Thermodynamics of proton dissociation in dilute aqueous solution. Part XIV. pK, ΔH°, and ΔS° values for proton dissociation from several pyrimidines and their nucleosides at 10 and 40 °C
Abstract
Thermodynamic pK, ΔH°, and ΔS° values have been determined for proton ionization from cytosine, cytidine, thymine, thymidine, and uracil at 10 and 40 °C, and from uridine at 10 °C. Electrostatics is shown to account primarily for the variation of the thermodynamic quantities with temperature. The ΔH° values at 10 and 40 °C are combined with values at 25 °C to calculate ΔCp values valid over the range 10–40 °C (10–25 °C in the case of uridine). Relationships between ΔCp and the charge types, and between the ΔH° values and the sites of protonation of cytosine and cytidine are discussed.