Elastic modulus of poly(isobutylene oxide) crystals parallel to the chain axis

The elastic tensile modulus of the crystalline regions parallel to the chain axis E₁ for poly(isobutylene oxide) (PIBO) was determined by an x-ray diffraction method. The stress-strain (σ—ε) curve calculated from the meridional reflection of (002) shows an inflection point at about 75 MN/m² or an extension of 0.25%. The observed moduli below and above this point are 29 and 47 GN/m², respectively, at room temperature. The initial lower modulus agrees well with the value, 29.7 GN/m², calculated on the basis of the double zigzag structure of PIBO chain determined by Kaji and Sakurada. The higher modulus may be due to an intrachain steric hindrance between the hydrogen atoms of the methylenic group in the main chain and those of the two side methyl groups.     

Imaging nanoscale electronic inhomogeneity in the lightly doped Mott insulator Ca(2-x)NaxCuO2Cl2

The spatial variation of electronic states was imaged in the lightly doped Mott insulator Ca(2-x)NaxCuO2Cl2 using scanning tunneling microscopy or spectroscopy. We observed nanoscale domains with a high local density of states within an insulating background. The observed domains have a characteristic length scale of 2 nm (approximately 4-5a, a: lattice constant) with preferred orientations along the tetragonal [100] direction. We argue that such spatially inhomogeneous electronic states are inherent to slightly doped Mott insulators and play an important role for the insulator to metal transition.     

A dodecameric porphyrin wheel

A dodecameric porphyrin wheel was prepared by Ag(I)-promoted intramolecular coupling of a linear porphyrin dodecamer and was observed by scanning tunneling microscopy (STM). Efficient energy hopping along the array was revealed by femtosecond transient anisotropy measurements.     

Piezoluminescence at the air-water interface through dynamic molecular recognition driven by lateral pressure application

The steroid cyclophanes with a cyclic core consisting of a 1,6,20,25-tetraaza[6.1.6.1]paracyclophane connected to four steroid moieties (cholic acid or cholanic acid) through a flexible l-lysine spacer were spread on water as Langmuir monolayers. The pi-A isotherm of the cholic-type steroid cyclophane includes a transition to the condensed phase with a limiting area of approximately 2 nm(2). This value is close to the cross-sectional area of the steroid cyclophane with a standing-up conformation of the cholic acid moieties, strongly suggesting that the cavity converts from a two-dimensional cavity to a three-dimensional cavity upon compressing the monolayer. Surface-reflective fluorescence spectroscopy of the monolayer using an aqueous fluorescent probe (6-(p-toluidino)naphthalene-2-sulfonate (TNS)) showed an abrupt increase in the TNS fluorescence intensity at a molecular area of 2 nm(2). Efficient binding of the guest probe would occur upon the completion of the three-dimensional cavity. Repeated compression and expansion induces periodic changes in the fluorescence intensity. This indicates a piezoluminescence effect through the catch and release of the TNS guest upon dynamic cavity formation. Analyses of the binding behavior of TNS to the steroid cyclophane resulted in binding constants in the range of approximately (5-9) x 10(4) M(-1) which are similar to that observed in lipid bilayer media (K = 5.1 x 10(4) M(-1)). The fluorescence intensity within the condensed phase was significantly increased with increasing pressure, suggesting that suppression of the molecular motion of the bound TNS may retard the nonemission process. Similar monolayer experiments were carried out with the monolayer of the cholanic-type steroid cyclophane that cannot form an open conformation on water. Both the phase transition in the pi-A isotherm and the change in the fluorescence intensity were negligible, confirming that the dynamic characteristic of the cavity is indispensable for the efficient pressure-induced binding of the guest and the consequent luminescence.     

Effect of ionic surfactants on the oscillation frequency of one-electrode-separated piezoelectric quartz crystals modified with chitosan and its derivative

From the pH dependence of oscillation frequencies of one-electrode-separated piezoelectric quartz crystals (ESPQCs) modified with chitosan and N-(1,3-dicarboxypropyl) chitosan (DCPC) in buffer solutions, it was deduced that the chitosan and DCPC films on an ESPQC contained water and that the water content depended on pH. Contrary to the expectation based on the Sauerbrey equation, the binding of ionic surfactants to chitosan and DCPC films increased the frequencies. This apparently abnormal phenomenon was explained by the release of water in swollen films. The frequency of the DCPC-modified ESPQC increased on addition of sodium dodecyl sulfate and hexadecyltrimethylammonium chloride at pH lower and higher, respectively, than 7.8. A linear relationship between surfactant concentration and frequency shift, whose slope depended on only the chain length of the surfactant alkyl group, was obtained in the range 5–50 µmol dm^–3 hexadecyltrimethylammonium chloride. The DCPC-modified ESPQC can be used for a quantitative determination of cationic surfactants in this concentration range.     

Reaction of coordinated phosphines—II: Arylation of substituted olefins by palladium(II) acetate and triarylphosphine

Phenylation of 1-octene, cyclohexene, styrene, acrylonitrile, vinyl acetate, ethyl acrylate, and ethyl but-3-enoate with Pd(PAr₃)₂(OAc)₂ was carried out in acetic acid at 50°. para-Substituted triphenylphosphine palladium acetate complex produced corresponding para substituted phenyl derivatives.     

A dipole-moment study of substituted pyrazines and quinoxalines

An attempt has been made to rationalize the dipole moments of 2-chloro-, 2-ethoxy-, 2-ethylthio-, 2-amino-, 2-ethylamino- and 2-diethylamino-pyrazine in terms of substituentring mesomeric effect. In 2-substituted pyrazines, the substituent mainly interacts with the ortho-to-substituent ring-nitrogen atom. Preferred conformations are proposed for 2-ethoxypyrazine and 2-methoxypyridine, 2-ethylthiopyrazine and 2-methylthiopyridine, 2,5-diethoxypyrazine, 2,3-dimethoxyquinoxaline and 2,3-bis(methylthio)quinoxaline. The dipole moments of aminopyridines, amino-s-triazine and methoxy-s-triazine are also interpreted.     

Anomalous pressure dependence of the superconducting transition temperature of beta-pyrochlore AOs2O6 oxides

High-pressure effects on the superconducting transitions of beta-pyrochlore oxide superconductors AOs(2)O(6) (A = Cs,Rb,K) are studied by measuring resistivity under high pressures up to 10 GPa. The superconducting transition temperature T(c) first increases with increasing pressure in every compound and then exhibits a broad maximum at 7.6 K (6 GPa), 8.2 K (2 GPa), and 10 K (0.6 GPa) for A = Cs, Rb, and K, respectively. Finally, the superconductivity is suppressed completely at a critical pressure near 7 GPa and 6 GPa for A = Rb and K and probably above 10 GPa for A = Cs. Characteristic changes in the coefficient A of the T(2) term in resistivity and residual resistivity are observed, both of which are synchronized with the corresponding change in T(c).     

Gold(I)-phosphine catalyst for the highly chemoselective dehydrogenative silylation of alcohols

[reaction: see text] A gold(I) complex of Xantphos AuCl(xantphos) catalyzes the dehydrogenative silylation of alcohols with high chemoselectivity and solvent tolerance. It is selective for the silylation of hydroxyl groups in the presence of alkenes, alkynes, alkyl halides (RCl, RBr), ketones, aldehydes, conjugated enones, esters, and carbamates.