Evidence for the coexistence of two different mechanisms for the occurrence of anti-Kasha S2 (1 (1)Bu) fluorescence from alpha,omega-diphenylpolyenes

Fluorescence, fluorescence excitation, and absorption spectra have been measured for diphenylpolyenes with the polyene double bond number (n) from three to seven in solvents with different polarizabilities at room temperature. These polyenes exhibit anti-Kasha S(2) (1 (1)B(u)) fluorescence beside conventional S(1) (2 (1)A(g)) fluorescence in room temperature solution. It is shown that there are two different mechanisms for occurrence of the S(2) (1 (1)B(u)) fluorescence of diphenylpolyenes. S(2) fluorescence occurs through the thermal population of the S(1) state for the shorter diphenylpolyenes (n=3 and 4), while it occurs as prompt S(2) fluorescence due to inefficient S(2)-->S(1) internal conversion for the longer diphenylpolyenes (n=6 and 7). With diphenyldecapentaene (n=5), S(2) fluorescence based on both mechanisms is observed depending on the polarizability of the solvent used. The present results provide deeper insight into the mechanism for the occurrence of anti-Kasha S(2) fluorescence of polyenes.     

STM-based molecular detection of "catch-and-release" of protons for bipyridine bound to phenylene-ethynylene thiol

The protonation/deprotonation response of a novel bipyridine containing (phenylene-ethynylene) thiol adsorbed to a Au surface was investigated with scanning tunneling microscopy (STM), showing reversible changes in the average heights (approximately 50 spots) and the height distribution arising from protonation/deprotonation.     

Accelerating Flat Universe and Analytic Study of the m-z Relation

An accelerating flat universe with a variable cosmological term is obtained in the Robertson-Walker metric. The variable cosmological term is defined by the correction terms of the metric tensor field. Simple solutions of the scale factor and the cosmological term are shown. In this model of the universe, the magnitude-redshift relation is analytically studied to see if the model reproduces the tendency of the present observational data. The equation of state parameter is touched.     

Mercuric triflate catalyzed hydroxylative carbocyclization of 1,6-enynes

[reaction: see text] Hg(OTf)(2) exhibits remarkable catalytic activity for the hydroxylative cyclization of 1,6-enynes. The present procedure should involve a sequence of mercuration of a terminal alkyne, carbocyclization, hydration, and protodemercuration that regenerates the catalyst.     

Emulsion Combustion and Flame Spray Synthesis of Zinc Oxide/Silica Particles

Two flame spray methods, emulsion combustion method (ECM) and flame spray pyrolysis (FSP), were compared for synthesis of pure and mixed SiO₂ and ZnO nanoparticles. The effect of silicon precursor was investigated using liquid hexamethyldisiloxane (HMDSO) or SiO₂ sol, while for ZnO zinc acetate (ZA) was used. Gas phase reaction took place when using HMDSO as Si precursor, forming nanoparticles, whereas the SiO₂ sol used as Si source was not evaporated in the flame, creating large aggregates of the sol particles (e.g. 1 m). The FSP of ZA produced ZnO homogeneous nanoparticles. Lower flame temperatures in ECM than in FSP resulted in mixed gas and liquid phase reaction, forming ZnO particles with inhomogeneous sizes. The FSP of HMDSO and ZA led to intimate gas-phase mixing of Zn and Si, suppressing each other's particle growth, forming nanoparticles of 19 nm in BET-equivalent average primary particle diameter. Nucleation of ZnO and SiO₂ occurred independently by ECM of HMDSO and ZA as well as by FSP of the SiO₂ sol and ZA, creating a ZnO and SiO₂ mixture. The reaction of ZnO with SiO₂ was likely to be enhanced by ECM of the SiO₂ sol and ZA where both Zn and Si species were not evaporated completely, resulting in ZnO, -willemite and Zn_1.7SiO₄ mixed phase.     

Direct micropatterning of high dielectric BaTiO3 films by laser-induced pyrolysis with a nano-crystalline seeding technique

A direct patterning method of dielectric BaTiO₃ (BT) films is proposed, which applies laser-induced pyrolysis in combination with nano-crystalline seeding technique. A precursor solution of a BT complex alkoxide containing BT nano-crystalline particles with polyvinylpyrollidone (PVP) as dispersion stabilizer was spin-coated on Pt substrate. An Ar⁺ laser beam was focused and scanned on spin-coated BT films, which induced pyrolysis and crystallization of the films with spatial selectivity. Micropatterns were obtained by striping laser-unirradiated regions on the films with HCl aqueous solution. Raman spectra of the micropattern confirmed that the structures were tetragonal crystalline BT. Clear micropatterns with a line width of ca. 3 μm and an interval of 5 μm were formed at PVP concentrations of 25 and 50 kg/m³. The dielectric constant and dissipation factor of the film fabricated at a laser energy density of 27 MW/cm² and a scanning speed of 25 μm/s attained 76.2 and 0.07, respectively, for a measurement frequency of 100 kHz.     

Characteristic reactions of group 9 transition metal compounds in organic synthesis

Group 9 metal compounds in organic synthesis have two characteristic reactions. The first occurs because the group 9 metals have a high affinity to carbon–carbon or carbon–nitrogen π‐bonds. The first type of characteristic reactions in these group 9 metal compounds includes Pauson–Khand reactions, the Pauson–Khand‐type reactions ([2 + 2 + 1] cyclization), the other cyclizations and coupling reactions. The second occurs because the group 9 metals have a high affinity to carbonyl groups. The second type of characteristic reactions includes carbonylations such as hydroformylations, the carbonylations of methanol, amidocarbonylations and other carbonylations. The first characteristic reactions are applied for the synthesis of fine chemicals such as pharmaceuticals and agrochemicals. However, the second characteristic reactions are utilized not only for fine chemicals but also for important bulk commodity chemicals such as aldehydes, carboxylic acids and alcohols. Copyright © 2009 John Wiley & Sons, Ltd.     

Spin-freezing processes around the tricritical point in Mn1−xTixSb

Transitions related to the spin-glass phase in Mn_1−xTi_xSb are revisited from the nonlinear ac susceptibility. Near the tricritical point (x≈0.8), the transition between ferromagnetic and reentrant spin-glass states is sharp. At x0.8, an anomally is found slightly above the temperature of usual spin-glass freezing.