The Intrinsic PkA-Values of Functional Groups in Enzymes: Improper Deductions from the Ph-Dependence of Steady-State Parameter

Abstract
For many years, the ease with which the pH of enzyme reactions could be varied has led to innumerable reports of the pH-dependence of the kinetic parameters of such reactions. These studies have been provided with a veneer of respectability by suggestions that they allow deductions to be made about the nature of the ionizing groups upon which the catalytic activity of the enzyme depends. It is the purpose of this article to summarize some of the reasons why a large proportion of pH-dependence studies yields little information about the real pKa-values of ionizing groups in enzymes, and still less about the identity of these groups.