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

  • Sun-Li Chong
  • Teemu Nissilä
  • Raimo A. Ketola
  • Sanna Koutaniemi
  • Marta Derba-Maceluch
  • Ewa J. Mellerowicz
  • Maija Tenkanen
  • Päivi Tuomainen
Original Paper

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.

Keywords

Acetylation 4-O-Methylglucuronoxylan Endo-1,4-β-d-xylanase AP-MALDI mass spectrometry Hardwood Arabidopsis thaliana 

Notes

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.

Supplementary material

216_2011_5370_MOESM1_ESM.pdf (1.8 mb)
ESM 1 (PDF 1.81 mb)

References

  1. 1.
    Aspinall GO (1980) Chemistry of cell wall polysaccharides. Biochem Plants 3:473–500Google Scholar
  2. 2.
    Timell TE (1967) Recent progress in the chemistry of wood hemicelluloses. Wood Sci Technol 1:45–70CrossRefGoogle Scholar
  3. 3.
    Teleman A, Lundqvist J, Tjerneld F, Stålbrand H, Dahlman O (2000) Characterization of acetylated 4-O-methylglucuronoxylan isolated from aspen employing 1H and 13C NMR spectroscopy. Carbohydr Res 329:807–815CrossRefGoogle Scholar
  4. 4.
    Naran R, Black S, Decker SR, Azadi P (2009) Extraction and characterization of native heteroxylans from delignified corn stover and aspen. Cellulose 16:661–675CrossRefGoogle Scholar
  5. 5.
    Goncalves VMF, Evtuguin DV, Domingues MRM (2008) Structural characterization of the acetylated heteroxylan from the natural hybrid Paulownia elongata/Paulownia fortunei. Carbohydr Res 343:256–266CrossRefGoogle Scholar
  6. 6.
    Evtuguin DV, Tomas JL, Silva AMS, Neto CP (2003) Characterization of an acetylated heteroxylan from Eucalyptus globulus Labill. Carbohydr Res 338:597–604CrossRefGoogle Scholar
  7. 7.
    Brown DM, Goubet F, Wong VW, Goodacre R, Stephens E, Dupree P, Turner SR (2007) Comparison of five xylan synthesis mutants reveals new insight into the mechanisms of xylan synthesis. Plant J 52:1154–1168CrossRefGoogle Scholar
  8. 8.
    Peña MJ, Zhong RQ, Zhou GK, Richardson EA, O’Neill MA, Darvill AG, York WS, Zheng HY (2007) Arabidopsis irregular xylem8 and irregular xylem9: implications for the complexity of glucuronoxylan biosynthesis. Plant Cell 19:549–563CrossRefGoogle Scholar
  9. 9.
    Wu AM, Rihouey C, Seveno M, Hörnblad E, Singh SK, Matsunaga T, Ishii T, Lerouge P, Marchant A (2009) The Arabidopsis IRX10 and IRX10-LIKE glycosyltransferases are critical for glucuronoxylan biosynthesis during secondary cell wall formation. Plant J 57:718–731CrossRefGoogle Scholar
  10. 10.
    Sjöström E (1993) Wood chemistry: fundamentals and applications, 2nd edn. Academic, CaliforniaGoogle Scholar
  11. 11.
    Lerouxel O, Choo TS, Seveno M, Usadel B, Faye L, Lerouge P, Pauly M (2002) Rapid structural phenotyping of plant cell wall mutants by enzymatic oligosaccharide fingerprinting. Plant Physiol 130:1754–1763CrossRefGoogle Scholar
  12. 12.
    Westphal Y, Schols HA, Voragen AGJ, Gruppen H (2010) MALDI-TOF MS and CE-LIF fingerprinting of plant cell wall polysaccharide digests as a screening tool for Arabidopsis cell wall mutants. J Agric Food Chem 58:4644–4652CrossRefGoogle Scholar
  13. 13.
