Solvothermal (and ionothermal) synthesis has been used in this work to prepare novel group 13 selenide materials. The new phases were characterised using single crystal and powder X-ray diffraction, spectroscopic methods (infrared and UV-Vis diffuse reflectance spectroscopy) and thermal analysis (thermogravimetric and elemental analysis). Other characterisation methods used include SQUID magnetometry and the measurement of optical properties. The effect of the structure directing organic molecule on the inorganic structure was investigated in this thesis, with a variety of novel materials synthesised. A family of one-dimensional chains have been prepared. The first, composed of fused four-membered rings, was found in [NH4][InSe2] (using 3,5-lutidine) and in a number of phases prepared with bicyclic superbases. The second chain-type, composed of fused four- and five-membered rings was found in [C6H16N2][Ga2-xInxSe3(Se2)] (0 < x < 2) and [C7H14N3][In2Se3(Se2)]. These chains contain a (Se2)2- perselenide bond, which was previously unreported for solvothermally prepared group 13 selenides. The third chain type, found in [C7H13N2][InSe(Se2)] and [C9H17N2][InSe(Se2)], contains fused five-membered rings. More complex one-dimensional ribbons were also prepared with superbases. Many two-dimensional layered phases have been prepared in this work. [NH4][InSe2], which contains supertetrahedral clusters, generates a second harmonic generation response. A novel phase which incorporated a transition metal into the structure has been found for [Mn(C6H14N2)3][H2O][(C6H14N2)2MnIn3(SH)2Se4.89(Se2)0.12]2. The novel hybrid gallium selenides, [Ga6Se9(C6H14N2)4][H2O] and [C6H14N2][Ga4Se6(C6H14N2)2] were also isolated. The novel layers in [C7H10N][In3Se5], contain a new octahedral building-block. A further layered material, [C8H12N][In3Se4.85(Se2)0.15] was prepared, where disorder of selenium was observed. Using weakly basic pyridine and its related methyl-substituted isomers (lutidines and picolines), a three-dimensional framework [C5H6N][In9Se14], was prepared and its ion-exchange capabilities studied. Further framework materials prepared in this work include: [enH2][NH4][In7Se12], [C6H14N2][(C6H12N2)2NaIn5Se9] and [In14Se21(Se2)3]6-. Using an ionothermal route, the known three-dimensional framework, [In33Se56]13- was prepared. The first indium selenide prepared using an ionic liquid, in this case, 1-ethyl-3-methyl-imidazolium bromide (EMIm-Br).

This thesis describes the fabrication, characterisation and validation of two novel immunosensors for the detection of the inflammation markers nerve growth factor-β (NGF) and psoriasin (S100-A7). The initial phase of sensor construction involves the electrodeposition of polyaniline onto commercial screen-printed carbon electrodes. A classical avidin-biotin link was then used to immobilise biotinylated antibodies. Fully fabricated immunosensors were incubated with their target antigen and interrogated with AC impedance to observe the change in real (Z‘) impedance (Ohms) with respect to antigen exposure. The Z‘ impedance was found to increase over physiologically significant concentration ranges of the target antigen. The effects of non-specific antigen binding were accounted for via controls using a non-specific antigen analogue for each immunosensor. The sensors reported here, after optimisation of the fabrication procedure using the BioDot AD3200 automatic dispensing system, are capable of detecting the presence and concentration of target antigen in a commercial sample within 35 minutes with a lower limit of detection (LLD) (a response observed that is more than three times the standard deviation of the immunosensors baseline impedance measurement) of 50pg ml- 1 for NGF and 250pg ml- 1 for psoriasin. An evaluation is also presented of the competitive advantage gained by companies such as Unilever by undertaking research projects in conjunction with universities and forming other such strategic networks. As part of this EngD project, a review paper concerning antibody based sensors in the past decade was written and is now submitted ready for publishing in the peer reviewed journal 'Biosensors and Bioelectronics‘. A further two papers describing the development, characterisation and validation of the NGF and psoriasin immunosensors described within this thesis have also been submitted for publishing in 'Biosensors and Bioelectronics‘.

