In low GC Gram-positive bacteria, the phenomenon of carbon catabolite repression is dependent on a metabolite-activated bifunctional protein kinase/phosphorylase. In Clostridium acetobutylicum ATCC 824, the hprK gene encodes the bifunctional protein kinase/phosphorylase that is …
Electrochemistry and polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS) measurements were used to characterize the structure and organization of a mimetic biological membrane supported at a Au(111) electrode surface to determine the influence of molec…
Phosphoinositides are lipid signals that control cellular processes and are particularly closely associated with the control of membrane trafficking. PtdIns(3,5) \(\char{cmmi10}{0x50}\)\(_2\) is the most recently identified phosphoinositide and was previously recognised as contr…
The introduction of electron capture dissociation mass spectrometry in 1998 has provided a unique technique for the analysis of peptides and proteins, especially for the identification and localisation of posttranslational modifications. Despite many successes debate continues o…
The addition of allylmetals to aldehydes, particularly in an asymmetric fashion, is of prime importance in the synthetic chemist’s arsenal of C–C bond-forming methodologies, as the secondary homoallylic alcohol products are primed for further transformations. So far, reagent-con…
The glycolipid α-galactosyl ceramide, α-GalCer, has been shown to stimulate the proliferation of murine spleen cells and activate the immune system. Stimulation occurs through binding of the glycolipid to the protein CD1d. Subsequent presentation of the CD1d−glycolipid complex t…
N-Methylwelwitindolinone C isothiocyanate (7), isolated from the blue green algae Hapalosiphon welwitschii and Westiella intricate, is a structurally novel alkaloid related to the welwitindolinone family. This thesis describes studies towards the total synthesis of this natural …
The main objective of this research was to understand phenomena occurring during food digestion and nutrients absorption in the small intestine from an engineering perspective. Intestinal flow and mixing processes were simulated using a dynamic in vitro Small Intestine Model (SI…
The development and availability of more sophisticated techniques for probing the local structure of materials has shown the prevalence and significance of poorly crystalline and amorphous phases in a wide range of biological processes. Such techniques, including pair distributi…
The work described in this thesis concerns the synthesis, DNA binding and cytotoxicity studies of new Rh(III) supramolecular complexes. Chapter 1 reviews DNA molecular recognition by synthetic agents; exploring the different DNA binding modes and their importance in the anticanc…
The meta photocycloaddition between a substituted aryl ring and alkene affords architecturally complex tricylic intermediates that have been utilised to investigate three different areas of synthetic organic chemistry. Firstly, a novel palladium catalysed oxidative fragmentation…
The folding of a protein from a linear chain of amino acids into its functional native state is one of the most widely investigated yet enigmatic events to take place in the natural world. An ever‐increasing number of proteins and peptides are known to fold, or “misfold”, into p…
The Synaptonemal Complex (SC) is a proteinaceous structure that connects homologous chromosomes lengthwise during meiotic prophase. In budding yeast, the SC consists of two parallel axes that become connected by the central element protein, Zip1 that extends along the chromosome…
Chapter One presents an overview of olefin polymerisation, which provides the context for the majority of the work described in later chapters. Both Ziegler-Natta and late transition metal systems are described. Chapter Two describes the synthesis and reactivity of trisamido tit…
Part 1. Synthesis of Stereodefined Heterocyclic Rings. We wish to report the development of novel methodology for the synthesis of stereodefined heterocyclic rings, which could be used for the synthesis of natural products containing for example tetrahydrofuran motifs, such as m…
The discovery of the novel thermal cyclization of enediyne molecules within the Parsons group during studies directed towards the total synthesis of lactonamycin has stimulated an intense research into the cyclization of the enediynes. In this research different functionalised e…
The function of biological macromolecules is inherently linked to their complex conformational behaviour. As a consequence, the corresponding potential energy landscape encompasses multiple minima. Some of the intermediate structures between the initial and final states can be c…
Homocysteine is an amino acid formed by the metabolism of methionine. Increased plasma homocysteine concentrations are associated with cardiovascular disease, and it has been suggested that homocysteine lowering therapy may reduce cardiovascular risk. Plasma homocysteine measure…
This thesis reports the synthesis and analysis of a number of organometallic compounds, focusing primarily on novel structures containing Sn and P atoms. Chapter 1 contains a literature review examining the different structural and bonding properties and reactions of C4H4, P4 an…