High Sensitivity and Analyte Capture with Desorption/Ionization Mass Spectrometry on Silylated Porous Silicon

Sunia A. Trauger, Eden P. Go, Zhouxin Shen,§ Junefredo V. Apon, Bruce J. Compton, Edouard S. P. Bouvier, M. G. Finn, and Gary Siuzdak*
Departments of Molecular Biology and Chemistry and The Scripps Center for Mass Spectrometry, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, California 92037, Waters Corporation, 34 Maple Street, Milford Massachusetts 01757, and Mass Consortium Corporation, 3030 Bunker Hill Street, San Diego, California 92109
Anal. Chem., 2004, 76 (15), pp 4484–4489
DOI: 10.1021/ac049657j
Publication Date (Web): June 22, 2004
Copyright © 2004 American Chemical Society

Abstract

Silylation chemistry on porous silicon provides for ultrahigh sensitivity and analyte specificity with desorption/ionization on silicon mass spectrometry (DIOS-MS) analysis. Here, we report that the silylation of oxidized porous silicon offers a DIOS platform that is resistant to air oxidation and acid/base hydrolysis. Furthermore, surface modification with appropriate hydrophobic silanes allows analytes to absorb to the surface via hydrophobic interactions for direct analyte extraction from complex matrixes containing salts and other nonvolatile interferences present in the sample matrix. This enables rapid cleanup by simply spotting the sample onto the modified DIOS target and removing the liquid phase containing the interferences. This approach is demonstrated in the analysis of protein digests and metabolites in biofluids, as well as for the characterizing of inhibitors from their enzyme complex. An unprecedented detection limit of 480 molecules (800 ymol) for des-Arg9-bradykinin is reported on a pentafluorophenyl-functionalized DIOS chip.

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History

  • Published In Issue August 01, 2004
  • Received for review March 3, 2004. Accepted May 18, 2004.

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