Influence of the Coordination of Donor Solvent Molecules to 1,4,7,10-Tetramethyl-1,4,7,10- tetraazacyclododecanenickel(II) and Analogous Nickel(II) Complexes on Their Steric Factors

Coordination equilibrium constants (K _NiS) of some donor solvent molecules to 1,4,7,10-tetramethyl-1,4,7,10-tetraazacyclododecanenickel(II) ([Ni(Me₄[12]aneN₄)]²⁺) were determined in nitrobenzene (a noncoordinating bulk solvent). The first (K _NiS1) and second stepwise coordination equilibrium constants (K _NiS2) for 1,4,7,10-tetraazacyclododecanenickel(II) ([Ni([12]aneN₄)]²⁺), 1,4,8,11-tetraazac yclotetradecane- nickel(II) ([Ni([14] aneN₄)]²⁺), 1,4,8,11-tetrathiacyclotetra-decanenickel(II) ([Ni([14]aneS₄)]²⁺) were also reinvestigated. The K _NiS values for [Ni(Me₄[12]aneN₄)]²⁺ were compared to those of [Ni([12]aneN₄)]²⁺, (1R,4S, 8R,11S)-1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecanenickel(II) (R,S,R,S-[Ni(Me₄[14]aneN₄)]²⁺), R,R,S,S-[Ni(Me₄[14]aneN₄)]²⁺, [Ni([14]aneN₄)]²⁺, and [Ni([14]aneS₄)]²⁺. Coordination of pyridine (Py), N,N,N′,N′-tetramethylurea (TMU), and N,N-dimethylacetamide (DMA) to [Ni(Me₄[12]aneN₄)]²⁺ was observed, although these donor solvent molecules did not coordinate to R,S,R,S-[Ni(Me₄[14]aneN₄)]²⁺. The K _NiS values for Py, TMU, and DMA are 7.9, 2.8, and 9.0 dm³⋅mol⁻¹, respectively. Some hydrogen-bonding waters were coordinated to R,S,R,S-[Ni(Me₄[14]aneN₄)]²⁺, but such waters did not coordinate to [Ni(Me₄[12] aneN₄)]²⁺. Also, the K _NiS2 values were larger than the corresponding K _NiS1 values for [Ni([14]aneS₄)]²⁺. Furthermore, the K _NiS1 values for [Ni([12]aneN₄)]²⁺ were the largest among these nickel(II) complex cations. The K _NiS, K _NiS1, and K _NiS2 values are discussed in terms of properties of the donor solvents and steric strains of these nickel(II) complex cations.     

An Integrated Version of Varadhan’s Asymptotics for Lower-Order Perturbations of Strong Local Dirichlet Forms

The studies of J. A. Ramírez, Hino–Ramírez, and Ariyoshi–Hino showed that an integrated version of Varadhan’s asymptotics holds for Markovian semigroups associated with arbitrary strong local symmetric Dirichlet forms. In this paper, we consider non-symmetric bilinear forms that are the sum of strong local symmetric Dirichlet forms and lower-order perturbed terms. We give sufficient conditions for the associated semigroups to have asymptotics of the same type.     

Density-fluctuation-induced swelling of polymer thin films in carbon dioxide

We report an anomalous swelling of polymer thin films in carbon dioxide (CO(2)) which is associated (in both locus and form) with the density fluctuation ridge that forms along the extension of the coexistence curve of gas and liquid in the P-T phase diagram. Neutron reflectivity results showed that CO(2) could be sorbed to a large extent ( approximately 60%) in thin polymer films even when the bulk miscibility of the polymer with CO(2) is very poor. The anomalous swelling is found to scale with the polymer radius of gyration (R(g)) and extends to a distance approximately 10 R(g).     

A novel synthesis of half-protected 1,3-dicarbonyl compounds

It has been found that the reaction of enol silyl ethers with 2-ethoxy-1,3-dithiolane proceeds smoothly in the presence of zinc chloride catalyst to afford half-protected 1,3-dicarbony1 compounds in moderately good yields.     

Atomicm absorption spectrometric determination of the isotopic composition of lithium by an ultimate absorbance-ratio technique

The conventional absorbance-ratio technique for determining the isotopic composition of lithium by atomic absorption spectrometry is improved by the use of “ultimate absorbance ratios” of sample solutions. These ratios are obtained by extrapolating the linear portion of lithium content/absorbance-ratio plots to the intercept at 0 mol m^?3 lithium. These graphs are obtained measuring the absorbances of solutions of known ⁶Li abundance and of various lithium contents with natural and ⁶Li-enriched lithium hollow-cathode lamps. Linear calibration is attained over the range 0.0–99.3% ⁶Li, and the lithium isotopic abundance can be determined with an absolute error of ±0.7% ⁶Li for > 0.01 mol m^?3 lithium solutions. The method requires neither prior measurement of the total lithium content in sample solutions nor adjustment of the content to match that in the standard solutions.     

Large‐scale SPH simulations of droplet impact onto a liquid surface up to the consequent formation of Worthington jet

In this study, the whole process of liquid droplet impact onto a liquid surface up to the consequent formation of the central column was simulated using the smoothed particle hydrodynamics method (SPH), and compared with an experiment using a high‐speed video camera. The surface tension tensor for the particle‐based expression was adequately included as the gradient of the surface tension and that enabled the simulation leading to the formations of crater and crown as well as the consequent central column. The simulated time series of the crater depth and diameter and crown height corresponded quantitatively well with the experimental result up to the rebound motion while discrepancies remained as a lower central column height in the simulation, and this seemed to be ascribed to the difficulty in realizing the complex surface structure that inevitably appeared in the fast rebound motion. Copyright © 2009 John Wiley & Sons, Ltd.     

Development of quality assessment method for optically active food flavor chemicals

A quality assessment method for commercially available, optically active flavor compounds, namely, menthol, menthyl acetate, borneol, perillaldehyde, and 1,8-cineol, was developed. A gas chromatograph equipped with a flame ionization detector and a DB-5ms capillary column was used for the chemical purity test. A GC/MS with a beta-DEX cyclodextrin column was used for the optical purity test, by which the enantiomeric separation of each flavor compound was achieved. Enantiomeric excess was calculated as an expression of optical purity. Of the 25 standard samples subjected to the chemical purity test, six were found to have lower purity than the data provided by the manufacturers. When the same samples were subjected to the optical purity test, 11 were found to have lower purity than that indicated on the reagent labels. These results suggest that there is a need to conduct an optical purity test, in addition to a chemical purity test, for the quality assessment of flavor standards.