Initially the aims of this thesis were to settle conflicting literature that arose based on the consistency of results obtained from the synthesis of branched polymers, using divinyl monomer ethylene glycol dimethacrylate (EGDMA), by catalytic chain transfer polymerisation (CCTP). By polymerisation of EGDMA using a range of catalyst concentrations, and introduction of comonomers, a range of branched polymers were obtained, all of which retained high levels of vinyl functionality in the resulting products. With the increasing popularity of click chemistry, the natural progression of this work lent towards the functionalisation of these branched vinyl containing polymers by thiol- Michael addition, using a range of commercial thiols, in the creation of branched highly functional polymers, which display enhanced solution properties compared to their linear counterparts, from a small commercial monomer set. The desire to synthesise highly functional polymers led to investigation of epoxide containing monomer, glycidyl methacrylate (GMA), which has proven to be versatile to a range of functionalities. The synthesis of linear GMA homopolymers via CCTP resulted in polymers with the potential for dual functionalisation, at both epoxide and ω- unsaturated groups; to which, thiol-Michael addition and self-catalysed epoxide ringopening with amines was investigated in the synthesis of a range of functional polymers, from a single polymer precursor. Finally the copolymerisation of EGDMA and GMA via CCTP was investigated in the synthesis of branched functional polymers, whereby the level of vinyl groups retained and epoxide functionality can be tuned through monomer ratios. Site selective functionalisation of the high level of epoxide and vinyl groups was conducted using both thiol-Michael addition and self-catalysed ring-opening of epoxides with functional amines. By site selective functionalisation with both hydrophobic and hydrophilic groups, amphiphilic branched copolymers are obtained, with the potential for the synthesis of branched polymers capable of self-assembly.

Chapter 1 is a general introduction of the whole thesis and it features the main concepts of this project. Chapter 2 reports the synthesis and self- assembly of a temperature-responsive DMAP containing nanoreactor. The DMAP motif is incorporated in to a monomer and polymerized by RAFT with styrene in order to form the hydrophobic block of a polymeric micelle. The shell of the micelle is formed by chain extension of the styrenic block with NIPAM, which provides temperature responsive properties to the system. In Chapter 3, the concept of using polymeric micelles to catalyze organic reactions in water is presented and compared to surfactant based micelles in the context of molecular recognition, achieving enzyme-like specific catalysis by tethering the catalyst in the well-defined hydrophobic core of a polymeric micelle In Chapter 4, the incorporation of different catalytic amino motifs into a polymer backbone is investigated by RAFT polymerization in order to catalyze the reaction between polyalcohols and polyisocyanates in the formation of polyurethane foams. In the final chapter, the stimuli-responsive properties of DMAEA containing polymers are investigated. DMAEA is copolymerized by RAFT with the non-responsive MA at different loadings in order to study how the distance between amine motifs affects the polymer LCST and pKas .values

