Positive and negative analyte ion yield in matrix-assisted laser desorption/ionization revisited

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Author(s) Hillenkamp, Franz, Wäfler, Esther, Jecklin, Matthias C., Zenobi, Renato
Publication Type Journal Items, Publication Status: Published
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Title Positive and negative analyte ion yield in matrix-assisted laser desorption/ionization revisited
Author(s) Hillenkamp, Franz
Wäfler, Esther
Jecklin, Matthias C.
Zenobi, Renato
Journal or Series Title International journal of mass spectrometry
Volume Number 285
Issue Number 3
Start Page 114
End Page 119
ISSN 1387-3806
Publisher Elsevier
Publication Place Amsterdam
Publication Date 2009
Keyword(s) MALDI
Plume reactions
Proton transfer
Abstract The most commonly accepted model for the formation of analyte ions in MALDI-MS assumes a primary ionization of the matrix e.g., by photoionization, leading among others to stable protonated and deprotonated matrix ions, respectively. Peptide and protein ions are then formed by secondary proton transfer reactions in the expanding plume. This model had been checked experimentally by comparing the yield of positive to negative ions of three peptides (Bradykinin, Angiotensin I and Fibrinopeptide A) and six matrices (alpha-cyano-4-hydroxycinnamicacid (CHCA), 2,5-dihydroxybenzoicacid (DHB), 6-aza-2-thiothymine (ATT), 4-nitroaniline (4-NA), 2-amino-5-nitro-4-picoline (ANP), 5-aminoquinolione (5-AQ)), differing in gas-phase basicity by about 100kJ/mole [M. Dashtiev, E. Wafler, U. Rohling, M. Gorshkov, F. Hillenkamp, R. Zenobi, Int. J. Mass Spetrom. 268 (2007) 122). The data have been revisited for a more general and in-depth analysis. Model predictions are presented for a wide range of experimental parameters, in particular for ranges of the gas-phase basicity and acidity of analyte and matrix and for different molar ratios of analyte to matrix as well as the yield of primary matrix ions. It is shown that the observed ion yields cannot be explained by any single and consistent set of parameters. It is concluded that the existing simple model needs be modified to fully explain the experimental findings. Such modifications should primarily address the formation of negative matrix and analyte ions.
DOI 10.1016/j.ijms.2009.02.028
Additional Notes Received 24 December 2008, Revised 23 February 2009, Accepted 24 February 2009, Available online 24 March 2009
Document Type Article
Publication Status Published
Language English
Assigned Organisational Unit(s) 03430
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NEBIS System Number 000024690
Source Database ID PP-50257
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  author = "Hillenkamp, Franz and W{\"{a}}fler, Esther and Jecklin, Matthias C. and Zenobi, Renato",
  title = "{P}ositive and negative analyte ion yield in matrix-assisted laser desorption/ionization revisited",
  journal = "International journal of mass spectrometry",
  year = 2009,
  volume = "285",
  number = "3",
  pages = "114--119",

E-Citations record created: Wed, 23 Jun 2010, 20:09:41 CET