The selected matrix influences the matrix-assisted laser desorption/ionization time-of-flight mass spectral patterns of partially deuterated glycosaminoglycan disaccharides

Rapid Commun Mass Spectrom. 2016 Oct 15;30(19):2164-70. doi: 10.1002/rcm.7694.


Rationale: If carbohydrates are investigated by nuclear magnetic resonance (NMR) spectroscopy, they are normally dissolved in deuterated solvents, such as D2 O. The incorporation of deuterium leads to a high complexity of subsequently recorded mass spectra and reduced sensitivity because different deuterated ions become detectable. Here, we demonstrate that the applied matrix-assisted laser desorption/ionization (MALDI) matrix solution has a considerable impact on the observed isotopic distribution.

Methods: Unsaturated disaccharides of chondroitin (CS) and dermatan sulfate (DS) were prepared by enzymatic digestion of the polysaccharides in D2 O and analyzed by MALDI time-of-flight mass spectrometry (TOF MS) using 2,5-dihydroxybenzoic acid (DHB) and 9-aminoacridine (9-AA) according to previously published protocols.

Results: The extent of deuteration of a given compound can be easily determined by using the mass shift between the non-deuterated and deuterated ions. However, such a determination is more difficult when considering sugars due to their high content of exchangeable groups. Therefore, both the solvent and the matrix have a considerable impact on the MS patterns. Additionally, there are significant differences if the spectra are recorded at different laser fluences.

Conclusions: Great caution should be taken when the deuterium content of disaccharides is determined by MALDI MS. Aside from the use of non-protic solvents, DHB is the matrix of choice, whereas 9-AA shows a considerable influence on the observed isotope pattern in dependence on the applied laser fluence. Copyright © 2016 John Wiley & Sons, Ltd.

Publication types

  • Evaluation Study

MeSH terms

  • Deuterium / chemistry
  • Disaccharides / chemistry*
  • Gentisates / chemistry
  • Glycosaminoglycans / chemistry*
  • Magnetic Resonance Spectroscopy
  • Molecular Weight
  • Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization / methods*


  • Disaccharides
  • Gentisates
  • Glycosaminoglycans
  • Deuterium