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(a) Radical fragmentation pathways depict formation of an a-type and x•-ion pair at the canonical Glu residue following hydrogen abstraction from the β-carbon (original site labelled in red in all four mechanisms). b) For isoGlu, the analogous pathway leads to loss of COOH. (b,c) IsoGlu residues also yield mass-shifted a- and x-type ions due to the additional backbone carbon, following α- or γ- hydrogen abstraction.
