Vibronic Structures in Absorption and Fluorescence Spectra of Firefly Oxyluciferin in Aqueous Solutions

To elucidate the factors determining the spectral shapes and widths of the absorption and fluorescence spectra for keto and enol oxyluciferin and their conjugate bases in aqueous solutions, the intensities of vibronic transitions between their ground and first electronic excited states were calculated for the first time via estimation of the vibrational Franck–Condon factors. The major normal modes, overtones and combination tones in absorption and fluorescence spectra are similar for all species. The theoretical full widths at half maximum of absorption spectra are 0.4–0.7 eV and those for the fluorescence spectra are 0.4–0.5 eV, except for phenolate‐keto that exhibits exceptionally sharp peak widths due to the dominance of the 0–0′ or 0′–0 band. These spectral shapes and widths explain many relevant features of the experimentally observed spectra.     

Phenomenological kinetics of the thermal decomposition of sodium hydrogencarbonate

Aiming to find rigorous understanding and novel features for their potential applications, the physico-geometrical kinetics of the thermal decomposition of sodium hydrogencarbonate (SHC) was investigated by focusing on the phenomenological events taking place on a single crystalline particle during the course of the reaction. The overall kinetics evaluated by systematic measurements of the kinetic rate data by thermogravimetry under carefully controlled conditions were interpreted in association with the morphological studies on the precursory reaction, mechanism of surface reaction, structure of the surface product layer, diffusion path of evolved gases, crystal growth of the solid product, and so on. The precursory reaction was identified as the decomposition of impurity, taking place at the boundary between the surface of the SHC crystal and the adhesive small SHC particles deposited on the surface. In flowing dry N(2), the thermal decomposition of SHC proceeds by two-dimensional shrinkage of the reaction interface controlled by chemical reaction with the apparent activation energy of about 100 kJ mol(-1), after rapid completion of the surface reaction and formation of porous surface product layer. Atmospheric CO(2) and water vapor influence differently on the overall kinetics of the thermal decomposition of SHC. Added gas phase of CO(2) slightly inhibits the overall rate because of the increasing contribution of the surface reaction. Under higher water vapor pressure, the physico-geometrical mechanism of the surface reaction changes drastically, indicating the preliminary reformation of reactant surface and the formation of needle crystals of solid product on the surface. The mechanistic change and extended contribution of the surface reaction result in the deceleration of the surface reaction and acceleration of the established reaction.     

A general method for construction of (<Emphasis Type="Italic">t</Emphasis>, <Emphasis Type="Italic">n</Emphasis>)-threshold visual secret sharing schemes for color images

This paper is concerned with the construction of basis matrices of visual secret sharing schemes for color images under the (t, n)-threshold access structure, where n ≥ t ≥ 2 are arbitrary integers. We treat colors as elements of a bounded semilattice and regard stacking two colors as the join of the two corresponding elements. We generate n shares from a secret image with K colors by using K matrices called basis matrices. The basis matrices considered in this paper belong to a class of matrices each element of which is represented by a homogeneous polynomial of degree n. We first clarify a condition such that the K matrices corresponding to K homogeneous polynomials become basis matrices. Next, we give an algebraic scheme for the construction of basis matrices. It is shown that under the (t, n)-threshold access structure we can obtain K basis matrices from appropriately chosen K − 1 homogeneous polynomials of degree n by using simple algebraic operations. In particular, we give basis matrices that are unknown so far for the cases of t = 2, 3 and n − 1.     

Laser ablation synthesis of monodispersed magnetic alloy nanoparticles

Monodispersed CoPt alloy nanoparticles were synthesized by a pulsed laser ablation (PLA) technique coupled with a low-pressure operating differential mobility analyzer (LP-DMA). The CoPt alloy nanoparticles were generated by laser ablating a solid Co–Pt target. In CoPt alloy nanoparticles synthesized from a target with a Co composition of 75 at%, the nanoparticle surfaces were covered by an oxide layer and exhibited a core-shell structure. In contrast, no shell was observed in particles generated from a target with a Co:Pt ratio of 50:50 at%. According to an EDX analysis, the compositions of the individual nanoparticles were almost the same as that of the target material. Finally, the magnetic hysteresis loops of the CoPt alloy nanoparticles exhibited ferromagnetism.     

Application of metalloporphyrins and methylviologen-pendent iron porphyrin to reduction of diphenylsulfoxide

In the two-electron reduction of diphenylsulfoxide to diphenylsulfide, which is considered a model reaction of sulfite reduction catalyzed by sulfite reductase, methylviologen-pendent iron(III) porphyrin exhibits much higher catalytic activity than usual iron(III) and manganese(III) tetraphenylporphyrins, while cobalt(II) tetraphenylporphyrin exhibits much less catalytic activity than the others. Discussion about the active species and the reason of the acceleration by methylviologen-pendent is presented.     

Quantitative analysis of triphenylboron in environmental water samples by liquid chromatography/mass spectrometry.

Liquid chromatography/mass spectrometry (LC/MS) has been applied to the analysis of triphenylboron, which has been produced as a substitute for organotin compounds, in water. Although commercial triphenylboron compounds are produced as pyridinyl complexes, the chemical form in water is supposed to be mainly triphenylboron after liberating pyridine. The triphenylborons were extracted from water with an Empore C18 extraction disk under acidic condition, and the extracts were introduced directly into a liquid chromatograph-mass spectrometer equipped with a negative ion electrospray ionization interface. Identification of the compounds was performed with specific ions produced from the triphenylboron, and a quantitative analysis was carried out using the peak areas. The average recoveries from distilled water, seawater and river water at 0.30 ng/ml were 92.3, 100 and 85.3%, respectively. A detection limit of 0.023 ng/ml for triphenylboron was achieved.     

ESR of copper tutton salts around 0.1 K

A remarkable H/T effect in the intensity of ESR absorption is reported for the case of two Cu Tutton salts studied at 9.4 GHz and at temperatures down to 37 mK. Results can be reasonably expressed by the Brillouin function for $\text{S =}\text{1}\text{2}$.     

PSDF of log-amplitude scintillation for 7 μm band laser beam with absorption by water vapour

The power spectral density function (PSDF) of the log-amplitude scintillation for an infrared laser beam was measured experimentally. To investigate the contribution of the absorption and the dispersion that cause the scintillation, we chose 16 wavelengths of infrared light and one wavelength of visible light. It is found that the spectral density of scintillation for the infrared beam does not agree with that for the visible beam, as predicted by Tatarskii's theory in the low-frequency region below 1 Hz. This disagreement between the experiment and the theory in the low-frequency region should be attributed to water vapour absorption.     

Momentum distribution of Hückel π electrons

The momentum distribution and related physical properties are examined for π molecular orbitals (MOs) of a conjugated hydrocarbon system obtained by the empirical Hückel method. Several general rules are derived and the momentum-space aspect of the Hückel π electron theory is clarified.