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Article

Selective Metabolite and Peptide Capture/Mass Detection Using Fluorous Affinity Tags

Supporting Info

Eden P. Go,^† Wilasinee Uritboonthai,^† Junefredo V. Apon,^† Sunia A. Trauger,^† Anders Nordstrom,^† Grace O'Maille,^† Scott M. Brittain,^‡ Eric C. Peters,*^‡ and Gary Siuzdak*^†

Department of Molecular Biology and The Center for Mass Spectrometry, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, California 92037, and The Genomics Institute of the Novartis Research Foundation, 10675 John Jay Hopkins Drive, San Diego, California 92121

J. Proteome Res., 2007, 6 (4), pp 1492–1499

DOI: 10.1021/pr060608s

Publication Date (Web): March 8, 2007

†

The Scripps Research Institute.

‡

The Genomics Institute of the Novartis Research Foundation.

To whom correspondence should be addressed. E-mail addresses: epeters@gnf.org and siuzdak@scripps.edu.

Abstract

A new and general methodology is described for the targeted enrichment and subsequent direct mass spectrometric characterization of sample subsets bearing various chemical functionalities from highly complex mixtures of biological origin. Specifically, sample components containing a chemical moiety of interest are first selectively labeled with perfluoroalkyl groups, and the entire sample is then applied to a perfluoroalkyl-silylated porous silicon (pSi) surface. Due to the unique hydrophobic and lipophobic nature of the perfluorinated tags, unlabeled sample components are readily removed using simple surface washes, and the enriched sample fraction can then directly be analyzed by desorption/ionization on silicon mass spectrometry (DIOS−MS). Importantly, this fluorous-based enrichment methodology provides a single platform that is equally applicable to both peptide as well as small molecule focused applications. The utility of this technique is demonstrated by the enrichment and mass spectrometric analysis of both various peptide subsets from protein digests as well as amino acids from serum.

Keywords: affinity • fluorous • mass spectrometry • metabolites • porous silicon

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