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.
Similar content being viewed by others
References
Cooks, R.G., Kruger, T.L.: Intrinsic basicity determination using metastable ions. J. Am. Chem. Soc. 99, 1279–1281 (1977)
Cooks, R.G., Koskinen, J.T., Thomas, P.D.: The kinetic method of making thermochemical determinations. J. Mass Spectrom. 34, 85–92 (1999)
McLuckey, S.A., Cameron, D., Cooks, R.G.: Proton affinities from dissociations of proton-bound dimers. J. Am. Chem. Soc. 103, 1313–1317 (1981)
Majumdar, T.K., Clairet, F., Tabet, J.C., Cooks, R.G.: Epimer distinction and structural effects on gas-phase acidities of alcohols measured using the kinetic method. J. Am. Chem. Soc. 114, 2897–2903 (1992)
Cheng, X., Wu, Z., Fenselau, C.: Collision energy dependence of proton-bound dimer dissociation: entropy effects, proton affinities, and intramolecular hydrogen-bonding in protonated peptides. J. Am. Chem. Soc. 115, 4844–4848 (1993)
Drahos, L., Peltz, C., Vékey, K.: Accuracy of enthalpy and entropy determination using the kinetic method: are we approaching a consensus? J. Mass Spectrom. 39, 1016–1024 (2004)
Ervin, K.M., Armentrout, P.B.: Systematic and random errors in ion affinities and activation entropies from the extended kinetic method. J. Mass Spectrom. 39, 1004–1015 (2004)
Nold, M.J., Cerda, B.A., Wesdemiotis, C.: Proton affinities of the N- and C-terminal segments arising upon the dissociation of the amide bond in protonated peptides. J. Am. Soc. Mass Spectrom. 10, 1–8 (1999)
Vekey, K.: Internal energy effects in mass spectrometry. J. Mass Spectrom. 31, 445–463 (1996)
Drahos, L., Vekey, K.: How closely related are the effective and the real temperature. J. Mass Spectrom. 34, 79–84 (1999)
Wenthold, P.G.: Determination of the proton affinities of bromo- and iodoacetonitrile using the kinetic method with full entropy analysis. J. Am. Soc. Mass Spectrom. 11, 601–605 (2000)
Armentrout, P.B.: Entropy measurements and the kinetic method: a statistically meaningful approach. J. Am. Soc. Mass Spectrom. 11, 371–379 (2000)
Bouchoux, G., Buisson, D.-A., Bourcier, S., Sablier, M.: Application of the kinetic method to bifunctional bases ESI tandem quadrupole experiments. Int. J. Mass Spectrom. 228, 1035–1054 (2003)
Drahos, L., Vekey, K.: Entropy evaluation using the kinetic method: is it feasible? J. Mass Spectrom. 38, 1025–1042 (2003)
Fournier, F., Afonso, C., Fagin, A.E., Gronert, S., Tabet, J.-C.: Can cluster structure affect kinetic method measurements? The curious case of glutamic acid's gas-phase acidity. J. Am. Soc. Mass Spectrom. 19, 1887–1896 (2008)
Bouchoux, G., Defaye, D., McMahon, T., Likholyot, A., Mo, O., Yanez, M.: Structural and energetic aspects of the protonation of phenol, catechol, resorcinol, and hydroquinone. Chem.–Eur. J. 8, 2900–2909 (2002)
Barbour, J.B., Karty, J.M.: Resonance and field/inductive substituent effects on the gas-phase acidities of para-substituted phenols: a direct approach employing density functional theory. J. Phys. Org. Chem. 18, 210–216 (2005)
Fujio, M., McIver Jr., R.T., Taft, R.W.: Effects of the acidities of phenols from specific substituent-solvent interactions. Inherent substituent parameters from gas-phase acidities. J. Am. Chem. Soc. 103, 4017–4029 (1981)
Boggs, P.T., Byrd, R.H., Rogers, J.E., Schnabel, R.B.: ODRPACK Version 2.01 Software for Weighted Orthogonal Distance Regression. National Institute of Standards and Technology, Gaithersburg (1992)
Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Zakrzewski, V.G., Montgomery, J.A., Stratmann, R.E., Burant, J.C., Dapprich, S., Millam, J.M., Daniels, A.D., Kudin, K.N., Strain, M.C., Farkas, O., Tomasi, J., Barone, V., Cossi, M., Cammi, R., Mennucci, B., Pomelli, C., Adamo, C., Clifford, S., Ochterski, J., Petersson, G.A., Ayala, P.Y., Cui, Q., Morokuma, K., Rega, N., Salvador, P., Dannenberg, J.J., Malick, D.K., Rabuck, A.D., Raghava-chari, K., Foresman, J.B., Cioslowski, J., Ortiz, J.V., Baboul, A.G., Stefanov, B.B., Liu, G., Liashenko, A., Piskorz, P., Komaromi, I., Gomperts, R., Martin, R.L., Fox, D.J., Keith, T., Al-Laham, M.A., Peng, C.Y., Nanayakkara, A., Challacombe, M., Gill, P.M.W., Johnson, B., Chen, W., Wong, M.W., Andres, J.L., Gonzalez, C., Head-Gordon, M., Replogle, E.S., Pople, J.A.: Gaussian 03. Gaussian, Inc, Pittsburgh (2002)
Nikolaev, E.N., Popov, I.A., Kharybin, O.N., Kononikhin, A.S., Nikolaeva, M.I., Borisov, Y.V.: In situ recognition of molecular chirality by mass spectrometry. Hydration effects on differential stability of homo- and heterochiral dimethyl tartrate clusters. Int. J. Mass Spectrom. 265, 347–358 (2007)
Ma, S., Wang, F., Cooks, R.G.: Gas-phase acidity of urea. J. Mass Spectrom. 33, 943–949 (1998)
Mezzache, S., Bruneleau, N., Vekey, K., Afonso, C., Karoyan, P., Fournier, F., Tabet, J.C.: Improved proton affinity measurements for proline and modified prolines using triple quadrupole and ion trap mass spectrometers. J. Mass Spectrom. 40, 1300–1308 (2005)
Afonso, C., Modeste, F., Breton, P., Fournier, F., Tabet, J.C.: Proton affinities of the commonly occuring L-amino acids by using electrospray ionization-ion trap mass spectrometry. Eur. J. Mass Spectrom. 6, 443–449 (2000)
Bourgoin-Voillard, S., Fournier, F., Afonso, C., Zins, E.L., Jacquot, Y., Pepe, C., Leclercq, G., Tabet, J.C.: Electronic effects of 11β substituted 17β-estradiol derivatives and instrumental effects on the relative gas phase acidity. J. Am. Soc. Mass Spectrom. 23, 2167–2177 (2012)
Chernushevich, I.V.: Duty cycle improvement for a quadrupole-time-of-flight mass spectrometer and its use for precursor ion scans. Eur. J. Mass Spectrom. 6, 471–479 (2000)
McMahon, T.B., Kebarle, P.: Intrinsic acidities of substituted phenols and benzoic acids determined by gas-phase proton-transfer equilibriums. J. Am. Chem. Soc. 99, 2222–2230 (1977)
Lorenz, U.J., Rizzo, T.R.: Multiple isomers and protonation sites of the phenylalanine/serine dimer. J. Am. Chem. Soc. 134, 11053–11055 (2012)
Jia, B., Angel, L.A., Ervin, K.M.: Threshold collision-induced dissociation of hydrogen-bonded dimers of carboxylic acids. J. Phys. Chem. A 112, 1773–1782 (2008)
Ervin, K.M.: Microcanonical analysis of the kinetic method. The meaning of the "effective temperature.". Int. J. Mass Spectrom. 195/196, 271–284 (2000)
March, R.E.: An introduction to quadrupole ion trap mass spectrometry. J. Mass Spectrom. 32, 351–369 (1997)
Shukla, A.K., Futrell, J.H.: Tandem mass spectrometry: dissociation of ions by collisional activation. J. Mass Spectrom. 35, 1069–1090 (2000)
Rodgers, M.T., Armentrout, P.B.: Statistical modeling of competitive threshold collision-induced dissociation. J. Chem. Phys. 109, 1787–1800 (1998)