    Jacobs A, Dahlman O (2001) Enhancement of the quality of MALDI mass spectra of highly acidic oligosaccharides by using a Nafion-coated probe. Anal Chem 73:405–410CrossRefGoogle Scholar
  14. 14.
    Enebro J, Momcilovic D, Siika-aho M, Karlsson S (2009) Investigation of endoglucanase selectivity on carboxymethyl cellulose by mass spectrometric techniques. Cellulose 16:271–280CrossRefGoogle Scholar
  15. 15.
    Jacobs A, Larsson PT, Dahlman O (2001) Distribution of uronic acids in xylans from various species of soft- and hardwood as determined by MALDI mass spectrometry. Biomacromolecules 2:979–990CrossRefGoogle Scholar
  16. 16.
    Kabel MA, Schols HA, Voragen AGJ (2002) Complex xylo-oligosaccharides identified from hydrothermally treated Eucalyptus wood and brewery's spent grain. Carbohydr Polym 50:191–200CrossRefGoogle Scholar
  17. 17.
    Teleman A, Nordstrom M, Tenkanen M, Jacobs A, Dahlman O (2003) Isolation and characterization of O-acetylated glucomannans from aspen and birch wood. Carbohydr Res 338:525–534CrossRefGoogle Scholar
  18. 18.
    Teleman A, Lundqvist J, Tjerneld F, Stålbrand H, Dahlman O (2002) Characterization of water-soluble hemicelluloses from spruce and aspen employing SEC/MALDI mass spectroscopy. Carbohydr Res 337:711–717CrossRefGoogle Scholar
  19. 19.
    Korner R, Limberg G, Mikkelsen JD, Roepstorff P (1998) Characterization of enzymatic pectin digests by matrix-assisted laser desorption/ionization mass spectrometry. J Mass Spectrom 33:836–842CrossRefGoogle Scholar
  20. 20.
    Zaia J (2004) Mass spectrometry of oligosaccharides. Mass Spectrom Rev 23:161–227CrossRefGoogle Scholar
  21. 21.
    Powell AK, Harvey DJ (1996) Stabilization of sialic acids in N-linked oligosaccharides and gangliosides for analysis by positive ion matrix-assisted laser desorption/ionization mass spectrometry. Rapid Commun Mass Spectrom 10:1027–1032CrossRefGoogle Scholar
  22. 22.
    Bagag A, Laprevote O, Hirsch J, Kovacik V (2008) Atmospheric pressure photoionization mass spectrometry of per-O-methylated oligosaccharides related to d-xylans. Carbohydr Res 343:2813–2818CrossRefGoogle Scholar
  23. 23.
    Fernandez LEM, Obel N, Scheller HV, Roepstorff P (2003) Characterization of plant oligosaccharides by matrix-assisted laser desorption/ionization and electrospray mass spectrometry. J Mass Spectrom 38:427–437CrossRefGoogle Scholar
  24. 24.
    Matamoros Fernandez LE, Obel N, Scheller HV, Roepstorff P (2004) Differentiation of isomeric oligosaccharide structures by ESI tandem MS and GC-MS. Carbohydr Res 339:655–664CrossRefGoogle Scholar
  25. 25.
    Reis A, Pinto P, Evtuguin DV, Neto CP, Domingues P, Ferrer-Correia AJ, Domingues MRM (2005) Electrospray tandem mass spectrometry of underivatised acetylated xylo-oligosaccharides. Rapid Commun Mass Spectrom 19:3589–3599CrossRefGoogle Scholar
  26. 26.
    Reis A, Pinto P, Coimbra MA, Evtuguin DV, Neto CP, Ferrer Correia AJ, Domingues MRM (2004) Structural differentiation of uronosyl substitution patterns in acidic heteroxylans by electrospray tandem mass spectrometry. J Am Soc Mass Spectrom 15:43–47CrossRefGoogle Scholar
