Protecting structure analyses of organic molecule-protected nanoscopic noble metal clusters

The stabilizing structure of cationic surfactant-protected platinum clusters in water and tertiary amine-protected rhodium clusters in chloroform, prepared by photo- and hydrogen-reduction, respectively, was investigated. These nanoscopic noble metal clusters present a narrow size distribution and are stable. The structural information of protective organic molecules on the surface of metal clusters was studied by transmission electron microscopy and hydrodynamic radius measurements according to the Taylor dispersion method. The size of the entire cluster with the protective layer surrounding the metal surface, obtained as Stokes' radii by the Taylor dispersion method, is considered to be fairly consistent with the sum of the naked particle size, obtained by transmission electron micrographs, and the size of the adsorbed protective layer, supporting the conformational information.     

Estimating the amplitude of measurement noise present in chaotic time series

We propose a method for estimating the amplitude of measurement noise present in chaotic time series. This method is based on the evaluation of initial errors for a given time series and for a new one synthesized by adding an adequate amount of noise to the given one. The method is valid over a much wider range of noise levels than the previous methods are because it is not based on the detail of dynamical structure which generates the data. In addition, it is possible to check if the method is valid for the given data prior to its application. To confirm the effectiveness of the method we show the results of numerical experiments and apply the method to chaotic data obtained from an electrochemical experiment. (c) 1999 American Institute of Physics.     

Inside view of cell locomotion through single-molecule: fast F-/G-actin cycle and G-actin regulation of polymer restoration

The actin cytoskeleton drives cell locomotion and tissue remodeling. The invention of live-cell fluorescence single-molecule imaging opened a window for direct viewing of the actin remodeling processes in the cell. Since then, a number of unanticipated molecular functions have been revealed. One is the mechanism of F-actin network breakdown. In lamellipodia, one third of newly polymerized F-actin disassembles within 10 seconds. This fast F-actin turnover is facilitated by the filament severing/disrupting activity involving cofilin and AIP1. Astoundingly fast dissociation kinetics of the barbed end interactors including capping protein suggests that F-actin turnover might proceed through repetitive disruption/reassembly of the filament near the barbed end. The picture of actin polymerization is also being revealed. At the leading edge of the cell, Arp2/3 complex is highly activated in a narrow edge region. In contrast, mDia1 and its related Formin homology proteins display a long-distance directional molecular movement using their processive actin capping ability. Recently, these two independently-developed projects converged into a discovery of the spatiotemporal coupling between mDia1-mediated filament nucleation and actin disassembly. Presumably, the local concentration fluctuation of G-actin regulates the actin nucleation efficiency of specific actin nucleators including mDia1. Pharmacological perturbation and quantitative molecular behavior analysis synergize to reveal hidden molecular linkages in the actin turnover cycle and cell signaling.     

Chain-terminus triggered chiral memory in an optically inactive 3(10)-helical peptide

A new optically inactive 3(10)-helical peptide with a side-chain cross-linking was found to exhibit chiral memory stored in the peptide backbone, whose chirality was induced by a noncovalent interaction of a chiral molecule at the N-terminal end of the peptide.     

DFT studies of the characteristics of Pd−Pt core-shell clusters

It is reported that Pd?Pt core-shell type nanoclusters in which the inner atoms of the Pd cluster are substituted by Pt significantly enhance the catalytic activity for cycloocatdiene hydrogenation. In order to discuss the electronic states of core-shell clusters, DFT calculations were carried out for Pd₁₃, Pt₁₃, Pt/Pd₁₂, Pd/Pt₁₂ Pd₃₈ and Pd₆/Pt₃₂ clusters. From these calculations, it was found that the charge transfer between the core atoms and the shell atoms played an important role for the modification of the electronic state of the surface atoms in them.     

Pd(II)-catalyzed asymmetric addition of malonates to dihydroisoquinolines

We have developed a highly efficient reaction for catalytic asymmetric addition of malonates to dihydroisoquinolines using chiral Pd(II) complexes. In the reactions, substrates with various substitution patterns were available, and the reactions were complete within several hours (<3 h in most cases) under mild reaction conditions, affording various optically active C1-substituted tetrahydroisoquinoline derivatives (up to 98% yield, up to 97% ee). Furthermore, slow addition of DDQ allowed the in situ generation of the reactive intermediate from the corresponding N-Boc-protected amine, and dehydrogenative addition reaction was successfully demonstrated.     

Deposition of thin mesoporous silica films on glass substrates from basic solution

Transparent thin (ca. 100 nm) films of silica-surfactant mesostructured materials were deposited on borosilicate glass plates and soda-lime glass tubes from aqueous solutions containing tetraethoxysilane, alkyltrimethylammonium chloride, ammonia, and methanol. By calcination in air, the films became mesoporous (BET surface area of 700-900 m2 g-1) with pore diameter 2.0-2.8 nm.     

Efficient approach to 1,2-diazepines via formal diazomethylene insertion into the C-C bond of cyclobutenones

Efficient monocyclic 1,2-diazepine formation via a tandem electrocyclization reaction of cyclobutenones with lithiodiazoacetate is demonstrated. The reaction proceeds through an oxy anion-accelerated 4π-ring opening of cyclobutene followed by an 8π-ring closure of the resultant oxy anion-substituted diazo-diene under mild conditions to furnish a 1,2-diazepine via formal diazomethylene insertion into the C-C bond of cyclobutenone.