Electron capture dissociation of protonated proteins is selective and mainly results inN-Ca bond breakage. The mechanism behind is still up for much debate and some of the main questions are: is the fragmentation statistical? Where does the electron go? What is the role of the recombination energy (RE) of the charged groups? Is hydrogen or proton transfer necessary? Most likely one mechanism is not sufficient to explain all data published by various groups.  In this talk I will address the role of the RE. By the addition of charge tags we are able to control and vary the REs of the charged groups. Thus, we can change the probability for the electron to end up at either the N- or the C-terminal residue. We find, that the RE have little influence on the ratio between the yield of c and z ions when no mobile protons are present [1]. [1] C. S. Jensen, A. I. S. Holm, H. Zettergern, J. B. Overgaard, P. Hvelplund, S. Br�ndsted Nielsen, J. Am. Soc. Mass Spectrom., 2009, 20, 1881-1889

Electron capture induced dissociation of peptides:
Does the recombination energy of the charged groups play a role in determining the
charge partitioning between c and z ions?

240th National Meeting (2010)

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Electron capture induced dissociation of peptides: Does the recombination energy of the charged groups play a role in determining the charge partitioning between c and z ions?