Abstract
Infrared multiple photon dissociation (IRMPD) spectroscopy was used to study formation of b +2 from nicotinyl-glycine-glycine-methyl ester (NicGGOMe). IRMPD shows that NicGGOMe is protonated at the pyridine ring of the nicotinyl group, and more importantly, that b +2 from NicGGOMe is not protonated at the oxazolone ring, as would be expected if the species were generated on the conventional b + n /y + n oxazolone pathway, but at the pyridine ring instead. IRMPD data support a hypothesis that formation of b +2 from NicGGOMe involves mobilization and transfer of an amide position proton during the fragmentation reaction.
Article PDF
Avoid common mistakes on your manuscript.
References
Rodriquez, C. F.; Cunje, A.; Shoeib, T.; Chu, I. K.; Hopkinson, A. C.; Siu, K. W. M. Proton Migration and Tautomerism in Protonated Triglycine. J. Am. Chem. Soc. 2001, 123, 3006–3012.
Wu, R.; Mc Mahon, T. B. Infrared Multiple Photon Dissociation Spectroscopy as Structural Confirmation for GlyGlyGlyH+ and AlaAlaAlaH+ in the Gas Phase: Evidence for Amide Oxygen as the Protonation Site. J. Am. Chem. Soc. 2007, 129, 11312–11313.
Papayannopoulos, I. A. The Interpretation of Collision-Induced Dissociation Tandem Mass Spectra of Peptides. Mass Spectrom. Rev. 1995, 14, 49–73.
Yalcin, T.; Khouw, C.; Csizmadia, I. G.; Peterson, M. R.; Harrison, A. G. Why are B Ions Stable Species in Peptide Spectra? J. Am. Soc. Mass Spectrom. 1995, 6, 1165–1174.
Yalcin, T.; Csizmadia, I. G.; Peterson, M. B.; Harrison, G. The Structure and Fragmentation of B n (n ≥ 3) Ions in Peptide Spectra. J. Am. Soc. Mass Spectrom. 1996, 7, 233–242.
Nold, M. J.; Wesdemiotis, C.; Yalcin, T.; Harrison, G. Amide Bond Dissociation in Protonated Peptides. Structures of the N-Terminal Ionic and Neutral Fragments. Int. J. Mass Spectrom. Ion Processes. 1997, 164, 137–153.
Paizs, B.; Lendvay, G.; Vékey, K.; Suhai, S. Formation of b +2 Ions from Protonated Peptides: An Ab Initio Study. Rapid Commun. Mass Spectrom. 1999, 13, 525–533.
Harrison, A. G.; Csizmadia, I. G.; Tang, T.-H. Structure and Fragmentation of b2 Ions in Peptide Mass Spectra. J. Am. Soc. Mass Spectrom. 2000, 11, 427–436.
Paizs, B.; Suhai, S. Combined Quantum Chemical and RRKM Modeling of the Main Fragmentation Pathways of Protonated GGG: II. Formation of b2, y1, and y2 Ions. Rapid Commun. Mass Spectrom. 2002, 16, 375–389.
Paizs, B.; Suhai, S. Towards Understanding the Tandem Mass Spectra of Protonated Oligopeptides: I: Mechanism of Amide Bond Cleavage. J. Am. Soc. Mass Spectrom. 2004, 15, 103–112.
Polfer, N. C.; Oomens, J.; Suhai, S.; Paizs, B. Spectroscopic and Theoretical Evidence for Oxazolone Ring Formation in Collision-Induced Dissociation of Peptides. J. Am. Chem. Soc. 2005, 127, 17154–17155.
Polfer, N. C.; Oomens, J.; Suhai, S.; Paizs, B. Infrared Spectroscopy and Theoretical Studies on Gas-Phase Protonated Leu-Enkephalin and Its Fragments: Direct Experimental Evidence for the Mobile Proton. J. Am. Chem. Soc. 2007, 120, 5887–5897.
Jones, J. L.; Dongré, A. R.; Somogyi, Á.; Wysocki, V. H. Sequence Dependence of Peptide Fragmentation Efficiency Curves Determined by Electrospray Ionization/Surface-Induced Dissociation Mass Spectrometry. J. Am. Chem. Soc. 1994, 116, 8368–8369.
