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We propose a new formula for the mineral nickelskutterudite, based on our observation that either (or both) Co or Fe3+ are essential structure constituents. The crystal structure of nickelskutterudite, (Ni,Co,Fe) As-3, cubic, Im (3) over bar, Z = 8: a = 8.2653(6) angstrom, V = 564.65(7) angstrom, has been refined to R-1 = 1.4% for 225 unique reflections I > 2 sigma(1) collected on a Bruker X8 four-circle diffractometer equipped with fine-focus, sealed tube MoKa radiation and an APEX-II CCD detector. This is the first report of the crystal structure of nickelskutterudite. Nickelskutterudite, a member of the skutterudite group of isostructural minerals, adopts a distorted perovskite structure with notably tilted octahedra and an unoccupied to partially occupied icosahedral metal site. In the structure of nickelskutterudite, there is one metal (B) site occupied by Ni, Co, or Fe in octahedral coordination with six As atoms. Procrystal electron density analysis shows each As anion is bonded to two cations and two As anions, resulting in a four-membered ring of bonded As with edges 2.547 and 2.475 angstrom. The extreme tilting of BAs6 octahedra is likely a consequence of the As-As bonding. The nickelskutterudite structure differs from the ideal perovskite structure (A(4)B(4)X(12)) in that As4 anion rings occupy three of the four icosahedral cages centered on the A sites. There are reported synthetic phases isomorphous with skutterudite with the other A site completely occupied by a cation (AB(4)X(12)). Electron microprobe analyses of nickelskutterudite gave an empirical chemical formula of (Ni0.62Co0.28Fe0.12)(Sigma 1.02)(AS(2.95)S(0.05))(Sigma 3.00) normalized to three anions. Pure NiAs3 nickelskutterudite, natural or synthesized, has not been reported. In nature, nickelskutterudite is always observed with significant Co and Fe, reportedly because all non-bonded valence electrons must be spin-paired. This suggests that nickelskutterudite must contain Co3+ and Fe2+, consistent with previous models since Ni4+ cannot spin-pair its seven non-bonded electrons, Co3+ and Fe2+, which can spin-pair all non-bonded electrons, are required to stabilize the structure. No anion deficiencies were found in the course of this study so, including the structurally necessary Co and Fe, the chemical formula of nickelskutterudite (currently given as NiAs3-x, by the IMA) should be considered (Ni,Co,Fe)As-3.

This thesis presents the results of geoarchaeological investigations conducted at two new test pits, M11 and M12, at the paleoanthropological site of Dmanisi during the 2012 field season. This research is important for understanding the site formation processes occurring along the north-south axis of the Dmanisi site and how that affects the chronostratigraphic sequence and interpretation of archaeological materials here. With these excavations we can build a stronger interpretation for how broader areas of this site formed and changed both geologically and archaeologically. The geologic results of this study indicate that changes in sediment deposition and development episodes can affect interpretations of how long these sediments accumulated, how likely bones are to preserve, as well as how secondary gravel deposition can influence several archaeological interpretations. The archaeological results suggest that there could have been changes in occupation intensity between the stratum A and B phases although different rates of sediment deposition and surface stability could affect such artifact accumulations. In addition, during the stratum B phase there appears to be little change in artifact procurement behaviors and reduction characteristics by these hominins. The overall results of this research indicate that geologic factors should be addressed and cautions should be taken prior to making interpretations about archaeological assemblages.

Several biomarkers (cell viability and phagocytosis) based on earthworm (Lumbricus terrestris) immune cells (coelomocytes), together with whole-worm mortality (LC/LD50's), were used to assess a bioremediation attempt to reduce pentachlorophenol (PCP) toxicity in a former wood processing hazardous waste site (HWS).

The focus of this thesis was to gather and analyze micromorphological and petrographic data on soils at the archaeological site of Dmanisi in order to better understand the extent to which the deposition and alteration of the sediments has affected the preservation of artifacts and faunal remains. A major goal of this research was to test hypothesis related to why bone material is discovered in some strata and not in others. This research focuses on the application of micromorphology (supplemented with other methods) to the soils through the use of petrographic analysis of thin sections and scanning electron microscopy. These techniques complement previous field analyses by providing a quantitative assessment of individual strata through point counting and chemical mapping. The results of this research support the hypothesis that the sediments are predominantly mafic ashes, while showing that there is very little soil development in the strata. This suggests quick episodic burial in a relatively dry climate, confirming the hypothesis for a short time sequence in the strata. Additionally, differential weathering probably did not play a significant role in the differential abundance of bone remains among the strata at Dmanisi.

Mémoire numérisé par la Division de la gestion de documents et des archives de l'Université de Montréal.

