Electrical Network of Single‐Crystalline Metal Oxide Nanoclusters Wired by π‐Molecules

In a mixed‐valence polyoxometalate, electrons are usually delocalized within the cluster anion because of low level of inter‐cluster interaction. Herein, we report the structure and electrical properties of a single crystal in which mixed‐valence polyoxometalates were electrically wired by cationic π‐molecules of tetrathiafulvalene substituted with pyridinium. Electron‐transport characteristics are suggested to represent electron hopping through strong interactions between cluster and cationic π‐molecules.     

Dissipative crystallization of aqueous mixtures of potassium salts of poly(riboguanylic acid) and poly(ribocytidylic acid)

Drying patterns of aqueous solutions of potassium salts of poly(riboguanylic acid) (KPolyG), poly(ribocytidylic acid) (KPolyC), and their mixtures KPolyG + KPolyC were studied on a cover glass, a watch glass, and a glass dish at room temperature. Accumulation of the polymers forming the broad rings near the outside edge and also in the inner area of the dried film was observed. The fine multiple ring structures formed, which supports the fact that the affinity of the polymer with the substrate is strong. Typical microscopic drying patterns of KPolyG, KPolyC, and KPolyG + KPolyC were spherulites, dendritic long rods, and sword (harberd)-like rods, respectively. The patterns changed depending on the location in the dried film. The dendritic long rods and sword-like rods were assigned to the crystals of double-stranded and/or triple-stranded helices of the G:C and 2G:C complexes. Cross-like drying patterns that originated from the salt-polymer interaction are also observed. The relationship between the polymer complexation of KPolyG + KPolyC systems and the drying patterns is similar to that of KPolyA (potassium salt of poly(adenylic acid)) + KPolyU (potassium salt of poly(uridylic acid)).     

Cationic gel crystals and amorphous solids of lightly cross-linked poly(2-vinylpyridine) spheres in the deionized aqueous suspension

Colloidal crystallization and amorphous solidification of deionized suspensions of the polydispersed cationic gel spheres of lightly cross-linked poly(2-vinylpyridine), CAIBA-P2VP (107～113 nm in diameter, ±19～22 nm in dispersity), have been studied from the reflection spectroscopy, morphology, phase diagram, and elastic property. Crystallization takes place even for the polydispersed cationic gel spheres by the significant contribution of the extended electrical double layers formed around the spheres. Critical concentrations of melting coexisted with ion exchange resins were around 0.02 in volume fraction and high compared with those of other cationic and anionic gel crystals examined hitherto. The densities (ρ) of CAIBA-P2VP in suspension state, i.e., weight percent of the gel spheres divided by the corresponding volume percent, was around 0.3. The ρ values decreased sharply with decreasing size of P2VP gel spheres, which supports the small gel spheres containing much water inside and being softer than the large ones. The closest intersphere distances of the crystals and/or amorphous solids were much longer than the hydrodynamic diameters of the gel spheres especially at low sphere concentrations. Fluctuation parameters (b) evaluated from the rigidities of CAIBA-P2VP (0.15～0.28) were large compared with those of gel crystals of large-sized P2VP-based cationic gel spheres, anionic thermosensitive gel spheres of poly(N-isopropylacrylamide) (0.05～0.09) and further much larger than those of typical colloidal hard spheres (around 0.03). The dispersity in sphere size played an important role for distinguishing crystal and amorphous solid. Importance of the extended electrical double layers around the cationic gel spheres is supported in addition to the excluded volume effect of the sphere themselves on the crystallization and/or solidification.     

Synthesis and reactions of optically pure cyclohexyl(o-methoxyphenyl)phosphine-borane and t-butyl-(o-methoxyphenyl)phosphine-borane

Cyclohexyl(o-methoxyphenyl)menthyloxyphosphineborane and t-butyl(o-methoxyphenyl)menthyloxyphosphine-borane were prepared from dichlorocyclohexylphosphine and t-butyldichlorophosphine by successive treatments with (−)-menthol, o-methoxyphenylmagnesium bromide, and borane-THF complex. The separated pure diastereomers of each of the compounds underwent reaction with lithium naphthalenide to afford optically pure cyclohexyl(o-methoxyphenyl)phosphine-borane and t-butyl(o-methoxyphenyl)phosphine-borane, respectively. These secondary phosphine-boranes reacted readily with various electrophiles in the presence of bases with virtually net retention of configuration. A new chiral phosphine ligand, (S,S)-1,2-bis[cyclohexyl(o-methoxyphenyl)phosphino]ethane was synthesized via the optically pure phosphine-boranes.     

