Various quinoxalines, in association with N-methyld-iethanolamine as synergist, were used to initiate the polymerisation of acrylates. It was found that the quinoxalines where used with amine synergist are efficient Type II initiators. It was also found that the cure of the acrylate is faster when oxygen is present in the reaction mixture than when it is absent. The photoinitiating efficiency of 2-Methyl-1-[4-(methylthio)phenyl]-2- morpholinopropane-1-one (IRG-907) was compared to different initiators using RTIR spectroscopy and N-Isopropylmorpholine(IPM) was used as a model to investigate the properties of the morpholino sustit.uent present in IRG-907. It was shown by RTIR spectroscopy, photocalorimetry,bulk polymerisation and the curing of thin films that 1PM acts as a physical quencher for the triplet state of IRG-907 and that it is a very poor hydrogen donor. Sensitisation of IRG-907 by lix was also investigated and it wasconfirmed that lix can sensitise the cleavage of 1RG907. Photoinduced fragmentation of aminoalcohols by quinoxalines are discussed and the reactivity of the aminoalcohols reflect their ability to undergo electron transfer and to fragment. A wide range of aminoalcohols were synthesised and used as synergist in the polymerisation of a number of acrylates using different methods and the photoyellowing and photooxidation of aminoalcohols were also investigated. Some mixed acrylate-cinnamate systems were prepared to investigate a new dual cure system. The conversion percentage was found to be very low. The lack of cure is probably due to the cinnamates are scavenging the benzoyl radicals.

Trialkyl tin compounds have been shown to be potent inhibitors of oxidative phosphorylation, oligomycin sensitive ATPase activity and other ATP-dependent reactions of beef heart mitochondria. Unlike oligomycin inhibition of these reactions, trialkyl tin inhibition is reversible by dithiols such as 2,3-dimercaptopropanol. The OS-ATPase activity was found to be 6-10 times more sensitive than oxidative phosphorylation to inhibition by trialkyl tins. This differential sensitivity to trialkyl tin inhibition is discussed in relation to the current theories on energy coupling. Binding studies with [3H]-DBCT have indicated the presence of two types of binding sites designated high affinity (kD ~ 0.3 uM) and low affinity (KD ~ 30 uM) binding sites. The concentration of the high affinity binding site is ~ 2.0 nmol/mg protein in submitochondrial particles and saturation of these sites correlated with the inhibition of the oligomycin sensitive ATPase activity. Extraction and isolation experiments have shown that DBCT binds to a small lipophilic, non-protein molecule. Dihydrolipoic acid has been shown to drive ATP synthesis by acting as a NAD-linked substrate. Fatty acids, oleoyl-phosphate, oleoyl-lipoate and other lipids were found to inhibit succinate driven ATP synthesis and other energy-linked reactions in mitochondria and submitochondrial particles. In addition, a new method for the measurement of nanomoles amount of lipoic acid and lipoamide is reported. The method involves the cyclic reduction of 5,5-dithiobis (2-nitrobenzoic acid) by NADH via a system containing lipoamide dehydrogenase and lipoic acid (or lipoamide).

The effect of different N-pentyl-2-pyridylmethanimine (NPMI) derivatives upon the rate of copper(I) mediated atom transfer radical cyclisation (ATRC) of mono-bromo- and trichloro-acetamides were investigated. 6-Functionalised NPMI derivatives retarded the rate of ATRC due to steric effects, while for the 5-substituted analogues, inductively increasing the electron density of the pyridine nitrogen increased the rate of ATRC. Multidentate amine derived copper(l) halide complexes were found to mediate the ATRC of I-halo-N-propargylacetamides. The cyclisation of trichloro- and dichloroacetamide precursors leads to a,B-unsaturated y-Iactams containing the gem-dihalide functional group, while monohaloacetamides gave rise to either cyclised atom transfer or reduction products depending upon the solvent and catalyst used. The tripyridyJamine (TPA) copper(I) halide complex facilitates the efficient ATRC of bromo-enamides to give plactams exclusively with no formation of y-Iactams. Initial products result from 4-exo bromine atom transfer and subesqucnt elimination can be readily achieved to furnish the corresponding alkenes. A range of fused bicyclic lactams were prepared via copper(l) mediated 5-endo ATRC of halo-N-(cycloalk-1-enyl)acetamides and the use of this methodology for the synthesis of the Iycorane and erythrinane alkaloid skeletons was investigated.

