Investigation of Deprotonation Reactions on Globular and Denatured Proteins at Atmospheric Pressure by ESSI-MS

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Author(s) Touboul, David, Jecklin, Matthias Conradin, Zenobi, Renato
Publication Type Journal Items, Publication Status: Published
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Title Investigation of Deprotonation Reactions on Globular and Denatured Proteins at Atmospheric Pressure by ESSI-MS
Author(s) Touboul, David
Jecklin, Matthias Conradin
Zenobi, Renato
Journal or Series Title Journal of the American Society for Mass Spectrometry
Volume Number 19
Issue Number 4
Start Page 455
End Page 466
ISSN 1044-0305
Publisher Elsevier Science
Publication Place New York
Publication Date 2008
Abstract Deprotonation reactions of multiply charged protein ions have been studied by introducing volatile reference bases at atmospheric pressure between an electrosonic spray ionization (ESSI) source and the inlet of a mass spectrometer. Apparent gas-phase basicities (GBapp) of different charge states of protein ions were determined by a bracketing approach. The results obtained depend on the conformation of the protein ions in the gas phase, which is linked to the type of buffer used (denaturing or nondenaturing). In nondenaturing buffer, the GBapp values are consistent with values predicted by the group of Kebarle using an electrostatic model (J. Mass Spectrom. 2002, 38, 618) based on the crystal structures, but taking into account salt bridges between ionized basic and acidic sites on the protein surface. A new basicity order for the most basic sites was therefore obtained. An excellent agreement with the charge residue model (CRM) is obtained when comparing the observed and calculated maximum charge state. Decharging of the proteins in the electrosonic spray process could be also useful in the study on noncovalent complexes, by decreasing repulsive electrostatic interactions. A unified mechanism of the ESSI process is proposed.
DOI 10.1016/j.jasms.2007.12.011
Additional Notes Received 3 October 2007, Revised 30 December 2007, Accepted 30 December 2007, Published online 17 January 2008
Document Type Article
Publication Status Published
Language English
Assigned Organisational Unit(s) 03430
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NEBIS System Number 000541631
Source Database ID PP-40957
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  author = "Touboul, David and Jecklin, Matthias Conradin and Zenobi, Renato",
  title = "{I}nvestigation of {D}eprotonation {R}eactions on {G}lobular and {D}enatured {P}roteins at {A}tmospheric {P}ressure by {E}{S}{S}{I}-{M}{S}",
  journal = "Journal of the American Society for Mass Spectrometry",
  year = 2008,
  volume = "19",
  number = "4",
  pages = "455--466",

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