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The major emphasis of this thesis is the statistical analysis of the biological affinity of Ontario Iroquois populations within the context of the Ontario Iroquois Tradition. The statistical comparison is based on a study of the dental morphology of the permanent crowns of three ossuary populations. A total of 64 dental morphological traits are considered. The three dental samples studied include two protohistoric Neutral ossuary populations and a protohistoric Huron ossuary population. The results of the statistical analysis indicate a greater degree of biological affinity between the two protohistoric Neutral ossuary populations than between the Neutral ossuary populations and protohistoric Huron ossuary population. The dental morphological evidence parallels the present model of the Ontario Iroquois Tradition which is based on archaeological, ethnohistoric and linguistic studies. This model indicates a cultural divergence between the four entario Iroquois groupings - the Neutral, Huron, Erie and Petun - which occurred circa 1400 A.D. Up until this point, dental studies of the Ontario Iroquois have been limited in number. This thesis indicates the potential of dental morphological analysis for making a major contribution to our current understanding of the Ontario Iroquois. In addition, it hopefully provides a preliminary step towards a uniform framework within which future Ontario Iroquois studies can be carried out. Master of Arts (MA)

Pre-oxidation is commonly used to mitigate the formation of byproducts during post-disinfection. A comparative study of the impact of four pre-oxidants, ozone (O-3), chlorine dioxide (ClO2), permanganate (Mn(vii)) and ferrate (Fe(vi)), on the formation of trihalomethanes (THMs), haloacetonitriles (HANs) and adsorbable organic halogens (AOX) in chlorinated synthetic and real waters was conducted. The pre-oxidant doses were based on their impact on natural organic matter reactivity measured by the electron donating capacity before chlorination. The influence of pH (6.5-8.1) and bromide (0-500 mu g L-1) was evaluated in terms of disinfection byproduct (DBP) formation and theoretical toxicity assessment (based on THM and HAN formation). All oxidants were efficient in mitigating chlorinated DBPs, except Mn(vii) which had little impact on THM formation. O(3)was generally more efficient than the other oxidants in mitigating AOX and THM formation, all pre-oxidants readily reduced the formation of HANs (>45% reduction at high dose). pH depression improved AOX mitigation by O(3)and Fe(vi) but diminished Mn(vii) efficiency for all DBPs. Pre-oxidation was less efficient in mitigating brominated DBPs and generally enhanced the bromine substitution factor. Although HANs were formed at low concentrations compared to THMs, they dominated the calculated toxicity, particularly the brominated HANs. The increased dibromoacetonitrile formation after pre-oxidation was a major factor counteracting the benefits of the overall DBP mitigation. In the presence of bromide, the pre-oxidant dose should be optimized to decrease the reactivity of the matrix while controlling the toxicity induced by formation of brominated DBPs, notably brominated HANs.

Lipids are important cellular components which can be significantly altered in a range of disease states including prostate cancer. Here, a unique systematic approach has been used to define lipid profiles of prostate cancer cell lines, using quantitative mass spectrometry (LC-ESI-MS/MS), FTIR spectroscopy and fluorescent microscopy. All three approaches identified significant difference in the lipid profiles of the three prostate cancer cell lines (DU145, LNCaP and 22RV1) and one non-malignant cell line (PNT1a). Specific lipid classes and species, such as phospholipids (e.g., phosphatidylethanolamine 18:1/16:0 and 18:1/18:1) and cholesteryl esters, detected by LC-ESI-MS/MS, allowed statistical separation of all four prostate cell lines. Lipid mapping by FTIR revealed that variations in these lipid classes could also be detected at a single cell level, however further investigation into this approach would be needed to generate large enough data sets for quantitation. Visualisation by fluorescence microscopy showed striking variations that could be observed in lipid staining patterns between cell lines allowing visual separation of cell lines. In particular, polar lipid staining by a fluorescent marker was observed to increase significantly in prostate cancer lines cells, when compared to PNT1a cells, which was consistent with lipid quantitation by LC-ESI-MS/MS and FTIR spectroscopy. Thus, multiple technologies can be employed to either quantify or visualise changes in lipid composition, and moreover specific lipid profiles could be used to detect and phenotype prostate cancer cells Refereed/Peer-reviewed

Live cell imaging can provide important information on cellular dynamics; however, the full utilisation of this technology has been hampered by the limitations of imaging reagents. Metal-based complexes have the potential to overcome many of the issues common to many current imaging agents. The rhenium (I)-based complex fac-[Re(CO)(3)(1,10-phenanthroline)(4-pyridyltetrazolate)], herein referred to as ReZolve-ER, shows promise as a live cell imaging agent with rapid cell uptake, low cytotoxicity, resistance to photobleaching and compatibility with multicolour imaging. ReZolve-ER localised to the nuclear membrane/endoplasmic reticulum (ER) and allowed the detection of exocytotic events at the plasma membrane. Thus, we present a new imaging agent for monitoring live cell events in real time, which is ideal for imaging either short- or long-time courses. Refereed/Peer-reviewed