The study involved the desig~ constructio~ optimisation and utilisation of a novel tandem time-of-flight (TOF-TOF) instrument. The instrument was designed to use a laser ion source capable of laser desorption or matrix-assisted laser desorption/ionisation. The instrument used a twin ion mirror geometry in which the first ion mirror was a single-stage ion mirror, while the second ion mirror was a quadratic-field ion mirror. The instrument was designed for highenergy (>10keV) collision-induced dissociation (CID). The initial design criteria of a tandem time-of-flight spectrometer are discussed. The design and construction of the vacuum chamber and pumping system are discussed. The design and construction of the laser ion source are covered in detail. Computer simulations of typical ion trajectories were calculated using the SIMION program. The design and construction of the steering optics, single-stage ion mirror and pulsed mass gate are discussed. Computer simulations of ion trajectories were used to characterise the ion optical properties of the system. Experiments to characterise the energy focusing properties and transmission of the single-stage ion mirror were conducted. The mass resolving power of the single-stage ion mirror were characterised. The single-stage ion mirror achieved a resolution of2000 full-width half-maximum (FWHM). The design and construction of the differentially pumped collision-cell and the quadratic-field ion mirror are outlined. Experiments to demonstrate the transmission of the collision-cell and quadratic-field ion mirror are discussed. Experiments to characterise the energy focusing properties of the quadratic-field ion mirror were conducted. The full instrument achieved precursor mass resolving powers of approximately 7000 (FWHM) for laser desorbed species and 3500 (FWHM) for MALDI generated peptide species. Initial CID results are presented. The study thoroughly discusses the problems with the current instrument configuration and goes on to propose solutions to the problems encountered.

Microwave mediated H/D exchanges have been studiedin this thesis. The purpose of these studies is to validate an efficient method for replacing hydrogen by deuterium in molecules with biological and pharmaceutical activity. As a result of this, such deuterated compounds would be helpful during the investigation of pharmacological and metabolic studies. At the beginning of this research, aniline derivatives weremainly employed as substrates. Their importance in drug synthesis makes the corresponding labelled compounds useful as building blocks. During these studies a Pt catalyst wasemployed. As a consequence of its strong efficiency, fully deuterated compounds were obtained in many cases. In the first part of this research, yields were based on ratios between non-deuterated and deuterated original compounds. However, due to solubility problems and metal-complex formation, this parameter was found to vary considerably. Therefore, an analytical method, involving introduction of a non-deuterated acetyl group to the labelled substratewas employed, so that the acetyl group could be regarded as an internal reference for 1HNMR integration, allowing quantification of deuterium incorporation at all positions in the molecular structure. Kinetic experiments have also enabled the best conditions to be defined for the exchange reactions. Lastly, as a consequence of a reductive process, Pt0 has been recognized as a serious problem for calculating final yield. An appropriate method for eliminating it from the solutions has therefore been applied. A valid Pt mediated H/D mechanism has been proposed, based on suggestions from the literature that Pt can move around both aromatic rings and alkyl side chains. To try to get evidence for such a mechanism, different alkylanilines have been used, giving useful information regarding metal activity, particularly with respect to steric aspects. In the last part of the work, as a consequence of its importance in pharmaceutical chemistry, heterocyclic derivatives have been investigated. Satisfactory results have permitted the method to be explioted for some relevant drugs.

The reaction of HCl with clean, Cu(100) and (111), and Au/ Cu(100) surfaces was investigated using x-ray photoelectron spectroscopy (XPS) and scanning tunneling microscopy (STM) under ultra high vacuum (UHV) conditions. Exposure of the Cu(100) and (111) samples to HCl at room temperature leads to the formation of a saturated copper chloride monolayer. In the case of Cu(100), the saturated coverage was half monolayer corresponding to a c(2x2)-Cl reconstruction (half monolayer is 7.25x1014 cm-2) while for Cu(111) it was one third monolayer consistent with the reconstruction of (√3x√3)R30o (one third monolayer 5.9x1014 cm-2). The interaction of HCl with preoxidised Cu(100) and (111) showed different behaviour from those of clean copper surface depending on the way of interaction of oxygen with copper surface. Interaction of HCl with peroxidised Cu(111) at saturation oxygen coverage leads to the adsorption of chlorine on top of the copper surface with one third coverage. In contrast, presence of oxygen on Cu(100) surface at saturation coverage or less leads to adsorb chlorine but with an excess in chlorine concentration (more than the expected c(2x2) coverage). Oxidized Cu(100) and (111) surface at elevated temperature leads to the formation multi oxide layer. The two oxide surfaces („‟44‟‟ and „‟29‟‟) observed at the Cu(111) depend on the temperature of the substrate at the time of oxidation. The (√2x2√2)R45o structure was observed on the Cu(100) surface on heating which is the same structure formed at saturation coverage at room temperature. Interaction of HCl with Cu(100) and (111) surfaces covered by multilayers of oxide lead to adsorption of chlorine on top of the copper surface with a coverage more than more than the saturation coverage. Interaction of HCl with Au/Cu(100) showed two different behaviour depending on the gold coverage. Au/Cu(100) alloy formed at half monolayer of gold coverage, forming c(2x2) structure. Exposure of the Au/Cu(100) alloy at half monolayer of gold coverage to HCl leads to the formation of c(2x2)-Cl structure with saturation coverage of half monolayer in similar manner of interaction of HCl with the clean cu(100) surface. Interaction of HCl with Au/Cu(100) surface at gold coverage more than half monolayer leads to a dealloying of the gold from the copper surface and forming the Au(111) surface. Cu-Cl formed underneath the Au(111) surface with excess of chlorine concentration.

