[en] The early mechanisms of matrix-assisted laser desorption/ionization in-source decay (MALDI-ISD) are described herein. MALDI-ISD is initiated by the hydrogen transfer from excited matrix molecules to the carbonyl oxygen of the peptide backbone, which is followed by a radical-induced cleavage, producing the c′/z• fragment pair. As expected, the use of 2,5-DHB or 1,5-DAN was efficient to induce MALDI-ISD, and the strongest intensity of MALDI-ISD fragments was observed when laser shots were performed on matrix crystals. In contrast, the hydrogen radical transfer reaction was suppressed by using ionic liquid and amorphous structure of 2,5-DHB and 1,5-DAN mixture as a matrix. Our results suggest that the hydrogen transfer occurs on the matrix crystal during the dissipation of the laser energy and before desorption, following ISD fragments formed in the MALDI plume.
Research Center/Unit :
Giga-Systems Biology and Chemical Biology - ULiège
Brown, R. S.; Lennon, J. J. Sequence-Specific Fragmentation of Matrix-Assisted Laser-Desorbed Protein/Peptide Ions Anal. Chem. 1995, 67, 3990-3999
Hardouin, J. Protein Sequence Information by Matrix-Assisted Laser Desorption/Ionization In-Source Decay Mass Spectrometry Mass Spectrom. Rev. 2007, 26, 672-682
Reiber, D. C.; Grover, T. A.; Brown, R. S. Identifying Proteins Using Matrix-Assisted Laser Desorption/Ionization In-Source Fragmentation Data Combined with Database Searching Anal. Chem. 1998, 70, 673-683
Katta, V.; Chow, D. T.; Rohde, M. F. Applications of In-Source Fragmentation of Protein Ions for Direct Sequence Analysis by Delayed Extraction MALDI-TOF Mass Spectrometry Anal. Chem. 1998, 70, 4410-4416
Lennon, J. J.; Walsh, K. A. Direct Sequence Analysis of Proteins by In-Source Fragmentation during Delayed Ion Extraction Protein Sci. 1997, 6, 2446-2453
Takayama, M. N-Cα Bond Cleavage of the Peptide Backbone via Hydrogen Abstraction J. Am. Soc. Mass Spectrom. 2001, 12, 1044-1049
Köcher, T.; Engström, Å.; Zubarev, R. A. Fragmentation of Peptides in MALDI In-Source Decay Mediated by Hydrogen Radicals Anal. Chem. 2005, 77, 172-177
Asakawa, D.; Smargiasso, N.; De Pauw, E. Discrimination of Isobaric Leu/Ile Residues by MALDI In-Source Decay Mass Spectrometry J. Am. Soc. Mass Spectrom. 2013, 24, 297-300
Asakawa, D.; Sakakura, M.; Takayama, M. Influence of Initial Velocity of Analytes on In-Source Decay Products in MALDI Mass Spectrometry Using Salicylic Acid Derivative Matrices. Int. J. Mass Spectrom., in press.
Asakawa, D.; Takayama, M. Cα-C Bond Cleavage of the Peptide Backbone in MALDI In-Source Decay Using Salicylic Acid Derivative Matrices J. Am. Soc. Mass Spectrom. 2011, 22, 1224-1233
Asakawa, D.; Takayama, M. Specific Cleavage at Peptide Backbone C α-C and CO-N Bonds during Matrix-Assisted Laser Desorption/Ionization In-Source Decay Mass Spectrometry with 5-Nitrosalicylic Acid as the Matrix Rapid Commun. Mass Spectrom. 2011, 25, 2379-2383
Asakawa, D.; Takayama, M. Fragmentation Processes of Hydrogen-Deficient Peptide Radicals in Matrix-Assisted Laser Desorption/Ionization In-Source Decay Mass Spectrometry J. Phys. Chem. B 2012, 116, 4016-4023
Scott, C. T. J.; Kosmidis, C.; Jia, W. J.; Ledingham, K. W. D.; Singhal, R. P. Formation of Atomic Hydrogen in Matrix-Assisted Laser Desorption Ionization Rapid Commun. Mass Spectrom. 1994, 8, 829-831
Zubarev, R. A. Reactions of Polypeptide Ions with Electrons in the Gas Phase Mass Spectrom. Rev. 2003, 22, 57-77
Takayama, M. In-Source Decay Characteristics of Peptides in Matrix-Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometry J. Am. Soc. Mass Spectrom. 2001, 12, 420-427
Demeure, K.; Quinton, L.; Gabelica, V.; De Pauw, E. Rational Selection of the Optimum MALDI Matrix for Top-Down Proteomics by In-Source Decay Anal. Chem. 2007, 79, 8678-8685
Quinton, L.; Demeure, K.; Dobson, R.; Gilles, N.; Gabelica, V.; De Pauw, E. New Method for Characterizing Highly Disulfide-Bridged Peptides in Complex Mixtures: Application to Toxin Identification from Crude Venoms J. Proteome Res. 2007, 6, 3216-3223
Strupat, K.; Kampmeier, J.; Horneffer, V. Investigations of 2,5-DHB and Succinic Acid as Matrices for UV and IR MALDI. Part II: Crystallographic and Mass Spectrometric Analysis Int. J. Mass Spectrom. Ion Processes 1997, 169/170, 43-50
Collette, C.; Drahos, L.; De Pauw, E.; Vékey, K. Comparison of the Internal Energy Distributions of Ions Produced by Different Electrospray Sources Rapid Commun. Mass Spectrom. 1998, 12, 1673-1678
Luo, G.; Marginean, I.; Vertes, A. Internal Energy of Ions Generated by Matrix-Assisted Laser Desorption/Ionization Anal. Chem. 2002, 74, 6185-6190
Gabelica, V.; Schulz, E.; Karas, M. Internal Energy Build-up in Matrix-Assisted Laser Desorption/Ionization J. Mass Spectrom. 2004, 39, 579-593
Fukuyama, Y.; Iwamoto, S.; Tanaka, K. Rapid Sequencing and Disulfide Mapping of Peptides Containing Disulfide Bonds by Using 1,5-Diaminonaphthalene as a Reductive Matrix J. Mass Spectrom. 2006, 41, 191-201
Zubarev, R. A.; Kruger, N. A.; Fridriksson, E. K.; Lewis, M. A.; Horn, D. M.; Carpenter, B. K.; McLafferty, F. W. Electron Capture Dissociation of Gaseous Multiply-Charged Proteins Is Favored at Disulfide Bonds and Other Sites of High Hydrogen Atom Affinity J. Am. Chem. Soc. 1999, 121, 2857-2862
Demeure, K.; Gabelica, V.; De Pauw, E. New Advances in the Understanding of the In-Source Decay Fragmentation of Peptides in MALDI-TOF-MS J. Am. Soc. Mass Spectrom. 2010, 21, 1906-1917
Calligaris, D.; Villard, C.; Terras, L.; Braguer, D.; Verdier-Pinard, P.; Lafitte, D. MALDI In-Source Decay of High Mass Protein Isoforms: Application to α- and β-Tubulin Variants Anal. Chem. 2010, 82, 6176-6184
Asakawa, D.; Takayama, M. Mass Spectrometric Characterization of Phosphorylated Peptides Using MALDI In-Source Decay via Redox Reactions J. Mass Spectrom. 2012, 47, 180-187
Smargiasso, N.; Quinton, L.; De Pauw, E. 2-Aminobenzamide and 2-Aminobenzoic Acid as New MALDI Matrices Inducing Radical Mediated In-Source Decay of Peptides and Proteins J. Am. Soc. Mass Spectrom. 2012, 23, 469-474
