Calorimetric Study of the Oxidation of Dithiothreitol

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Abstract
The enthalpy changes of the oxidation of dithiothreitol (DTT) by ferricyanide were measured calorimetrically in the pH range of 6 to 13 in various buffer solutions at 298 K. By combining the results of potentiometric titrations with the pH dependence of the observed enthalpy changes, the enthalpy changes of DTT oxidation and of the ionization of DTT sulfhydryls were evaluated. The enthalpy changes of oxidation of the non-ionized and the fully ionized DTT were found to be ΔHDTT (non-ionized) = 32±3 kJ mol−1 and ΔHDTT (fully ionized) = −38±3 kJ mol−1, respectively. The enthalpy changes of the first and the second ionizations of DTT sulfhydryls were found to be ΔH1 = 48±2 kJ mol−1 and ΔH2 = 21±3 kJ mol−1, respectively.

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