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Analysis of Biomolecules by Atmospheric Pressure Visible-Wavelength MALDI-Ion Trap-MS in Transmission Geometry

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Journal of The American Society for Mass Spectrometry

Abstract

We report the development of a new AP visible-wavelength MALDI-ion trap-MS instrument with significantly improved performance over our previously reported system (Int. J. Mass Spectrom. 315, 66–73 (2012)). A Nd:YAG pulsed laser emitting light at 532 nm was used to desorb and ionize oligosaccharides and peptides in transmission geometry through a glass slide. Limits of detection (LODs) achieved in MS mode correspond to picomole quantities of oligosaccharides and femtomole quantities of peptides. Tandem MS (MS/MS) experiments enabled identification of enzymatically digested proteins and oligosaccharides by comparison of MS/MS spectra with data found in protein and glycan databases. Moreover, the softness of ionization, LODs, and fragmentation spectra of biomolecules by AP visible-wavelength MALDI-MS were compared to those obtained by AP UV MALDI-MS using a Nd:YAG laser emitting light at 355 nm. AP visible-wavelength MALDI appears to be a softer ionization technique then AP UV MALDI for the analysis of sulfated peptides, while visible-wavelength MALDI-MS, MS/MS, and MS/MS/MS spectra of other biomolecules analyzed were mostly similar to those obtained by AP UV MALDI-MS. Therefore, the methodology presented will be useful for MS and MSn analyses of biomolecules at atmospheric pressure. Additionally, the AP visible-wavelength MALDI developed can be readily used for soft ionization of analytes on various mass spectrometers.

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Acknowledgments

This work was supported by research funds from the University of Toledo (D.I.). The authors thank Walter Berger, Jr. for machining parts for the AP MALDI source, Dr. Yong Wah Kim for his help with fixing and maintaining the ion trap instrument, Dr. Ming Liu for the gift of the cholecystokinin peptide, and Technical Support from Thermo Scientific for useful advice.

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Authors and Affiliations

  1. Department of Chemistry, University of Toledo, Toledo, OH, 43606, USA

    Raymond E. West III, Eric W. Findsen & Dragan Isailovic

Authors
  1. Raymond E. West III
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  2. Eric W. Findsen
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  3. Dragan Isailovic
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Corresponding author

Correspondence to Dragan Isailovic.

Electronic Supplementary Material

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Figure S1

AP visible-wavelength MALDI MS/MS/MS spectra of selected ions from (a) angiotensin II (m/z 931.45) and (b) [Glu]-fibrinopeptide B (m/z 1553.60) (DOC 124 kb)

Figure S2

AP visible-wavelength MALDI MS spectra of doubly charged ion of insulin (m/z 2867.62) and triply charged ion of insulin (m/z 1912.13). (DOC 111 kb)

Figure S3

AP visible-wavelength MALDI mass spectrum corresponding to the LOD of angiotensin II (19 fmol). (DOC 98 kb)

Figure S4

AP UV MALDI mass spectra of (a) raffinose (59 nmol), (b) maltoheptaose (26 nmol), (c) angiotensin II (28 nmol), and (d) [Glu]-fibrinopeptide B (19 nmol) acquired in positive ion mode. DHB and 2-amino-3-nitrophenol were used as the matrices for the analysis of oligosaccharides and peptides, respectively. (DOC 132 kb)

Figure S5

AP UV MALDI MS/MS spectra of (a) raffinose (m/z 527.13), (b) maltoheptaose (m/z 1175.47), (c) angiotensin II (m/z 1046.60), and (d) [Glu]-fibrinopeptide B (m/z 1571.87). (DOC 163 kb)

Figure S6

AP UV MALDI MS/MS/MS spectra of selected ions from (a) angiotensin II (m/z 931.53) and (b) [Glu]-fibrinopeptide B (m/z 1552.67). (DOC 139 kb)

Figure S7

AP UV MALDI mass spectrum corresponding to the LOD of angiotensin II (190 amol). (DOC 97 kb)

Figure S8

AP UV MALDI mass spectrum of 3 pmol BSA tryptic digest. (DOC 92 kb)

Figure S9

AP visible-wavelength MALDI mass spectrum of cholecystokinin amide fragment 26–33 (2.6 nmol) obtained in negative ion mode. This spectrum shows the deprotonated ion (m/z 1141.60) and minimal amounts of desulfated (m/z 1061.20) ion due to fragmentation. (DOC 74 kb)

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West, R.E., Findsen, E.W. & Isailovic, D. Analysis of Biomolecules by Atmospheric Pressure Visible-Wavelength MALDI-Ion Trap-MS in Transmission Geometry. J. Am. Soc. Mass Spectrom. 24, 1467–1476 (2013). https://doi.org/10.1007/s13361-013-0691-0

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