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Improving the Sensitivity of Mass Spectrometry by Using a New Sheath Flow Electrospray Emitter Array at Subambient Pressures

  • Focus: Advancing High Performance Mass Spectrometry: Research Article
  • Published:
Journal of The American Society for Mass Spectrometry

Abstract

Arrays of chemically etched emitters with individualized sheath gas capillaries were developed to enhance electrospray ionization (ESI) efficiency at subambient pressures. By incorporating the new emitter array in a subambient pressure ionization with nanoelectrospray (SPIN) source, both ionization efficiency and ion transmission efficiency were significantly increased, providing enhanced sensitivity in mass spectrometric analyses. The SPIN source eliminates the major ion losses of conventional ESI-mass spectrometry (MS) interfaces by placing the emitter in the first reduced pressure region of the instrument. The new ESI emitter array design developed in this study allows individualized sheath gas around each emitter in the array making it possible to generate an array of uniform and stable electrosprays in the subambient pressure (10 to 30 Torr) environment for the first time. The utility of the new emitter arrays was demonstrated by coupling the emitter array/SPIN source with a time of flight (TOF) mass spectrometer. The instrument sensitivity was compared under different ESI source and interface configurations including a standard atmospheric pressure single ESI emitter/heated capillary, single emitter/SPIN and multi-emitter/SPIN configurations using an equimolar solution of nine peptides. The highest instrument sensitivity was observed using the multi-emitter/SPIN configuration in which the sensitivity increased with the number of emitters in the array. Over an order of magnitude MS sensitivity improvement was achieved using multi-emitter/SPIN compared with using the standard atmospheric pressure single ESI emitter/heated capillary interface.

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Acknowledgment

Portions of this research were supported by the National Center for Research Resources (RR18522), National Cancer Institute (1R33CA155252), National Institute of General Medical Sciences Sciences (P41 GM103493-1), the Laboratory Directed Research and Development Program at Pacific Northwest National Laboratory (PNNL), and by the Department of Energy Office of Biological and Environmental Research Genome Sciences Program under the Pan-omics project. All the experiments were performed in the Environmental Molecular Sciences Laboratory, a US Department of Energy (DOE) national scientific user facility located at PNNL in Richland, Washington. PNNL is a multiprogramming national laboratory operated by Battelle for the DOE under contract DE-AC05-76RLO01830.

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Authors and Affiliations

  1. Biological Sciences Division, Pacific Northwest National Laboratory, Richland, WA, 99352, USA

    Jonathan T. Cox, Ioan Marginean, Richard D. Smith & Keqi Tang

  2. Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, WA, 99352, USA

    Ryan T. Kelly

Authors
  1. Jonathan T. Cox
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  2. Ioan Marginean
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  3. Ryan T. Kelly
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  4. Richard D. Smith
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  5. Keqi Tang
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Corresponding author

Correspondence to Keqi Tang.

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Figure SM1

Optical image of complete emitter assembly (a). Photomicrograph of a 10-emitter array with individualized sheath gas capillaries (b) (DOCX 4427 kb)

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Cox, J.T., Marginean, I., Kelly, R.T. et al. Improving the Sensitivity of Mass Spectrometry by Using a New Sheath Flow Electrospray Emitter Array at Subambient Pressures. J. Am. Soc. Mass Spectrom. 25, 2028–2037 (2014). https://doi.org/10.1007/s13361-014-0856-5

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  • DOI: https://doi.org/10.1007/s13361-014-0856-5

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