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Critical Evaluation of Kinetic Method Measurements: Possible Origins of Nonlinear Effects

  • Research Article
  • Published:
Journal of The American Society for Mass Spectrometry

Abstract

The kinetic method is a widely used approach for the determination of thermochemical data such as proton affinities (PA) and gas-phase acidities (ΔH° acid ). These data are easily obtained from decompositions of noncovalent heterodimers if care is taken in the choice of the method, references used, and experimental conditions. Previously, several papers have focused on theoretical considerations concerning the nature of the references. Few investigations have been devoted to conditions required to validate the quality of the experimental results. In the present work, we are interested in rationalizing the origin of nonlinear effects that can be obtained with the kinetic method. It is shown that such deviations result from intrinsic properties of the systems investigated but can also be enhanced by artifacts resulting from experimental issues. Overall, it is shown that orthogonal distance regression (ODR) analysis of kinetic method data provides the optimum way of acquiring accurate thermodynamic information.

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Acknowledgments

The authors acknowledge financial support from Research Minister, CNRS, and UPMC. C.A. acknowledges the Région Haute Normandie for financial support. P.B.A. thanks the National Science Foundation, CHE-1049580, for support of this research.

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Author notes

  1. Sandrine Bourgoin-Voillard

    Present address: Cibles diagnostiques ou thérapeutiques et vectorisation de drogues dans le cancer du poumon INSERM U823, Institut Albert Bonniot, Université Joseph Fourier Plate-forme de Protéomique Promethée, Institut de Biologie et Pathologie, CHU de Grenoble BP217, 38043, Grenoble Cedex 9, France

Authors and Affiliations

  1. Institut Parisien de Chimie Moléculaire, UMR CNRS 7201, Université Pierre et Marie Curie-Paris6, Paris, France

    Sandrine Bourgoin-Voillard, Carlos Afonso, Denis Lesage & Jean-Claude Tabet

  2. UMR CNRS 6014 COBRA, Université de Rouen, INSA de Rouen, Mont-Saint-Aignan, France

    Carlos Afonso

  3. Laboratoire de Dynamique, Interactions et Réactivité, LADIR, UMR 7075, CNRS, Université Pierre et Marie Curie-Paris6, Paris, France

    Emilie-Laure Zins

  4. Department of Chemistry, University of Utah, Salt Lake City, UT, 84112, USA

    P. B. Armentrout

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  1. Sandrine Bourgoin-Voillard
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  2. Carlos Afonso
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  6. P. B. Armentrout
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Correspondence to P. B. Armentrout.

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Bourgoin-Voillard, S., Afonso, C., Lesage, D. et al. Critical Evaluation of Kinetic Method Measurements: Possible Origins of Nonlinear Effects. J. Am. Soc. Mass Spectrom. 24, 365–380 (2013). https://doi.org/10.1007/s13361-012-0554-0

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