Matrix‐free high‐resolution imaging mass spectrometry with high‐energy ion projectiles

Abstract

Abstract The importance of imaging mass spectrometry (MS) for visualizing the spatial distribution of molecular species in biological tissues and cells is growing. We have developed a new system for imaging MS using MeV ion beams, termed MeV‐secondary ion mass spectrometry (MeV‐SIMS) here, and demonstrated more than 1000‐fold increase in molecular ion yield from a peptide sample (1154 Da), compared to keV ion irradiation. This significant enhancement of the molecular ion yield is attributed to electronic excitation induced in the near‐surface region by the impact of high energy ions. In addition, the secondary ion efficiency for biologically important compounds (>1 kDa) increased to more than 10 10 cm −2 , demonstrating that the current technique could, in principle, achieve micrometer lateral resolution. In addition to MeV‐SIMS, peptide compounds were also analyzed with cluster‐SIMS and the results indicated that in the former method the molecular ion yields increased substantially compared to the latter. To assess the capability of MeV‐SIMS to acquire heavy‐ion images, we have prepared a micropatterned peptide surface and successfully obtained mass spectrometric imaging of the deprotonated peptides ( m / z 1153) without any matrix enhancement. The results obtained in this study indicate that the MeV‐SIMS technique can be a powerful tool for high‐resolution imaging in the mass range from 100 to over 1000 Da. Copyright © 2008 John Wiley & Sons, Ltd.