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Fragmentation patterns depend on how energy is transferred to the precursor ion, the amount of energy transferred, and how the transferred energy is internally distributed. Precursor ions can be activated (with increased internal energy) in many different ways. Nomenclature for oligosaccharide fragments (including glycolipids, when R = ceramide) (Costello, C. The numbers indicate the site of the sugar residue: y, z, b, and c ions are fragments due to glycosidic cleavages (cutting glycosidic bonds holding two adjacent sugar residues), whereas a and x ions result from cross-ring cleavage. Oligosaccharides (including glycolipids)įor oligosaccharides, fragments containing the reducing end (reducing end is on the right-hand side in the figure) are labeled x, y, or z, depending on the site of the cleavage, whereas fragments containing the other end are labeled a, b, or c. The numbers indicate the number of amino acid residues in the fragment ion. Peptidesįragments containing the N-terminus are labeled a, b, or c, depending on the site of the cleavage, whereas fragments containing the C-terminus are labeled x, y, or z.
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phospholipids, etc., do not yet have established nomenclature systems. Peptides and oligosaccharides (including glycolipids) follow different systems of nomenclature for their fragment ions.
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Typical Tandem-in-Time MS/MS instruments include ion trap and FT-ICR MS. The generated product ions can be detected either in the external trap (lower mass resolution, but faster) by or by FTMS (higher mass accuracy and resolution, but slower). Hybrid Ion Trap/FTMSįor the hybrid ion trap/FTMS (FT-ICR or Orbitrap) instruments, precursor ions are selected and fragmented in an external ion trap. The generated product ions are detected by time-of-flight (TOF) mass spectrometry. In the QTOF, precursor ions are selected in the Quadrupole and sent to the Collision Cell for fragmentation. The generated product ions are sent to Quad 3 for mass scanning. Precursor ions are selected in Quad 1 and sent to Quad 2 for dissociation (fragmentation). Three Quadrupoles (Quad 1, Quad 2, and Quad 3) are lined up in a row. Typical Tandem MS in space instruments include QqQ, QTOF, and hybrid ion trap/FTMS, etc. Since Tandem MS involves three distinct steps of selection-fragmentation-detection, the separation of these three steps can be realized in space or in time. For example, selected product ions generated in MS2 can be further fragmented to produce another group of product ions (MS3) and so on. The selection-fragmentation-detection sequence can be further extended to the first-generation product ions.
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Once samples are ionized (by ESI, MALDI, EI, etc.) to generate a mixture of ions, precursor ions of a specific mass-to-charge ratio ( m/z) are selected (MS1) and then fragmented (MS2) to generate a product ions for detection. The following scheme explains how Tandem MS works. College Students & Early Career Scientists.FSU Magnet Research & Development, Inc.