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Reduction of spectral interferences using ultraclean gold nanowire arrays in the LDI-MS analysis of a model peptide

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Abstract

The surface chemistry of gold nanowires (AuNWs) has been systematically assessed in terms of contamination and cleaning processes. The nanomaterial’s surface quality was correlated to its performance in the matrix-free laser desorption ionization mass spectrometry (LDI-MS) analysis of low molecular weight analytes. Arrays of AuNWs were deposited on glass slides by means of the lithographically patterned nanowire electrodeposition technique. AuNWs were then characterized in terms of surface chemical composition and morphology using X-ray photoelectron spectroscopy, scanning electron microscopy and atomic force microscopy. AuNWs were subjected to a series of well-known cleaning procedures with the aim of producing the best performing surfaces for the LDI-MS detection of leucine enkephalin, chosen as a model analyte with a molar mass below 1,000 g/mol. Prolonged cyclic voltammetry in 2 M sulfuric acid and, most of all, oxygen plasma cleaning for 5 min provided the best results in terms of simpler (interference-free) and more intense mass spectrometry spectra of the reference compound. The analyte always ionized as the sodiated adduct, and leucine enkephalin limits of detection of 0.5 and 2.5 pmol were estimated for the positive and negative analysis modes, respectively. This study points out the tight correlation existing between the chemical status of the nanostructure surface and the AuNW-assisted LDI-MS performance in terms of reproducibility of spectra, intensity of analyte ions and reduction of interferences.

SEM (a-d) and AFM (e-f) pictures and LDI-MS spectra of leu-enk analyte (g-h) obtained with untreated (left side) and oxygen plasmatreated (right side) gold nanowire arrays supported on glass slide

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Acknowledgments

N.C., L.C. and R.A.P. acknowledge the financial support from the Italian Project “Nanomaterials & Laser Ionization Mass Spectrometry: A New Bio-analytical Approach” FIRB Futuro in Ricerca 2008, funded by the Ministero dell’Istruzione, dell’Università e della Ricerca. S.C.K., D.K.T and R.M.P. acknowledge the financial support of this work through the US National Science Foundation (contract CHE 1306928). N.C. warmly thanks F. Palmisano for scientific discussions on MS experiments.

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Author notes

  1. L. Colaianni

    Present address: Laboratorio Campionamenti Qualità Materie Prime Ecologia ILVA S.p.A., Stabilimento di Taranto, 74123, Taranto, Italy

  2. S. C. Kung

    Present address: Applied Materials Inc., 974 E. Arques Avenue, M/S 81305, Sunnyvale, CA, 94085, USA

  3. D. K. Taggart

    Present address: General Monitors, 26776 Simpatica Cir, Lake Forest, CA, 92630, USA

Authors and Affiliations

  1. Dipartimento di Chimica, Università degli Studi di Bari “Aldo Moro”, Via Orabona 4, 70126, Bari, Italy

    L. Colaianni, R. A. Picca & N. Cioffi

  2. Department of Chemistry, Natural Science 2, University of California, Irvine, Irvine, CA, 92697, USA

    S. C. Kung, D. K. Taggart & R. M. Penner

  3. Mass Spectrometry Facility, University of California, Irvine, Irvine, CA, 92697, USA

    J. Greaves

  4. Centro Interdipartimentale di Ricerca S.M.A.R.T., Università degli Studi di Bari “Aldo Moro”, Via Orabona 4, 70126, Bari, Italy

    N. Cioffi

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  1. L. Colaianni
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Colaianni, L., Kung, S.C., Taggart, D.K. et al. Reduction of spectral interferences using ultraclean gold nanowire arrays in the LDI-MS analysis of a model peptide. Anal Bioanal Chem 406, 4571–4583 (2014). https://doi.org/10.1007/s00216-014-7876-7

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