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Several chiral macrocyclic crown ethers and related analogues have shown to be capable of / Thesis (PhD-Chemistry)-University of KwaZulu-Natal, Durban, 2004

Unable to copy abstract. / Thesis (M.Sc.)-University of KwaZulu-Natal, Westville, 2011.

Thesis (Ph. D.)--University of Hong Kong, 2009. / Includes bibliographical references. Also available in print.

Thesis (M.S.)--Florida State University, 2006. / Advisor: Armen Zakarian, Florida State University, College of Arts and Sciences, Dept. of Chemistry. Title and description from dissertation home page (viewed Sept. 19, 2006). Document formatted into pages; contains xiv, 120 pages. Includes bibliographical references.

Thesis (M. Sc.)--University of Canterbury, 2006. / Typescript (photocopy). "July 2006." Includes bibliographical references (leaves 69-72). Also available via the World Wide Web.

Thesis (Ph. D.)--University of Texas at Austin, 2007. / Vita. Includes bibliographical references.

This thesis describes the synthesis of macrocyclic and interlocked receptors which exploit halogen- and hydrogen-bonding intermolecular interactions for anion recognition. <strong>Chapter One</strong> introduces the field of supramolecular chemistry, with particular focus on applications of host–guest chemistry to anion coordination and anion templation in the construction of mechanically interlocked molecules. <strong>Chapter Two</strong> details the synthesis of a series of cyclic and cage-like porphyrin-based receptors which bind anions through halogen- and hydrogen-bonding interactions. The ability of these receptor systems to bind and sense anionic guest species is investigated and comparisons between hydrogen- and halogen-bonding are discussed. <strong>Chapter Three</strong> reports anion-templated pseudorotaxane assemblies stabilised by both halogen- and hydrogen-bonding. The related catenanes are also prepared and their affinity for anions is investigated. The first examples of interpenetrated and interlocked architectures constructed by a single charge-assisted halogen bond are also reported. <strong>Chapter Four</strong> describes the synthesis of a 1,3-dialkyl-1,2,3-triazolium-containing threading component, whose anion binding properties are studied and compared with other threading molecules. The ability of this novel thread to form pseudorotaxanes is investigated and the preparation of the related rotaxane species is outlined. <strong>Chapter Five</strong> discusses attempts to prepare rotaxanes with improved anion binding affinities through increasing the lipophilicity of the anion binding clefts. Several novel rotaxanes are described and their anion binding properties are probed. <strong>Chapter Six</strong> describes the experimental procedures used in this work and the characterisation of compounds presented in chapters two to five. <strong>Chapter Seven</strong> summarises the conclusions of this thesis.

The membrane-spanning phospholipids of the domain Archaea are postulated to provide membrane stability; this thesis reports the design and synthesis of a synthetic membrane-spanning macrocyclic lipid to test this hypothesis. Protected glutaric anhydride reacted with 10-undecyn-1-ol to produce a glutarate monoester. Copper-mediated azide-alkyne coupling (CuAAC) using 1,5-diazido-3-oxapentane(bis-azide) afforded a dicarboxylicacid with a hydrophobic chain of sufficient length to span a 35 Å bilayer membrane. The carboxylic acids were each esterified with an equivalent of 10-undecyn-1-ol. After optimization an 87% yield was obtained in the closure of the 72-membered macrocycle with the bis-azide using CuAAC. Deprotection and coupling with p-nitrophenyl phosphorodichloridate completed the synthesis. Two other phospholipids, a linear bolaamphiphile derived from the precursor to the second click reaction, and a linear amphiphile created from a glutarate bis-dodecyl ester, were also synthesized to provide controls for probing the orientation of the macrocyclic phospholipid in the bilayer membrane of vesicles. The amphiphile, linear bolaamphiphile, and macrocyclic bolaamphiphile were synthesized in 4, 5, and 6 steps with yields of 19, 4, and 5% respectively. The hydrophilic head group of the macrocyclic phospholipid was designed to release p-nitrophenolate in basic conditions from the p-nitrophenylphosphate head group to produce an absorbance at 400 nm. This assay was expected to elucidate the membrane-spanning orientation of the phospholipid in the bilayer membrane of vesicles. The final target compound failed to release p-nitrophenolate under basic conditions and underwent phosphate elimination to produce an α, β-unsaturated ester instead. Although the macrocyclic lipid produced associates with membranes and may be membrane-spanning, this lipid design was unable to reveal its membrane orientation. / Graduate

In an effort to increase the thermodynamic stability and the kinetic inertness of the complexes, the five new azamacrobicyclic ligands derived from TACN, cyclen, and cyclam have been prepared. The ligands were decorated with phosphinate or phosphonate pendant arms to maintain fast complexation. Since the ascending importance of targeted diagnostic and therapy, the bone-targeted non-bridged cyclam derivative with phosphinate-bis(phosphonate) pendant arm (H5TE1PBP) has also been synthesized. The ligands were studied with respect to their application. The bridged TACN (H2bpbtacn) and cyclen (H4bpbcen) ligands show high macrocyclic basicity (logK1 = 12.25 and 12.70, respectively). The thermodynamic stability of H2bpbtacn with Cu(II) ion is more than ten orders of magnitude lower than that of the NOTA ligand. The stability constants of H4bpbcen with Cu(II) and Zn(II) ions are comparable to those given for the DOTA. The stability of Ln(III)-bpbcen complexes is 7-10 orders of magnitude lower compared to DOTA complexes. For both ligands, the lower thermodynamic stability of the complexes is attributed to the high rigidity of the ligand structure. The bridged cyclam derivatives with phosphonate (H4TE2P), bis(phosphinate) (H4TE2bpin), or phosphinate (H2TE2PH) pendants are characterized by high stability of...