Plant Physiology Preview Published on March 4, 2004; 10.1104/pp.103.033506
Received September 17, 2003
Returned for revision October 19, 2003
Accepted December 4, 2003
The Nature of Arsenic-Phytochelatin Complexes inHolcus lanatus and Pteris cretica
Andrea Raab , Jörg Feldmann , and Andrew A. Meharg *
Department of Chemistry, University of Aberdeen, Meston Building, Meston Walk, Aberdeen AB24 3UE, United Kingdom (A.R., J.F.); and School of Biological Sciences, University of Aberdeen, Cruickshank Building, St. Machar Drive, Aberdeen, AB24 3UU, United Kingdom (A.A.M.).
* Corresponding author; email: a.meharg{at}abdn.ac.uk.
We have developed a method to extract and separate phytochelatins (PCs)--metal(loid) complexes using parallel metal(loid)-specific (inductively coupled plasma-mass spectrometry) and organic-specific (electrospray ionization-mass spectrometry) detection systems--and use it here to ascertain the nature of arsenic (As)-PC complexes in plant extracts. This study is the first unequivocal report, to our knowledge, of PC complex coordination chemistry in plant extracts for any metal or metalloid ion. The As-tolerant grass Holcus lanatus and the As hyperaccumulator Pteris cretica were used as model plants. In an in vitro experiment using a mixture of reduced glutathione (GS), PC2, and PC3, As preferred the formation of the arsenite [As(III)]-PC3 complex over GS-As(III)-PC2, As(III)-(GS)3, As(III)-PC2, or As(III)-(PC2)2 (GS: glutathione bound to arsenic via sulphur of cysteine). In H. lanatus, the As(III)-PC3 complex was the dominant complex, although reduced glutathione, PC2, and PC3 were found in the extract. P. cretica only synthesizes PC2 and forms dominantly the GS-As(III)-PC2 complex. This is the first evidence, to our knowledge, for the existence of mixed glutathione-PC-metal(loid) complexes in plant tissues or in vitro. In both plant species, As is dominantly in non-bound inorganic forms, with 13% being present in PC complexes for H. lanatus and 1% in P. cretica.
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