Oil Migration in Chocolate

Oil migration in filled chocolates limits shelf life due to texture changes and loss of visual appeal. Spatial and temporal oil concentration changes of a two-layer chocolate and peanut butter filling system, which models a filled chocolate, were monitored by magnetic resonance imaging. Formulations of chocolate varied with respect to particle size, milk fat content and emulsifier level. Sorption-time experimental data was used to establish the best fit diffusion coefficient for a Fickian diffusion model. On the basis of the comparison of spatial experimental data to the model, Fickian diffusion alone does not account for oil migration. Authors' address: Michael J. McCarthy, Department of Food Science and Technology, University of California, One Shields Avenue, Davis, CA 95616, USA     

Off-shell effects in quasielastic electron nucleus scattering

Using the Ward-Takahashi identity, on-shell condition, bound Dirac equation and off-shell expansion, a reduced version of half off-shell virtual photon nucleon vertex has been suggested. The vertex are decomposed into several different order terms: the on-shell terms, first and second off-shell terms. The off-shell behaviour of the form factors is discussed in the one meson loop model. Using the reduced vertex and parametrized off-shell form factors the quasielastic response functions are calculated for several nuclei at ¦q¦–k_f and for⁵⁶Fe at large ¦q¦ up to 1.14 GeV/c and at ?q²=0.9 (GeV/c)². The Coulomb sums are evaluated and a comparison of the theoretical prediction with data is given. The off-shell electron nucleon cross section is calculated and compared with the “cc1” off-shell extrapolation.     

Improved high-performance liquid chromatographic assay for the determination of ethionamide in serum

A solid-phase extraction (SPE) method was developed to simplify the preparation of human serum prior to high-performance liquid chromatography of ethionamide (ETA). Octadecyl SPE columns were used. Serum constituents were removed from the column with water, and ETA was eluted with methanol. Samples were evaporated to dryness, reconstituted in mobile phase, and assayed. The method is reproducible, with a recovery of ETA of 64%, comparable to the more tedious liquid-liquid extraction method for ETA.     

Synthesis of indaphyrins: meso-tetraarylsecochlorin-based porphyrinoids containing direct o-phenyl-to-beta-linkages

The synthesis of indaphyrins, novel meso-tetraarylsecochlorin-derived chromophores incorporating o-phenyl-to-beta-linkages, is described. Oxidative diol cleavage of meso-tetraaryl-2,3-dihydroxy-2,3-chlorins results in the formation of a secochlorin bisaldehyde. Depending on the reaction conditions during the ring cleavage reaction, one or two of the aldehyde groups react with the adjacent o-phenyl positions, leading to an intramolecular electrophilic aromatic substitution of the o-phenyl proton, and the establishment of a direct o-phenyl-to-beta-linkage. The initially formed carbinol is spontaneously oxidized to the corresponding ketone. This modification forces the aryl groups into co-planarity with the macrocycle, allowing for interactions between the pi-electrons of the aryl groups, the ketone linkage, and those of the chromophore, resulting in a significant electronic modulation of the porphyrinic pi-system. The UV-vis spectroscopic properties of the free base, CuII, NiII, and ZnII indaphyrins are discussed.     

Solvents showing the external heavy atom effect in phosphorimetry

Ten solvents containing heavy atoms were examined for suitability for use in the external heavy atom effect for routine phosphorimetry. In previous work only iodine-containing solvent systems have been used, and the incongruity of enhancement results for structurally similar compounds suggests that the ultraviolet transmission characteristics of the solvent systems may be responsible for fractional enhancements. In this study the effect of chlorine-, bromine-, and iodine-containing solvent systems on phosphorescence and fluorescence intensities was investigated. Generally, chlorine-, and bromine-containing solvent systems showed a significant improvement in phosphorimetric enhancements with slightly longer lifetimes than in solvent systems containing iodine. As expected from their smaller spin-orbit coupling, chlorine-containing solvent systems yield smaller enhancements than bromine-containing solvent systems. Solvent systems containing bromine seem to offer the best compromise between ultraviolet transmission characteristics and large spin-orbit coupling constants.     

Fourier transform microwave spectroscopy of vinyldiacetylene, vinyltriacetylene, and vinylcyanodiacetylene

The rotational spectra of the three carbon chain molecules vinyldiacetylene (hex-1-ene-3,5-diyne, C(6)H(4)), vinyltriacetylene (oct-1-ene-3,5,7-triyne, C8H4), and its cyano analog vinylcyanodiacetylene (1-cyanohex-5-ene-1,3-diyne, C7H3N) have been observed for the first time by Fourier transform microwave spectroscopy of a supersonic molecular beam. The molecules were observed as products of an electrical discharge through selected precursor mixtures: ethylene/diacetylene and vinylacetylene/diacetylene for the pure hydrocarbon molecules and vinylacetylene/cyanoacetylene for vinylcyanodiacetylene. The measurements yield precise sets of rotational constants that compare very well with theoretical constants obtained by quantum chemical calculations at the B3LYP/cc-pVTZ level of theory. Since these three carbon chains are similar in structure and composition to known astronomical molecules and because of their significant polarity, all three are candidates for radio astronomical detection.