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 13C‐labeled isotopomers and 2H‐labeled isotopomers. For both CID and IRMPD energy‐resolved measurements were carried out. Individual fragmentation pathways were studied at MS2 and MS3 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.

Mass Spectrometric Identification of Metabolites after Magnetic-Pulse Treatment of Infected Pyrus communis L. Microplants

“…In assigning MS peaks of CB (B) via Equations ( 2), ( 3) and ( 6), we used the molecular structures of MS ions proposed on the basis of GC-MS analysis of products of γ-radiolysis of α-D-glucose, α-D-fructos, cellobiose, and their silylated derivatives, respectively [53][54][55][56][57][58][59][60][61][62][63][64][65][66]. Chemometrics of measurands of CBs (A) and (B), silylated 4-desoxy-glucose, and silylated α-2-deoxy-D-glucose (2DG) show |r| = 0.7753 when looking at the results from CB (A) and 4-desoxy-D-glucose (4DG); |r| = 0.9411 5 when examining ions of CB (B) and 4DG; |r| = 0.9743 2 when looking at data on 2DG and 4DG; and |r| = 0.9494 5 when examining the variables of 2DG and silylated D-gluconic acid (Figure S8).…”