Differentiation of Closely Related Isomers: Application of Data Mining Techniques in Conjunction with Variable Wavelength Infrared Multiple Photon Dissociation Mass Spectrometry for Identification of Glucose-Containing Disaccharide Ions

Abstract

Data mining algorithms have been used to analyze the infrared multiple photon dissociation (IRMPD) patterns of gas-phase lithiated disaccharide isomers irradiated with either a line-tunable CO(2) laser or a free electron laser (FEL). The IR fragmentation patterns over the wavelength range of 9.2-10.6 μm have been shown in earlier work to correlate uniquely with the asymmetry at the anomeric carbon in each disaccharide. Application of data mining approaches for data analysis allowed unambiguous determination of the anomeric carbon configurations for each disaccharide isomer pair using fragmentation data at a single wavelength. In addition, the linkage positions were easily assigned. This combination of wavelength-selective IRMPD and data mining offers a powerful and convenient tool for differentiation of structurally closely related isomers, including those of gas-phase carbohydrate complexes.

Differentiation of Disaccharide Isomers by Temperature-Dependent In-Source Decay (TDISD) and DART-Q-TOF MS/MS

“…The structures of the oligosaccharides are in many cases related to their multiple important biological functions, while structural analysis of carbohydrates is still challenging because of the enormous structural diversity and microheterogeneity [16][17][18]. With the development of MS, MS-based technology has become a pivotal methodology for structural elucidation of carbohydrates [19][20][21][22][23][24][25][26][27][28]. In our recent reports [22][23][24], oligosaccharide isomers were successfully distinguished by laserenhanced in-source decay (LEISD) of matrix-assisted laser desorption/ionization (MALDI) MS or 1-phenyl-3-methyl-5-pyrazolone labeling technique in conjunction with electrospray ionization (ESI) tandem mass spectrometry.…”

“…The monosaccharide structural isomers could exhibit different mobility drift times in both drift tube and traveling wave ion mobility mass spectrometry, depending on differences in their anomeric and stereochemical configurations [26]. For disaccharide isomers, they can be distinguished by traveling wave ion mobility mass spectrometry using CO 2 as drift gas [27] or data mining techniques in conjunction with variable wavelength infrared multiple photon dissociation mass spectrometry [28].…”

Gas Phase Chemistry of Li+with Amides: the Observation of LiOH Loss in Mass Spectrometry

“…On the other hand, the mass spectrometric fragmentations of metal cationized, especially lithiated biomolecules, have attracted much attention because of the desire to measure intrinsic metal ion affinity and identify the binding sites [14,15], and because the interesting dissociation pathways exhibited by these compounds are usually different from the protonated and deprotonated analogues [16,17]. Recently, the fragmentation behaviors of lithiated species have been reported for peptides, fatty acids, phospholipids, polytetrahydrofuran, cardiolipins, thioesters, cholesteryl esters, and disaccharides [18][19][20][21][22][23][24][25][26].…”

Differentiation of disaccharide isomers via a combination of IR and UV photodissociation mass spectrometry

“…For the latter case mentioned above, the methods of gas‐phase photon action spectroscopy in the IR or UV regions provide unique and valuable information about their structures and relative dynamics 38–50 . However, the collection of spectra usually needs longer time and higher requirements for researchers.…”