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Uptake and speciation of selenium in garlic cultivated in soil amended with symbiotic fungi (mycorrhiza) and selenate

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Abstract

The scope of the work was to investigate the influence of selenate fertilisation and the addition of symbiotic fungi (mycorrhiza) to soil on selenium and selenium species concentrations in garlic. The selenium species were extracted from garlic cultivated in experimental plots by proteolytic enzymes, which ensured liberation of selenium species contained in peptides or proteins. Separate extractions using an aqueous solution of enzyme-deactivating hydroxylamine hydrochloride counteracted the possible degradation of labile selenium species by enzymes (such as alliinase) that occur naturally in garlic. The selenium content in garlic, which was analysed by ICP–MS, showed that addition of mycorrhiza to the natural soil increased the selenium uptake by garlic tenfold to 15 μg g−1 (dry mass). Fertilisation with selenate and addition of mycorrhiza strongly increased the selenium content in garlic to around one part per thousand. The parallel analysis of the sample extracts by cation exchange and reversed-phase HPLC with ICP–MS detection showed that γ-glutamyl-Se-methyl-selenocysteine amounted to 2/3, whereas methylselenocysteine, selenomethionine and selenate each amounted to a few percent of the total chromatographed selenium in all garlic samples. Se-allyl-selenocysteine and Se-propyl-selenocysteine, which are selenium analogues of biologically active sulfur-containing amino acids known to occur in garlic, were searched for but not detected in any of the extracts. The amendment of soil by mycorrhiza and/or by selenate increased the content of selenium but not the distribution of detected selenium species in garlic. Finally, the use of two-dimensional HPLC (size exclusion followed by reversed-phase) allowed the structural characterisation of γ-glutamyl-Se-methyl-selenocysteine and γ-glutamyl-Se-methyl-selenomethionine in isolated chromatographic fractions by quadrupole time-of-flight mass spectrometry.

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Acknowledgements

The authors thank Dr. Laurent Ouerdane for his help with ESI–MS/MS experiments. The cultivation of garlic at PRI was part of SEAFOODplus, an integrated research project financially supported by the EU under FP6 (http://www.seafoodplus.org).

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Authors and Affiliations

  1. Department of Food Chemistry, Danish Institute for Food and Veterinary Research, 2860, Søborg, Denmark

    Erik H. Larsen, Marianne Hansen, Peter Have Rasmussen & Jens J. Sloth

  2. CNRS UMR 5034, Hélioparc, 2, Av. Angot, 64053, Pau, France

    Ryszard Lobinski, Rafal Ruzik & Lena Mazurowska

  3. Department of Analytical Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664, Warsaw, Poland

    Ryszard Lobinski, Rafal Ruzik & Lena Mazurowska

  4. Plant Research International (PRI), Wageningen University and Research Centre, P.O. Box 16, 6700 AA, Wageningen, The Netherlands

    Karin Burger-Meÿer, Olga Scholten & Chris Kik

  5. Centre for Genetic Resources, The Netherlands (CGN), Wageningen University and Research Centre, P.O. Box 16, 6700 AA, Wageningen, The Netherlands

    Chris Kik

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  1. Erik H. Larsen
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  2. Ryszard Lobinski
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  3. Karin Burger-Meÿer
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  4. Marianne Hansen
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  9. Olga Scholten
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  10. Chris Kik
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Correspondence to Erik H. Larsen.

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Larsen, E.H., Lobinski, R., Burger-Meÿer, K. et al. Uptake and speciation of selenium in garlic cultivated in soil amended with symbiotic fungi (mycorrhiza) and selenate. Anal Bioanal Chem 385, 1098–1108 (2006). https://doi.org/10.1007/s00216-006-0535-x

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  • DOI: https://doi.org/10.1007/s00216-006-0535-x

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