Aniline-terephthalaldehyde resin p-toluenesulfonate (ATRT) as a highly efficient and reusable catalyst for alcoholysis,hydrolysis, and acetolysis of epoxides

Alcoholysis, hydrolysis, and acetolysis of epoxides were carried out in the presence of a catalytic amount of aniline-terephthalaldehyde resin p-toluenesulfonate (ATRT) to give the corresponding β-substituted alcohols in good yields. Alcoholysis and hydrolysis of epoxides catalyzed by ATRT proceeded faster than those by pyridinium p-toluenesulfonate (PPTS).     

The Renner effect in triatomic molecules with application to CH+, MgNC and NH2

We have developed a computational procedure, based on the variational method, for the calculation of the rovibronic energies of a triatomic molecule in an electronic state that become degenerate at the linear nuclear configuration. In such an electronic state the coupling caused by the electronic orbital angular momentum is very significant and it is called the Renner effect. We include it, and the effect of spin-orbit coupling, in our program. We have developed the procedure to the point where spectral line intensities can be calculated so that absorption and emission spectra can be simulated. In order to gain insight into the nature of the eigenfunctions, we have introduced and calculated the overall bending probability density function f(p) of the states. By projecting the eigenfunctions onto the Born-Oppenheimer basis, we have determined the probability density functions f+(rho) and f-(rho) associated with the individual Born-Oppenheimer states phi(-)elec and phi(+)elec. At a given temperature the Boltzmann averaged value of the f(p) over all the eigenstates gives the bending probability distribution function F(rho), and this can be related to the result of a Coulomb Explosion Imaging (CEI) experiment. We review our work and apply it to the molecules CH2+, MgNC and NH2, all of which are of astrophysical interest.     

Variable-priority queue and doughnut routing

This paper proposes a new data structure called a variable-priority queue. The queue supports, in addition to the ordinary queue operations, an operation MIN to find an item of minimum key and three operations to change keys of items. Any sequence of these m operations can be processed in O(m) time. Furthermore, as its application, this paper presents two efficient algorithms for network problems. The first finds multicommodity flows in cycles in linear time. The second, using the first, finds edge-disjoint paths connecting terminal pairs in a doughnut-shaped grid. The grid is bounded by two nested rectangles, and terminals are specified on the two rectangular boundaries outside the four corners. If there are k terminal pairs and all the terminals are ordered in clockwise order around rectangles, then the algorithm decides in O(k) time whether there are edge-disjoint paths connecting terminals in the grid, and actually finds edge-disjoint paths in O(k log k) time.     

A bayesian approach to binary response curve estimation

Summary The purpose of the present paper is to propose a practical procedure for the estimation of the binary response curve. The procedure is based on a model which approximates the response curve by a finely segmented piecewise constant function. To obtain a stable estimate we assume a prior distribution of the parameters of the model. The prior distribution has several parameters (hyper-parameters) which are chosen to minimize an information criterion ABIC. The procedure is applicable to data consisting of observations of a binary response variable and a single explanatory variable. The practical utility of the procedure is demonstrated by examples of applications to the dose response curve estimation, to the intensity function estimation of a point process and to the analysis of social survey data. The application of the procedure to the discriminant analysis is also briefly discussed. The Institute of statistical mathematics     

Refractive index behavior of SiO2-P2O5 glass in optical fiber application

The refractive index of SiO₂-P₂O₅ glass prepared by a modified chemical vapor deposition method is measured using an interference microscope. It is found that the refractive index in bulk form increases linearly at 9.5×10^-4 (mol.%)^-1 as the P₂O₅ concentration increases. It is also found that quenching at extremely high speed reduces the refractive index over 2 mol.% P₂O₅. The wavelength dispersion of the refractive index dn/dλ is constant up to 5 mol.% P₂O₅ producing a refractive index difference of 5×10^-3 compared with fused silica. Consequently, this glass materials is thought to be suitable for wide band-width optical fiber applications.