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Ellagitannins have Greater Oxidative Activities than Condensed Tannins and Galloyl Glucoses at High pH: Potential Impact on Caterpillars

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Abstract

Plants synthesize a diversity of tannin structures but little is known about whether these different types have different oxidative activities in herbivores. Oxidative activities of hydrolyzable and condensed tannins were compared at pH 10 with two methods: EPR spectrometry was used to quantify semiquinone radicals in anoxic conditions and a spectrophotometric assay was used to measure the rate of browning of phenolics oxidized in ambient oxygen conditions. A little-studied group of hydrolyzable tannins (ellagitannins) contained the most active tannins examined, forming high concentrations of semiquinone radicals and browning at the highest rates. On average, galloyl glucoses and high-molecular-weight gallotannins had intermediate to low oxidative activities. Condensed tannins generally formed low levels of semiquinone radicals and browned most slowly. The results suggest that ellagitannin-rich plants have active oxidative defenses against herbivores, such as caterpillars, whereas the opposite may hold true for plants that contain predominantly condensed tannins or high-molecular-weight gallotannins.

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Acknowledgments

This project was supported by the National Research Initiative of the USDA Cooperative State Research, Education and Extension Service grant number 2004-35302-14940 to R. Barbehenn and C.P. Constabel. Support for J.-P. Salminen was provided by grant number 204209 from the Academy of Finland. Jonna Kenttä, Riitta Koivikko, Maria Lahtinen, Jaana Liimatainen, Tuuli Luomahaara, Angelica Preetz, and Victor Turhanen assisted with the isolation of tannins. We thank Michael M. Martin for suggesting revisions to this paper, and Jari Sinkkonen for drawing the chemical structures.

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Authors and Affiliations

  1. Departments of Molecular, Cellular and Developmental Biology and Ecology and Evolutionary Biology, University of Michigan, Ann Arbor, MI, 48109-1048, USA

    Raymond V. Barbehenn & Christopher P. Jones

  2. Department of Chemistry and Biochemistry, Miami University, Oxford, OH, 45056, USA

    Ann E. Hagerman

  3. Laboratory of Organic Chemistry and Chemical Biology, Department of Chemistry, University of Turku, Turku, FI-20014, Finland

    Maarit Karonen & Juha-Pekka Salminen

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  1. Raymond V. Barbehenn
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Correspondence to Raymond V. Barbehenn.

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Barbehenn, R.V., Jones, C.P., Hagerman, A.E. et al. Ellagitannins have Greater Oxidative Activities than Condensed Tannins and Galloyl Glucoses at High pH: Potential Impact on Caterpillars. J Chem Ecol 32, 2253–2267 (2006). https://doi.org/10.1007/s10886-006-9143-7

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