title: The AIBLHiCoS Method: Predicting Aqueous pKa Values from Gas-Phase Equilibrium Bond Lengths.
abstract: The proposed AIBLHiCoS method predicts a given compound's pKa in aqueous solution from a single ab initio bond length only, after geometry optimization in the gas phase. Here we provide simple and predictive equations for naphthols and chemically similar biomolecules. Each linear equation corresponds to a High-Correlation Subset (HiCoS) that expresses the novel type of linear free energy relationship discovered here. The naphthol family exhibits a clear and strong relationship with the phenol family, with the "active" C-O bond always producing the highest correlations. The proposed method can isolate erroneous experiments and operate in non-aqueous solution and at different temperatures. Moreover, the existence of "active fragments" is demonstrated in a variety of sizable biomolecules for which the pKa is successfully predicted.
authors.affiliation: Manchester Institute of Biotechnology (MIB) , 131 Princess Street, Manchester M1 7DN, United Kingdom.|School of Chemistry, University of Manchester , Oxford Road, Manchester M13 9PL, United Kingdom.
authors.forename: Cate
authors.initials: C
authors.lastname: Anstöter
authors.affiliation: Manchester Institute of Biotechnology (MIB) , 131 Princess Street, Manchester M1 7DN, United Kingdom.|School of Chemistry, University of Manchester , Oxford Road, Manchester M13 9PL, United Kingdom.
authors.forename: Beth A
authors.initials: BA
authors.lastname: Caine
authors.affiliation: Manchester Institute of Biotechnology (MIB) , 131 Princess Street, Manchester M1 7DN, United Kingdom.|School of Chemistry, University of Manchester , Oxford Road, Manchester M13 9PL, United Kingdom.
authors.forename: Paul L A
authors.initials: PL
authors.lastname: Popelier
mesh_terms: D005740:Gases; D007700:Kinetics; D010636:Phenols / Q000737:chemistry*; D013816:Thermodynamics; D014867:Water / Q000737:chemistry
chemical_list: D005740:Gases; D010636:Phenols; D014867:Water