The amber suppression technology is an intracellular methodology that allows position specific incorporation of a specific non-natural amino acid (NAA) into proteins using imported NAA-specific machinery during protein translation. The method has been utilised to incorporate over 50 NAAs into proteins (e.g. those that confer unique reactivity (and allow subsequent conjugation of additional factors), installation of post-translational modification mimics, modulation of protein function and those that aid in structural determination). Therefore, the aim of the work presented within this Thesis was to explore the use of this technology in novel applications; namely the installation and study of a reactive moiety within a defined environment and the creation of a ‘biological switch’ to control the production of the protein and subsequently a cellular phenotype. It was demonstrated that incorporation of the NAA, azidophenylalanine, within the hydrophobic pocket of T4 Lysozyme (T4LazF) could provide a protein scaffold to stabilise, shield and thereby allow exploration of the chemical reactivity of the photoreactive aryl azide moiety using various spectroscopic techniques. Specifically, electron paramagnetic spectroscopy of irradiated T4LazF demonstrated that the singlet phenyl nitrene species had been captured. To create a ‘biological switch’ to control the production of a protein and the subsequent cellular phenotype, the duality of the amber suppression method was the basis for the novel application rather than the chemical reactivity of the NAA. E. coli and mammalian cell motility readout systems were successfully created using flagellin (non-flagellate) and Rac1 (GTPase protein involved in lamellipodia production) knockout cell lines respectively in conjunction with specially created plasmid constructs. However, complexities regarding the implementation of amber suppression in order to control this motility via the presence/absence of NAA limited the functionality of these readout systems. The work presented has advanced the field of amber suppression and NAA technology by demonstrating that generating reactive intermediates derived from NAAs within a defined chemical environment of a protein provides a novel technique to generate and study highly reactive intermediates. In addition, it has been shown that the amber suppression technology has potential to act as a biological switch to control cellular responses.

In this project, density functional theory calculations were performed to study the adsorption of ethylene glycol to the MgO (100), MgO (130), Al2O3 (0001), PdO (101) surfaces, as well as Au38 and Au38O16 nanoparticles. Adsorption of ethylene glycol is favourable to all of these surfaces with Al2O3 (0001) and PdO (101) showing the most favourable adsorption at -168 kJ mol-1 and -135 kJ mol-1 respectively. The MgO surfaces showed adsorption energies between -80 kJ mol-1 and -100 kJ mol-1, and the gold nanoparticles showed lower adsorption energies at approximately -35 kJ mol-1. Barriers to O-H activation and C-H activation of ethylene glycol were also studied on these surfaces. The barriers to O-H activation were small over each of the surfaces (between 8 and 46 kJ mol-1) and large for the gold nanoparticles (108 kJ mol-1). The barriers to C-H activation were very large over the MgO surfaces (>300 kJ mol-1), and lower over the PdO (101) surface (63 kJ mol-1) and the gold nanoparticles (68 kJ mol-1). C-H activation was found to not be possible over the Al2O3 (0001) surface. Classical molecular dynamics studies were performed on various water and methanol mixtures as well as in the presence of a hydroxylated Al2O3 (0001) surface. It was found that in methanol there are on average 1.1 oxygen – oxygen close contacts with other methanol molecules in pure methanol, and water has on average between 2.03 and 2.86 oxygen – oxygen close contacts, with more being present at higher temperatures. The presence of a hydroxylated aluminium oxide surface induces local ordering in the methanol molecules resulting in an increase in methanol – methanol and water – methanol oxygen – oxygen contacts, however there is a decrease in water oxygen – water oxygen contacts.