  27. 27.
    Quemener B, Ordaz-Ortiz JJ, Saulnier L (2006) Structural characterization of underivatized arabino-xylo-oligosaccharides by negative-ion electrospray mass spectrometry. Carbohydr Res 341:1834–1847CrossRefGoogle Scholar
  28. 28.
    Reinhold VN, Reinhold BB, Costello CE (1995) Carbohydrate molecular weight profiling, sequence, linkage, and branching data: ES-MS and CID. Anal Chem 67:1772–1784CrossRefGoogle Scholar
  29. 29.
    Harvey DJ (2006) Analysis of carbohydrates and glycoconjugates by matrix-assisted laser desorption/ionization mass spectrometry: an update covering the period 1999-2000. Mass Spectrom Rev 25:595–662CrossRefGoogle Scholar
  30. 30.
    Laiko VV, Baldwin MA, Burlingame AL (2000) Atmospheric pressure matrix-assisted laser desorption/ionization mass spectrometry. Anal Chem 72:652–657CrossRefGoogle Scholar
  31. 31.
    Creaser CS, Reynolds JC, Harvey DJ (2002) Structural analysis of oligosaccharides by atmospheric pressure matrix-assisted laser desorption/ionization quadrupole ion trap mass spectrometry. Rapid Commun Mass Spectrom 16:176–184CrossRefGoogle Scholar
  32. 32.
    Zhang J, LaMotte L, Dodds ED, Lebrilla CB (2005) Atmospheric pressure MALDI fourier transform aass spectrometry of labile oligosaccharides. Anal Chem 77:4429–4438CrossRefGoogle Scholar
  33. 33.
    Moyer SC, Marzilli LA, Woods AS, Laiko VV, Doroshenko VM, Cotter RJ (2003) Atmospheric pressure matrix-assisted laser desorption/ionization (AP MALDI) on a quadrupole ion trap mass spectrometer. Int J Mass Spectrom 226:133–150CrossRefGoogle Scholar
  34. 34.
    Tan PV, Taranenko NI, Laiko VV, Yakshin MA, Prasad CR, Doroshenko VM (2004) Mass spectrometry of N-linked oligosaccharides using atmospheric pressure infrared laser ionization from solution. J Mass Spectrom 39:913–921CrossRefGoogle Scholar
  35. 35.
    Gullón P, González-Muñoz MJ, Domínguez H, Parajó JC (2008) Membrane processing of liquors from Eucalyptus globulus autohydrolysis. J Food Eng 87:257–265CrossRefGoogle Scholar
  36. 36.
    Zablackis E, Huang J, Mueller B, Darvill AG, Albersheim P (1995) Characterization of the cell-wall polysaccharides of Arabidopsis thaliana leaves. Plant Physiol 107:1129–1138CrossRefGoogle Scholar
  37. 37.
    Packer NH, Lawson MA, Jardine DR, Redmond JW (1998) A general approach to desalting oligosaccharides released from glycoproteins. Glycoconj J 15:737–747CrossRefGoogle Scholar
  38. 38.
    Enebro J, Karlsson S (2006) Improved matrix-assisted laser desorption/ionization time-of-flight mass spectrometry of carboxymethyl cellulose. Rapid Commun Mass Spectrom 20:3693–3698CrossRefGoogle Scholar
  39. 39.
    Salo PK, Salomies H, Harju K, Ketola RA, Kotiaho T, Yli-Kauhaluoma J, Kostiainen R (2005) Analysis of small molecules by ultra thin-layer chromatography-atmospheric pressure matrix-assisted laser desorption/ionization mass spectrometry. J Am Soc Mass Spectrom 16:906–915CrossRefGoogle Scholar
  40. 40.