This study is concerned with the development and application of electrochemical techniques combined with confocal laser scanning microscopy (CLSM) as a probe of the kinetics of electrochemical and surface reactions at different interfaces. A CLSM set up has been designed which combines electrochemical and microscopic techniques to extend the applications of CLSM in a new research fields. This methodology has been applied to various electrochemical systems in this thesis. The electrochemical activity of ultramicroelectrodes (UMEs) has been quantified using CLSM. A special optically transparent electrode, comprising a thin film of carbon nanotube network has been developed for these studies. The methodology comprises of tracking the dynamic, reversible concentration profiles of electroactive and photoactive tris(2,2'- bipyridine)ruthenium(II) species in aqueous solutions during cyclic voltammetry experiments. A decrease of the solution intensity is recorded at and around the UME surface during the oxidation of luminescent Ru(bpy)3 2+ to non-luminescent Ru(bpy)3 3+, followed by an increase of the intensity signal in the reverse scan direction as the oxidized Ru(bpy)3 3+ is consumed at the electrode surface. A three dimensional map of the concentration gradients of Ru(bpy)3 2+ is constructed by collecting sections of the object across the normal to the electrode plane at the steady state current regime. The first use of CLSM coupled with scanning electrochemical microscopy (SECM) has been introduced as a means of time dependent visualisation and measurement of proton dispersion at dental enamel surfaces and the effectiveness of inhibitors on substrates. This new technique provides an analytical method with high spatial and temporal resolution permitting sub-second analysis of treatment effects on enamel substrates. In this case the UME tip of SECM is used to generate protons galvanostatically in a controlled manner and the resulting proton fields were quantified by CLSM using a pH sensitive fluorophore. Given the advantage of SECM to deliver high controllable, and local acid challenges in a defined way, and the high temporal and spatial resolution in the millisecond and micrometer range, respectively, in CLSM allows the surface kinetics of dissolution and the effect of barriers on the enamel surfaces to be evaluated. Finite element model has been used to describe the dissolution process, which allows the kinetics to be evaluated quantitatively, simply by measuring the size of pH profiles over time. Fluoride and zinc were used as treatments for enamel surfaces to investigate the effect of inhibitors on proton distribution, since they are generally considered to impede the dissolution process. Proton lateral diffusion at modified surfaces was also investigated using CLSM and SECM to validate the use of these techniques. A disc UME was brought close to the membrane and the oxidation of water was induced. Proton lateral diffusion was observed as a change in pH along the membrane. Different electrostatic interactions were investigated by functionalising the surface with different phospholipid head group and polypeptide multilayer films, since they are thought to have an effect on facilitate or retreat the process. Anionic lipids head groups share protons as acid-anion dimmers and thus trap and conduct protons along the head group domain of bilayers that contain such anionic lipids. The results also indicate the rate and mobility of proton diffusion along membrane are largely determined by the local structure of the bilayer interface.

The structure of glasses and devitrified phases, in Tl2O⋅GeO2 and Tl2O⋅B2O3 systems, have been investigated using solid-state nuclear magnetic resonance (NMR), neutron diffraction and Raman spectroscopy. Gas pycnometry, thermal analysis and powder X-ray diffraction (XRD) have also been used to characterise and measure properties of glasses and devitrified phases. The crystallisation study showed that metastable crystalline phases were obtained from lowtemperature heat-treatment. X-ray diffraction of devitrification products, obtained at higher temperature, indicates crystallisation of the corresponding, more stable, stoichiometric compounds from the glass but with one or more second phases. Thallium NMR studies reveal that various chemical environments of thallium are present in the heat-treated samples. For the Tl2Ge4O9 sample, whose crystal structure is known, magic angle spinning NMR reveals the presence of one thallium site, the [Ge3O9] ring structure was observed using Raman spectroscopy. A germanate anomaly is present in the thallium germanate glasses indicated by a minimum value of molar volume at x ~ 0.15. Neutron diffraction and Raman spectroscopy confirm the change in the coordination number of germanium from [GeO4] to [GeO6 or 5]. Tl solid-state NMR suggests that at least two thallium sites are also present in the glass, low and high coordinated thallium. Tl-NMR spectra are broad and shifted mainly due to the chemical shift dispersion and chemical shift anisotropy interaction, respectively. T2 measurements confirmed that dipole-dipole and pseudodipole or exchange interactions are stronger in high thallium content glasses. A 203Tl enrichment study determined that the broadening due to the exchange interaction is ~ 10 kHz. Only three crystalline thallium borate phases were obtained, either singly or in combination with each other. Density data, X-ray diffraction patterns and solid-state NMR results of the three phases formed support what structural information exists in the literature. Chemical shift interaction and chemical shift dispersion contribute to the line broadening and lineshape of Tl NMR of TlB5O8 and TlB3O5 containing sample. Dipolar interaction and the Tl…Tl exchange interaction are stronger in the Tl2B4O7 sample. The chemical shift anisotropy parameters of TlB5O8 and TlB3O5 are presented. A borate anomaly is present in thallium borate glasses with a minimum value of molar volume at x ~ 0.28. Neutron diffraction and solid-state NMR spectroscopy confirm the change in the coordination number of boron to oxygen atoms from [BO3] to [BO4]. N4 values obtained from both techniques are very close and are larger than found for alkali borate glasses. Raman spectroscopy also reveals the changes in boron-oxygen superstructural units. 205Tl solid-state NMR suggests that at least two thallium sites are present in the glass, low and high coordinated thallium. Tl-NMR spectra are broad and shifted mainly due to the chemical shift dispersion and chemical shift anisotropy interaction, respectively. T2 measurement confirmed that dipole-dipole and exchange interactions occur in glasses throughout the range of studied compositions.

