Synthesis of a porphyrin-fullerene pinwheel

We disclose the synthesis of a porphyrin-fullerene pinwheel that was subsequently observed by scanning tunneling microscopy. The molecule was designed to further our understanding of fullerene-surface interactions, directional control, and surface-rolling versus pivoting capabilities of this class of nanomachines. The inner porphyrin provides the square planar configuration that might lead to realization of the pinwheel spiraling motion on surfaces.     

In vitro translation with [<Superscript>34</Superscript>S]-labeled methionine,selenomethionine, and telluromethionine

Heteroisotope and heteroatom tagging with [³⁴S]-enriched methionine (Met), selenomethionine (SeMet), and telluromethionine (TeMet) was applied to in vitro translation. Green fluorescent protein (GFP) and JNK stimulatory phosphatase-1 (JSP-1) genes were translated with wheat germ extract (WGE) in the presence of Met derivatives. GFPs containing Met derivatives were subjected to HPLC coupled with treble detection, i.e., a photodiode array detector, a fluorescence detector, and an inductively coupled plasma mass spectrometer (ICP-MS). The activities of JSP-1-containing Met derivatives were also measured. GFP and JSP-1 containing [³⁴S]-Met and SeMet showed comparable fluorescence intensities and enzyme activities to those containing naturally occurring Met. TeMet was unstable and decomposed in WGE, whereas SeMet was stable throughout the experimental period. Thus, although Te was the most sensitive to ICP-MS detection among S, Se, and Te, TeMet was less incorporated into the proteins than Met and SeMet. Finally, the potential of heteroisotope and heteroatom tagging of desired proteins in in vitro translation followed by ICP-MS detection was discussed. Figure TeMet was less incorporated into GFP than Met and SeMet due to its instability in WGE     

Hydrolytic Degradation and Monomer Recovery of Poly(butylene succinate) and Poly(butylene succinate/adipate) in the Melt

Aliphatic dicarboxylic acid/aliphatic diol‐derived polyesters, poly(butylene succinate) and poly(butylene succinate/adipate), have been hydrolytically degraded in the melt in high‐temperature and high‐pressure water over a wide temperature range of 180–300 °C for periods of up to 30 min. The formation/decomposition of succinic acid (SA), adipic acid (AA), and butane‐1,4‐diol (BD), plus the molecular weight change of PBS and PBSA were then investigated. SA and AA were recovered at maximum yields of 65–80%, whereas BD was recovered at a maximum yield of only 30%, probably because of its decomposition. The obtained results were compared with those reported for aliphatic hydroxycarboxylic acid‐derived polyesters and aromatic dicarboxylic acid/aliphatic diol‐derived polyesters.

     

Tetrahedral Oligothiophenes; Synthesis,X‐ray Analysis,and Optoelectronic Properties of Highly Symmetrical, 3D‐Branched Oligothiophenes

Tetrakis(bithienyl)methane and tetrakis(terthienyl)methane have been synthesized from tetrakis(2‐thienyl)methane by use of Suzuki–Miyaura coupling as a key reaction. Their trimethylsilyl (TMS) derivatives are also synthesized. X‐ray analysis reveals that each oligothiophene moiety tends to adopt anti‐conformations and show relatively small torsion angles between the adjacent thiophene rings. While the longest absorption maxima of these tetrakis(oligothienyl)methanes exhibit only a slight bathochromic shift compared to the corresponding linear oligothiophene derivative, tetrakis(bithienyl)methane and its TMS derivative exhibit an appreciable red‐shift in their fluorescence spectra. The intramolecular interaction between thienyl groups of tetrakis(2‐thienyl)methane is supported by DFT calculation.     

Correlated equilibrium and concave games

This paper shows that if a game satisfies the sufficient condition for the existence and uniqueness of a pure-strategy Nash equilibrium provided by Rosen (Econometrica 33:520, 1965), then the game has a unique correlated equilibrium, which places probability one on the unique pure-strategy Nash equilibrium. In addition, it shows that a weaker condition suffices for the uniqueness of a correlated equilibrium. The condition generalizes the sufficient condition for the uniqueness of a correlated equilibrium provided by Neyman (Int J Game Theory 26:223, 1997) for a potential game with a strictly concave potential function. I thank the editor, an associate editor, and an anonymous referee for detailed comments and suggestions, which have substantially improved this paper. Special thanks are due to the referee for pointing out Lemmas 4 and 5. I acknowledge financial support by The Japan Economic Research Foundation and by MEXT, Grant-in-Aid for Scientific Research. All remaining errors are mine.     

A strong bound on the integral of the central path curvature and its relationship with the iteration-complexity of primal-dual path-following LP algorithms

The main goals of this paper are to: i) relate two iteration-complexity bounds derived for the Mizuno-Todd-Ye predictor-corrector (MTY P-C) algorithm for linear programming (LP), and; ii) study the geometrical structure of the LP central path. The first iteration-complexity bound for the MTY P-C algorithm considered in this paper is expressed in terms of the integral of a certain curvature function over the traversed portion of the central path. The second iteration-complexity bound, derived recently by the authors using the notion of crossover events introduced by Vavasis and Ye, is expressed in terms of a scale-invariant condition number associated with m × n constraint matrix of the LP. In this paper, we establish a relationship between these bounds by showing that the first one can be majorized by the second one. We also establish a geometric result about the central path which gives a rigorous justification based on the curvature of the central path of a claim made by Vavasis and Ye, in view of the behavior of their layered least squares path following LP method, that the central path consists of long but straight continuous parts while the remaining curved part is relatively “short”. R. D. C. Monteiro was supported in part by NSF Grants CCR-0203113 and CCF-0430644 and ONR grant N00014-05-1-0183. T. Tsuchiya was supported in part by Japan-US Joint Research Projects of Japan Society for the Promotion of Science “Algorithms for linear programs over symmetric cones” and the Grants-in-Aid for Scientific Research (C) 15510144 of Japan Society for the Promotion of Science.     

Spontaneous formation of a chiral supramolecular superhelix in the crystalline state using a single-stranded tetranuclear metallohelicate

An unprecedented one-handed coiled-coil structure was formed in the crystal of a Zn(3)La tetranuclear metallohelicate, in which the handedness of both the helical component and the helical array was well controlled by the chiral auxiliary of the flexible acyclic ligand.     

Electrochemical activity of nanocrystalline Fe3O4 in aprotic Li and Na salt electrolytes

Fe₃O₄ powders, whose average particle sizes were 400 nm, 100 nm, and 10 nm in diameter, were prepared in order to investigate the effect of particle size on their electrochemical activity. X-ray diffraction and electron microscopy measurements confirmed that all the prepared samples were identified as inverse-spinel type Fe₃O₄, whose crystallite/particle sizes were between 400 nm and 10 nm. We found that the electrochemical activity of Fe₃O₄ in a lithium salt electrolyte was enhanced with a decrease in the particle size from 400 nm to 10 nm. The 10 nm nanocrystalline Fe₃O₄ powder demonstrated the high discharge capacities of about 130 and 160 mAh g⁻¹ with a satisfactory capacity retention as the active cathode material of Li and Na batteries, respectively.     

Facile unidirectional alignment of mesochannels in a mesoporous silica film on a freshly cleaved mica surface

The alignment of mesochannels in a mesoporous silica film on a freshly cleaved mica surface, prepared by an evaporation-induced self-assembly process, is unexpectedly found to be unidirectional with the narrowest directional distribution.