Abstract
We have used synchrotron-based X-ray fluorescence and absorption techniques to establish both metal distribution and complexation in mature wheat grains. In planta, extended X-ray absorption fine structure (EXAFS) spectroscopy reveals iron phytate and zinc phytate structures in aleurone cells and in modified aleurone cells in the transfer region of the grain: iron is coordinated octahedrally by six oxygen atoms and fewer than two phosphorous atoms. Zinc is coordinated tetrahedrally by four oxygen atoms and approximately 1.5 phosphorus atoms in an asymmetric coordination shell. We also present evidence of modified complexation of both metals in transgenic grain overexpressing wheat ferritin. For zinc, there is a consistent doubling of the number of complexing phosphorus atoms. Although there is some EXAFS evidence for iron phytate in ferritin-expressing grain, there is also evidence of a structure lacking phosphorus. This change may lead to an excess of phosphorus within the storage regions of grain, and in turn to the demonstrated increased association of phosphorus with zinc in ferritin-expressing grains. Derivative X-ray absorption spectra also suggest that mineral complexation in the transfer region of ferritin-expressing grains is quite different from that in wild-type grain. This may explain why the raised levels of minerals transported to the developing grain accumulate within the crease region of the transgenic grain.
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Acknowledgments
This work was supported in part by HarvestPlus (Washington, DC, USA). Rothamsted Research receives strategic support from the Biotechnology and Biological Science Research Council of the UK. Access to the Diamond Light Source synchrotron facility was made available by the Science and Technology Facilities Council of the UK. The authors are grateful for two anonymous reviews which helped improve the manuscript considerably. We are also grateful to Gerhard Leubner for allowing us to use the images in Fig. 1.
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775_2013_1000_MOESM1_ESM.pdf
Comparison of single-shell and asymmetric-shell zinc phytate models to EXAFS data collected from Bobwhite aleurone cells. The asymmetric model not only provides a lower reduced χ 2 (χ 2 red.), indicating a better fit to the experimental data, but also provides a visually better description of the second-shell feature at approximately 3.5 Å in the Fourier transform. Details of the models are provided in the text (PDF 73 kb)
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Neal, A.L., Geraki, K., Borg, S. et al. Iron and zinc complexation in wild-type and ferritin-expressing wheat grain: implications for mineral transport into developing grain. J Biol Inorg Chem 18, 557–570 (2013). https://doi.org/10.1007/s00775-013-1000-x
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DOI: https://doi.org/10.1007/s00775-013-1000-x