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Manipulating the Mass Spectrometric Properties of Peptides through Selective Chemical Modification

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Sample Preparation in Biological Mass Spectrometry

Abstract

Mass spectrometry is routinely applied to the detection of chemically modified peptides, and researchers deliberately induce chemical modifications in peptides for a variety of reasons. One motivation for doing so is to manipulate the behavior of the peptide in the mass spectrometer itself. Ionization efficiency, for example, can be selectively enhanced or suppressed in MALDI MS, and the charge state distribution altered in ESI. Addition of fixed or localized charges can enhance or suppress entire ion series upon CID, with dramatic effects in MALDI, and more subtle changes in ESI. Newer activation techniques such as ECD and ETD can be favorably combined with ESI and charge derivatization to simplify product ion spectra and map sites of posttranslational modification. Peptides containing specific amino acids and PTMs can be targeted for selective detection or recognized amid a complex background of other peptides by virtue of characteristic product ions or neutral losses conferred by a well-chosen chemical modification. The mass spectrometrist thus possesses a rich set of chemical modifications that can be applied to achieve specific goals in peptide and protein analysis.

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Authors and Affiliations

  1. Protein Chemistry Department, Genentech, Inc., South San Francisco, CA, 94080, USA

    David Arnott

  2. Protein Chemistry Department, Genentech, Inc, South San Francisco, CA, USA

    Peter S. Liu, Patricia Molina, Lilian Phu & Wendy N. Sandoval

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  1. David Arnott
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  2. Peter S. Liu
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  3. Patricia Molina
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  4. Lilian Phu
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  5. Wendy N. Sandoval
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Correspondence to David Arnott .

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Editors and Affiliations

  1. , Department of Genetics and Complex Disea, Harvard School of Public Health, Harvard, Huntington Ave., SPH-1 665, Boston, 02115, Massachusetts, USA

    Alexander R. Ivanov

  2. , Research and Development, Pressure BioSciences, Inc., Norfolk Ave. 14, South Easton, 02375, Massachusetts, USA

    Alexander V. Lazarev

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Arnott, D., Liu, P.S., Molina, P., Phu, L., Sandoval, W.N. (2011). Manipulating the Mass Spectrometric Properties of Peptides through Selective Chemical Modification. In: Ivanov, A., Lazarev, A. (eds) Sample Preparation in Biological Mass Spectrometry. Springer, Dordrecht. https://doi.org/10.1007/978-94-007-0828-0_2

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