1πσ* or 1nσ* mediated dissociation of X-H and X-CH3 bonds (where X = N, O or S) has been studied herein, progressing previous work into the role of 1πσ* and 1nσ* states as mediators for excited state relaxation. By investigating the role of these states in excited state dynamics of sub-units and analogues of biomolecular systems, spectroscopic signatures can be observed with greater ease. These signatures may then be extended to elucidate the role of these dissociative states in excited state relaxation processes of more realistic systems, namely DNA bases and amino acids. The work undertaken in this thesis specifically focuses on 1πσ* mediated hydrogen elimination from imidazole and mequinol, as well as 1πσ* or 1nσ* mediated CH3 elimination in anisole, thioanisole and mequinol. Through the use of time resolved velocity map imaging, the timescale for these dissociation processes can be determined by independently measuring the radicals produced with a characteristic kinetic energy. From these timescales, information about the rate of coupling to these 1πσ* and 1nσ* states can be inferred. The results obtained show that population of these states can occur via several different mechanisms including: direct excitation; coupling through conical intersections; and tunnelling. The results also project the importance of 1πσ* or 1nσ* mediated processes in much larger biological systems, strongly suggesting the need to extend these measurements and begin to bridge the gap between the microscopic, such as DNA bases and amino acids, and the macroscopic, such as oligonucleotides and polypeptides.

This thesis describes the synthesis of methyleneaziridines bearing aryl groups and investigates some of their chemistry, focusing on thermal rearrangements and metal catalysed reactions. The inclusion of an N-aryl group is desirable as it is thought it might facilitate new types of reactions to be developed for use in organic synthesis. In chapter one, the synthesis of methyleneaziridines with N-EWGs and N-aryl groups is investigated. Starting by exploring the possibility of using coppercatalysed nitrene cyclisation, a common method for the synthesis of aziridines, the synthesis of N-tosyl and N-troc methyleneaziridines was attempted. This led into the synthesis of N-mesityl methyleneaziridine which was achieved in 85% yield by ring closure of N-(2-iodopro-2-en-1-yl)-2,4,6-trimethylaniline using sodium amide in ammonia. The effect of the leaving group (Br vs I) on the relative rates of such ring closure reactions was explored and it was established that iodides cyclise at a higher rate. Chapter two describes the thermal rearrangement of N-mesityl methyleneaziridines. A kinetic study was conducted to show the increased propensity for N-mesityl methyleneaziridine to rearrange to the cyclopropylimine, compared to N-alkyl methyleneaziridines. The application of this rearrangement for the preparation of cyclopropylamines was explored. Chapter three looks at metal-catalysed reactions of methyleneaziridines. It was shown that N-mesityl methyleneaziridine will participate in a palladium-catalysed reaction. Carbonylation reaction of methyleneaziridines, as reported by Alper1 and Pauson-Khand reactions were also explored. A novel methyleneaziridine containing cobalt/alkyne complex was produced in 40% yield.

