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Desorption–ionization mass spectrometry on porous silicon

Nature volume 399, pages 243–246 (1999)Cite this article

Abstract

Desorption mass spectrometry has undergone significant improvements since the original experiments were performed more than 90 years ago1. The most dramatic change occurred in the early1980s with the introduction of an organic matrix2,3,4 to transfer energy to the analyte. This reduces ion fragmentation but also introduces background ions from the matrix. Here we describe a matrix-free strategy forbiomolecular mass spectrometry based on pulsed-laser desorption–ionization from a porous silicon5 surface. Our method uses porous silicon to trap analytes deposited on the surface, and laser irradiation to vaporize and ionize them. We show that the method works at femtomole and attomole levels of analyte, and induces little or no fragmentation, in contrast to what is typically observed with other such approaches6,7,8,9,10,11. The ability to perform these measurements without a matrix3,4,12,13 also makes itmore amenable to small-molecule analysis. Chemical14 and structural15 modification of the porous silicon has enabled optimization of the ionization characteristics of the surface. Our technique offers good sensitivity as well as compatibility with silicon-based microfluidics and microchip technologies.

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Figure 1: Experimental configuration for the DIOS-MS experiments.
Figure 2: Examples of mass spectral data obtained with DIOS.
Figure 3: Analysis of WIN antiviral drug (500 fmol) using different desorption/ionization techniques.
Figure 4: DIOS mass spectra of des-arg-bradykinin using small quantities of sample and in the presence of salt.

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Acknowledgements

We thank J. Boydston, Z. Shen, R. G. Cooks and M. Duncan for their comments, T.Hollenbeck for suggesting the acronym DIOS, K. Harris for his initial analyses of porous silicon surfaces, and M. P. Stewart and T. Geders for preparing oxidized and p-type porous silicon samples. G.S. is grateful for partial funding by an NIH grant; J.M.B. thanks Purdue University for support and the Camille and Henry Dreyfus Foundation for a New Faculty Award.

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Authors and Affiliations

  1. Departments of Molecular Biology and Chemistry, The Scripps Research Institute, BCC157, 10550 North Torrey Pines Road, La Jolla, 92037, California, USA

    Jing Wei & Gary Siuzdak

  2. Department of Chemistry, Purdue University, West Lafayette, 47907-1393, Indiana, USA

    Jillian M. Buriak

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  1. Jing Wei
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Correspondence to Jillian M. Buriak.

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Wei, J., Buriak, J. & Siuzdak, G. Desorption–ionization mass spectrometry on porous silicon. Nature 399, 243–246 (1999). https://doi.org/10.1038/20400

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