Abstracts Chemistry

Molecular recognition of DNA by metal co-ordination complexes

by Ivan Greguric

This thesis reports the design, synthesis, optical resolution of polypyridyl metal complexes and their molecular recognition of DNA. These metal complexes have been synthesised to bind DNA intercalation in a sequence selective manner. Modifications have manipulated the intercalative segments to bind to DNA in a rigid fashion by appending chemical groups directly to the aromatic extensions of the fragment. Also the ancillary non-intercalative ligands comprised of either bidentates or tetradentates, have been specifically chosen to deliver appended groups along the DNA sugar phosphate backbone, for hydrogen bonding and van der Waals interactions. Classical and chromatographic separation methods were investigated to separate the optical isomers of these ruthenium (II) complexes. A liquid recycling chromatography system was most successfully employed. Stereoselective synthesis was also investigated. Ultimately, it has been shown that the systematic modification of simple metal complexes is a useful method in determining the interactions of simple metal for nucleic acids. Doctor of Philosophy (PhD)