Ortho Effect in the Bergman Cyclization: Electronic and Steric Effects in Hydrogen Abstraction by 1-Substituted Naphthalene 5,8-Diradicals

We present a detailed theoretical study of geometries, electronic structure, and energies of transition states and intermediates completing the full Bergman cycloaromatization pathway of ortho-substituted enediynes with a focus on polar and steric contributions to the kinetics and thermodynamics of hydrogen abstraction. This study provides a rare unambiguous example of remote substitution that affects reactivity of a neutral reactive intermediate through an σ framework.

Feminist Tigers and Patriarchal Lions: Rhetorical Strategies and Instrument Effects in the Struggle for Definition and Control over Development in Nepal

This article offers an analysis of a struggle for control of a women’s development project in Nepal. The story of this struggle is worth telling, for it is rife with the gender politics and neo-colonial context that underscore much of what goes on in contemporary Nepal. In particular, my analysis helps to unravel some of the powerful discourses, threads of interest, and yet unintended effects inevitable under a regime of development aid. The analysis demonstrates that the employment of already available discursive figures of the imperialist feminist and the patriarchal third world man are central to the rhetorical strategies taken in the conflict. I argue that the trans-discursive or “borderland” nature of development in general and women’s development in particular result in different constructions of “development” goals, means and actors based not only on divergent cultural categories but on historically specific cultural politics. I argue further that the apolitical discourse of development serves to cloak its inherently political project of social and economic transformation, making conflicts such as the one that occurred in this case not only likely to occur but also likely to be misunderstood.

Audience Effects in COgnitive Task Performance in Capuchin Monkeys (Cebus apella)

Primates as a taxonomic Order have the largest brains corrected for body size in the animal kingdom. These large brains have allowed primates to evolve the capacity to demonstrate advanced cognitive processes across a wide array of abilities. Nonhuman primates are particularly adept at social learning, defined as the modification of behavior by observing the actions of others. Additionally, primates often exploit resources differently depending on their social context. In this study, capuchin monkeys (Cebus apella) were tested on a cognitive task in three social contexts to determine if social context influenced their performance on the task. The three social contexts included: alone, having a dominant individual in an adjacent compartment, and having a subordinate individual in the adjacent compartment. The benefits to this design were thatthe social context was the only variable influencing performance, whereas in previous studies investigating audience effects other animals could physically and directly influence a subject's performance in an open testing situation. Based on past studies, Ipredicted that the presence of a dominant individual would reduce cognitive task performance compared to the other conditions. The cognitive test used was a match-tosample discrimination task in which animals matched combinations of eight geometric shapes. Animals were trained on this task in an isolated context until they reached a baseline level of proficiency and were then tested in the three social contexts in a random order multiple times. Two subjects (Mt and Dv) have successfully completed trials under all conditions. Results indicated that there were no significant difference in taskperformance across the three conditions (Dv x^2 (1) = 0.42, p=0.58; Mt x^2 (1) = 0.02, p=0.88). In all conditions, subjects performed significantly above chance (i.e., 39/60 trials determined by a binomial distribution). Results are contrary to previous studies thatreport low status monkeys 'play dumb' when testing in a mixed social context, possibly because other studies did not account for aggressive interference by dominants while testing. Results of this study suggest that the mere presence of a dominant individualdoes not necessarily affect performance on a cognitive task, but rather the imminence of physical aggression is the most important factor influencing testing in a social context.

Childhood Adoption: Long-Term Effects in Adulthood

Clinicians and researchers have characterized early life experiences as permanent and stable influences on the personality and subsequent life experiences of an individual. Recent conceptualizations have suggested that personal and environmental factors influencing development are not deterministic. Multiple pathways into adulthood are possible. Adoption is one potential early life stressor that may illustrate the usefulness of such conceptualizations for assessing long-term effects in adulthood. Previous studies of adoption have characterized the effects of adoption into adolescence and young adulthood. The purpose of this study was to provide an initial assessment of the long-term impact of adoption. The participants were taken from the Swedish Adoption/Twin Study of Aging. From the original sample, we identified a subsample of 60 pairs of twins who were separated and reared apart, with one member being raised by a biological parent or parents and the other by an adoptive parent or parents with no biological relationship. A series of univariate and multivariate analyses were undertaken to assess the elements associated with being reared in either an adoptive home or the home of biological parent(s). The results suggest few significant effects of adoption on the adult adjustment of adoptees. In particular, the results reflect the important mediating role of childhood socioeconomic status, suggesting that the stress of adoption itself is mediated by the type of rearing environment provided by the adoption process.

The Role of Anharmonicity in Hydrogen-Bonded Systems: The Case of Water Clusters

The nature of vibrational anharmonicity has been examined for the case of small water clusters using second-order vibrational perturbation theory (VPT2) applied on second-order Møller–Plesset perturbation theory (MP2) potential energy surfaces. Using a training set of 16 water clusters (H2O)n=2–6,8,9 with a total of 723 vibrational modes, we determined scaling factors that map the harmonic frequencies onto anharmonic ones. The intermolecular modes were found to be substantially more anharmonic than intramolecular bending and stretching modes. Due to the varying levels of anharmonicity of the intermolecular and intramolecular modes, different frequency scaling factors for each region were necessary to achieve the highest accuracy. Furthermore, new scaling factors for zero-point vibrational energies (ZPVE) and vibrational corrections to the enthalpy (ΔHvib) and the entropy (Svib) have been determined. All the scaling factors reported in this study are different from previous works in that they are intended for hydrogen-bonded systems, while others were built using experimental frequencies of covalently bonded systems. An application of our scaling factors to the vibrational frequencies of water dimer and thermodynamic functions of 11 larger water clusters highlights the importance of anharmonic effects in hydrogen-bonded systems.

The Role of Anharmonicity in Hydrogen-Bonded Systems: The Case of Water Clusters

The nature of vibrational anharmonicity has been examined for the case of small water clusters using second-order vibrational perturbation theory (VPT2) applied on second-order Møller–Plesset perturbation theory (MP2) potential energy surfaces. Using a training set of 16 water clusters (H2O)n=2–6,8,9 with a total of 723 vibrational modes, we determined scaling factors that map the harmonic frequencies onto anharmonic ones. The intermolecular modes were found to be substantially more anharmonic than intramolecular bending and stretching modes. Due to the varying levels of anharmonicity of the intermolecular and intramolecular modes, different frequency scaling factors for each region were necessary to achieve the highest accuracy. Furthermore, new scaling factors for zero-point vibrational energies (ZPVE) and vibrational corrections to the enthalpy (ΔHvib) and the entropy (Svib) have been determined. All the scaling factors reported in this study are different from previous works in that they are intended for hydrogen-bonded systems, while others were built using experimental frequencies of covalently bonded systems. An application of our scaling factors to the vibrational frequencies of water dimer and thermodynamic functions of 11 larger water clusters highlights the importance of anharmonic effects in hydrogen-bonded systems.