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Ceramics used for medical purposes are known as bioceramics, such as hydroxyaptite (HA), which is one of the most well studied bioceramics because of its similar composition to human bone and also good biocompatibility, is bioactive and has excellent osteoconductivity. In addition many properties of HA can be improved by the addition of specific elements into its structure. The research in this thesis investigates the substitution of some selected elements into the structure of HA and subsequent characterisation in terms of physical, mechanical and biological responses. Si/S-HA and Sr/B/S-HA was obtained from Lucideon and Ho/HA was synthesised in house. Initially a cell response to a variety of element oxides was performed to identify elements to avoid or potentially use for substitution. Dysprosium (Dy), erbium (Er), europium (Eu), gadolinium (Gd), holmium (Ho) and praseodymium (Pr) at 100 ppm showed better results for alkaline phosphatase activity than 25 ppm in culture medium.2.5 and 5 mol.% of Ho was substituted into HA structure using a wet chemical method of synthesis. The samples were sintered at 1200°C for 10 hours. There was high crystallinity when 2.5 mol.% of Ho was added into the HA structure. Substitution of Ho in HA structure had the effect of shortening in a axis and elongation in c axis along with the higher concentration of Ho ion.2 mol.% of Si and S was also substituted into HA structure, where both elements Si and S replace PO4 site in HA structure. Si substituted in SiO4 form and S substituted in SO4 form for PO4 as confirmed by FT-IR results. Osteoblast-like cells cultured on Si/S-HA showed an increase in alkaline phosphatase, collagen type I and ostecalcin on samples sintered at high temperature. Sr/B/S-HA was also made where 2 mol.% of each element was substituted into the HA structure. The best condition of sintering temperature for Sr/B/S-HA was 1100°C for 10 hrs due to the resulting small grain size, improved cell adhesion and more collagen and osteocalcin production. These results suggest that the substitution of elements into the HA structure can provide novel bioceramics for control of physical mechanical and cell responses properties.

In many series of compounds, intensity of biological activity and chemical reactivity are proportional. Generally whenever a alkyl group replaces a reactive hydrogen atom, as would be the case for an N-substituted hydroxylamine as compared to hydroxylamine, the over-all biological activity of the resulting compound is lower than that of its nonalkylated analogue. Since toxicity and physiological activity are not proportional, this comparison can only suggest possible types of derivatives to prepare and test.

Surfaces of low carbon steel sheet were modified by exposure to highly caustic aqueous solutions containing either chromium or aluminum cations. Corrosion resistances of such surfaces were compared with that of steel surfaces exposed to plain caustic aqueous solution. In all cases a highly uniform, black coating having a spinel structure similar to magnetite (Fe3O4) was obtained. The coated steel surfaces were characterized using X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and Fourier transform infrared spectrophotometry (FTIR). Polarization resistances (Rp) of modified steel surfaces were measured and compared with that of bare steel surfaces. Results indicate that chromium (Fe2+ Fe3+x Cr3+1-x) or aluminum (Fe2+ Fe3+x Al3+1-x) substituted spinel phases formed on steel surfaces showed higher Rp values compared to only magnetite (Fe2+ 2Fe3+O4) phase formed in the absence of either chromium or aluminum cations. Average Rp values for steel surfaces with chromium containing spinel phase were much higher (21.8 k?) as compared to 1.7 k? for bare steel surfaces. Steel surfaces with aluminum containing spinel phase and steels with plain magnetite coated samples showed average Rp values of 3.3 k? and 2.5 k? respectively. XPS and EDS analysis confirmed presence of cations of chromium and aluminum in Fe3O4 in cation substituted samples. FTIR results showed all coating phases were of spinel form with major absorption bands centered at either 570 cm-1 or 600 cm-1 assigned to Fe3O4 and ?-Fe2O3 respectively.

