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The research reported herein involves synthetic metal complexes of relevance to dioxygenase enzymes (Ni(II)-containing acireductone dioxygenase (Ni(II)-ARD) and quercentinase (2,4-flavonol dioxygenase) that promote oxidative carbon-carbon bond cleavage and CO release. The experiments focus on the elucidation of structure-reactivity relationships and evaluation of the conditions under which CO is generated. It had been proposed that hydrogen bond donors in the secondary environment of the active site metal center in Ni(II)-ARD influence the coordination of the acireductone substrate on the nickel center. To evaluate this proposal, we investigated the Ni(II) coordination chemistry of an acireductone-type enolate anion using a supporting chelate ligand having two internal hydrogen bond-donors. The resulting complex exhibited differences in terms of the organic product distribution in a CO release reaction resulting from oxidative C-C bond cleavage of the enolate ligand relative to this reported for the iv hydrophobic, 6-Ph2TPA-supported (6-Ph2TPA = N,N-bis((6-phenyl-2-pyridyl)methyl)- N-((2-pyridyl)methyl)amine) analogue. In another study, we found that changes in the supporting chelate ligand or metal center influenced the coordination chemistry of the acireductone-type enolate anion. This chemistry highlighted the propensity of the enolate to undergo isomerization without CO release in the presence of water. Rigorously excluding water enabled the isolation of a Ni(II) enolate complex of the 6-PhTPA ligand and examination of its oxidative CO release chemistry, as well as the spectroscopic characterization of the first Co(II) complex of an acireductone-type enolate. To elucidate factors influencing the CO-release reactivity of metal-flavonoid complexes, some of which have relevance to quercentinase enzymes, we synthesized and characterized the first series of structurally-related metal-flavonolate complexes [(6- Ph2TPA)M(3-Hfl)]X (M = Mn(II), Co(II), Ni(II), Cu(II), Zn(II), Cd(II), Hg(II); X = OTfor ClO4 - ). Exposure of these complexes to UV light initiated photooxidative carboncarbon bond cleavage and CO release in a metal-dependent manner, with closed-shell d 10 metals giving rise to the highest rate of CO release. These studies suggest that metal flavonolate species may be useful as a new type of photo-induced CO release molecules (CORMs). Such species are of current interest for possible therapeutic applications.

<p>The aquatic plant <i>Ipomoea aquatica</i> is a popular vegetable in Southeast Asia, often cultivated in nutrient rich and polluted waters. The overall aim of this thesis was to estimate potential risks for human health and reduced plant growth due to accumulation and toxicity of total-Hg, methyl-Hg, Cd and Pb.</p><p>In plants from cultivations in Thailand, the concentrations of Cd and Pb in the shoots were well beneath recommended maximum values for human consumption, but at some sites the Hg concentrations were high. It was demonstrated that <i>I. aquatica</i> has the capacity to accumulate much higher Cd and Pb concentrations in the shoots than found in field-cultivations, before exhibiting toxic symptoms. The Hg concentrations, however, occasionally reached levels that are toxic for the plant. Up to11% of total-Hg was methyl-Hg, the most toxic Hg species, though at one site it was 50-100%. To study if methyl-Hg is formed in <i>I.</i> <i>aquatica</i>, plants were exposed to inorganic Hg through the roots. Of the Hg that reached the young, metabolically active parts of the shoots, a part was transformed to methyl-Hg. A major proportion of absorbed metals was retained in the roots, which had a high tolerance for high internal metal concentrations. </p><p>The nutrient level did influence accumulation and effects of Hg, Cd and Pb in<i> I. aquatica</i>. Low external nutrient levels resulted in increased metal accumulation in the shoots and in metal-induced toxic effects in the plant at low external metal levels. A generous supply of sulphur or nitrogen induced formation of thiol-rich peptides in <i>I. aquatica</i>, compounds that have a metal detoxifying effect in plants. </p><p>To conclude, the levels of Cd and Pb in field cultivated <i>I. aquatica</i> do not pose any apparent threat to human health or risk for reduced plant growth. The levels of Hg however, were high at some sites and could be a health threat, for children and foetuses in particular, and especially considering the presence of methyl-Hg. The use of fertilizers is favourable as it reduces the risk for increased metal concentrations in <i>I.</i> <i>aquatica</i> and for reduced crop yields. </p>

The aquatic plant Ipomoea aquatica is a popular vegetable in Southeast Asia, often cultivated in nutrient rich and polluted waters. The overall aim of this thesis was to estimate potential risks for human health and reduced plant growth due to accumulation and toxicity of total-Hg, methyl-Hg, Cd and Pb. In plants from cultivations in Thailand, the concentrations of Cd and Pb in the shoots were well beneath recommended maximum values for human consumption, but at some sites the Hg concentrations were high. It was demonstrated that I. aquatica has the capacity to accumulate much higher Cd and Pb concentrations in the shoots than found in field-cultivations, before exhibiting toxic symptoms. The Hg concentrations, however, occasionally reached levels that are toxic for the plant. Up to11% of total-Hg was methyl-Hg, the most toxic Hg species, though at one site it was 50-100%. To study if methyl-Hg is formed in I. aquatica, plants were exposed to inorganic Hg through the roots. Of the Hg that reached the young, metabolically active parts of the shoots, a part was transformed to methyl-Hg. A major proportion of absorbed metals was retained in the roots, which had a high tolerance for high internal metal concentrations. The nutrient level did influence accumulation and effects of Hg, Cd and Pb in I. aquatica. Low external nutrient levels resulted in increased metal accumulation in the shoots and in metal-induced toxic effects in the plant at low external metal levels. A generous supply of sulphur or nitrogen induced formation of thiol-rich peptides in I. aquatica, compounds that have a metal detoxifying effect in plants. To conclude, the levels of Cd and Pb in field cultivated I. aquatica do not pose any apparent threat to human health or risk for reduced plant growth. The levels of Hg however, were high at some sites and could be a health threat, for children and foetuses in particular, and especially considering the presence of methyl-Hg. The use of fertilizers is favourable as it reduces the risk for increased metal concentrations in I. aquatica and for reduced crop yields.