Substituent effects on the gas-phase fragmentation reactions of protonated peptides containing benzylamine-derivatized lysyl residues

Rapid Communications in Mass Spectrometry : RCM
E S SimonP C Andrews

Abstract

Motivated by the need for chemical strategies designed to tune peptide fragmentation to selective cleavage reactions, benzyl ring substituent influence on the relative formation of carbocation elimination (CCE) products from peptides with benzylamine-derivatized lysyl residues has been examined using collision-induced dissociation (CID) tandem mass spectrometry. Unsubstituted benzylamine-derivatized peptides yield a mixture of products derived from amide backbone cleavage and CCE. The latter involves side-chain cleavage of the derivatized lysyl residue to form a benzylic carbocation [C(7)H(7)](+) and an intact peptide product ion [(MH(n))(n+) - (C(7)H(7))(+)]((n-1)+). The CCE pathway is contingent upon protonation of the secondary ε-amino group (N(ε)) of the derivatized lysyl residue. Using the Hammett methodology to evaluate the electronic contributions of benzyl ring substituents on chemical reactivity, a direct correlation was observed between changes in the CCE product ion intensity ratios (relative to backbone fragmentation) and the Hammett substituent constants, σ, of the corresponding substituents. There was no correlation between the substituent-influenced gas-phase proton affinity of N(ε) and the relative ratios of CCE...Continue Reading

References

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Mar 11, 2006·The Journal of Organic Chemistry·Israel Fernández, Gernot Frenking
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May 18, 2010·Journal of the American Society for Mass Spectrometry·Eric S SimonPhilip C Andrews
Nov 1, 1994·Journal of the American Society for Mass Spectrometry·J K EngJ R Yates

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Jun 15, 2013·Rapid Communications in Mass Spectrometry : RCM·E S SimonP C Andrews

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