The work reported in this thesis outlines the gold(I)-catalysed synthesis of cyclic sulfamidates by intramolecular allene hydroamination. Work carried out in an attempt to prepare a novel acyl anion equivalent is also included but endeavours were halted after one year of study. The thesis is divided into six chapters: Chapter one provides an introduction to the reactivity of gold, current metal-catalysed hydroamination reactions and allene structure, synthesis and reactivity. The current synthetic methods for the preparation of sulfamidates and their uses is also covered. Chapter two outlines the attempted use of the Burgess reagent to prepare olefinically substituted sulfamidates and the attempts to reverse regioselectivity in sulfamidate synthesis. Chapter three includes an initial proof of concept in gold(I) catalysis and an account of substrate synthesis. Allenes were synthesised by Crabbé homologation or Johnson- Claisen rearrangement reactions. The allenes were then converted to the corresponding sulfamates. Chapter four outlines our studies of gold(I)-catalysed hydroamination. This includes optimisation of catalyst and the effects of substitution on reaction rate and stereochemical hypothesis. The current scope and limitations of this chemistry is also discussed. Chapter five outlines the research work attempted within the first year of study. The work focussed on the attempted preparation of a thermally unmasked acyl anion equivalent. Chapter six provides a formal report of the experimental procedures. Stereochemical abstract: All compounds with stereogenic centres were prepared as racemic mixtures but only one enantiomer is represented in the schemes.

No description available.

No description available.

Seconcary phosphine oxide, (S,S-2.5-diphenylphospholane-1 oxide (2.26) has been synthesied from (S,S)-2,5-diphenylphospholanic acid, and its rhodium complex, Rh(2.23)2( cod)] [SbF 6] (2.29) has been crystallographically characterised. Secondary phosphite oxides were synthesised by the reaction of PCh, BuOH and 3,3-R-1,1-bi-2-naphthol in which R = H (3.7a), Me (3.7b) and Ph (3.7c). [M(L) (cod)J[SbF6] (L = 2.26, 3.7a, 3.7c) were tested as catalysts for the asymmetric hydrogenation of methylacetamido cinnamate (MAC), methylacetamido acrylate C~lAA) and dimethyl itaconate (DMI). BINOL derived complexes were hydrolytically unstable and poor enantioselectivity was observed in the catalysis. With hydroxyphospholane complex (2.29) the absolute configuration of the major enantiomer formed depended on the solvent used for the reaction. Hydroxyphospholane complex (2.29) was used as a precursor for the synthesis of chiral diphosphine complexes possessing an OZO inorganic backbone. Deprotonation of (2.29) formed the POHOP pseudo-chelate complex and the O(BF2)O backbone fmmed as a result of the reaction of the [BF4r counterion of [Rh(2.26h(cod)][BF4]. The anionic O(SnCIR2)O backbones were synthesised by the reaction of the deprotonated hydroxyphospholane complex with a dichlorostannane (R = Me, Ph). The neutral backbones, O(SnPh2)O, O(ZrCp2)O and O(HfCp2)O, were formed as a result of the elimination of gaseous methane from the reaction of complex (2.29) with SnMe2Ph2, ZrCp2Me2 and HfCp2Me2 respectively. The phospho lane-derived PCH2CH2CH2P chelate was synthesised from the secondary phospholane and 1,3-dichloropropane. The resultant bis(phospholane) with the (CH2)3 backbone was coordinated to rhodium and applied as an asymmetric hydrogenation catalyst. The OZO-backbone complexes were also tested as catalysts for the asymmetric hydrogenation of MAC, MAA and DMI. The C3 backbone complex was a more selective catalyst for DMI but conversely the OZO backbone complexes gave higher enantioselectivity in the hydrogenation of MAC and MAA where enantiomeric excess of 85-99% were achieved. The analogous reactions to form OZO backbones from the BINOL derived oxide complexes were attempted, but were problematic. O(BPh2)O, O(ZrCp2)O and O(HfCp2)O backbones have been synthesised from [Rh(7.3a)2(cod)][SbF6J but resistance of the hydrolytically sensitive oxide complex towards deprotonation has hindered the formation of other inorganic backbones. The hydrolytic sensitivity of the complexes also impeded their function as hydrogenation catalysts, in which generally low enantioselectivity was observed. Secondary aniinophospholane ligands (5.4-5.6) were synthesised by a condensation reaction of (R,R)-2,5-diphenyl-l-chlorophospholane and primary amines RNH2 (R = iPr (5.4), tBu (5.5), Tol (5.6)). N_iPr substituted aminophospholane (5.4) was coordinated to rhodium and the resultant [Rh(5.4)2(nbd)][BF4J complex crystallographically characterised and tested as an asymmetric hydrogenation catalyst, although low enantioselectivity was observed. Preliminary investigation of a novel route to aminophospholane/Rh complexes for a potentially high-throughput approach, from the rhodium complex of 2,5-diphenyl-l-chlorophospholane, has been developed.

