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Feasibility of using atmospheric pressure matrix-assisted laser desorption/ionization with ion trap mass spectrometry in the analysis of acetylated xylooligosaccharides derived from hardwoods and Arabidopsis thaliana

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Abstract

The atmospheric pressure matrix-assisted laser desorption/ionization with ion trap mass spectrometry (AP-MALDI-ITMS) was investigated for its ability to analyse plant-derived oligosaccharides. The AP-MALDI-ITMS was able to detect xylooligosaccharides (XOS) with chain length of up to ten xylopyranosyl residues. Though the conventional MALDI–time-of-flight/mass spectrometry (TOF/MS) showed better sensitivity at higher mass range (>m/z 2,000), the AP-MALDI-ITMS seems to be more suitable for detection of acetylated XOS, and the measurement also corresponded better than the MALDI-TOF/MS analysis to the actual compositions of the pentose- and hexose-derived oligosaccharides in a complex sample. The structures of two isomeric aldotetrauronic acids and a mixture of acidic XOS were elucidated by AP-MALDI-ITMS using multi-stages mass fragmentation up to MS3. Thus, the AP-MALDI-ITMS demonstrated an advantage in determining both mass and structures of plant-derived oligosaccharides. In addition, the method of combining the direct endo-1,4-β-d-xylanase hydrolysis of plant material, and then followed by AP-MALDI-ITMS detection, was shown to recognize the substitution variations of glucuronoxylans in hardwood species and in Arabidopsis thaliana. To our knowledge, this is the first report to demonstrate the acetylation of glucuronoxylan in A. thaliana. The method, which requires only a small amount of plant material, such as 1 to 5 mg for the A. thaliana stem material, can be applied as a high throughput fingerprinting tool for the fast comparison of glucuronoxylan structures among plant species or transformants that result from in vivo cell wall modification.

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Acknowledgements

We thank Dr. Nisse Kalkkinen and Gunilla Rönnholm (Protein Chemistry Research Group, Institute of Biotechnology, Helsinki) for the help in MALDI-TOF/MS analysis. We thank Prof. Juan Carlos Parajó of University of Vigo, Spain for the XOS sample isolated from hydrothermally treated E. globulus wood and Prof. Stefan Willför of Åbo Akademi University, Finland for the aspen, birch and eucalyptus wood powders. The financial support from the Academy of Finland and Formas through the WoodWisdom-Net Programme (HemiPop project no. 1124281) and Glycoscience Graduate School (S.-L.C) are gratefully acknowledged.

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Authors and Affiliations

  1. Department of Food and Environmental Sciences, Faculty of Agriculture and Forestry, University of Helsinki, P.O. Box 27, 00014, Helsinki, Finland

    Sun-Li Chong, Sanna Koutaniemi, Maija Tenkanen & Päivi Tuomainen

  2. Centre for Drug Research, Faculty of Pharmacy, University of Helsinki, P.O. Box 56, 00014, Helsinki, Finland

    Teemu Nissilä & Raimo A. Ketola

  3. Division of Pharmaceutical Chemistry, Faculty of Pharmacy, University of Helsinki, P.O. Box 56, 00014, Helsinki, Finland

    Teemu Nissilä & Raimo A. Ketola

  4. Umeå Plant Science Centre, Department of Forest Genetics and Plant Physiology, Swedish University of Agricultural Sciences, 901-83, Umeå, Sweden

    Marta Derba-Maceluch & Ewa J. Mellerowicz

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  1. Sun-Li Chong
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Chong, SL., Nissilä, T., Ketola, R.A. et al. Feasibility of using atmospheric pressure matrix-assisted laser desorption/ionization with ion trap mass spectrometry in the analysis of acetylated xylooligosaccharides derived from hardwoods and Arabidopsis thaliana . Anal Bioanal Chem 401, 2995–3009 (2011). https://doi.org/10.1007/s00216-011-5370-z

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