Gas-phase formation of large neutral alkaline-earth metal tryptophan complexes

Abstract

We report on the first observation of isolated large neutral metal amino acid complexes such as Trp n Me k , with Me = Ca, Ba, Sr, cluster combinations covering n = 1–33, k = 0..2 and masses beyond 6500 u. The cluster beam is generated using UV laser desorption from a mixed powder of alkaline-earth metal salts and tryptophan inside a cluster mixing channel. The particles are detected using VUV photoionization followed by time-of-flight mass spectroscopy. The enhanced stability of metal amino acid clusters over pure amino acid clusters is substantiated in molecular dynamics simulations by determining the gain in binding energy related to the inclusion of the metal atoms.

References

  1. 1.

    Grotemeyer, J.; Bosel, U.; Walter, K.; Schlag, E. W. A General Soft Ionization Method for Mass Spectrometry: Resonance Enhanced Multi-Phonon Ionization of Biomolecules. J. Am. Chem. Soc. 1986, 21, 645–653.

    CAS  Google Scholar 

  2. 2.

    Tanaka, K.; Waki, H.; Ido, Y.; Akita, S.; Yoshida, Y.; Yoshida, T.; Matsuo, T. Protein and Polymer Analyses up to m/z 100,000 by Laser Ionization Time-of-Flight Mass Spectrometry. Rapid Commun. Mass Spectrom. 1988, 2, 151–153.

    CAS  Article  Google Scholar 

  3. 3.

    Karas, M.; Hillenkamp, F. Laser Desorption Ionization of Proteins with Molecular Mass Exceeding 10,000 Daltons. Anal. Chem. 1988, 60, 2299–2301.

    CAS  Article  Google Scholar 

  4. 4.

    Fenn, J. B.; Mann, M.; Meng, C. K.; Wong, S. F.; Whitehouse, C. M. Electrospray Ionization for Mass Spectrometry of Large Biomolecules. Science. 1989, 246, 64–71.

    CAS  Article  Google Scholar 

  5. 5.

    Schalley, C. A. Molecular Recognition and Supramolecular Chemistry in the Gas Phase. Mass Spectrom. Rev. 2001, 20, 253–309.

    CAS  Article  Google Scholar 

  6. 6.

    Arndt, M.; Nairz, O.; Voss-Andreae, J.; Keller, C.; G. van der Zouw, G.; Zeilinger, A. Wave-Particle Duality of C60 Molecules. Nature. 1999, 401, 680–682.

    CAS  Article  Google Scholar 

  7. 7.

    Hackermüller, L.; Uttenthaler, S.; Hornberger, K.; Reiger, E.; Brezger, B.; Zeilinger, A.; Arndt, M. Wave Nature of Biomolecules and Fluorofullerenes. Phys. Rev. Lett. 2003, 91, 90408–90412.

    Article  Google Scholar 

  8. 8.

    Gerlich, S.; Hackermüller, L.; Hornberger, K.; Stibor, A.; Ulbricht, H.; Gring, M.; Goldfarb, F.; Savas, T.; Müri, M.; Mayor, M.; Arndt, M. A Kapitza-Dirac-Talbot-Lau interferometer for highly polarizable molecules. Nat. Phys. 2007, 3, 711–715.

    CAS  Article  Google Scholar 

  9. 9.

    Marksteiner, M.; Kiesewetter, G.; Hackermüller, L.; Ulbricht, H.; Arndt, M. Cold Beams of Biomolecules for Quantum Optics. Acta Phys. Hung. 2007, B 26/12, 87–94.

    Google Scholar 

  10. 10.

    Antoine, R.; Dugourd, P.; Rayane, D.; Benichou, E.; Broyer, M.; Chandezon, F.; Guet, C. Direct Measurement of the Electric Polarizability of Isolated C60 Molecules. J. Chem. Phys. 1999, 110, 9771–9772.

    CAS  Article  Google Scholar 

  11. 11.

    Berninger, M.; Stefanov, A.; Deachapunya, S.; Arndt, M. Polarizability Measurements in a Molecule Near-Field Interferometer. Phys. Rev. A. 2007, 76, 013607–013611.

    Article  Google Scholar 

  12. 12.

