Understanding the fragmentation of glucose in mass spectrometry

Abstract The fragmentation mechanism of D‐glucose was investigated in detail by two different fragmentation techniques, namely, collision‐induced dissociation (CID) and infrared multiphoton dissociation (IRMPD) using all six 13 C‐labeled isotopomers and 2 H‐labeled isotopomers. For both CID and IRMPD energy‐resolved measurements were carried out. Individual fragmentation pathways were studied at MS 2 and MS 3 levels. Additionally, we have developed an HPLC‐tandem MS method to separate the anomers of D‐glucose using a HILIC column and investigated their fragmentation patterns individually. We propose a complete fragmentation landscape of D‐glucose, demonstrating that a rather simple multifunctional molecule displays extreme complexity in gas phase dissociation, following multiple parallel fragmentation routes yielding a total of 23 distinct fragment ions. The results allowed a detailed formulation of the complex fragmentation mechanism of D‐glucose. The results have immediate consequences for the full structure analysis of complex carbohydrates.