The objective of this work is to advance the state-of-the-art in electrospray/ion trap mass spectrometry of biomolecules by extending its mixture analysis capabilities and its useful range of structural analysis from molecules ranging in mass up to about 2-4 kDa to molecules ranging in mass up to several tens of kiloDaltons. The two major emphasis areas in this work are to improve understanding of the factors that underlie the dissociation behavior of moderately sized proteins (less than 60 kDa) and to develop new experiments for complex bio-polymer mixture analysis based on ion/ion chemistry. This work will permit applications to be considered that involve the direct interrogation of, for example, whole proteins. Such applications might include rapid protein identification, rapid identification of post-translational modifications, rapid analysis of protein variants, etc. The quadrupole ion trap is already a remarkably powerful tool for the manipulation and mass/charge analysis of biologically-derived ions. This work will allow for a dramatic expansion in the size of bio-polymer that can be studied via tandem mass spectrometry with a bench-top instrument. The proposed effort seeks to develop new tools for deriving structural information from high mass ions, with particular emphasis on proteins. Instrumentation will be developed to allow for new studies designed to improve understanding of the ion/ion reactions of proteins and the unimolecular (i.e. dissociation) reactions of proteins. Specifically, new instrumental developments will be made to enhance both the range of ion/ion chemistry that can be studied and to improve the figures of merit of mass analysis of high mass ions.

National Institute of Health (NIH)
National Institute of General Medical Sciences (NIGMS)
Research Project (R01)
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Special Emphasis Panel (ZRG1-BMT (01))
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Edmonds, Charles G
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Purdue University
Schools of Arts and Sciences
West Lafayette
United States
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Peng, Zhou; Pilo, Alice L; Luongo, Carl A et al. (2015) Gas-Phase Amidation of Carboxylic Acids with Woodward's Reagent K Ions. J Am Soc Mass Spectrom 26:1686-94
Pilo, Alice L; Bu, Jiexun; McLuckey, Scott A (2015) Transformation of [M + 2H](2+) Peptide Cations to [M - H](+), [M + H + O](+), and M(+•) Cations via Ion/Ion Reactions: Reagent Anions Derived from Persulfate. J Am Soc Mass Spectrom 26:1103-14
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Rojas-Betancourt, Stella; Stutzman, John R; Londry, Frank A et al. (2015) Gas-Phase Chemical Separation of Phosphatidylcholine and Phosphatidylethanolamine Cations via Charge Inversion Ion/Ion Chemistry. Anal Chem 87:11255-62
Peng, Zhou; McLuckey, Scott A (2015) C-terminal peptide extension via gas-phase ion/ion reactions. Int J Mass Spectrom 391:17-23
Gilbert, Joshua D; Fisher, Christine M; Bu, Jiexun et al. (2015) Strategies for generating peptide radical cations via ion/ion reactions. J Mass Spectrom 50:418-26
Peng, Zhou; McGee, William M; Bu, Jiexun et al. (2015) Gas phase reactivity of carboxylates with N-hydroxysuccinimide esters. J Am Soc Mass Spectrom 26:174-80
Pilo, Alice L; McLuckey, Scott A (2014) Oxidation of methionine residues in polypeptide ions via gas-phase ion/ion chemistry. J Am Soc Mass Spectrom 25:1049-57
McGee, William M; McLuckey, Scott A (2014) Efficient and directed peptide bond formation in the gas phase via ion/ion reactions. Proc Natl Acad Sci U S A 111:1288-92
McGee, William M; McLuckey, Scott A (2013) Gas Phase Dissociation Behavior of Acyl-Arginine Peptides. Int J Mass Spectrom 354-356:181-187

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