School of Chemistry - Theses

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    The coordination of nickel in hyperaccumulating plants
    Callahan, Damien L. ( 2007-10)
    The co-ordination of Ni in hyperaccumulator plants was investigated using a number of mass spectrometry (MS)-based analytical techniques. Initial field studies on nickeliferous (lateritic) soils in Western Australia failed to identify plants containing elevated metal concentrations. For this reason, Ni-hyperaccumulators were collected from known ultramafic sites in New Caledonia, as well as grown under controlled conditions. Using electrospray ionization MS a Ni-nicotianamine (Ni-NA) complex [NiII(C12H20N3O6)]+ was identified in the South African Ni-hyperaccumulator Berkheya coddii. The association between Ni and NA was examined further in a range of Thlaspi species which accumulate different concentrations of Ni and Zn in their foliar tissues. In order to quantitate the concentration of NA a new liquid chromatography-MS (LC-MS) based analytical protocol was developed which allowed the quantification of NA and free amino acids. From the analysis of the leaf tissue in Thlaspi a strong correlation emerged between Ni and NA but not Zn. This suggested that NA plays a role in the transport of Ni in Ni-hyperaccumulating Thlaspi plants. An inverse proportionality was found between Fe and Ni. Higher NA production could be related to maintenance of Fe homeostasis. A correlation was also found between Zn and asparagine. These results are consistent with the operation of separate transport mechanisms for Ni and Zn. Further extreme examples of Ni-hyperaccumulation were also examined using LC-MS and metabolite profiling based on gas chromatography-MS (GC-MS). (For complete abstract open document)