    Deachapunya, S.; Fagan, P. J.; Major, A. G.; Reiger, E.; Ritsch, H.; Stefanov, A.; Ulbricht, H.; Arndt, M. Slow Beams of Massive Molecules. Eur. Phys. J. D. 2007, 46, 307–313.

    Article  Google Scholar 

  13. 13.

    Stillinger, F. H.; Weber, T. A. Packing Structures and Transitions in Liquids and Solids. Science. 1984, 225, 983–989.

    CAS  Article  Google Scholar 

  14. 14.

    de Broglie, L. Waves and Quanta. Nature. 1923, 112, 540.

    Article  Google Scholar 

  15. 15.

    Mühlberger, F.; Wieser, J.; Morozov, A.; Ulrich, A.; Zimmermann, R. Single-Photon Ionization Quadrupole Mass Spectrometr with an Electron Beam Pumped Excimer Light Source. Anal. Chem. 2005, 77, 2218–2226.

    Article  Google Scholar 

  16. 16.

    Arps, J.; Chen, C. H.; Mccann, M. P.; Datskou, I. Ionization of Organic Molecules Using Coherent Vacuum Ultraviolet Light. Appl. Spectroc. 1989, 43, 1211–1214.

    CAS  Article  Google Scholar 

  17. 17.

    Hanley, L.; Edirisinghe, P. D.; Calaway, W. F.; Veryovkin, I. V.; Pellin, M. J.; Moore, J. F. 7.87 eV Postionization of Peptides Containing Tryptophan or Derivatized with Fluorescein. App. Surf. Sci. 2006, 252, 6723–6726.

    CAS  Article  Google Scholar 

  18. 18.

    Aicher, K. P.; Wilhelm, U.; Grotemeyer, J. Multiphoton Ionization of Molecules: A Comparison Between Femtosecond and Nanosecond Laser Pulse Ionization Efficiency. J. Am. Soc. Mass Spectrom. 1995, 6, 1059–1068.

    CAS  Article  Google Scholar 

  19. 19.

    Ding, D.; Huang, J.; Compton, R. N.; Klots, C. E.; Haufler, R. E. CW Laser Ionization of C60 and C70. Phys. Rev. Lett. 1994, 73, 1084–1087.

    CAS  Article  Google Scholar 

  20. 20.

    Schlag, E.; Grotemeyer, J.; Levine, R. Do Large Molecules Ionize?. Chem. Phys. Lett. 1992, 190, 521–527.

    CAS  Article  Google Scholar 

  21. 21.

    Becker, C. H.; Wu, K. J. On the Photoionization of Large Molecules. J. Am. Soc. Mass Spectrom. 1995, 6, 883–888.

    CAS  Article  Google Scholar 

  22. 22.

    Dey, M.; Grotemeye, J. Cluster form of Biomolecules in the Gas Phase. Eur. Mass Spectrom. 1995, 6, 95–103.

    Article  Google Scholar 

  23. 23.

    Kim, N. J.; Kang, H.; Jeong, G.; Kim, Y. S.; Lee, K. T.; Kim, S. K. Anomalous Fragmentation of Hydrated Clusters of DNA Base Adenine in UV Photoionization. J. Phys. Chem. A. 2000, 104, 6552–6557.

    CAS  Article  Google Scholar 

  24. 24.

    Denifl, S.; Zappa, F.; Mähr, I.; Lecointre, J.; Probst, M.; Märk, T. D.; Scheier, P. Mass Spectrometric Investigation of Anions Formed Upon Free Electron Attachment to Nucleobase Molecules and Clusters Embedded in Superfluid Helium Droplets. Phys. Rev. Lett. 2006, 97, 043201–043204.

    Article  Google Scholar 

  25. 25.

    Dunbar, R. C.; Polfer, N. C.; Oomens, J. Gas-Phase Zwitterion Stabilization by a Metal Dication. J. Am. Chem. Soc. 2007, 129, 14562–14563.

    CAS  Article  Google Scholar 

  26. 26.

    Hu, P.; Gross, M. Gas-Phase Interaction of Transition-Metal Ions and Di- and Tripeptides: A Comparison with Alkaline-Earth-Metal-Ion Interactions. J. Am. Chem. Soc. 1993, 115, 8821–8828.

    CAS  Article  Google Scholar 

  27. 27.

    Jurchen, J. C.; Garcia, D. E.; Williams, E. R. Gas-Phase Dissociation Pathways of Multiply Charged Peptide Clusters. J. Am. Soc. Mass Spectrom. 2003, 14, 1373–1386.

