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Derivatization of Surface-Bound Peptides for Mass Spectrometric Detection via Threshold Single Photon Ionization

Praneeth D. Edirisinghe,^† Syed S. Lateef,^† Carrie A. Crot,^† Luke Hanley,*^† Michael J. Pellin,^‡ Wallis F. Calaway,^‡ and Jerry F. Moore*^‡

Department of Chemistry, University of Illinois at Chicago, Chicago, Illinois 60607, and Materials Science Division, Argonne National Laboratory, Argonne, Illinois 60439

Anal. Chem., 2004, 76 (15), pp 4267–4270

DOI: 10.1021/ac049434t

Publication Date (Web): June 24, 2004

†

University of Illinois at Chicago.

To whom correspondence should be addressed: (e-mail) lhanley@uic.edu. moore@anl.gov.

‡

Argonne National Laboratory.

Abstract

Chemical derivatization of peptides allows efficient F₂ laser single photon ionization (SPI) of Fmoc-derivatized peptides covalently bound to surfaces. Laser desorption photoionization mass spectrometry using 337-nm pulses for desorption and 157.6-nm pulses for threshold SPI forms large ions identified as common peptide fragments bound to either Fmoc or the surface linker. Electronic structure calculations indicate the Fmoc label is behaving as an ionization tag for the entire peptide, lowering the ionization potential of the complex below the 7.87-eV photon energy. This method should allow detection of many molecular species covalently or electrostatically bound to surfaces.

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