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While analyzing tandem mass spectra of tryptic tripeptides, intense unassigned peaks were observed, corresponding to neutral loss of 45 Da from a2 ions. This process was confirmed by MS3 experiments. Based on exact mass analysis, the loss was ascribed to (NH3 + CO) or formamide. The proposed mechanism involves a cyclic form of the a2 ions. The structure of the a2 − 45 ions was confirmed by their fragmentation...
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