Precursor chemistry for oxide related materials

This thesis describes modelling, synthesis, spectroscopic and physical characterisation, as well as application of Magnesium, Calcium and Copper β-diketonate, β-ketoiminate, β-diiminate, Schiff base, amide and fluorenyl compounds. The selected compounds could potentially find application in materials deposition using Atomic Layer Deposition (ALD), MOCVD, CVD and Sol-Gel techniques. Quantum chemical modelling was used as a tool to perform the comprehensive and rapid study of magnesium and calcium precursor molecules in order to predict which of them would be more successful in ALD of metal oxides. Precursor chemistry plays a key role in ALD, since precursors must be volatile, thermally stable, chemisorb on the surface and react rapidly with existing surface groups. This Thesis describes one aspect of this, surface reactivity between ligands and hydroxyl groups, via a gas-phase model with energetics computed at the level of Density Functional Theory (DFT). A number of different synthetic strategies, both aerobic and anaerobic, were investigated for the synthesis of the described metal complexes. These included the use of different metal starting reagents such as, anhydrous and hydrated inorganic metal salts, metal alkyls and Grignard reagents. Some of previously unreported metal complexes of homoleptic and heteroleptic magnesium, calcium and copper β-diketonates, β-ketoiminates, β-diiminates, amides and Schiff base type were synthesised and characterised: [Mg(hfpd)2(DipPa)], [Mg(hfpd)2(MapH)2], [Mg(hf-ebp)(THF)2], [Mg(tf-Pap)Cl(THF)2], [Ca(PhNacnac)2], [Cu(tf-Pap)2], [Cu(PhNacnac)2], [Cu(hf-ebp)], [Cu(DipPa)] and [Cu(DipPa)2(4,4’-bypy)]. A comprehensive study on the thermal properties of magnesium, calcium and copper β-diketonates, β-ketoiminates, β-diiminates, Schiff base, amide and fluorenyl complexes was performed using TGA and sublimation of selected compounds. Atomic Layer Deposition of MgO using magnesium β-ketoiminate – [bis{(4-N-phenyl)-2-pentonato} magnesium] and β-diketonate - [bis(1,1,1,5,5,5-hexafluoropentane-2,4-dionato)(THF)magnesium hydrate] was performed on Si(100) substrates at 180°C and 0.2 Torr using O2 plasma.

Taming hazardous chemistry in flow: The continuous processing of diazo and diazonium compounds

The synthetic utilities of the diazo and diazonium groups are matched only by their reputation for explosive decomposition. Continuous processing technology offers new opportunities to make and use these versatile intermediates at a range of scales with improved safety over traditional batch processes. In this minireview, the state of the art in the continuous flow processing of reactive diazo and diazonium species is discussed.

Chamber investigations of atmospheric mercury oxidation chemistry

Mercury is a potent neurotoxin even at low concentrations. The unoxidised metal has a high vapour pressure and can circulate through the atmosphere, but when oxidised can deposit and be accumulated through the food chain. This work aims to investigate the oxidation processes of atmospheric Hg0(g). The first part describes efforts to make a portable Hg sensor based on Cavity Enhanced Absorption Spectroscopy (CEAS). The detection limit achieved was 66 ngm−3 for a 10 second averaging time. The second part of this work describes experiments carried out in a temperature controlled atmospheric simulation chamber in the Desert Research Institute, Reno, Nevada, USA. The chamber was built around an existing Hg CRDS system that could measure Hg concentrations in the chamber of<100 ngm−3 at 1 Hz enabling reactions to be followed. The main oxidant studied was bromine, which was quantified with a LED based CEAS system across the chamber. Hg oxidation in the chamber was found to be mostly too slow for current models to explain. A seven reaction model was developed and tested to find which parameters were capable of explaining the deviation. The model was overdetermined and no unique solution could be found. The most likely possibility was that the first oxidation step Hg + Br →HgBr was slower than the preferred literature value by a factor of two. However, if the more uncertain data at low [Br2] was included then the only parameter that could explain the experiments was a fast, temperature independent dissociation of HgBr some hundreds of times faster than predicted thermolysis or photolysis rates. Overall this work concluded that to quantitatively understand the reaction of Hg with Br2, the intermediates HgBr and Br must be measured. This conclusion will help to guide the planning of future studies of atmospheric Hg chemistry.

