THE DESIGN AND SYNTHESIS OF SILOXANE PRECURSORS FOR CHIRAL PERIODIC MESOPOROUS ORGANOSILICA MATERIALS

The development of cost-effective and reliable methods for the synthesis and separation of asymmetric compounds is paramount in helping to meet society’s ever-growing demand for chiral small molecules. Of these methods, chiral heterogeneous supports are particularly appealing as they allow for the reuse of the chiral source. One such support, based on the synergy between chiral organic units and structurally stable inorganic silicon scaffolds are periodic mesoporous organosilicas (PMOs). In the work described herein, I examine some of the factors governing the transmission of chirality between chiral dopants and prochiral bulk phases in chiral PMO materials. In particular, the exploration of 1,1’-binaphthalene-bridged chiral dopants with a focus on the point of attachment into the materials. Moreover, the effects of ordering in the materials are examined and reveal that chirality transfer is more facile in materials with molecular-scale order then those containing amorphous walls. Secondly, the issues surrounding the synthesis and purification of aryl-triethoxysilanes as siloxane precursors are addressed. Both the introduction of a two-carbon linker and the direct attachment of allyl and mixed allyldiethoxysilane species are explored. This work demonstrates that allyldiethoxysilanes are ideal, in that they are stable enough to permit facile synthesis, while still being able to hydrolyze completely to produce well-ordered materials. Lastly, the production of new bulk phases for chiral PMO materials is examined by introducing new prochiral nitrogen-containing siloxane precursors. Biphenyldiamine and bipyridine-bridged siloxane precursors are readily synthesized on reasonable scales. Their use as the bulk siloxane precursor in the production of PMO materials however, is precluded by insufficient gelation and additional siloxane precursors are necessary for the production of ordered materials. In addition to the research detailed above that forms the body of this thesis, two short works are appended. The first details the production of polythiophene assemblies mediated through coordination nanospaces, while the second explores the production of N-heterocyclic carbene functionalized gold nanoparticles through ligand exchange.

The Significance of the Disputed Territory in Bechuanaland 1887-1893

British Imperial policy in Southern Africa in the last three decades of the nineteenth century oscillated between two extremes. It began in the early 1870's with Lord Kimberley's attempt to effect confederation as a means of devolving Imperial responsibility and expenditure. It ended in 1899 with Britain's active intervention against the Boers. For most of the remaining years of those decades a middle course was adopted while the British Government struggled to reconcile its diverse political interests. Strategy, supremacy, economy, humanitarianism, and recognition of colonial aspirations were all at one time or another, in varying degrees, motivating forces behind Imperial policy. Many historians have pointed out how incompatible many of these ends were and how the attempt to pursue them all at once almost inevitably ended in at least one of them being sacrificed on the way. This study focusses on a relatively minor problem over a period of about seven years. It attempts to show how the British Government tried to reconcile, in this case, the predominant motives of economy and supremacy. The problem of the Disputed Territory now seems like a small fish in a big ocean because non the great hopes and fears that it raised were ever realized. But the anticlimactic nature of the outcome of events should not be allowed to conceal two important points: first, that the problem loomed large at the time in the eyes of the Imperial Government; and second, that in the case of its policy towards the Disputed Territory, the Government gained a greater degree of success in trying to reconcile seemingly incompatible ends than it did in many other instances.

Recent Armenian Developments

The War has brought us into a close relation with Armenia. The annihilation of her people in 1915 and 1916 aroused universal sympathy. For the most of us Armenia, hitherto, had been relegated to a position of partial obscurity in the Near East. We were acquainted with the fact that they had suffered persecution beore at Turkish hands but an indifference born of unfamiliarity with her history, customs and people still continued with us. However much the gulf separating ourselves and these people has been narrowed by the war it is only by an actual journey into their life past and present that we can ever come into a full appreciation of a people who despite persecution and oppression are potentially fine citizens.