Stilbene containing polymers are a group of interesting and versatile polymers. The pendent phenyl ring along the polymer backbone can impart unusual rigidity to the polymer backbone due to steric repulsion. By functionalizing stilbene, a variety of functional groups and ionic groups can be precisely placed along the polymer chain with tunable charge density. Therefore, stilbene containing polymers are potentially rod-like polyelectrolytes with controllable charges and charge density. They are the basis of a novel group of rigid synthetic polyelectrolytes and can be used for furthering our knowledge of rigid polyelectrolytes. A novel series of methyl substituted stilbenes were synthesized and copolymerized with maleic anhydride. A conversion-time study was undertaken to understand the methyl substituent effect on copolymerization rates. Methyl substituted stilbene-maleic anhydride copolymer compositions were determined by quantitative ¹³C 1D NMR. SEC measurements showed the weight average molecular weights of these copolymers vary from 3 000 to over 1 000 000 g/mol. No glass transition temperature or crystalline melting temperature was observed between 0 °C and 250 °C by DSC. TGA showed that these polymers have 5% weight loss around 290 °C. Precursors to a polycation and a polyanion based on functionalized stilbenes and maleimides have been prepared: poly(di-t-butyl-(E)-4,4′-stilbenedicarboxylate-co- N-(4-(t-butoxycarbonyl)phenyl)maleimide) and poly(N,N,Nâ ,Nâ -tetraalkyl-4,4′-di- aminostilbenes-co-N-4-(N′,N′-dimethylaminophenyl)-maleimide). These copolymer precursors were characterized by ¹H NMR, SEC, TGA, and DSC. The ¹H NMR spectrum indicated the rigidity of copolymer backbones. SEC measurements showed the weight average molecular weights of these copolymers vary from 5 000 to 11 700 g/mol. No glass transition temperature or crystalline melting temperature was observed between 0 °C and 175 °C by DSC for poly(di-t-butyl-(E)-4,4′-stilbenedicarboxylate-co-N-(4-(t-butoxy- carbonyl)phenyl)maleimide). TGA showed that this polymer has 5% weight loss around 210 °C and 26% weight loss on the first stage of decomposition which corresponds to elimination of t-butyl functional group in the copolymer. The homopolymerization of EMS-III via free radical polymerization, anionic polymerization and cationic polymerization was attempted. However, no polymer was obtained from any of these polymerization methods. In anionic polymerization, the solution changed to red upon the addition of the initiator sec-bu-Li, indicating the successful addition of the sec-bu-Li to EMS-III. However, the initiated monomer did not propagate to form homopolymer. / Master of Science

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A number of N-substituted-3-hydroxy-3-phenylphthal-imidines and some of the isomeric amides have been prepared in order to study changes in the infrared spectra of these compounds due to structural changes in the molecule, particularly with reference to a hydroxyl band at 3.0µ and a carbonyl band at 5.75µ.

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The synthesis of amines bearing an adjacent quaternary stereocentre is challenging. Work within our group has demonstrated that the intramolecular transfer of an aryl group within a lithiated benzylic urea is possible. Subsequent cleavage of this urea moiety allows the synthesis of chiral aryl amines bearing quaternary stereocentres. This thesis details investigations into the lithiation of allylic and vinylic ureas. A sequential transformation of allyl ureas into diarylallyl ureas has been developed, a reaction that can be carried out enantioselectively using chiral lithium amides. Deprotection of the urea allows for the isolation of amines bearing highly substituted centres. It has been shown that the use of the acid-labile vinylic protecting groups allows the corresponding Cbz protected diarylallyl amines to be synthesised. Investigations have demonstrated that these analogues can be converted into otherwise synthetically challenging diarylglycine derivatives. During these investigations it has also been shown that carbolithiation of vinyl ureas is possible. The ureas formed from this tandem β-alkylation/α-arylation sequence can then be converted to their highly substituted amine counterparts in good yields. A range of allylic ureas has been investigated; their synthesis and reactivity upon lithiation are discussed within this thesis.