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Electron Capture Dissociation in Fourier Transform Mass Spectrometry

by Kim F. Haselmann

I am currently doing a Ph.D. in chemistry at University of Southern Denmark in the mass spectrometry laboratory under the guidance of Dr. Roman A. Zubarev. My project title is "Ion chemistry by Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR-MS)". My main research area are electrospray (ESI) mass spectrometry of biomolecules. Proteins and peptides can be sequence in the gas phase by FT-MS in several different ways. The conventional fragmentation technique is Collisionally activated dissociation (CAD), where ions with increased kinetic energy are colliding with an inert target gas and breaks up. The technique has certain drawbacks as insurfficient sequence information and not able to localise post-translational modification as the bond of lowest energy are the ones to break up first. Here electron capture dissociation have proofed it advantages as a complementary fragmentation technique, where multiply charged cations capture electrons of low kinetic energy and fragments. Also other ion-electron induced dissociation techniques are investigated e.g. Electron detachment dissociation (EDD), hot ECD and electron excitation dissociation (EED) etc.

References:

Budnik, B.A., Haselmann, K.F., Zubarev, R.A. Electron detachment dissociation of peptide di-anions: an electron-hole recombination phenomenon. Chem. Phys. Lett. 342, 299 (2001).

Olsen J.V., Haselmann, K.F., Nielsen, M.L., Budnik B.A., Nielsen P.E., Zubarev, R.A. Comparison of electron capture dissociation and collisionally activated dissociation of polycations of peptide nucleic acids. Rapid Commun. Mass Spectrom. 15, 969 (2001).

Budnik, B.A., Nielsen, M.L., Olsen, J.V., Haselmann, K.F., Horth, P., Haehnel, W., Zubarev, R.A. Can relative cleavage frequencies in peptides provide additional sequence information?. ICR/IonTrap Newsletter. 63, 4 (2001).

Haselmann, K.F., Budnik, B.A., Olsen, J.V., Nielsen, M.L., Reis, C.A., Clausen, H., Johnsen, A.H., Zubarev, R.A. Advantages of external accumulation for electron capture dissociation in Fourier-transform mass spectrometry. Anal. Chem. 73, 2998 (2001).

Haselmann, K.F., Budnik, B.A., Zubarev, R.A. Electron capture dissociation of b2+ peptide fragments reveals the presence of the acylium structure. Rapid Commun. Mass Spectrom. 14, 2342 (2000).

Stensballe, A., Jensen, O.N., Olsen, J.V., Haselmann, K.F., Zubarev, R.A. Electron capture dissociation of multiply phosphorylated peptides. Rapid Commun. Mass Spectrom. 14, 1793 (2000).

Nielsen, M.L., Budnik, B.A., Haselmann, K.F., Olsen, J.V., Zubarev, R.A. Intramolecular hydrogen atom transfer in hydrogen-deficit polypeptide radical cations. Chem. Phys. Lett. 330, 558 (2000).