ArticleBiochimica et biophysica acta. General subjects2018
Accounting for apparent deviations between calorimetric and van't Hoff enthalpies.
Article in Biochimica et biophysica acta. General subjects, 2018. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 4 papers.
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4 citing papers in PubMed.
- Solvation free energy in governing equations for DNA hybridization, protein-ligand binding, and protein folding.FEBS open bio · 2024Article
- Dual Effect of Secondary Solutes on Binding Equilibria: Contributions from Solute-Reactant Interactions and Solute-Water Interactions.ACS omega · 2024Article
- Analysis of the Structural Dynamics of Proteins in the Ligand-Unbound and -Bound States by Diffracted X-ray Tracking.International journal of molecular sciences · 2023Review
- Estimation of non-constant variance in isothermal titration calorimetry using an ITC measurement model.PloS one · 2020Article
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3 authors.
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Abstract
backgroundIn theory, binding enthalpies directly obtained from calorimetry (such as ITC) and the temperature dependence of the binding free energy (van't Hoff method) should agree. However, previous studies have often found them to be discrepant.
methodsExperimental binding enthalpies (both calorimetric and van't Hoff) are obtained for two host-guest pairs using ITC, and the discrepancy between the two enthalpies is examined. Modeling of artificial ITC data is also used to examine how different sources of error propagate to both types of binding enthalpies.
resultsFor the host-guest pairs examined here, good agreement, to within about 0.4kcal/mol, is obtained between the two enthalpies. Additionally, using artificial data, we find that different sources of error propagate to either enthalpy uniquely, with concentration error and heat error propagating primarily to calorimetric and van't Hoff enthalpies, respectively.
conclusionsWith modern calorimeters, good agreement between van't Hoff and calorimetric enthalpies should be achievable, barring issues due to non-ideality or unanticipated measurement pathologies. Indeed, disagreement between the two can serve as a flag for error-prone datasets. A review of the underlying theory supports the expectation that these two quantities should be in agreement. GENERAL SIGNIFICANCE: We address and arguably resolve long-standing questions regarding the relationship between calorimetric and van't Hoff enthalpies. In addition, we show that comparison of these two quantities can be used as an internal consistency check of a calorimetry study.
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