Preparation and in Situ Characterization of Surfaces Using Soft Landing in a Fourier Transform Ion Cyclotron Resonance Mass Spectrometer

Jormarie Alvarez and R. Graham Cooks
Department of Chemistry, Purdue Univeristy, West Lafayette, Indiana 47907
S. E. Barlow, Daniel J. Gaspar, Jean H. Futrell, and Julia Laskin*
Fundamental Science Directorate and Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, Washington 99352
Anal. Chem., 2005, 77 (11), pp 3452–3460
DOI: 10.1021/ac0481349
Publication Date (Web): May 3, 2005
Copyright © 2005 American Chemical Society

Abstract

Mass-selected peptide ions produced by electrospray ionization were deposited onto fluorinated self-assembled monolayer surfaces (FSAM) surfaces by soft landing using a Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS) specially designed for studying interactions of large ions with surfaces. Analysis of the modified surface was performed in situ by combining 2-keV Cs+ secondary ion mass spectrometry with FT-ICR detection of the sputtered ions (FT-ICR-SIMS). Regardless of the initial charge state of the precursor ion, the SIMS mass spectra included singly protonated peptide ion, peptide fragment ions, and peaks characteristic of the surface in all cases. In some experiments, multiply protonated peptide ions and [M + Au]+ ions were also observed upon SIMS analysis of modified surfaces. For comparison with the in situ analysis of the modified surfaces, ex situ analysis of some of the modified surfaces was performed by 25-keV Ga+ time-of-flight−secondary ion mass spectrometry (TOF-SIMS). The ex situ analysis demonstrated that a significant number of soft-landed peptide ions remain charged on the surface even when exposed to air for several hours after deposition. Charge retention of soft-landed ions dramatically increases the ion yields obtained during SIMS analysis and enables very sensitive detection of deposited material at less than 1% of monolayer coverage. Accumulation of charged species on the surface undergoes saturation due to coulomb repulsion between charges at close to 30% coverage. We estimated that close to 1 ng of peptide could be deposited on the spot area of 4 mm2 of the FSAM surface without reaching saturation.

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This article has been cited by 10 ACS Journal articles (5 most recent appear below).

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    In situ Studies of Soft- and Reactive Landing of Mass-Selected Ions Using Infrared Reflection Absorption Spectroscopy

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      A new ion soft landing instrument has been built for the controlled deposition of mass selected polyatomic ions. The instrument has been operated with an electrospray ionization source; its major components are an electrodynamic ion funnel to reduce ion ...

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History

  • Published In Issue June 01, 2005
  • Received for review December 17, 2004. Accepted April 7, 2005.

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