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Laserspray and Matrix-Assisted Ionization Inlet Coupled to High-Field FT-ICR Mass Spectrometry for Peptide and Protein Analysis

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Journal of The American Society for Mass Spectrometry

Abstract

We present the first coupling of laser spray ionization inlet (LSII) and matrix assisted ionization inlet (MAII) to high-field Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) for generation of electrospray-like ions to take advantage of increased sensitivity, mass range, and mass resolving power afforded by multiple charging. We apply the technique to top-down protein analysis and characterization of metalloproteins. We also present a novel method for generation of multiply-charged copper–peptide complexes with varying degrees of copper adduction by LSII. We show an application of the generated copper–peptide complexes for protein charge state and molecular weight determination, particularly useful for an instrument such as a linear ion trap mass analyzer.

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Acknowledgment

The authors acknowledge support for this work by NSF Division of Materials Research through DMR-06-54118 and the State of Florida, and NSF CAREER 0955975 to S.T. The authors thank John P. Quinn and Daniel McIntosh for assistance with fabrication of the sample holder and Dr. Vadislav Lobodin for insightful discussions.

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Authors and Affiliations

  1. National High Magnetic Field Laboratory, Florida State University, Tallahassee, FL, 32310, USA

    Leonard Nyadong, Christopher L. Hendrickson & Alan G. Marshall

  2. Department of Chemistry, Wayne State University, Detroit, MI, 48202, USA

    Ellen D. Inutan & Sarah Trimpin

  3. Department of Chemistry and Biochemistry, Florida State University, Tallahassee, FL, 32303, USA

    Xu Wang, Christopher L. Hendrickson & Alan G. Marshall

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  1. Leonard Nyadong
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  2. Ellen D. Inutan
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  3. Xu Wang
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  4. Christopher L. Hendrickson
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  5. Sarah Trimpin
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  6. Alan G. Marshall
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Corresponding author

Correspondence to Alan G. Marshall.

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Figure S1

14.5 T FT-ICR mass spectra of des-Arg1-bradykinin at different time intervals across the total ion chromatogram profile at an HMC temperature of 150 °C, obtained by matrix-assisted ionization inlet: 0.5-0.7 min (top), 1.0-1.2 min (middle), 2.0-2.2 min (bottom). Asterisks denote chemical noise. (PPT 124 kb)

Figure S2

14.5 T FT-ICR mass spectra of des-Arg1-bradykinin obtained by matrix-assisted ionization inlet (top) and electrospray ionization (bottom). (PPT 115 kb)

Figure S3

Ion source fragmentation efficiency as a function of nozzle skimmer voltage for des-Arg1-bradykinin, obtained by matrix-assisted ionization inlet (blue) and electrospray ionization (red). Mass spectra were acquired following ion source collision-induced dissociation in the LTQ multipole region. (PPT 121 kb)

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Nyadong, L., Inutan, E.D., Wang, X. et al. Laserspray and Matrix-Assisted Ionization Inlet Coupled to High-Field FT-ICR Mass Spectrometry for Peptide and Protein Analysis. J. Am. Soc. Mass Spectrom. 24, 320–328 (2013). https://doi.org/10.1007/s13361-012-0545-1

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