Evidence for the Presence of Two Kinetically Distinct Active Forms of Ribonuclease T2

Abstract
A kinetic study was made of the (Aspergillus oryzae) RNase-T2-catalyzed transphosphorylation of 2 adenine nucleotides, adenylyl(3''-5'')uridine and adenosine 3''-(1-naphthyl)phosphate. Rates were measured at pH values ranging from 2.6-8.2. The observed shape of the plot of log kcat against pH for both the natural and the synthetic substrate suggests that there exist 2 parallel rate-determining pathways. Two pH-independent rate constants and 3 Ki of the enzyme-substrate complexes were obtained by nonlinear iterative least-squares analysis. Detailed interpretation of the pH profiles was carried out and it is proposed that carboxylate anion is likely to deprotonate O-2'' at 4 < pH < 6 but at pH > 6 an alternative general base would play this role more effectively than the carboxylate group. Another base in its protonated cationic form is responsible for the general acid catalysis.