Supercritical C02 (SCC02) has attracted increasing attention as a promising alternative for volatile organic solvent s, due to its abundance, non-toxic, non-flammable, and non-hazardous properties which make C02 a strong candidate for use as a green solvent. However, SCC02 is generally a very poor solvent, especially for polar and high molecular weight solutes, which has largely limited the applications of this supercritical liquid as a processing medium. On the other hand, emulsions and microemulsions have been widely accepted as effective media to stabilize immiscible components, such as water and oil. Studies have been carried out extensively for water-in-scC02 (w/c) microemulsions over the last two decades, in particular, Small-Angle Neutron Scattering (SANS) has been recognised as a powerful technique characterise the self-assembly structures, and frequently applied to investigate such systems. In this thesis, the validity of contrast variation SANS (CV-SANS) has been examined in w/c microemulsions by employing mixtures of D20 and H20 as contrast agents. With this method, the core-shell structure of w/c microemulsions has been highlighted, which allows behaviour of the microemulsions and in particular, the properties of surfactant films to be studied in detail. In addition, a systematic study has also been conducted on the effects of amphiphilic additives known as 'hydrotropes' on surfactant films in both water-in-oil and water-in -C02 microemulsions. Based on these observations, a novel surfactant has been synthesised and applied to w/c microemulsions as an additive, which effectively triggers elongation of microemulsion droplets. This work takes significant step in both exploring the fundamental aspect of the self-assembly structures in C02, and also for the optimization of the physicochemical properties of such systems for potential applications.

Microwave spectroscopy allows study of the bond lengths and angles of molecules and molecular complexes. Gas phase molecules are exposed to microwave radiation while entrained within a molecular beam. The observed microwave spectrum can be used to calculate the physical dimensions of the molecules being excited. This thesis primarily discusses the building and modification of a chirped-pulse Fourier transform microwave (CP-FTMW) spectrometer and its use in conjunction with an established Balle-Flygare Fourier transform microwave (BF-FTMW) spectrometer in order to efficiently record and assign spectra. The CP-FTMW spectrometer was built and extensively used to observe spectra in the 6.5-19 GHz range. It is possible to measure a spectrum in one day using this spectrometer when it would require many weeks of manual measurements on the BF-FTMW spectrometer to do so. This thesis will explore weakly-bound complexes involving two subunits, the first being a Lewis base such as ethene, ethyne, ammonia or carbon monoxide, and the second an electron acceptor such as the iodine in CF3I, or the metal in the metal halides, AgCl or CuCl. These weakly bound molecular complexes present an opportunity to examine the fundamental interactions between the electron donor of the Lewis base molecules and the electron acceptor of the partner molecule. Five molecular complexes in their ground rotational state consisting of CF3I bonding to various Lewis bases have been investigated. These weakly bound complexes in the form CF3I ·· . B have the structure of a C3v molecule. Under this treatment CF3I··· Kr, CF3I··· CO, CF3I··· NH3, CF3I···N(CH3)3 and CF3I···PH3 have been found to have quartic force constants, kδ of between 3 and 12 Nm-1. The complexes CF3I···NH3, CF3I···N(CH3)3 and CF3I··· PH3 have been found to display evidence for internal rotation of the smaller Lewis base subunits with respect to the heavier CF3I subunit on the C3 axis of symmetry. These are assigned as A and E states, to which the internal rotation quantum number m transitions correspond to m = 0 and m = ±1 respectively. Several complexes in the form C2Hn···M - Cl where n = 2 or 4 and M = Cu or Ag. These molecules are found to have planar C2v symmetry.

Three routes into phosphine-containing thiophene-based macromolecules are reported. The phosphinothiophenes were prepared with the ultimate aim of forming metal-functionalised polymers.

This thesis describes the synthesis and catalytic testing of new bis(diphenylphosphino)amine 'PNP' ligands for use in chromium catalysed trimerisation, rhodium catalysed asymmetric hydrogenation and palladium catalysed telomerisation. Chapter 1 presents an overview of catalysis with particular emphasis on the importance of ligand design, homogeneous and heterogeneous asymmetric catalysis, oligomerisation, concluding with future prospects . Chapter 2 investigates the application of bis(diarylphosphino)amine ligands in telomerisation catalysis, comparison of PNP ligands with the benchmark ligand triphenylphosphine, optimization of the telomerisation of carbon dioxide with l,3-butadiene to give a highly active and selective novel catalyst system. Chapter 3 describes the synthesis of soft donor PNP ligands, their complexation with chromium precursors and their application in oligomerisation and co-oligomerisation catalysis with ethene, carbon dioxide, heterodienes and alkynes. Chapter 4 introduces bis(diarylphosphino) amino acid ester based ligands, their synthesis, and complexation to transition metals. The application of these ligands in asymmetric hydrogenation catalysis of methylamino cinnamic methyl ester (MAC) and methylamino methyl ester (MAA). Chapter 5 extends the synthesis of amino acid ester ligand to tripeptide backbone bis(diarylphosphino)amine ligands, development of synthetic methodology, complexation to platinum, palladium and rhodium precursors, characterisation and application in asymmetric catalysis. Chapter 6 contains the experimental details for the preceeding chapters.