Helicity Induction and Memory of the Macromolecular Helicity in a Polyacetylene Bearing a Biphenyl Pendant

A novel, cis‐transoidal poly‐(phenylacetylene) bearing a carboxybiphenyl group as the pendant (poly‐ 1 ) was prepared by polymerization of (4′‐ethoxycarbonyl‐4‐biphenylyl)acetylene with a rhodium catalyst followed by hydrolysis of the ester groups. Upon complexation with various chiral amines and amino alcohols in dimethyl sulfoxide (DMSO), the polymer exhibited characteristic induced circular dichroism (ICD) in the UV/Vis region due to the predominantly one‐handed helix formation of the polymer backbone as well as an excess of a single‐handed, axially twisted conformation of the pendant biphenyl group. Poly‐ 1 complexed with (R)‐2‐amino‐1‐propanol showed unique time‐dependent inversion of the macromolecular helicity. Furthermore, the preferred‐handed helical conformation of poly‐ 1 induced by a chiral amine was further “memorized” after the chiral amine was replaced with achiral 2‐aminoethanol or n‐butylamine in DMSO. In sharp contrast to the previously reported memory in poly((4‐carboxyphenyl)acetylene), the present helicity memory of poly‐ 1 was accompanied by memory of the twisted biphenyl chirality in the pendants. Unprecedentedly, the helicity memory of poly‐ 1 with achiral 2‐aminoethanol was found to occur simultaneously with inversion of the axial chirality of the biphenyl groups followed by memory of the inverted biphenyl chirality, thus showing a significant change in the CD spectral pattern.     

Amplified Chirality Transfer to Aromatic Molecules through Non-specific Inclusion by Amorphous,Hyperbranched Poly(fluorenevinylene) Derivatives

Optically active, hyperbranched, poly(fluorene-2,4,7-triylethene-1,2-diyl) [poly(fluorenevinylene)] derivatives bearing a neomenthyl group and a pentyl group at the 9-position of the fluorene backbone at various ratios acted as a chirality donor (host polymers) efficiently included naphthalene, anthracene, pyrene, 9-phenylanthracene, and 9,10-diphenyanthracene as a chirality acceptor (guest molecules) in their interior space in film as well as in solution, with the guest molecules exhibiting intense circular dichroism through chirality transfer with chirality amplification. The efficiency of the chirality transfer was much higher with higher-molar-mass polymers than lower-molar-mass ones as well as with hyperbranched polymers compared to the analogous linear ones. The hyperbranched polymers include the small molecules in their complex structure without any specific interactions at various stoichiometries. The included molecules may have ordered intermolecular arrangement that may be somewhat similar to those of liquid crystals. Naphthalene, anthracene, and pyrene included in the polymer exhibited efficient circularly polarized luminescence, where the chirality was remarkably amplified in excited states, and anthracene exhibited especially high anisotropies in the emission on the order of 10⁻².     

Second order optimality for estimators in time series regression models

We consider the second order asymptotic properties of an efficient frequency domain regression coefficient estimator proposed by Hannan [Regression for time series, Proc. Sympos. Time Series Analysis (Brown Univ., 1962), Wiley, New York, 1963, pp. 17-37]. This estimator is a semiparametric estimator based on nonparametric spectral estimators. We derive the second order Edgeworth expansion of the distribution of . Then it is shown that the second order asymptotic properties are independent of the bandwidth choice for residual spectral estimator, which implies that has the same rate of convergence as in regular parametric estimation. This is a sharp contrast with the general semiparametric estimation theory. We also examine the second order Gaussian efficiency of . Numerical studies are given to confirm the theoretical results.     

A new control scheme of multilevel quantum system based on effective decomposition by intense CW lasers

We propose a new scheme for quantum dynamics control of multilevel system using intense lasers. To do so, we apply intense CW lasers to create a strongly coupled subsystem with which one can make the complementary space effectively isolated, and we apply the established control schemes to the isolated subsystem. We have also obtained an effective Hamiltonian for the target subsystem with the help of the second-order perturbation theory. Numerical demonstrations on model systems show that the present decomposition scheme effectively works for population dynamics control. It is also found that relaxation processes can be suppressed under the proposed scheme.     

Static and dynamical magnetic characters in doped Cu oxides

The discovery of the spin density wave (SDW) state defined as stripe in the doped Cu oxides becomes a central issue in the elucidation of the high-temperature superconducting mechanism. We present the coexistence of the stripe order and superconductivity, and the change of the stripe structure associated with the insultor–metal transition. Both static and dynamical SDW are robust of the high-temperature superconducting Cu oxides.     

Shape Estimation of Anisometric Particles Using Size Measurement Techniques

This study was conducted to establish a simple method for evaluating the morphology of fine anisometric particles using size measurement techniques. The size distributions of mica particles and carbon fibers classified into narrower size ranges were measured by gravitational sedimentation and laser diffraction techniques. The ratio of mean diameters determined for flaky particles strongly depended on the aspect ratio, i.e. flatness. The relationship between particle shape and diameter is discussed theoretically. The experimental results were similar to those predicted. The flatness of fine particles can be evaluated by the ratio of the median diameter determined by laser diffraction to that determined by sedimentation.