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Detection and localization of novel hordatine-like compounds and glycosylated derivates of hordatines by imaging mass spectrometry of barley seeds

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Abstract

Mass spectrometry imaging was applied on germinated barley for the detailed localization of metabolites in longitudinal and transversal seed sections. Among others, 20 m/z signals occurred in three regular peak clusters with specific, distinct localizations in embryo tissues. High resolution FT-ICR MS, MALDI-TOF MS/MS, and UHPLC-ESI MS/MS served for the identification and structural characterization of these compounds. Only five metabolites were published in their structures, namely the antifungal compounds hordatine A and B in non-glycosylated and glycosylated forms. All other non-identified cluster compounds were of hordatine-like structure and differed by systematic O-methylations, hydroxylations, and glycosylations. These differences in molecular structures correlated to distinct localization patterns within the embryo and might serve for the regulation of antifungal properties. Based on the structural investigations by mass spectrometry, an array of different hordatines that comprises the five published hordatines, 15 novel hordatine derivates and their six precursors could be localized in the embryo of germinated barley. Implications for the biosynthetic pathway and transport processes are discussed.

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Abbreviations

a.u.:

Arbitrary unit

ACT:

Agmatine coumaroyltransferase

CID:

Collision induced dissociation

cv.:

Cultivar

Da:

Dalton

DHB:

2,5-Dihydroxybenzoate

ESI:

Electrospray ionization

FT-ICR:

Fourier transform-ion cyclotron resonance

GC:

Gas chromatography

HCAA:

Hydroxycinnamic acid amide

ITO:

Indium tin oxide

LC:

Liquid chromatography

m/z :

Mass to charge ratio

MALDI:

Matrix-assisted laser desorption/ionization

MS:

Mass spectrometry

MSI:

Mass spectrometry imaging

NMR:

Nuclear magnetic resonance

Q-TOF:

Quadrupole-time of flight

TIC:

Total ion count

UHPLC:

Ultra high-performance liquid chromatography

References

  • Bowles D, Isayenkova J, Lim E, Poppenberger B (2005) Glycosyltransferases: managers of small molecules. Curr Opin Plant Biol 8:254–263

    Article  CAS  PubMed  Google Scholar 

  • Briggs DE (1998) Malts and malting. Blackie Academic & Professional, London

    Google Scholar 

  • Burhenne K (2003) A new class of N-hydroxycinnamoyltransferases. Purification, cloning, and expression of a barley agmatine coumaroyltransferase (EC 2.3.1.64). J Biol Chem 278:13919–13927

    Article  CAS  PubMed  Google Scholar 

  • Gorzolka K, Lissel M, Kessler N, Loch-Ahring S, Niehaus K (2012) Metabolite fingerprinting of barley whole seeds, endosperms, and embryos during industrial malting. J Biotechnol 159:177–187

    Article  CAS  PubMed  Google Scholar 

  • Kageyama N, Inui T, Komura H (2011) Elucidation of chemical structures of components responsible for beer aftertaste. J Am Soc Brew Chem 69(4):255–259

    CAS  Google Scholar 

  • Kohyama N, Ono H (2013) Hordatine A β-d-glucopyranoside from ungerminated barley grains. J Agric Food Chem 61:1112–1116

    Article  CAS  PubMed  Google Scholar 

  • Kristensen BK, Bloch H, Rasmussen SK (1999) Barley coleoptile peroxidases. Purification, molecular cloning, and induction by pathogens. Plant Physiol 120:501–512

    Article  CAS  PubMed Central  PubMed  Google Scholar 

  • Lee YJ, Perdian DC, Song Z, Yeung ES, Nikolau BJ (2012) Use of mass spectrometry for imaging metabolites in plants. Plant J 70:81–95

    Article  CAS  PubMed  Google Scholar 

  • Megason SG, Fraser SE (2007) Imaging in systems biology. Cell 130:784–795

    Article  CAS  PubMed  Google Scholar 

  • Nomura T, Ishizuka A, Kishida K, Islam AKMR, Endo TR, Iwamura H, Ishihara A (2007) Chromosome arm location of the genes for the biosynthesis of hordatines in barley. Genes Genet Syst 82:455–464

    Article  CAS  PubMed  Google Scholar 

  • Ogura Y, Ishihara A, Iwamura H (2001) Induction of hydroxycinnamic acid amides and tryptophan by jasmonic acid, abscisic acid and osmotic stress in barley leaves. Z Naturforsch C J Biosci 56:193–202

    CAS  Google Scholar 

  • Peukert M, Matros A, Lattanzio G, Kaspar S, Abadía J, Mock H (2012) Spatially resolved analysis of small molecules by matrix-assisted laser desorption/ionization mass spectrometric imaging (MALDI-MSI). New Phytol 193:806–815

    Article  CAS  PubMed  Google Scholar 

  • Smith TA, Best GR (1978) Distribution of the hordatines in barley. Phytochemistry 17:1093–1098

    Article  CAS  Google Scholar 

  • Smith CA, O’Maille G, Want EJ, Qin C, Trauger SA, Brandon TR, Custodio DE, Abagyan R, Siuzdak G (2005) METLIN: a metabolite mass spectral database. Ther Drug Monit 27:747–751

    Article  CAS  PubMed  Google Scholar 

  • Stoessl A (1967) The antifungal factors in barley. IV. Isolation, structure, and synthesis of the hordatines. Can J Chem 45:1745–1760

    Article  CAS  Google Scholar 

  • Stoessl A, Unwin CH (1970) The antifungal factors in barley. V. Antifungal activity of the hordatines. Can J Bot 48:465–470

    Article  CAS  Google Scholar 

  • Vanbeneden N, Gils F, Delvaux F, Delvaux FR (2007) Variability in the release of free and bound hydroxycinnamic acids from diverse malted barley (Hordeum vulgare L.) cultivars during wort production. J Agric Food Chem 55:11002–11010

    Article  CAS  PubMed  Google Scholar 

  • Zaima N, Goto-Inoue N, Hayasaka T, Setou M (2010) Application of imaging mass spectrometry for the analysis of Oryza sativa rice. Rapid Commun Mass Spectrom 24:2723–2729

    Article  CAS  PubMed  Google Scholar 

Download references

Acknowledgments

The authors highly acknowledge the support by Bruker Daltonics GmbH, who offered MALDI-FT-ICR MS imaging technology. Namely, we would like to thank Michael Becker and Jens Fuchser (Bruker Daltonics) for their helpful advice in data analyses. The authors further acknowledge the support of DFG grant “Mass Spectrometry Imaging”. Karin Gorzolka was supported by the CLIB2021 graduate cluster and by a scholarship of Bielefeld University.

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Authors and Affiliations

  1. Proteome and Metabolome Research, Faculty of Biology, Center for Biotechnology (CeBiTec), Universitätsstraße 25, 33615, Bielefeld, Germany

    Karin Gorzolka, Hanna Bednarz & Karsten Niehaus

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  1. Karin Gorzolka
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  2. Hanna Bednarz
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  3. Karsten Niehaus
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Correspondence to Karin Gorzolka.

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Gorzolka, K., Bednarz, H. & Niehaus, K. Detection and localization of novel hordatine-like compounds and glycosylated derivates of hordatines by imaging mass spectrometry of barley seeds. Planta 239, 1321–1335 (2014). https://doi.org/10.1007/s00425-014-2061-y

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  • DOI: https://doi.org/10.1007/s00425-014-2061-y

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