Accurate proton affinity and gas-phase basicity values of molecules important in biocatalysis

The Journal of Physical Chemistry B vol. 114  p. 13911-13921  DOI: 10.1021/jp107450n
PMID/PMCID: PMC2970571 Published: 2010-11-04 


Adam Moser, Kevin Range, Darrin M. York [ ]

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Abstract

Benchmark quantum calculations of proton affinities and gas-phase basicities of molecules relevant to biochemical processes, particularly acid/base catalysis, are presented and compared for a variety of multilevel and density functional quantum models. Included are nucleic acid bases in both keto and enol tautomeric forms, ribose in B-form and A-form sugar pucker conformations, amino acid side chains and backbone molecules, and various phosphates and phosphoranes, including thio substitutions. This work presents a high-level thermodynamic characterization of biologically relevant protonation states and provides a benchmark database for development of next-generation semiempirical and approximate density functional quantum models and parametrization of methods to predict pKa values and relative solvation energies.