Principles of hydrogen radical mediated peptide/protein fragmentation during matrix‐assisted laser desorption/ionization mass spectrometry

摘要: Matrix-assisted laser desorption/ionization in-source decay (MALDI-ISD) is a very easy way to obtain large sequence tags and, thereby, reliable identification of peptides and proteins. Recently discovered new matrices have enhanced the MALDI-ISD yield opened research avenues. The use reducing oxidizing for proteins favors production fragmentation pathways involving "hydrogen-abundant" "hydrogen-deficient" radical precursors, respectively. Since an matrix provides information on peptide/protein sequences complementary that obtained with matrix, employing both potentially useful strategy de novo peptide sequencing. Moreover, pseudo-MS(3) method about N- C-terminus extremities in allows C-terminal side fragments be discriminated within complex mass spectrum. combination high resolution Fourier transform-ion cyclotron resonance (FTICR) analyzer software suitable facilitates interpretation spectra. A deeper understanding process necessary fully exploit this method. Thus, review focuses first mechanisms underlying processes, followed by discussion applications field proteomics. © 2014 Wiley Periodicals, Inc., Mass Spec Rev 35:535-556, 2016.