Calorimetric vs. van't Hoff binding enthalpies from isothermal titration calorimetry: Ba2+-crown ether complexation

Biophysical Chemistry
Laura S Mizoue, Joel Tellinghuisen

Abstract

The 1:1 complexation reaction between Ba(2+) and 18-crown-6 ether is re-examined using isothermal titration calorimetry (ITC), with the goal of clarifying previously reported discrepancies between reaction enthalpies estimated directly (calorimetric) and indirectly, from the temperature dependence of the reaction equilibrium constant K (van't Hoff). The ITC thermograms are analyzed using three different non-linear fit models based on different assumptions about the data error: constant, proportional to the heat and proportional but correlated. The statistics of the fitting indicate a preference for the proportional error model, in agreement with expectations for the conditions of the experiment, where uncertainties in the delivered titrant volume should dominate. With attention to proper procedures for propagating statistical error in the van't Hoff analysis, the differences between Delta H(cal) and Delta H(vH) are deemed statistically significant. In addition, statistically significant differences are observed for the Delta H(cal) estimates obtained for two different sources of Ba(2+), BaCl(2) and Ba(NO(3))(2). The effects are tentatively attributed to deficiencies in the standard procedure in ITC of subtracting a blank obtain...Continue Reading

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Feb 11, 2004·Analytical Biochemistry·Laura S Mizoue, Joel Tellinghuisen

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Citations

Jul 12, 2011·Analytical Biochemistry·Neil A DemarseLee D Hansen
Oct 15, 2013·Journal of Pharmaceutical and Biomedical Analysis·Piotr DraczkowskiKrzysztof Jozwiak
Jul 8, 2009·International Journal of Molecular Sciences·Lina BaranauskieneDaumantas Matulis
Feb 11, 2004·Analytical Biochemistry·Laura S Mizoue, Joel Tellinghuisen
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Sep 29, 2004·Analytical Biochemistry·Joel Tellinghuisen
Nov 21, 2015·Biochimica Et Biophysica Acta·Piotr DraczkowskiKrzysztof Jozwiak
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Jul 21, 2006·The Journal of Physical Chemistry. B·Joel Tellinghuisen
Sep 14, 2007·The Journal of Physical Chemistry. B·Joel Tellinghuisen

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