Journal
JOURNAL OF THE AMERICAN SOCIETY FOR MASS SPECTROMETRY
Volume 22, Issue 3, Pages 582-590Publisher
SPRINGER
DOI: 10.1007/s13361-010-0047-y
Keywords
Multivariate analysis; Principal Component Analysis (PCA); Electron Detachment Dissociation (EDD); Glycosaminoglycans (GAGs); Epimers; Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS)
Funding
- National Research Foundation of Korea [NRF-2009-0075245]
- National Institutes of Health [2R01-GM038060-20]
- Center for Research Resource of the National Institutes of Health [P41RR005351]
- National Research Foundation of Korea [핵06A3004, 2009-0075245] Funding Source: Korea Institute of Science & Technology Information (KISTI), National Science & Technology Information Service (NTIS)
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The structural characterization of glycosaminoglycan (GAG) carbohydrates by mass spectrometry has been a long-standing analytical challenge due to the inherent heterogeneity of these biomolecules, specifically polydispersity, variability in sulfation, and hexuronic acid stereochemistry. Recent advances in tandem mass spectrometry methods employing threshold and electron-based ion activation have resulted in the ability to determine the location of the labile sulfate modification as well as assign the stereochemistry of hexuronic acid residues. To facilitate the analysis of complex electron detachment dissociation (EDD) spectra, principal component analysis (PCA) is employed to differentiate the hexuronic acid stereochemistry of four synthetic GAG epimers whose EDD spectra are nearly identical upon visual inspection. For comparison, PCA is also applied to infrared multiphoton dissociation spectra (IRMPD) of the examined epimers. To assess the applicability of multivariate methods in GAG mixture analysis, PCA is utilized to identify the relative content of two epimers in a binary mixture.
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