Sphingolipids and ceramides are essential components of cellular membranes and important signalling molecules. Because of a growing appreciation for their diverse biological roles, understanding of the biosynthesis and regulation of sphingolipids has recently become a key goal in drug discovery. Serine palmitoyltransferase (SPT) is a pyridoxal 5′-phosphate (PLP)-dependent enzyme that catalyses the condensation between L-serine and a long-chain acyl thioester such as palmitoyl-CoA (C16-CoA). This first step in sphingolipid biosynthesis is conserved in all organisms studied to date, from microbes to man. The fungal natural product myriocin is a potent inhibitor of SPT; however, the molecular details of inhibition are not fully understood. Myriocin contains a long alkyl chain and a polar head group thus it displays features of both SPT substrates. Therefore, the prevailing hypothesis is that inhibition of SPT occurs because myriocin acts as a mimic of a key transition state of the catalytic mechanism. Through a combination of UV-vis spectroscopy, mass spectrometry, x-ray crystallography and enzyme inhibition assays it has been possible to study the interaction between S. paucimobilis SPT and myriocin. I have shown that myriocin initially forms an inhibitory PLP:myriocin aldimine complex in the active site that displays a Ki of 967 nM. Interestingly, this complex is susceptible to unexpected, slow enzymatic degradation. The mechanism for myriocin breakdown has been elucidated as a retro-aldol type reaction, which results in cleavage of the C2-C3 bond producing a C18 aldehyde. This aldehyde is then capable of covalently modifying the active site lysine265, forming a second (suicide) inhibitory complex and rendering the enzyme catalytically inactive. Substitution of the active site lysine produced SPT K265A, an inactive enzyme that did not catalyse the breakdown of the PLP:myriocin complex. However, the determination of the crystal structure of the SPT K265A:PLP-myriocin complex revealed that the myriocin had undergone decarboxylation. Nevertheless, this SPT:PLP:decarboxymyriocin structure revealed details about myriocin’s mechanism of inhibition for the first time. The novel mechanism of myriocin degradation has implications on the structure activity relationship (SAR) and design of drugs targeted towards SPT, the role of feedback regulation by long chain aldehydes and further expands the range of reactions catalysed by this important enzyme. As well as inhibition studies the structure of bacterial SPT was also examined by preparing an N-terminally truncated S. paucimobilis SPT. This version, shortened by 21 amino acids, was ~5-fold slower than the wild-type enzyme and suggests that the N-terminus may play a role in catalysis. Additional work has been undertaken to study an unusual membrane-bound viral SPT, composed of two naturally fused open reading frames (SPT2-SPT1) with the proposed SPT2 domain at the N-terminus and the SPT1 domain at the C-terminus. To study soluble mimics of this interesting fusion I prepared a bacterial S. paucimobilis SPT fused wild-type and mutant construct and isolated a fused SPT2-SPT1 with what appears to be single PLPbinding site.

The Eastern box turtle (Terrapene carolina carolina) is one of the most common reptiles in North America, but is soon to be threatened due to increased urbanization, disease, and the pet and food trades. In order to assist resource managers in choosing suitable sites for relocation studies, more information on the winter ecology of this species is necessary. We examined the temperature tolerance, microhabitat and degree of philopatry to hibernacula for juvenile and adult E. box turtles for two consecutive winters in Charles City Co, VA. The turtles were tracked via radio telemetry to record point locations during the active and inactive seasons. iButton data loggers were attached to each turtle to record temperature throughout winter. Vegetation data were collected and analyzed to determine if there are microhabitat differences between adult and juvenile turtles, and between occupied and random plots. Philopatry to wintering hibernacula was determined by measurements in the field and using ArcGIS. Adults had significantly higher minimum temperatures than juveniles during the first winter (P=0.027), but not during the second winter (P=0.327). Shrub and canopy cover were marginally higher for random plots than for occupied turtle hibernacula plots (P=0.066 and P=0.092, respectively); however there were no significant differences for any of the vegetation variables between adults and juveniles. Some of the turtles demonstrated site fidelity of their hibernacula. The temperature data from this study suggests that juveniles may have poorer hibernacula selection and therefore lower minimum temperatures compared with adults, but this was not seen in our second season suggesting that juvenile turtles may learn to choose better hibernacula or to dig deeper. The difference in findings for the two winters could be attributed to illness by several of the turtles the first winter, by increased maturity in the juveniles the second winter or by the significant difference in ambient temperature for the two winters (P=0.0001). Juveniles do not differ from adults in microhabitat selection, therefore resource managers may not need to plan differently for juveniles and adults in relocation studies. We also conclude that both age groups of T. c. carolina exhibit site fidelity of hibernacula.

Provisional or unfinished images, forms and actions can sustain their status by continuing to change. This can resist programmed experience of their state, and shift their relationship as images within time. The sub-aesthetics of the unfinished and entropic can alter our understanding of where and how images are formed and located within time. My paintings each exist within their own emergent systems of time, structure and productive disorder. This thesis discusses these ideas in relation to DAY FOLDER and other work made during my MFA studies.

Mémoire numérisé par la Direction des bibliothèques de l'Université de Montréal.