Abstract
Gas-phase complexes of cysteine-containing peptides and Fe2+ were produced by fast atom bombardment and studied by tandem mass spectrometry. Specific and strong interactions of the iron and sulfur from the thiol group of the cysteine side chain are preserved in the gas phase and are the basis for highly specific fragmentation to give abundant [a n − 2H+Fe]+ ions, where n is position of the cysteine residue from the N-terminus of peptide. Metal/peptide complexes containing more than one Cys residue were also investigated; they display similar chemistry upon collisionally activated decompositions, indicating that the Fe2+ ion primarily binds at cysteine sites.
Similar content being viewed by others
References
Otsuka, S.; Yamanaka, T. Metalloproteins; Elsevier: Tokyo, 1988; Vol. 8, pp 95–265.
Matsubara, H.; Katsube, Y.; Wada, K. Iron–Sulfur Protein Research; Japan Scientific Societies Press: Tokyo, 1987.
Pettit, L. D. Perspectives on Bioinorganic Chemistry; JAI: London, 5–35.
Cowan, J. A. Inorganic Biochemistry: An Introduction; VCH: New York, 1993; pp 3–18.
Holm, R. H. “Synthetic Approaches to the Active Sites of Iron-Sulfur Proteins,” Acc. Chem. Res. 1977, 10, 427–434.
Ibers, J. A.; Holm, R. H. “Modeling Coordination Sites in Metallobiomolecules,” Science 1980, 209, 223–235.
Chakrabarti, P. “Geometry of Interaction of Metal Ions with Sulfur-Containing Ligands in Protein Structures,” Biochemistry 1989, 28, 6081–6085.
Tang, X.; Ens, W.; Standing, K. G.; Westmore, J. B. “Daughter Ion Mass Spectra from Cationized Molecules of Small Oligopeptides in a Reflecting Time-of-Flight Mass Spectrometer,” Anal. Chem. 1988, 60, 1791–1799.
Russell, D. H.; McGlohon, E. S.; Mallis, L. M. “Fast-Atom Bombardment Tandem Mass Spectrometry Studies of Organo-Alkali-Metal Ions of Small Peptides. Competitive Interaction of Sodium with Basic Amino Acid Substituents,” Anal. Chem. 1988, 60, 1818–1824.
Grese, R. P.; Cerny, R. L.; Gross, M. L. “Metal Ion-Peptide Interactions in the Gas Phase. A Tandem Mass Spectrometry Study of Alkali Metal Cationized Peptides,” J. Am. Chem. Soc. 1989, 111, 2835–2842.
Grese, R. P.; Gross, M. L. “Gas-Phase Interactions of Lithium Ions and Dipeptides,” J. Am. Chem. Soc. 1990, 112, 5098–5104.
Leary, J. A.; Zhou, Z. R.; Odgen, S. A.; Williams, T. D. “Investigations of Gas-Phase Lithium-Peptide Adducts: Tandem Mass Spectrometry and Semiempirical Studies,” J. Am. Soc. Mass Spectrom. 1990, 1, 473–480.
Lee, S.-W.; Kim, H. S.; Beauchamp, J. L. “Salt Bridge Chemistry Applied to Gas-Phase Peptide Sequencing: Selective Fragmentation of Sodiated Gas-Phase Peptide Ions Adjacent to Aspartic Acid Residues,” J. Am. Chem. Soc. 1998, 120, 3188–3195.
Teesch, L. M.; Adams, J. “Fragmentations of Gas-Phase Complexes between Alkali Metal Ions and Peptides: Metal Ion Binding to Carbonyl Oxygens and Other Neutral Functional Groups,” J. Am. Chem. Soc. 1991, 113, 812–820.
Teesch, L. M.; Orlando, R. C.; Adams, J. “Location of the Alkali Metal Ion in Gas-Phase Peptide Complexes,” J. Am. Chem. Soc. 1991, 113, 3668–3675.
Teesch, L. M.; Adams, J. “Intrinsic Interactions between Alkaline-Earth Metal Ions and Peptides: A Gas-Phase Study,” J. Am. Chem. Soc. 1990, 112, 4110–4120.
Hu, P.; Gross, M. L. “Strong Interactions of Anionic Peptides and Alkaline Earth Metal Ions: Metal-Ion-Bound Peptides in the Gas Phase,” J. Am. Chem. Soc. 1992, 114, 9153–9160.
Zhao, H.; Reiter, A.; Teesch, L. M.; Adams, J. “Gas-Phase Fragmentations of Anionic Complexes between Peptides and Alkaline Earth Metal Ions: Structure-Specific Side-Chain Interactions,” J. Am. Chem. Soc. 1993, 115, 2854–2863.
