Investigation of the Potential Energy Surface for the First Step in the Alkaline Hydrolysis of Methyl Acetate

The potential energy surface for the first step of the alkaline hydrolysis of methyl acetate was explored by a variety of methods. The conformational search routine within SPARTAN was used to determine the lowest energy am1 and pm3 structures for the anionic tetrahedral intermediate. Ab initio single point and geometry optimization calculations were performed to determine the lowest energy conformer, and the linear synchronous transition (lst) method was used to provide an initial structure for transition state optimization. Transition states were obtained at the am1, pm3, 3-21G, and 3-21 + G levels of theory. These transition states were compared with the anionic tetrahedral intermediates to examine the assumption that the intermediate is a good model for the transition state. In addition, the Cramer/Truhlar sm3 solvation model was used at the semiempirical level to compare gas phase and aqueous alkaline hydrolysis of methyl acetate.

Effects of Food Availability on Yolk Androgen Deposition in the Black-Legged Kittiwake (Rissa tridactyla), a Seabird with Facultative Brood Reduction

In birds with facultative brood reduction, survival of the junior chick is thought to be regulated primarily by food availability. In black-legged kittiwakes (Rissa tridactyla) where parents and chicks are provided with unlimited access to supplemental food during the breeding season, brood reduction still occurs and varies interannually. Survival of the junior chick is therefore affected by factors in addition to the amount of food directly available to them. Maternally deposited yolk androgens affect competitive dynamics within a brood, and may be one of the mechanisms by which mothers mediate brood reduction in response to a suite of environmental and physiological cues. The goal of this study was to determine whether food supplementation during the pre-lay period affected patterns of yolk androgen deposition in free-living kittiwakes in two years (2003 and 2004) that varied in natural food availability. Chick survival was measured concurrently in other nests where eggs were not collected. In both years, supplemental feeding increased female investment in eggs by increasing egg mass. First-laid ("A") eggs were heavier but contained less testosterone and androstenedione than second-laid ("B") eggs across years and treatments. Yolk testosterone was higher in 2003 (the year with higher B chick survival) across treatments. The difference in yolk testosterone levels between eggs within a clutch varied among years and treatments such that it was relatively small when B chick experienced the lowest and the highest survival probabilities, and increased with intermediate B chick survival probabilities. The magnitude of testosterone asymmetry in a clutch may allow females to optimize fitness by either predisposing a brood for reduction or facilitating survival of younger chicks.

Using the Natural Period of a Structure as an Indicator of the Significance of Second-Order Effects

This study investigates the feasibility of predicting the momentamplification in beam-column elements of steel moment-resisting frames using the structure's natural period. Unlike previous methods, which perform moment-amplification on a story-by-story basis, this study develops and tests two models that aim to predict a global amplification factor indicative of the largest relevant instance of local moment amplification in the structure. To thisend, a variety of two-dimensional frames is investigated using first and secondorder finite element analysis. The observed moment amplification is then compared with the predicted amplification based on the structure's natural period, which is calculated by first-order finite element analysis. As a benchmark, design moment amplification factors are calculated for each story using the story stiffness approach, and serve to demonstrate the relativeconservatism and accuracy of the proposed models with respect to current practice in design. The study finds that the observed moment amplification factors may vastly exceed expectations when internal member stresses are initially very small. Where the internal stresses are small relative to the member capacities, thesecases are inconsequential for design. To qualify the significance of the observed amplification factors, two parameters are used: the second-order moment normalized to the plastic moment capacity, and the combined flexural and axial stress interaction equations developed by AISC