Tsaprailis, G.; Nair, H.; Somogyi, Á.; Wysocki, V. H.; Zhong, W.; Futrell, J. H.; Summerfield, S. G.; Gaskell, S. J. Influence of Secondary Structure on the Fragmentation of Protonated Peptides. J. Am. Chem. Soc. 1999, 121, 5142–5154.
Wysocki, V. H.; Tsaprailis, G.; Smith, L. L.; Breci, L. A. Mobile and Localized Protons: A Framework for Understanding Peptide Dissociation. J. Mass Spectrom. 2000, 35, 1399–1406.
Tsang, C. W.; Harrison, A. G. Chemical Ionization of Amino Acids. J. Am. Chem. Soc. 1976, 98, 1301–1308.
Harrison, A. G.; Yalcin, T. Proton Mobility in Protonated Amino Acids and Peptides. Int. J. Mass Spectrom. Ion Processes. 1997, 165, 339–347.
Burlet, O.; Yang, C. Y.; Gaskell, S. J. Influence of Cysteine to Cysteic Acid Oxidation on the Collision-Activated Decomposition of Protonated Peptides: Evidence for Intraionic Interactions. J. Am. Soc. Mass Spectrom. 1992, 3, 337–344.
Cox, K. A.; Gaskell, S. J.; Morris, M.; Whiting, A. Role of the Site of Protonation in the Low-Energy Decompositions of Gas-Phase Peptide Ions. J. Am. Soc. Mass Spectrom. 1996, 7, 522–531.
Summerfield, S. G.; Whiting, A.; Gaskell, S. J. Intraionic Interactions in Electrosprayed Peptide Ions. Int. J. Mass Spectrom. Ion Processes. 1997, 162, 149–161.
Summerfield, S. G.; Cox, K. A.; Gaskell, S. J. The Promotion of d-Type Ions During the Low Energy Collision-Induced Dissociation of Some Cysteic Acid-Containing Peptides. J. Am. Soc. Mass Spectrom. 1997, 8, 25–31.
Tang, X.; Boyd, R. K. An Investigation of Fragmentation Mechanisms of Doubly Protonated Tryptic Peptides. Rapid Commun. Mass Spectrom. 1992, 6, 651–657.
Tang, X.; Thibault, P.; Boyd, R. K. Fragmentation Reactions of Multiply-Protonated Peptides and Implications for Sequencing by Tandem Mass Spectrometry with Low-Energy Collision-Induced Dissociation. Anal. Chem. 1993, 65, 2824–2834.
Csonka, I. P.; Paizs, B.; Lendavy, G.; Suhai, S. Proton Mobility in Protonated Peptides: A Joint Molecular Orbital and RRKM Study. Rapid Commun. Mass Spectrom. 2000, 14, 417–427.
Paizs, B.; Csonka, I. P.; Lendvay, G.; Suhai, S. Proton Mobility in Protonated Glycylglycine and N-Formylglycylglycinamide: A Combined Quantum Chemical and RKKM Study. Rapid Commun. Mass Spectrom. 2001, 15, 637–647.
Paizs, B.; Suhai, S. Fragmentation Pathways of Protonated Peptides. Mass Spectrom. Rev. 2004, 24, 508–548.
Polce, M. J.; Ren, D.; Wesdemiotis, C. Dissociation of the Peptide Bond in Protonated Peptides. J. Mass Spectrom. 2000, 35(12), 1391–1398.
Cordero, M. M.; Houser, J. J.; Wesdemiotis, C. The Neutral Products Formed During Backbone Fragmentations of Protonated Peptides in Tandem Mass Spectrometry. Anal. Chem. 1993, 65, 1594–1601.
Oomens, J.; Young, S.; Molesworth, S.; Van Stipdonk, M. Spectroscopic Evidence for an Oxazolone Structure of the b 2 Fragment Ion from Protonated Tri-alanine. J. Am. Soc. Mass Spectrom. 2009, 20, 334–339.
