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The aim of our project is to build new catalysts for the asymmetric epoxidation of alkenes using ð-interactions as fundamental factors for the control of the facial selectivity. It was decided to employ cinchona alkaloid derivatives as the basic core of our catalysts. We envisage that the alkene would interact selectively with the aromatic rings of the catalyst to give the corresponding epoxide in good enantiomeric excess. Quinuclidine derived cataysts of simplified structures were synthesised to find the best conditions for the experiments using chiral cinchona derivatives. An important result to be taken into account in the development of the chiral catalysts was the influence of the counterion on the conversion rate. The triflate gave the highest epoxidation rates for trans-â-methylstyrene. The use of a mixture MeOH/ DMM/ H2O led to a two fold increase in reaction rate and is recommended to increase the van der Waals interactions between the aromatic rings of the catalyst and the alkene. New catalyst amd a new epoxidation protocol for the epoxidation of alkenes mediated by dioxiranes have been disscussed .Encouraging results have been obtained from this work.

Lightning represents a key interaction with climate through its production of nitrogen oxides (NOx) which lead to ozone production. These NOx emissions are generally calculated interactively in chemistry-climate models but there has been little development of the representation of the lightning processes since the 1990s. In most models the parametrisation of lightning is based upon simulated cloud-top height. The aims of the thesis are: to explore existing schemes, and develop a new process-based scheme, to parametrise lightning; to use a new process-based lightning scheme to give insights regarding the role of lightning NOx in tropospheric chemistry; and to use alternative lightning schemes to improve the understanding of the response of lightning to climate change, and the consequent impacts on tropospheric chemistry. First, a new lightning parametrisation is developed using reanalysis data and satellite lightning observations which is based on upward cloud ice flux. This parametrisation is more closely linked to thunderstorm charging theory. It greatly improves the simulated zonal distribution of lightning compared to the cloud-top height approach, which overestimates lightning in the tropics. The new lightning scheme is then implemented in a chemistry-climate model, the UK Chemistry and Aerosol model (UKCA). It is evaluated against ozone sonde measurements with broad global coverage and improves the simulation of the annual cycle of upper tropospheric ozone concentration, compared to ozone simulated with the cloud-top height approach. This improvement in simulated ozone is attributed to the change in ozone production associated with the improved zonal distribution of simulated lightning. Subsequently, data from a chemistry-climate model intercomparison project (ACCMIP) are used to study the state-of-the-art in lightning NOx parametrisation along with its response to climate change. It is found that the models using the cloud-top height approach produce a very similar response of lightning NOx to changes in global mean surface temperature of +0.44± 0.05 TgNK-1, for a baseline emission of 5 TgN yr-1. However, two models using two alternative lightning schemes produce a weaker and a negative response of lightning to climate change. Finally, simulations in a future climate scenario for year 2100 in the UKCA model were performed with the cloud-top height and the ice flux parametrisations. The lightning response to climate change when using the cloud-top height scheme is in good agreement with the positive response found in the multi-model results of the cloud-top height approach. However, the new ice flux approach suggests that lightning will decrease in future. These opposing responses introduce large uncertainty into the projections of tropospheric ozone and methane lifetime in the future scenario. An analysis of the radiative forcing from these two species also shows the large uncertainty in the individual methane and ozone radiative forcings in the future. Due to the opposite effect that lightning NOx has on methane (loss) and ozone (production) the net radiative forcing effect of lightning in present-day and future is found to be close to zero. However, there is a small positive feedback suggested by the results of the cloud-top height approach, whereas no feedback is evident with the ice flux approach. These results show there are large and crucial uncertainties introduced by lightning parametrisation choice, not only in terms of the actual lightning distribution but also atmospheric composition and radiative forcing. The new ice-based parametrisation developed here offers a good alternative to the widely-used approach and can be used in future to model lightning and develop the understanding of associated uncertainties.

