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Spectroscopic Evidence for Lactam Formation in Terminal Ornithine b2+ and b3+ Fragment Ions

  • Zachary M. Smith
  • Xiye Wang
  • Jonathan R. Scheerer
  • Jonathan Martens
  • Giel Berden
  • Jos Oomens
  • Vincent Steinmetz
  • Arpad Somogyi
  • Vicki Wysocki
  • John C. PoutsmaEmail author
Research Article

Abstract

Infrared multiple photon dissociation action spectroscopy was performed on the AlaOrn b2+ and AlaAlaOrn b3+ fragment ions from ornithine-containing tetrapeptides. Infrared spectra were obtained in the fingerprint region (1000–2000 cm−1) using the infrared free electron lasers at the Centre Laser Infrarouge d’Orsay (CLIO) facility in Orsay, France, and the free electron lasers for infrared experiments (FELIX) facility in Nijmegen, the Netherlands. A novel terminal ornithine lactam AO+ b2+ structure was synthesized for experimental comparison and spectroscopy confirms that the b2+ fragment ion from AOAA forms a lactam structure. Comparison of experimental spectra with scaled harmonic frequencies at the B3LYP/6-31+G(d,p) level of theory shows that AO+ b2+ forms a terminal lactam protonated either on the lactam carbonyl oxygen or the N-terminal nitrogen atom. Several low-lying conformers of these isomers are likely populated following IRMPD dissociation. Similarly, a comparison of the experimental IRMPD spectrum with calculated spectra shows that AAO+ b3+-ions also adopt a lactam structure, again with multiple different protonation sites, during fragmentation. This study provides spectroscopic confirmation for the lactam cyclization proposed for the “ornithine effect” and represents an alternative bn+ structure to the oxazolone and diketopiperazine/macrocycle structures most often formed.

Keywords

IRMPD spectroscopy b2+ ions Peptide fragmentation 

Notes

Acknowledgements

The authors gratefully acknowledge the aid and expertise of the CLIO facility, P. Maître, Director. The authors also would like to thank the FELIX team for their aid and expertise. This research was supported by NIH Grant 1R15GM116180-01 and NSF Grant CHE: 1464763

Supplementary material

13361_2019_2244_MOESM1_ESM.docx (25 kb)
ESM 1 (DOCX 25 kb)

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Copyright information

© American Society for Mass Spectrometry 2019

Authors and Affiliations

  • Zachary M. Smith
    • 1
  • Xiye Wang
    • 1
  • Jonathan R. Scheerer
    • 1
  • Jonathan Martens
    • 2
  • Giel Berden
    • 2
  • Jos Oomens
    • 2
  • Vincent Steinmetz
    • 3
  • Arpad Somogyi
    • 4
  • Vicki Wysocki
    • 4
  • John C. Poutsma
    • 1
    Email author
  1. 1.Department of ChemistryThe College of William & MaryWilliamsburgUSA
  2. 2.Institute for Molecules and Materials, FELIX LaboratoryRadboud UniversityNijmegenThe Netherlands
  3. 3.Laboratorie de Chimie Physique, CNRS UMR 8000Université ParisOrsayFrance
  4. 4.Department of Chemistry and BiochemistryThe Ohio State UniversityColumbusUSA

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