible transformation between the blue smectic rod-like (C_nO-DTB)₂Ni complex and the red nematic Λ-like (C_nO-DTB)(C_nO-PTB)Ni complex is possible.