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After isolation of the ion m/z 628.3, the recorded MS 3 spectrum showed specific fragment ions indicating the cleavage of the amino acid valine ( m/z 628.3 [M+K] + 528.2, [M+K] + ) or the dipeptide L- O -Val-L-Val ( m/z 628.3 [M+K] + 427.1 [M+K] + ) to release the tetradepsipeptide L- O -Val-L-Val-D- O -Leu-D-Ala which could also be detected in the MS 4 spectrum after isolation of the fragment ion m/z 528.2