The adsorption of various guest molecules by the flexible 1,4-benzenedicarboxylate metal-organic framework (MOF), MIL-53, has been followed using in situ diffraction techniques. This crystalline MOF displays a structural expansion upon the adsorption of guest molecules, evident by a change in unit cell parameters, which allows adsorption to be followed using diffraction techniques. Adsorption studies were performed with the Fe(III) form of MIL-53 using both liquidand gas-phase guest molecules. The results from in situ X-ray diffraction (XRD) studies show that small aliphatic-alcohols give rise to a two-step expansion whereas branchedalcohols and larger aromatic molecules result in only a one-step expansion. The solvent used for liquid phase studies was shown to affect guest adsorption; benzothiophene and benzothiazole were adsorbed more quickly from a solution of heptane than from a solution of isopropanol. Gas phase studies were used to investigate the effect of occluded water molecules inside the pores of the framework upon the adsorption of methanol. A combination of XRD, thermogravimetry and inelastic neutron scattering studies were used to show that methanol does not displace water when hydrated MIL- 53(Fe) is used as an adsorbent. Two equivalents of methanol can be packed inside the pores of the framework, irrespective of the adsorbent being hydrated or dehydrated. Eight linker-modified MIL-53(Al) materials were supplied by research partners and in situ XRD studies were performed to reveal the effect of the modifications upon the adsorption of gas-phase molecules. The results show that the linkers change the behaviour of the material towards certain guest molecules and the most dramatic effect was seen when the benzene ring of the linker was replaced by cyclohexane. A series of cobalt (II) MOFs synthesised with carboxylate and pyridine-N-oxide linkers is presented. The effect of functionalising the pyridine ring upon the topology of the resulting framework was studied. Resonance and steric effects were found to influence the structure of the final product. One of the new materials has the potential to be used as an adsorbent due to a 3D porous structure.

Broad-Spectrum Chemokine Inhibitors (BSCIs) are a novel type of antiinflammatory drug, discovered by Fox and colleagues. We have shown that the syntheses of C-substituted γ-thialactams are possible via a modular approach starting from the simple amino acid cystine. These compounds are a new class of GPCR ligand, showing BSCI activity comparable to their non-sulfur counterparts. Initial migratory data suggests that these lactams are inhibitors of leukocyte migration and comparable to the analogous BSCI lactams at μM concentrations, with decreased activity at the nM scale. Efforts have been made to the synthesis of substituted piperidinones, as well as employing Jocic-Reeve-Corey-Link chemistry to the general synthesis of lactams, ultimately looking to the synthesis of C-substituted lactams. Attempting to utilise trichloromethyl carbinol chemistry for these purposes has led to the synthesis of stereochemically-pure heterocycles containing up to 3 stereocentres. α- Trichloromethyl carbinols and asymmetric transfer hydrogenation chemistry are used from simple starting materials. Developments of this type of chemistry will undoubtedly lay the foundations to produce further non-racemic substituted heterocycles which will be important both synthetically and biologically.