DeTuri, V.F., Ervin, K.M.: Competitive threshold collision-induced dissociation: gas-phase acidities and bond dissociation energies for a series of alcohols. J. Phys. Chem. A 103, 6911–6920 (1999)
Rodgers, M.T., Ervin, K.M., Armentrout, P.B.: Statistical modeling of collision-induced dissociation thresholds. J. Chem. Phys. 106, 4499–4508 (1997)
Armentrout, P.B., Ervin, K.M., Rodgers, M.T.: Statistical rate theory and kinetic energy-resolved ion chemistry: theory and applications. J. Phys. Chem. A 112, 10071–10085 (2008)
Holbrook, K.A., Pilling, M.J., Robertson, S.H.: Unimolecular Reactions, 2nd ed, Wiley: Chichester (1996)
Gilbert, R.G., Smith, S.C.: Theory of Unimolecular and Recombination Reactions, Blackwell Scientific Publishing: Oxford (1990)
Pak, A., Lesage, D., Gimbert, Y., Vekey, K., Tabet, J.-C.: Internal energy distribution of peptides in electrospray ionization: ESI and collision-induced dissociation spectra calculation. J. Mass Spectrom. 43, 447–455 (2008)
Naban-Maillet, J., Lesage, D., Bossée, A., Gimbert, Y., Sztáray, J., Vékey, K., Tabet, J.-C.: Internal energy distribution in electrospray ionization. J. Mass Spectrom. 40, 1–8 (2005)
Muntean, F., Armentrout, P.B.: Guided ion beam study of collision-induced dissociation dynamics: integral and differential cross sections. J. Chem. Phys. 115, 1213–1228 (2001)
Angel, L.A., Ervin, K.M.: Gas-phase acidities and O–H bond dissociation enthalpies of phenol, 3-methylphenol, 2,4,6-trimethylphenol, and ethanoic acid. J. Phys. Chem. A 110, 10392–10403 (2006)
Armentrout, P.B.: Mass spectrometry—not just a structural tool: the use of guided ion beam tandem mass spectrometry to determine thermochemistry. J. Am. Soc. Mass Spectrom. 13, 419–434 (2002)
Cooks, R.G., Patrick, J.S., Kotiaho, T., McLuckey, S.A.: Thermochemical determinations by the kinetic method. Mass Spectrom. Rev. 13, 287–339 (1994)
Linstrom, P.J., Mallard, W.G.: In: National Institute of Standards and Technology, Gaithersburg MD, 20899. Available at: http://webbook.nist.gov (2005)
Bouchoux, G.: Evaluation of the protonation thermochemistry obtained by the extended kinetic method. J. Mass Spectrom. 41, 1006–1013 (2006)
Remes, P.M., Glish, G.L.: On The time scale of internal energy relaxation of AP-MALDI and nano-ESI ions in a quadrupole ion trap. J. Am. Soc. Mass Spectrom. 20, 1801–1812 (2009)
Afonso, C., Lesage, D., Fournier, F., Mancel, V., Tabet, J.-C.: Origin of enantioselective reduction of quaternary copper d, l amino acid complexes under vibrational activation conditions. Int. J. Mass Spectrom. 312, 185–194 (2012)
Caldwell, G.W., Renneboog, R., Kebarle, P.: Gas-phase acidities of aliphatic carboxylic acids, based on measurements of proton-transfer equilibria. Can. J. Chem. 67, 611–618 (1989)
Graul, S.T., Schnute, M.E., Squires, R.R.: Gas-phase acidities of carboxylic acids and alcohols from collision-induced dissociation of dimer cluster ions. Int. J. Mass Spectrom. Ion Process. 96, 181–198 (1990)
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.
Author information
Authors and Affiliations
Corresponding author
Electronic supplementary material
Below is the link to the electronic supplementary material.
ESM 1
(DOC 881 kb)
Rights and permissions
About this article
Cite this article
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
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s13361-012-0554-0