Yoon, S. H.; Chamot-Rooke, J.; Perkins, B. R.; Hilderbrand, A. E.; Poutsma, J. C.; Wysocki, V. H. IRMPD Spectroscopy Shows that AGG Forms an Oxazolone b +2 Ion. J. Am. Chem. Soc. 2008, 130, 17644–17645.
Bulleigh, K.; Howard, A.; Do, T.; Wu, Q.; Anbalagan, V.; Van Stipdonk, M. Investigation of Intramolecular Proton Migration in A Series of Model, Metal-Cationized Tripeptides Using In-Situ Generation of an Isotope Label. Rapid Commun. Mass Spectrom. 2006, 20, 227–232.
Van Stipdonk, M. J.; Kerstetter, D. R.; Leavitt, C. M.; Groenewold, G. S.; Steill, J.; Oomens, J. Spectroscopic Investigation of H Atom Transfer in a Gas-Phase Dissociation Reaction: McLafferty Rearrangement of Model Gas-Phase Peptide Ions. Phys. Chem., Chem. Phys. 2008, 10, 3209–3221.
Oepts, D. van der Meer, A. F. G. van Amersfoort, P. W. The Free-Electron-Laser User Facility FELIX. Infrared Phys. Technol. 1995, 36297.
Polfer, N. C.; Oomens, J. Reaction Products in Mass Spectrometry Elucidated with Infrared Spectroscopy. Phys. Chem., Chem. Phys. 2007, 9, 3804–3817.
Valle, J. J.; Eyler, J. R.; Oomens, J.; Moore, D. T.; Van der Meer, A. F. G.; von Helden, G.; Meijer, G.; Hendrickson, C. L.; Marshall, A. G.; Blakney, G. T. Free Electron Laser-Fourier Transform Ion Cyclotron Resonance Mass Spectrometry Facility for Obtaining Infrared Multiphoton Dissociation Spectra of Gaseous Ions. Rev. Sci. Instrum. 2005, 76, 023103.
Mize, T. H.; Taban, I.; Duursma, M.; Seynen, M.; Konijnenburg, M.; Vijftigschild, A.; Doornik, C. V.; Rooij, G. V.; Heeren, R. M. A. A Modular Data and Control System to Improve Sensitivity, Selectivity, Speed of Analysis, Ease of Use, and Transient Duration in an External Source FTICR-MS. Int. J. Mass Spectrom. 2004, 235, 243–253.
Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Montgomery, J. A. Jr. Vreven, T.; Kudin, K. N.; Burant, J. C.; Millam, M.; yengar, S. S.; Tomasi, J.; Barone, V.; Mennucci, B.; Cossi, M.; Scalmani, G.; Rega, N.; Petersson, G. A.; Nakatsuji, H.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Klene, M.; Li, X.; Knox, J. E.; Hratchian, H. P.; Cross, J. B.; Bakken, V.; Adamo, C.; aramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Ayala, P. Y.; Morokuma, K.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Zakrzewski, V. G.; Dapprich, S.; Daniels, A. D.; Strain, M. C.; Farkas, O.; Malick, D. K.; Rabuck, A. D.; Raghavachari, K.; Foresman, J. B.; Ortiz, J. V.; Cui, Q.; Baboul, A. G.; Clifford, S.; Cioslowski, J.; Stefanov, B. B.; Liu, G.; Liashenko, A.; Piskorz, P.; Komaromi, I.; 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.; Gonzalez, C.; Pople, J. A. Gaussian 03, Rev. D. 01 Gaussian, Inc.: Wallingford, CT, 2004.
Author information
Authors and Affiliations
Corresponding author
Additional information
Published online July 1, 2009
Electronic supplementary material
Rights and permissions
About this article
Cite this article
Molesworth, S., Leavitt, C.M., Groenewold, G.S. et al. Spectroscopic evidence for mobilization of amide position protons during CID of model peptide ions. J Am Soc Mass Spectrom 20, 1841–1845 (2009). https://doi.org/10.1016/j.jasms.2009.06.007
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1016/j.jasms.2009.06.007