Anslyn, Eric V.568897182008-08-282008-08-282003http://hdl.handle.net/2152/863textIn section I, three-dimensional polymeric objects were fabricated using two-photon initiated polymerization (TPIP) with a two-photon absorbing chromophore and an acrylate resin. The feasibility of fabricating polymeric features on the nanoscale was explored using an enhanced field generated at the apex of a gold tip as the excitation source, as used in near-field excitation (NFE). In section II, C3-symmetric chiral receptors were used to direct enantioselective enolate alkylation. A series of host compounds was synthesized and 1:1 host to enolate binding was observed by 1 H NMR titration experiments. A moderate increase in the enantioselectivity of the alkylation of 2-acetylcyclohexanone was observed in the presence of host 2.22. Also in section II, the use of enolate stabilization via charge-pairing was investigated for the reduction of the pKa of 2- acetylcyclopentanone. In the presence of host 3.12, the pKa of 2- acetylcyclopentanone was reduced by 10 pKa units. In comparison with the 2.9 pKa unit shift observed with host 3.11, this result suggests that charge-pairing is more effective in stabilizing enolates in enzyme active sites than traditional hydrogen bonding.electronicengCopyright is held by the author. Presentation of this material on the Libraries' web site by University Libraries, The University of Texas at Austin was made possible under a limited license grant from the author who has retained all copyrights in the works.Organic compounds--SynthesisPhotopolymerizationThesis3118060