    Fauré R, Courtin CM, Delcour JA, Dumon C, Faulds CB, Fincher GB, Fort S, Fry SC, Halila S, Kabel MA, Pouvreau L, Quemener B, Rivet A, Saulnier L, Schols HA, Driguez H, O’Donohue MJ (2009) A brief and informationally rich naming system for oligosaccharide motifs of heteroxylans found in plant cell walls. Aust J Chem 62:533–537CrossRefGoogle Scholar
  41. 41.
    Sundberg A, Sundberg K, Lillandt C, Holmbom B (1996) Determination of hemicelluloses and pectins in wood and pulp fibers by acid methanolysis and gas chromatography. Nord Pulp Pap Res J 11:216–226CrossRefGoogle Scholar
  42. 42.
    Pastell H, Virkki L, Harju E, Tuomainen P, Tenkanen M (2009) Presence of 1→3-linked 2-O-β-d-xylopyranosyl-α-l-arabinofuranosyl side chains in cereal arabinoxylans. Carbohydr Res 344:2480–2488CrossRefGoogle Scholar
  43. 43.
    Li YCL, Cheng S-W, Chan T-WD (1998) Evaluation of ammonium salts as co-matrixes for matrix-assisted laser desorption/ionization mass spectrometry of oligonucleotides. Rapid Commun Mass Spectrom 12:993–998CrossRefGoogle Scholar
  44. 44.
    Biely P, Vršanská M, Tenkanen M, Kluepfel D (1997) Endo-β-1,4-xylanase families: differences in catalytic properties. J Biotechnol 57:151–166CrossRefGoogle Scholar
  45. 45.
    Rantanen H, Virkki L, Tuomainen P, Kabel M, Schols H, Tenkanen M (2007) Preparation of arabinoxylobiose from rye xylan using family 10 Aspergillus aculeatus endo-1,4-β-d-xylanase. Carbohydr Polym 68:350–359CrossRefGoogle Scholar
  46. 46.
    Pastell H, Tuomainen P, Virkki L, Tenkanen M (2008) Step-wise enzymatic preparation and structural characterization of singly and doubly substituted arabinoxylo-oligosaccharides with non-reducing end terminal branches. Carbohydr Res 343:3049–3057CrossRefGoogle Scholar
  47. 47.
    Teleman A, Tenkanen M, Jacobs A, Dahlman O (2002) Characterization of O-acetyl-(4-O-methylglucurono)xylan isolated from birch and beech. Carbohydr Res 337:373–377CrossRefGoogle Scholar
  48. 48.
    Reis A, Domingues MRM, Domingues P, Ferrer-Correia AJ, Coimbra MA (2003) Positive and negative electrospray ionization tandem mass spectrometry as a tool for structural characterization of acid released oligosaccharides from olive pulp glucuronoxylans. Carbohydr Res 338:1497–1505CrossRefGoogle Scholar
  49. 49.
    Domon B, Costello CE (1988) A systematic nomenclature for carbohydrate fragmentations in FAB-MS/MS spectra of glycoconjugates. Glycoconj J 5:397–409CrossRefGoogle Scholar

Copyright information

© Springer-Verlag 2011

Authors and Affiliations

  • Sun-Li Chong
    • 1
  • Teemu Nissilä
    • 2
    • 3
  • Raimo A. Ketola
    • 2
    • 3
  • Sanna Koutaniemi
    • 1
  • Marta Derba-Maceluch
    • 4
  • Ewa J. Mellerowicz
    • 4
  • Maija Tenkanen
    • 1
  • Päivi Tuomainen
    • 1
  1. 1.Department of Food and Environmental Sciences, Faculty of Agriculture and ForestryUniversity of HelsinkiHelsinkiFinland
  2. 2.Centre for Drug Research, Faculty of PharmacyUniversity of HelsinkiHelsinkiFinland
  3. 3.Division of Pharmaceutical Chemistry, Faculty of PharmacyUniversity of HelsinkiHelsinkiFinland
  4. 4.Umeå Plant Science Centre, Department of Forest Genetics and Plant PhysiologySwedish University of Agricultural SciencesUmeåSweden

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