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     

O− and OH− chemical ionization of some fatty acid methyl esters and triacylglycerols

O^? and OH^? react with fatty acid methyl esters (FAMES) under chemical ionization conditions both as Bronsted bases to form [M - H]^? and as nucleophiles to form the carboxylate ion RCOO^?. O^? shows a much greater tendency to react as a nucleophile than does OH^?. The [M - H]^? ions fragment by elimination of CH³OH, with unsaturation in certain positions in the fatty acid hydrocarbon chain promoting this elimination for unknown reasons. The reaction of O^? and OH^? with triacylglycerols leads to [M - H]^?, characteristic of the molecular mass, and to carboxylate ions characteristic of the fatty acid(s) present in the lipid. The presence of the three ester functions in the lipids greatly enhances the formation of carboxylate ions compared to the FAMES.     

Large Sample Properties of Mixture Models with Covariates for Competing Risks

We study the large-sample properties of a class of parametric mixture models with covariates for competing risks. The models allow general distributions for the survival times and incorporate the idea of long-term survivors. Asymptotic results are obtained under a commonly assumed independent censoring mechanism and some modest regularity conditions on the survival distributions. The existence, consistency, and asymptotic normality of maximum likelihood estimators for the parameters of the model are rigorously derived under general sufficient conditions. Specific conditions for particular models can be derived from the general conditions for ready check. In addition, a likelihood-ratio statistic is proposed to test various hypotheses of practical interest, and its asymptotic distribution is provided.     

SECOND BEST TAXES AND QUOTAS IN NITROGEN REGULATION

This paper investigates second best policies to regulate nitrogen leaching. When the policy maker controls the total nitrogen use, an overall tax is superior to an action equivalent overall quota. When the goal is to regulate the expected level of nitrogen leaching, expected profit of a risk neutral farmer is greater under an overall tax than under an overall quota under a reasonable condition. The welfare ranking of action equivalent taxes and quotas for a risk averse farmer is generally ambiguous. In the numerical analyses, overall taxes turned out to be superior to overall quotas with both targets, despite a very high value of absolute risk aversion, 0.01. These results suggest that an overall tax is probably a superior policy to an overall quota to regulate expected total nitrogen use or expected nitrogen leaching for risk neutral and most of risk averse farmers.     

Wilcoxon signed rank test using ranked-set sample

Ranked-set sampling is useful when measurements are destructive or costly to obtain but ranking of the observations is relatively easy. The Wilcoxon signed rank test statistic based on the ranked-set sample is considered. We compared the asymptotic relative efficiencies of the RSS Wilcoxon signed rank test statistic with respect to the SRS Wilcoxon signed rank test statistic and the RSS sign test statistic. Throughout the ARE’s, the proposed test statistic is superior to the SRS Wilcoxon signed rank test statistic and the RSS sign test statistic.     

Crossover Critical Behavior in the Three-Dimensional Ising Model

The character of critical behavior in physical systems depends on the range of interactions. In the limit of infinite range of the interactions, systems will exhibit mean-field critical behavior, i.e., critical behavior not affected by fluctuations of the order parameter. If the interaction range is finite, the critical behavior asymptotically close to the critical point is determined by fluctuations and the actual critical behavior depends on the particular universality class. A variety of systems, including fluids and anisotropic ferromagnets, belongs to the three-dimensional Ising universality class. Recent numerical studies of Ising models with different interaction ranges have revealed a spectacular crossover between the asymptotic fluctuation-induced critical behavior and mean-field-type critical behavior. In this work, we compare these numerical results with a crossover Landau model based on renormalization-group matching. For this purpose we consider an application of the crossover Landau model to the three-dimensional Ising model without fitting to any adjustable parameters. The crossover behavior of the critical susceptibility and of the order parameter is analyzed over a broad range (ten orders) of the scaled distance to the critical temperature. The dependence of the coupling constant on the interaction range, governing the crossover critical behavior, is discussed.     

Globally anisotropic high porosity silica aerogels

We discuss two methods by which high porosity silica aerogels can be engineered to exhibit global anisotropy. First, anisotropy can be introduced with axial strain (i.e. axial compression). In addition, intrinsic anisotropy can result during growth and drying stages and, suitably controlled, it can be correlated with preferential radial shrinkage in cylindrical samples. We have performed small angle X-ray scattering (SAXS) to characterize these two types of anisotropy. We show that global anisotropy originating from either strain or shrinkage leads to optical birefringence and that optical cross-polarization studies are a useful characterization of the uniformity of the imposed global anisotropy.     

Palladium-catalyzed C-N bond formation: synthesis of 1-aryl-1H-pyrazoles from β-bromovinyl aldehydes and arylhydrazines

Cyclic and acyclic β-bromovinyl aldehydes are cyclized with an array of arylhydrazines in toluene at 125 °C in the presence of a palladium catalyst and a phosphorus chelating ligand together with NaO^tBu to give 1-aryl-1H-pyrazoles in moderate to good yields.