Luminescent metal complexes are a valuable platform for the generation of cell imaging agents. However, many metal complexes are cationic, a factor that can dominate the intracellular accumulation to specific organelles. Neutral Re(I) complexes offer a more attractive platform for the development of bioconjugated imaging agents, where charge cannot influence their intracellular distribution. Herein, we report the synthesis of a neutral complex (ReAlkyne), which was used as a platform for the generation of four carbohydrate-conjugated imaging agents via Cu(I)-catalyzed azide-alkyne cycloaddition. A comprehensive evaluation of the physical and optical properties of each complex is provided, together with a determination of their utility as live cell imaging agents in H9c2 cardiomyoblasts. Unlike their cationic counterparts, many of which localize within mitochondria, these neutral complexes have localized within the endosomal/lysosomal network, a result consistent with examples of dinuclear carbohydrate-appended neutral Re(I) complexes that have been reported. This further demonstrates the utility of these neutral Re(I) complex imaging platforms as viable imaging platforms for the development of bioconjugated cell imaging agents. Refereed/Peer-reviewed

Three new complexes of formulation fac-[Re(CO)3(diim)L], where diim is either 1,10-phenanthroline or 1,10-phenanthroline functionalised at position 5 by a thioalkyl chain, and L is either a chloro or aryltetrazolato ancillary ligand, were synthesised and photophysically characterised. The complexes exhibit phosphorescent emission with maxima around 600 nm, originating from triplet metal-to-ligand charge transfer states with partially mixed ligand-to-ligand charge transfer character. The emission is relatively long-lived, within the 200-400 ns range, and with quantum yields of 2-4%. The complexes were trialed as cellular markers in live HeLa cells, along with two previously reported rhenium tetrazolato complexes bound to unsubstituted 1,10-phenanthroline. All five complexes exhibit good cellular uptake and non-specific perinuclear localisation. Upon excitation at 405 nm, the emission from the rhenium complexes could be clearly distinguished from autofluorescence, as demonstrated by spectral detection within the live cells. Four of the complexes did not appear to be toxic, however prolonged excitation could result in membrane blebbing. No major sign of photobleaching was detected upon multiple imaging on the same cell sample.

Four new tetrazole-containing species, in conjugation with terpyridine moieties through phenyl or pyridyl linkers, have been synthesised and characterised. In the series, the tetrazole functional groups are either in their acidic form or are alkylated at the N2 position with a methyl group. The photophysical properties of the species reveal moderate UV or efficient blue fluorescent emission, with photoluminescence quantum yields of around 30% and 80% for UV and blue emission, respectively. The spectral profiles can be reversibly modulated through protonation/deprotonation, with changes being consistent with an increase of the electron density on the tetrazole rings upon deprotonation or a decrease of the electron density on the terpyridines through protonation. The tetrazole-containing species were also investigated for fluorescence sensing of biologically and environmentally important metal ions, highlighting a ratiometric response to the presence of Zn2+. Furthermore, this ratiometric response could be well discriminated from that of interfering Cd2+ ions. Lastly, the species have been investigated as ligands for Eu3+ and Yb3+ cations, revealing efficient sensitisation, to give typical red and near-infrared emissions, respectively.

The biological behaviour in terms of cellular incubation and organelle specificity for two complexes of the type fac-[Re(CO)3(phen)L], where phen is 1,10-phenanthroline and L is either 3-pyridyltetrazolate or 4-cyanophenyltetrazolate, are herein investigated. The emission signal detected from the live insect Drosophila and human cell lines, generated by exploiting two-photon excitation at 830 nm to reduce cellular damage and autofluorescence, suggests photophysical properties that are analogous to those measured from dilute solutions, meaning that the complexes remain intact within the cellular environment. Moreover, the rhenium complex linked to 4-cyanophenyltetrazolate shows high specificity for the lipid droplets, whereas the complex bound to 3-pyridyltetrazolate tends to localise within the lysosomes. This differential localisation implies that in these complexes, organelle specificity can be achieved and manipulated by simple functional group transformations thus avoiding more complex bioconjugation strategies. More importantly, these results highlight the first example of phosphorescent labeling of the lipid droplets, whose important cellular functions have been recently highlighted along with the fact that their role in the metabolism of healthy and diseased cells has not been fully elucidated. Refereed/Peer-reviewed