Chemistry and synthesis of 3(2H)-furanones and 4,5-dihydro analogues: mechanistic investigations and stereochemical control

The subject matter of this thesis relates to the chemistry of the five-membered oxygen heterocycles – 3(2H)-furanones and their 4, 5-dihydro analogues. Chapter one of the thesis is a review of the relevant chemistry of the compounds: their synthesis and key transformations. In chapter two, new research on 3(2H)-furanones is outlined in two parts. The first describes an investigation into the cyclisation of α'-trialkylsilyloxyenone adducts with arenesulfenyl and selenenyl chlorides into the corresponding sulfur and selenium substituted 3(2H)-furanones without the involvement of a Lewis acid catalyst. The study, largely involving in situ NMR techniques, identified key features associated with the formation and reaction of the chlorosulfide and chloroselenide intermediates, including operation of the Thorpe-Ingold effect. The knowledge gained in this study was applied (the second part) to the synthesis of vinyl substituted furanone systems from α'-trialkylsilyloxydienones where choice of the reaction conditions and electrophilic reagent was a key feature. An important difference in the behaviour of arenesulfenyl and selenenyl halides towards conjugated dienes emerged from this work. This phase of the research concluded with a new synthesis of geiparvarin, a natural product possessing anti-tumour properties.

Superoxide dismutase mimics: chemistry, pharmacology, and therapeutic potential.

Oxidative stress has become widely viewed as an underlying condition in a number of diseases, such as ischemia-reperfusion disorders, central nervous system disorders, cardiovascular conditions, cancer, and diabetes. Thus, natural and synthetic antioxidants have been actively sought. Superoxide dismutase is a first line of defense against oxidative stress under physiological and pathological conditions. Therefore, the development of therapeutics aimed at mimicking superoxide dismutase was a natural maneuver. Metalloporphyrins, as well as Mn cyclic polyamines, Mn salen derivatives and nitroxides were all originally developed as SOD mimics. The same thermodynamic and electrostatic properties that make them potent SOD mimics may allow them to reduce other reactive species such as peroxynitrite, peroxynitrite-derived CO(3)(*-), peroxyl radical, and less efficiently H(2)O(2). By doing so SOD mimics can decrease both primary and secondary oxidative events, the latter arising from the inhibition of cellular transcriptional activity. To better judge the therapeutic potential and the advantage of one over the other type of compound, comparative studies of different classes of drugs in the same cellular and/or animal models are needed. We here provide a comprehensive overview of the chemical properties and some in vivo effects observed with various classes of compounds with a special emphasis on porphyrin-based compounds.

Trace gas measurements from infrared satellite for chemistry and climate applications

Space-borne thermal infrared instruments working in the nadir geometry are providing spectroscopic measurements of species that impact on the chemical composition of the atmosphere and on the climate forcing: H2O, CO2, N2O, CH4, CFCs, O3, and CO. The atmospheric abundances obtained from the analysis of IMG/ADEOS measurements are discussed in order to demonstrate the potential scientific return to be expected from future missions using advanced infrared nadir sounders. Some strengths and limitations of passive infrared remote sensing from space are illustrated. © 2003 European Geosciences Union.

Historical highlights in organoarsenic chemistry

Organoarsenic compounds have given insight into important theoretical topics in chemistry and proved to have beneficial pharmacological effects

Use Of Micro-Stereology And Quantitative Cyto-Chemistry To Determine The Effects Of Crude Oil-Derived Aromatic-Hydrocarbons On Lysosomal Structure And Function In A Marine Bivalve Mollusk Mytilus-Edulis

The marine bivalve mollusc,Mytilus edulis (blue mussel), is a noted accumulator of many environmental pollutants and is increasingly used for the chemical and biological assessment of environmental impact. The toxic effects of crude oil-derived aromatic hydrocarbons (30 μg/l total hydrocarbons) on the lysosomal-vacuolar system of the digestive cells have been investigated in cryostat sections of hexane-frozen digestive glands. Exposure to aromatic hydrocarbons reduced the cytochemically determined latency of lysosomal β-N-acetylhexosaminidase; lysosomal volume density and surface density increased while the numerical density decreased. Experimental exposure resulted in the formation of very large lysosomes which are believed to be largely autophagic in function and these results indicate a significant structural and functional disturbance of digestive cell lysosomes in response to hydrocarbons.