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이충식,장인애,송환보,문봉진,오한빈 대한화학회 2015 Bulletin of the Korean Chemical Society Vol.36 No.3
In tandem mass spectrometry, side-chain losses are known to provide information on the presence of certain amino acid residues, which can improve peptide identification. In this study, we examine whether side-chain losses also occur in free-radical-initiated peptide sequencing mass spectrometry (FRIPS MS). All four peptides examined here, i.e., ALPMHIR, YRPPGFSPFR, RPPGFSPYR, and YGGFLRRIRPKLK, showed extensive small group losses in the so-called (M• – X) region. Furthermore, peaks due to small group loss accompanying backbone fragmentations were also extensively observed. The observed small group losses, either radical or neutral side-chain losses, confirmed the presence of certain amino acids, even exhibiting signature peaks for isoleucine and leucine. In addition, mechanisms for small group losses in FRIPS MS are proposed.