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Cellulose, a sustainable raw material derived from nature, can be used for various applications following its functionalization and oxidation. Nanocellulose, inheriting the properties of cellulose, can offer new properties due to nanoscale effects, in terms of high specific surface area and porosity. The oxidation of cellulose can provide more active sites on the cellulose chains, improving its functionalization and broadening applications. Two kinds of oxidation and their corresponding applications are described in this thesis: periodate oxidation and Oxone® oxidation. 2,3-dialdehyde cellulose (DAC) beads were prepared from Cladophora nanocellulose via periodate oxidation, and were further modified with amines via reductive amination. Several diamines were selected as possible crosslinkers to produce porous DAC beads, which showed higher porosity, stability in alkaline solution and enhanced thermal stability. After functionalization of DAC beads with L-cysteine (DAC-LC), thiol, amine and carboxyl groups were introduced into the DAC beads, endowing the DAC-LC beads with high adsorption capacity for palladium. The synthesized DAC-LC beads were character­ized with SEM, FTIR, XPS, TGA, BET and XRD and the palladium adsorption process was investigated. Chitosan was employed as a crosslinker in functionalization of DAC beads (DAC-CS). The conditions for the synthesis of DAC-CS beads were screened and verifying the stability of the beads in alkaline solution. The DAC-CS beads produced were investigated using SEM, FTIR, XPS, TGA and BET, and the adsorption and desorption capacity of Congo red was studied, indicating DAC-CS beads have potential as sorbent. Oxone oxidation of cellulose is a novel one-pot oxidation method in which mainly the hydroxyl groups on C6 are oxidized to produce carboxylic acid groups on the cellulose chains. To increase the efficiency of Oxone oxidation, several reaction parameters were studied. Cellulose pulp and Cladophora nanocellulose were chosen as prototypes to investigate the effects of oxidation, and the physico­chemical properties of the oxidized products were characterized. Cellulose pulp, pretreated with Oxone oxidation, was disintegrated by homogenization to prepare cellulose nanofibers (CNF). The effect of pre­treat­ment on the preparation of CNF was studied, and the results indicated that Oxone oxidation was efficient in the production of CNF.

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This thesis describes the catalytic asymmetric epoxidation of olefins mediated by chiral iminum salts. The first chapter introduces some of the most novel and effective catalytic asymmetric methods for preparing chiral oxiranes. The second chapter is divided into three sections. The first section of chapter two is dedicated to our efforts to develop new aqueous oxidative conditions using both hydrogen peroxide and sodium hypochlorite as efficient, green oxidants that remove the temperature boundaries observed with the use of Oxone® as the stoichiometric oxidant. A wider range of available temperatures was examined allowing optimization of both oxidative systems. Ethereal hydrogen peroxide was observed to mediate asymmetric epoxidation within an acetonitrile monophasic co-solvent system giving enantioselectivities of up to 56%. When sodium hypochlorite was used in a biphasic solvent system in conjunction with dichloromethane; it was observed to mediate oxidation of the substrate alkenes in up to 71% ee. The second and third sections of chapter two are dedicated to our efforts to synthesize chiral iminium salts as catalysts for asymmetric epoxidation based on a biphenyl azepinium salt catalyst structure. From previous work within the Page group, the asymmetric synthesis and subsequent defined stereochemistry of a chiral carbon atom α to the iminium nitrogen atom was shown to have significant effect on the enantiocontrol of epoxidation using the iminium salt catalyst. Work was completed on biphenyl azepinium salt catalysts, inserting an alkyl or aryl Grignard reagent into the iminium bond using a pre-defined dioxane unit as a chiral auxiliary. Oxidation of the subsequent azepine gave a single diastereoisomerically pure azepinium salt. The methyl analogue of this sub-family of azepinium catalysts has been shown to give up to 81% ee for epoxidation of 1-phenylcyclohexene, furthermore, the binaphthalene azepinium salt with an additional methyl group was also synthesized and was shown to give up to 93% for epoxidation of 1-phenylcyclohexene. Continuation of the substitution α to the nitrogen atom gave rise to an interesting tetracyclic (biphenyl) azepinum salt catalyst. Construction of an asymmetric oxazolidine ring unit encapsulating the azepinium nitrogen and one of the methylene carbon atoms was achieved. In doing so two chiral centres α to the nitrogen atom were generated. The azepinium chiral carbon atom was populated by an addition methyl group with variation in the substitution on the oxazolidine chiral carbon atom. The benzyl analogue of this sub-family of tetracyclic azepinium catalysts has shown to give up to 79% ee for epoxidation 1-phenylcyclohexene. The third chapter is the experimental section and is dedicated to the methods of synthesis and characterization of the compounds mentioned in the previous chapter. X-ray reports regarding the crystallographic analysis of the structures presented in chapter two are provided in appendix A. Appendix B contains the analytical spectra for the determination of enantiomeric excess of the epoxides.