Absolute pKa Determinations for Substituted Phenols

The CBS-QB3 method was used to calculate the gas-phase free energy difference between 20 phenols and their respective anions, and the CPCM continuum solvation method was applied to calculate the free energy differences of solvation for the phenols and their anions. The CPCM solvation calculations were performed on both gas-phase and solvent-phase optimized structures. Absolute pKa calculations with solvated phase optimized structures for the CPCM calculations yielded standard deviations and root-mean-square errors of less than 0.4 pKa unit. This study is the most accurate absolute determination of the pKa values of phenols, and is among the most accurate of any such calculations for any group of compounds. The ability to make accurate predictions of pKa values using a coherent, well-defined approach, without external approximations or fitting to experimental data, is of general importance to the chemical community. The solvated phase optimized structures of the anions are absolutely critical to obtain this level of accuracy, and yield a more realistic charge separation between the negatively charged oxygen and the ring system of the phenoxide anions.

Comparison of CBS-QB3, CBS-APNO, and G3 predictions of gas phase deprotonation data

The G3, CBS-QB3, and CBS-APNO methods have been used to calculate ΔH and ΔG values for deprotonation of seventeen gas-phase reactions where the experimental values are reported to be accurate within one kcal/mol. For these reactions, the mean absolute deviation of these three methods from experiment is 0.84 to 1.26 kcal/mol, and the root-mean-square deviation for ΔG and ΔH is 1.43 and 1.49 kcal/mol for the CBS-QB3 method, 1.06 and 1.14 kcal/mol for the CBS-APNO method, and 1.16 and 1.28 for the G3 method. The high accuracy of these methods makes them reliable for calculating gas-phase deprotonation reactions, and allows them to serve as a valuable check on the accuracy of experimental data reported in the National Institutes of Standards and Technology database.

Examining the Role of Vocational Rehabilitation on Access to Care and Public Health Outcomes for People Living with HIV/AIDS

The purpose of this study is to examine the role of vocational rehabilitation services in contributing to the goals of the National HIV/AIDS strategy. Three key research questions are addressed: (a) What is the relationship among factors associated with the use of vocational rehabilitation services for people living with HIV/AIDS? (b) Are the factors associated with use of vocational rehabilitation also associated with access to health care, supplemental employment services and reduced risk of HIV transmission? And (c) What unique role does use of vocational rehabilitation services play in access to health care and HIV prevention? Survey research methods were used to collect data from a broad sample of volunteer respondents who represented diverse racial (37% Black, 37% White, 18% Latino, 7% other), gender (65% male, 34% female, 1% transgender) and sexual orientation (48% heterosexual, 44% gay, 8% bisexual) backgrounds. The fit of the final structural equation model was good (root mean square error of approximation = .055, Comparative Fit Index=.953, Tucker Lewis Index=.945). Standardized effects with bootstrap confidence intervals are reported. Overall, the findings support the hypothesis that vocational rehabilitation services can play an important role in health and prevention strategies outlined in the National HIV/AIDS strategy.