To study the effects of metal modification on titanium dioxide (TiO2) for photocatalytic reduction of carbon dioxide (CO2), a series of pure and metal modified TiO2 catalysts (referred as SG TiO2 and M/TiO2, respectively) were synthesized via a refined sol-gel process. The metals chosen to modify TiO2 included Cu, Zn, and Rh. These catalysts were then characterized by using various analytical techniques, including ICP-MS, powder XRD, XPS, TEM, N2 adsorption isotherms, Cu surface area and dispersion measurement, and DR UV-Vis. It was found that all the sol-gel derived TiO2 catalysts had the same crystalline phase of anatase, and similar particle sizes (11-16 nm) and surface areas (50.24-63.37 m2/g). It is worthy to note that, even though synthesized via the same sol-gel process, the three added metals modified their TiO2 supports differently. The added Cu and Zn were loaded on the surface ofTiO2 with their chemical states to be CU2O and ZnO, respectively. Whereas, the added Rh was substitutionally doped into the lattice of its TiO2 supports. The specific surface area and dispersion of the added Cu on the surface of CulTiO2 were further measured by using N2O as adsorbate. It was found that the aggregation of the added Cu occurred when the Cu ratio of Cu/TiO2 over-increased (over 0.03 wt%). The following CO2 photoreduction experiments confirmed that the added Cu and Rh were able to significantly improve the activity of TiO2 for CO2 photoreduction to methane, wherein the activities of the best performing 0.03 wt% Cu/TiO2 and 0.01 wt% Rh/TiO2 were around 10-times higher than that of SG/TiO2. The added Cu and Rh were expected to affect the activity of TiO2 via different ways. The combination of the loaded Cu and TiO2 was considered to be a composite semiconductor catalyst, and the Cu dispersion dominated the activity of Cu/TiO2. In comparison, the doped Rh was able to affect the activity of TiO2 by introducing an additional energy level to the band-gap of TiO2. Finally, TiO2 catalysts simultaneously loaded by Cu and doped by Rh (Rh/Cu/TiO2, synthesized via the identical sol-gel process) were also tested for CO2 photoreduction. The results indicate that the loaded Cu and doped Rh were able to synergistically enhance the activity of TiO2 for CO2 photoreduction, allowing the optimal Rh/Cu/TiO2 (0.06 wt% Rh/O.03 wt% Cu/TiO2) to present even better (at least 25 % higher) activity than any of the Cu/TiO2 or Rh/TiO2 in this work.

The research described in this thesis relates to the development and optimisation of a novel polymerisation reaction and its subsequent use in the generation of novel ‘Polymers of Intrinsic Microporosity’ (PIMs). The polymerisation reaction takes monomers containing two or more aromatic amines and fuses them together by the synthesis of a bridged bicyclic heterocyclic link called Tröger’s base (TB). This link not only strongly holds the polymer chain together, but also provides a site of contortion, which is necessary for a PIM to exhibit microporosity. The first part of this work introduces the background to the research, detailing the reasons behind the development of a new class of PIM and the competitor materials. Following this is detailed the optimisation of the TB forming condensation reaction and the synthesis of a variety of amine functionalised monomers. Also described in this section is the optimisation of a second condensation reaction used for the synthesis of a family of compounds based around a coumaron framework, all of which lack amine functionality. This precedes discussion of X-ray crystal structure analysis of several TB model compounds, amine functionalised monomers and coumaron-based compounds. After this is a description of the development of the novel TB polymerisation reaction, the results of the TB polymerisation of the amine functionalised monomers, characterisation of the successful polymers and the attempted polymerisation of two coumaron-based monomers. The final part of this work reports the experimental procedure for each compound together with full characterisation. In closing, the TB polymerisation reaction has successfully used for the production of highly stable and soluble PIMs exhibiting a wide range of microporosity, with BET surface areas ranging from 0 m2/g to 1035 m2/g. A few of these PIMs have been found to have excellent molecular weight, capable of forming strong membranes, suitable for gas separation, most notably for the purification of oxygen, hydrogen and carbon dioxide from nitrogen. Conversely, the synthesis of coumaron-based PIMs proved unsuccessful, but nevertheless this research should allow the future synthesis of a coumaron-based PIM. The research on TB polymerisation detailed in this thesis has contributed towards an International Patent122 and a paper in Science123so can be deemed to have been successful by that measure.