    CAS  Article  Google Scholar 

  28. 28.

    Ryzhov, V.; Dunbar, R. C.; Cerda, B.; Wesdemiotis, C. Cation-π Effects in the Complexation of Na+ and K+ with Phe, Tyr, and Trp in the Gas Phase. J. Am. Soc. Mass Spectrom. 2000, 11, 1037–1046.

    CAS  Article  Google Scholar 

  29. 29.

    Schanen, P.; Yang, D.; Weinkauf, R.; Schlag, E. Efficient Cationization by Cs + Adduct Ion Formation in a Supersonic Beam. Int. J. Mass Spectrom. Ion Processes. 1997, 167/168, 447–470.

    CAS  Article  Google Scholar 

  30. 30.

    Axelsson, J.; Scrivener, E.; Haddleton, D. M.; Derrick, P. J. Mass Discrimination Effects in an Ion Detector and Other Causes for Shifts in Polymer Mass Distributions Measured by Matrix-Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometry. Macromolecules. 1996, 29, 8875–8882.

    CAS  Article  Google Scholar 

  31. 31.

    Kale, L.; Skeel, R.; Bhandarkar, M.; Brunner, R.; Gursoy, A.; Krawetz, N.; Neal, P.; Phillips, J.; Shinozaki, A.; Varadarajan, K.; Schulten, K. NAMD2: Greater Scalability for Parallel Molecular Dynamics. J. Comp. Phys. 1999, 151, 283–312.

    CAS  Article  Google Scholar 

  32. 32.

    MacKerell, A. Jr.; Feig, M.; Brooks, C. III. Extending the Treatment of Backbone Energetics in Protein Force Fields: Limitations of Gas-Phase Quantum Mechanics in Reproducing Protein Conformational Distributions in Molecular Dynamics Simulations. J. Comput. Chem. 2004, 25, 1400–1445.

    CAS  Article  Google Scholar 

  33. 33.

    MacKerell, A. D. Jr.; Bashford, D.; Bellott, M.; Dunbrack, R. Jr.; Evanseck, J.; Field, M.; Fischer, S.; Gao, J.; Guo, H.; Ha, S.; Joseph-McCarthy, D.; Kuchnir, L.; Kuczera, K.; Lau, F. T. K.; Mattos, C.; Michnick, S.; Ngo, T.; Nguyen, D. T.; Prodhom, B.; Reiher, W. E. III; Roux, B.; Schlenkrich, M.; Smith, J. C.; Stote, R.; Straub, J.; Watanabe, M.; Wiorkiewicz-Kuczera, J.; Yin, D.; Karplus, M. All-Atom Empirical Potential for Molecular Modeling and Dynamics Studies of Proteins. J. Phys. Chem. B. 1998, 102, 3586–3616.

    CAS  Article  Google Scholar 

  34. 34.

    CPMD Version 3.11.1, Copyright IBM Corp 1990–2006, Copyright MPI für Festkörperforschung Stuttgart 1997–2001.

  35. 35.

    Lee, S. K.; Polyakova, Y.; Row, K. H. Interrelation of Retention Factor of Amino-Acids by QSPR and Linear Regression. Bull. Korean Chem. Soc. 2003, 24, 1757–1762.

    CAS  Article  Google Scholar 

  36. 36.

    Kamariotis, A.; Boyarkin, O. V.; Mercier, S. R.; Beck, R. D.; Bush, M. F.; Williams, E. R.; Rizzo, T. R. Infrared Spectroscopy of Hydrated Amino Acids in the Gas Phase: Protonated and Lithiated Valine. J. Am. Chem. Soc. 2006, 128, 905–916.

    CAS  Article  Google Scholar 

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Correspondence to Markus Arndt.

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Published online April 26, 2008

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Marksteiner, M., Haslinger, P., Ulbricht, H. et al. Gas-phase formation of large neutral alkaline-earth metal tryptophan complexes. J Am Soc Mass Spectrom 19, 1021–1026 (2008). https://doi.org/10.1016/j.jasms.2008.04.028

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Keywords

  • Cluster Size Distribution
  • Calcium Atom
  • CHARMM Force Field
  • Amino Acid Cluster
  • Tryptophan Molecule