Hu, P.; Gross, M. L. “Gas-Phase Interactions of Transition-Metal Ions and Di- and Tripeptides: A Comparison with Alkaline-Earth-Metal-Ion Interactions,” J. Am. Chem. Soc. 1993, 115, 8821–8828.
Galtin, C. L.; Turecek, F.; Vaisar, T. “Copper(II) Amino Acid Complexes in the Gas Phase,” J. Am. Chem. Soc. 1995, 117, 3637–3638.
Loo, J. A.; Hu, P.; Smith, R. D. “Interaction of Angiotensin Peptides and Zinc Metal Ions Probed by Electrospray Ionization Mass Spectrometry,” J. Am. Soc. Mass Spectrom. 1994, 5, 959–965.
Hu, P.; Sorensen, C.; Gross, M. L. “Influences of Peptide Side Chains on the Metal Ion Binding Site in Metal Ion-Cationized Peptides: Participation of Aromatic Rings in Metal Chelation,” J. Am. Soc. Mass Spectrom. 1995, 6, 1079–1085.
Bertini, I.; Gray, H. B.; Lippard, S. J.; Valentine, J. S. Bioinorganic Chemistry University Science Books. Mill Valley, CA, 1994; 8–9.
Petillot, Y.; Golinelli, M.; Forest, E.; Meyer, J. “Electrospray-Ionization Mass Spectrometry of Molecular Variants of a [2Fe–2S] Ferredoxin,” J. Biochem. Biophys. Res. Commun. 1995, 210, 686–694.
Sullards, C. M.; Adams, J. “On the Use of Scans at a Constant Ratio of B/E for Studying Decompositions of Peptide Metal(II)-Ion Complexes Formed by Electrospray Ionization J. Am. Soc. Mass Spectrom. 1995, 6, 608–610.
Hu, P.; Loo, J. A. “Gas-Phase Coordination Properties of Zn2+, Cu2+, Ni2+, and Co2+ with Histidine-Containing Peptides,” J. Am. Chem. Soc. 1995, 117, 11314–11319.
Vaisar, T.; Gatlin, C. L.; Turecek, F. “Metal–Ligand Redox Reactions in Gas-Phase Quaternary Peptide-Metal Complexes by Electrospray Ionization Mass Spectrometry,” Int. J. Mass Spectrom. Ion Processes 1997, 162, 77–87.
Li, H.; Siu, K. W. M.; Guevremont, R.; Yves Le Blanc, J. C. “Complexes of Silver(I) with Peptides and Proteins as Produced in Electrospray Mass Spectrometry,” J. Am. Soc. Mass Spectrom. 1997, 8, 781–792.
Nemirovskiy, O. V.; Gross, M. L. “Complexes of Iron(II) with Cysteine-Containing Peptides in the Gas Phase,” J. Am. Soc. Mass Spectrom. 1996, 7, 977–980.
Gross, M. L. “Tandem Mass Spectrometry: Multisector Magnetic Instruments. Tandem Mass Spectrometry: Multisector Magnetic Instruments,” in Methods in Enzymology, Vol. 193, Mass Spectrometry; McCloskey, J. A., Ed.; Academic: San Diego, 1990, 131–153.
Khrapova, N.; Malenkova, I.; Vanin, A. “S-Nitrosothiols and Dinitrosyl Iron Complexes as Source of Nitric Oxide in Animals,” Biofizika 1995, 40, 117–121.
Allen, M. H.; Hutchens, W. T. “Electrospray-Ionization Mass Spectrometry for the Detection of Discrete Peptide/Metal-Ion Complexes Involving Multiple Mysteine (sulfur) Ligands,” Rapid Commun. Mass Spectrom. 1992, 6, 308–312.
Bojesen, G. “The Order of Proton Affinites of the 20 Common L-α-Amino Acids,” J. Am. Chem. Soc. 1987, 109, 557–558.
Hunter, E. P.; Lias, S. G. “Evaluated Gas Phase Basicities and Proton Affinities of Molecules: An Update,” J. Phys. Chem. Ref. Data 1998, 27, 413–656.
Sigel, H.; Martin, R. B. “Coordinating Properties of the Amide Bond: Stability and Structure of Metal Ion Complexes of Peptides and Related Ligands,” Chem. Rev. 1982, 82, 386–403.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Nemirovskiy, O.V., Gross, M.L. Gas phase studies of the interactions of Fe2+ with cysteine-containing peptides. J Am Soc Mass Spectrom 9, 1285–1292 (1998). https://doi.org/10.1016/S1044-0305(98)00111-1
Received:
Revised:
Accepted:
Issue Date:
DOI: https://doi.org/10.1016/S1044-0305(98)00111-1