Development of Metal-based Catalysts for Phosphate Ester Hydrolysis
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The development of artificial metal-based catalytic systems for phosphate ester hydrolysis is the central focus of this work. Currently, significant efforts are concentrated in this field of research as phosphate esters are remarkably stable linkages and are found in the molecules of life DNA and RNA, as well as in toxic compounds, such as nerve agents, pesticides and herbicides. The thesis describes the design and synthesis of a series of N-functionalised azamacrocyclic ligands suitable for metal chelation. An efficient strategy is described, where an aminal precursor is used for the selective N-alkylation of a cyclen moiety, in order to obtain non-bridged and ethylene-bridged cyclen-based ligands. Thereafter, the synthesis of the tetraamine Co(III) and Zn(II) aqua-hydroxo complexes is detailed, followed by a study of the coordination chemistry of Co(III)-based cyclen complexes. Moreover, the redox behaviour of such complexes is investigated by means of cyclic voltammetry. The hydrolytic activity of these complexes towards phosphate ester substrates is then presented. The hydrolytic activity of the cyclen-based Co(III) complexes is shown to be extremely sensitive to modest changes in the ligand structures, even though they do not affect the coordination geometry. Cyclen-based Zn(II) complexes appear to have no appreciable activity towards hydrolysis of phosphate mono- and di-esters under the same experimental conditions. The effect of incorporating polymerisable tetraamine Co(III) complexes into the nanogels on their hydrolytic efficiency is also investigated using molecular imprinting technique. The design and synthesis of structurally similar tripodal ‘click’ ligands, suitable for the preparation of a range of d-block metal complexes is then presented. The coordination chemistry of the complexes of these structurally similar ligands is explored using a range of techniques including single crystal X-ray crystallography, EPR and UV-Vis spectroscopies and cyclic voltammetry. Due to their poor aqueous solubility various ways to improve this are also examined. Future developments of the metal-based catalysts are then discussed including key issues to be addressed to achieve their potential applications in biological systems.
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