Co-ordination behaviour of a novel tristhiourea tripodal ligand; structural variations in a series of transition metal complexes

The co-ordination chemistry of a tristhiourea tris(2-pyridylmethyl)amine ligand (L1) with a series of transition metal ions has been investigated. Crystallographic data show that large metal ions, with no geometrical preferences , such as Mn(II) and Cd(II), will form seven co-ordinate monocapped octahedral complexes, while smaller metal ions such as Zn(II) favour five co-ordinate trigonal bipyramidal structures. In a similar manner to the related bisthiourea complexes, the Ni(II) complex shows a strong preference for octahedral geometries resulting in the ligand binding asymmetrically. Spectroscopic (IR and NMR), spectrometric (MS) as well as electrochemical data for these complexes are reported

Using NLG to Manage Information in Medical Emergencies

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Co-ordination chemistry of a series of bi- and tripodal ligands

A structural investigation into a series of transition metal complexes forms the basis of Chapter 1. Specifically, this work focuses on the co-ordination chemistry of two bipodal ligand frameworks, L and L. Each ligand contains a ketone moiety which, in the case of L, has been shown to undergo hemi-ketal formation upon complexation in some instances, yielding dinuclear complexes of the form M2{(2-bipy)2C(OMe)0'}2 C104 2 (M = Fen or Zn11). Chapters 2 and 3 take a detailed look at a series of transition metal complexes formed by the tripodal bipyridine-based ligand frameworks, L - L. The tris-bipyridyl ligand, L, has been shown to enforce a predominantly trigonal prismatic co-ordination environment around a metal centre, even in cases where the metal has a strong stereoelectronic octahedral preference. For each ligand, the relationship between octahedral and trigonal prismatic character as the d-electron configuration of the metal centre is varied has been examined. Using the Cartesian co-ordinates obtained from crystallographic data sets, continuous shape mapping analysis (CShM) has been employed to assist in the quantification of the distortions away from these two ideal geometries. Chapters 4 and 5 report the protonation and stability constants for a series of potential MRI contrast agents which are based upon a tripodal ligand scaffold with a tris-pyridine core (L6 o - L ). This work examines how modifying the denticity of the ligands from four to six by changing the number of peripheral binding functions affects overall complex stability and the nature of species in solution. Chapter 6 investigates the efficacy of a series of gadolinium complexes as potential MRI contrast agents. This has been accomplished by measuring Tl relaxivities using a fast field- cycling (FFC) relaxometer

Raising Islands

In an era of dawning anthropogenic climate change, people of atoll nations face grievous threats to their future. Rising sea levels, warming oceans, and changing weather patterns conspire with economic isolation, rapidly growing populations, and the loss of traditional livelihoods to perpetuate conditions of dependence and wardship which threaten the very existence of their island homes. This project examines an atoll nation of the equatorial Pacific, the Republic of the Marshall Islands, where the outward appearance of pristine tropical paradise belies a tragic history of nuclear weapons and ballistic missile testing at the hands of the US military. While the islands have been consistently framed in rhetoric which stresses vulnerability, smallness and unsustainability, this project contests the limited scope of the regimes of power in Oceania by considering how the independent, grassroots actions of local groups of islanders have achieved surprising and dramatic results in defiance of the policies and planners at the top. In developing a design proposal for the contemporary condition, this thesis examines the persistent ways in which the islands and people are framed by outsiders. This project engages with the social, political and natural history of the atolls: common tropes are challenged by the actions and agency of a people who have dealt with imperialist outsiders in sophisticated and conscious ways. It explores the traditional cultural practices which enabled the ancestors of the Marshallese people to flourish, and suggests that it is at the level of actions by ordinary people that the most fertile potentials lie, and are in fact already being played out. What forms of urbanism might be appropriate in this environment? How can islanders effectively manage their landscape and engage with the natural processes - as their ancestors once did to a remarkable degree? By pairing traditional techniques with modern technologies, a proposal is synthesized which could empower the contemporary Marshallese to transform their landscape and develop sustainable livelihoods in this extreme and dynamic environmental condition: to build a future which offers the best aspects of both traditional and contemporary ways of life

Shaping and enforcing coordination spheres: probing the ability of tripodal ligands to favour trigonal prismatic geometry

The coordination chemistry of mono(2,2′-bipyrid-6-yl)bis(2-pyridyl)methanol (L1) and bis(2,2′-bipyrid-6-yl)mono(2-pyridyl)methanol (L2) are contrasted to tris(2,2′-bipyrid-6-yl)methanol (L3).L1andL2can produce octahedral complexes compared to the trigonal prismatic preference ofL3.</p

Developmental Regulation of an Adhesin Gene during Cellular Morphogenesis in the Fungal Pathogen Candida albicans

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