gold catalysts have been found to be effective for many oxidation reactions and it is known that the performance of these catalysts depends strongly on the particle size of Au nanoparticles. However, other factors have strong influence on the catalytic activity such as the preparation methods, choice of support, the structure and morphology of supports. The effect of support morphology and structure on the activity of Au catalysts was investigated using two hydrothermally prepared supports, CeO2 and MnO2. Ceria foams as a support for nano-clusters of gold were synthesised hydrothermally at 160 °C by the reaction of L-Asparagine and CeCl3.7H2O at different crystallisation times. The effect of the reaction time on the morphology of prepared CeO2 was investigated. The morphology varied remarkably and it was found to change from spherical particles to foam and eventually to a collapsed foam as the crystallisation time increased. Gold catalysts were prepared by sol-immobilisation, supported on the foam ceria and examined for solvent free oxidation of benzyl alcohol using molecular O2 as an oxidant and the effect of the support was compared with commercial ceria. Au/CeO2 foam catalysts were more active than the Au/commercialCeO2 although the Au nanoparticles were larger in ceria foam supports. This was due to the greater lability of surface oxygen in the foam support compared with commercial CeO2 materials. The Au/CeO2 foam catalyst was found to be reusable over three experiments. The effect of catalyst loading, oxygen pressure and reaction time-online were also studied. It was found that there was no mass transfer limitation when the mass of catalyst varied from 5 to 40 mg under the reaction conditions. The conversion of benzyl alcohol decreased as the oxygen pressure decreased which shows that oxygen was involved in the oxidation process. For time-online study, the conversion increased as the reaction time increased with slightly increase. MnO2 supports were synthesised by reacting MnSO4.H2O with (NH4)2S2O8 hydrothermally at 160 °C. Two different phases and morphologies of MnO2 were formed and as the reaction time increased the morphology changed from microspheres to nanowires and the MnO2 phase changed from α- to β-. Gold was deposited on all prepared MnO2 materials and the catalysts were examined for solvent free benzyl alcohol and CO oxidation. The influence of the preparation method on the catalytic activity was studied and sol-immobilisation was found to be the best for benzyl alcohol VII oxidation whereas the deposition-precipitation was found to be the best for CO oxidation. Impregnation method exhibited poor activity for both reactions. The effect of the morphology and phase on the catalyst activity for both reactions was researched and Au/α-MnO2 microspheres catalysts were best for benzyl alcohol oxidation while Au/β- MnO2 nanowires catalysts exhibited better performance for CO oxidation due to their smaller Au nanoparticles and easier surface reduction. The catalysts reusability, timeonline and the effect of catalyst loading were also studied of an Au/MnO2 microsphere catalyst for benzyl alcohol oxidation reaction. Vanadium phosphate catalysts have been extensively studied for the selective oxidation of butane to maleic anhydride. The catalytic activity of vanadium phosphates is greatly dependant on the preparation method of the catalyst precursor VOHPO4·0.5H2O. Poly (acrylic acid-co-maleic acid) copolymer, PAAMA, was employed as a structure directing agent in the preparation of VOHPO4.0.5H2O via two routes. The effect of PAAMA concentration on the structure morphology of VOHPO4·0.5H2O was studied in both preparation routes. As the concentration of PAAMA increased the morphology changed from rosette like for the standard precursors to rosette-like agglomerates with isolated rhomboidal platelets and eventually to isolated rhomboidal platelets at highest concentration of PAAMA. The XRD confirmed that all precursors were VOHPO4·0.5H2O but as the concentration of PAAMA increased the (001) reflection increased and the (220) reflection decreased. When these precursors were tested for butane selective oxidation, the standard precursors that contain rosettes VPO0 and VPD0 activated to the active phase ((VO)2P2O7) over typically observed time (> 100 h). While the precursors that had rosette-like agglomerates with isolated rhomboidal platelets and a relative intensity ratio of the (001)/(220) reflections of around 1.4, VPO5 and VPD15, activated much faster, less than 20 h with a comparable conversion and selectivity. The isolated rhomboidal platelets precursors which had a high relative intensity ratio of the (001)/(220) reflections, VPO15, VPO25 and VPD25, displayed very poor activity because the thin platelets were rapidly oxidised to αII-VOPO4 phase as confirmed by the XRD and Laser Raman Spectroscopy.

A series of novel multi-metallic luminescent Au(I) and Re(I) complexes have been synthesised targeting functionality as cellular imaging and/or therapeutic agents. Both the ligands and their complexes have been characterised by a variety of spectroscopic and spectrometric techniques. Several complexes were also characterised by X-ray crystal diffraction and/or elemental analysis. In both chapters two and three the modulation of the luminescent properties of a series of mono- and di-metallic [Re(CO)3(N^N)L]+ type complexes bearing functionalised alkyl chains by hydrophobically driven, intra- and intermolecular conformational changes is reported. Additionally, the first application of di-metallic Re(I) complexes in cellular imaging is reported with specific localisation in the nucleoli or ER and Golgi apparatus. In both chapters four and five the synthesis of novel mono- and di-metallic Au(I) complexes is reported. Several complexes demonstrated cytotoxicity as well as compartemental localisation in cellular imaging demonstrating their potential as dual-functional cellular imaging and/or therapeutic agents. As an extension to the work discussed in Chapters two to five, the synthesis of novel multi-metallic luminescent complexes is reported in Chapter six. For the tri-hetero-metallic complex incorporating Au(I) and Re(I) units, cytotoxicity towards four cancer cell lines and non-specific localization throughout the entire cell is described.