In this thesis the use of thin foil conical profile X-ray mirrors for high energy, large aperture, and lightweight telescopes is investigated. The telescope performance is studied using analytical solutions and ray tracing simulations. Expressions for the number of mirrors in a module, the collecting area, the efficiency of aperture utilisation, and the resolution are calculated for on-axis sources. For off-axis sources ray tracing is used and expressions to describe the performance are derived empirically. The sensitivity and effect of singly reflected rays on the image are also investigated, and the comparison is made with Wolter (I) profile optics. A technique for the production of super-smooth surfaces using a layer of acrylic lacquer is described. Several materials have been coated using this method to assess their suitability as potential mirror substrates. To quantitatively assess the quality of both substrate and lacquer finishes a program of X-ray scattering measurements has been carried out. Several different types of surfaces have been examined both before and after lacquer coating. Particular attention has been payed to the ability of the lacquer to remove surface features of different spatial wavelengths. An epoxy replicated test flat is also examined which provides an interesting comparison with the lacquer coating technique for the production of thin X-ray mirrors. As a consequence of the wide range of materials examined it has been possible to compare most of the different techniques for producing thin X-ray mirrors. There is no one solution for all applications and thin foil mirrors are indeed a competitive technology.

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Macrocycle (H2L1) was prepared by a Schiff base condensation reaction of 2,6-diformylpyridine and 1,3-diamino-2-propanol in the presence of Ba(II) as template ion. Seven-coordinate Mn(II) complexes were prepared by transmetallation reactions of the initial [Ba(H2L1)(μ1,2-ClO4)]2(ClO4)2 complex. Two mononuclear, ring-contracted complexes were obtained when methanol or ethanol were used as solvents in transmetallation reactions. For both complexes, X-ray analysis showed that the H2L1 macrocycle undergoes a ring-contraction via addition of methanol or ethanol across one imine bond, followed by a nucleophilic addition of the secondary amine across an adjacent imine bond resulting in a six-membered, hexahydropyrimidine ring sitting in a chair conformation. The ring-contraction process reduces the size of the cavity in the macrocycle to accommodate one Mn(II) ion in the macrocycle. The macrocyclic tetraimine ligand (H2L1) gave access to the polynuclear, ring-expanded assemblies, [Mn4(H2L*)Cl4][MnCl4] and [Mn4(H2L*)(N3)4](ClO4)2, when acetonitrile was used as a solvent. The macrocycle (H2L1) undergoes rearrangement from a 20-membered to a 40-membered tetranuclear Mn(II) complex. Manganese complexes of acyclic ligands, derived from 2,6-diformylpyridine and several aminoalcohols and aminophenols, were prepared and structurally characterised by X-ray crystallography. Most of the complexes are seven-coordinate with approximate pentagonal bipyramidal geometry, however, some five, six and seven-coordinate complexes were identified. Asymmetric and symmetric tripodal Schiff base ligands and their manganese complexes were also prepared and characterised. Additionally, N-alkylated benzimidazole 2,6-bis(1-butyl-1H-benzo[d]imidazol-2-yl)pyridine and its Mn(II) complexes were prepared and characterised. The potential application of the complexes has been tested in two main areas: (a) as new catalase mimics and (b) as new superoxide dismutase (SOD) mimics. The trinuclear, acyclic complex, [Mn3(L9)2(OAc)2(MeOH)2] 2MeOH, derived from 2,6-diformylpyridine and 2-aminophenol, was found to be the most efficient catalase mimic of the tested complexes with approximately 500 molecules of H2O2 broken down per second for each complex during the fastest rate of activity. Catalase testing showed that an increase of the arm size of the tripodal complexes produced an increase in activity overall for the complexes. Most of the complexes tested for catalase activity showed an induction period prior to the activity being observed. This may be due to a rearrangement occurring before catalase activity is observed. The tripodal complex, [Mn(L18)](ClO4)2 is the only complex to show a catalase activity without added base, but with a long induction period. The results that are presented indicate that the axial ligands have an effect on both the rate of catalase activity and the observed induction period. The SOD results indicated that the complex, [Mn(H2L6)Cl(H2O)]Cl H2O, derived from 2,6-diformylpyridine and 1 aminopropan-2-ol, shows the highest SOD activity amongst the complexes prepared, with a rate of 2.05x106 M-1s-1 and the IC50 value of 0.78 μM. Most of the complexes showed SOD activity with a rate around 105-106 M-1s-1. The SOD results showed that the axial ligands have an effect on SOD activity; strongly bound ligands such as thiocyanate and azide generally result in lower SOD activity. Most of the complexes showed both SOD and catalase activity. Ring-contracted complexes, [Mn(H3L2)(NCS)2] and [Mn(H3L3)(NCS)2], show high rates of superoxide dismutase activity but possess limited catalase activity.

Dissertation made openly available per email from author, 6/8/2016.

There is a continued interest in the properties of arsenic thiolate compounds for both industrial and biological uses. Recent discoveries in the medicinal properties of such compounds have resulted in a sustained need for the synthesis of new dithiarsolane compounds for research as anti-leukemic compounds. Close analogues of the 2-halo arsenic dithiolates, namely those with an arsenic-carbon bond instead of an arsenic-halide bond, have recently been shown to have some efficacy towards leukemia cells. Based on the hydrolytic character and the active role of glutathione with arsenic in vivo, the compounds reported here may also have such activity. Arsenic compounds have demonstrated biological activity in the literature, thus the hypothesis of this thesis is cyclized arsenic thiolates can be synthesized with the appropriate characteristics as to be potentially useful medicinal agents as well as provide new structural and reaction information. A series of arsenic and antimony di- and trithiolates has been synthesized and characterized. Those compounds include 2-chloro-1,3,2-dithiarsolane, 2-bromo- 1,3,2-dithiarsolane, 2-iodo-1,3,2-dithiarsolane, 2-chloro-1,3,2-dithiarsenane, 2-bromo- 1,3,2-dithiarsenane, 2-iodo-1,3,2-dithiarsenane, 3-chloro-4H,7H-5,6-benz-1,3,2- dithiarsepine, 2-chloro-benzo-1,3,2-dithiarsole, 1,2-bis-dithiarsolan-2-ylmercapto-ethane, tris-(pentafluorophenylthio)-arsen, bis(2-(1,3,2-benzodithiarsol-2ylsulfanyl)- benzenesulfide), 2-chloro-benzo-1,3,2-dithiastibole, and bis(2-(1,3,2-benzodithistibol)- 1,2-benzenedithiol. Elucidation of the pH characteristics of arsenic dithiolates within the human toxicity reaction pathway is an area of interest. It has been shown that the aqueous arsenic dithiolate stability depends on the size of the ring. 2-Chloro-1,3,2-dithiarsolane has been shown to be somewhat stable at both low and high pH as well as neutral pH. 1,2-bis- Dithiarsolan-2-ylmercapto-ethane is completely stable in a neutral aqueous solution. Glutathione does not permanently bind to arsenic even in overwhelming excess. In particular, these fully characterized compounds determine how reactive the AsS and AsCl linkages are under environmental and biological conditions, and provide a source of new reagents to examine in medical applications. Future applications may include the incorporation of the reported compounds in filtration and remediation technologies with further modification.

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