Thesis (Ph. D.)--University of Wyoming, 2006. / Title from PDF title page (viewed on Dec. 20, 2007). Includes bibliographical references.

In an attempt to expand the scope of titanacyclobutenes, malonate-derived ,-alkylpropargyl dibromides and ,-bis(bromopropargyl) malonates were prepared and examined for their reactivity with titanocene reagents. Unfortunately, all of the ,-alkylpropargyl dibromomalonates failed, presumably from chelation of the carbonyl oxygen followed by radical or nucleophilic attack. The ,-bis(bromopropargyl) malonate substrates allowed the successful synthesis of ester-functionalized allenyl or alkynyl-substituted bicyclic titanacyclobutene complexes. Allenyl-substitution is favoured when the being formed ring is small. When ring strain is minimal, cycloalkynes are obtained. An impressive example of a twelve-membered macrobicyclic titanacyclobutene was achieved, supported by extensive NMR spectroscopy and X-ray crystallography. 3-Propargyltitanium(III) complexes were synthesized and displayed equilibrium behaviour between the monomeric propargyl and dimeric di(titanacyclobutene) forms. Both steric and electronic effects are believed to be contributing factors for dimerization. Bimetallic titanacyclobutenes are obtained from the reaction of an epoxide and titanocene monochloride in the presence of a 3-propargyltitanium(III) complex.

The reactivity of bulky ligands with various transition metal complexes was studied to better understand the nature of organometallic electronic unsaturation and the role this plays in small molecule activation. A bulky stannyl hydride, tBu3SnH, was synthesized by a revised procedure that is far more facile and reproducible. This sterically encumbered ligand was shown to oxidatively add to a broad range of transition metal complexes, particularly those displaying carbonyl ligands, in greatly differing manners. Reaction of tBu3SnH with Ni(COD)2 and tBuNC was found to yield the mononuclear complex Ni(SntBu3)2(tBuNC)3. This compound possesses photochemical reactivity, most likely attributable to the massive steric bulk surrounding the Ni center, and generates electronically unsaturated metal centered radicals upon photolysis. This complex and its photochemical products were studied from both experimental and spectroscopic aspects. The stable organic radical TEMPO was also reacted with Ni(COD)2 to afford the unsaturated square planar complex Ni(TEMPO)2 which was studied both experimentally and spectroscopically. This deceivingly simple compound displays a wide spectrum of complicated reactivity and small molecule activation which may be utilized in future catalysis.

Synthesis of novel amphiphilic copolymers based on sugar moieties: development of new architectures and biomedical applications As early as in the 50’s, amphiphilic copolymers started to attract much interest in the frame of polymer science thanks to their self-assemblies as organized nano-structures in a selective solvent. The resulting micelles or vesicles have emerged as potentially useful materials in the biomedical field such as drug delivery systems when matching the specific conditions of size, coating nature and functionalization,… Moreover, active cell-targeting increases the therapeutic effect by selectively delivering the drug to the required cells. Accordingly, carbohydrates have drawn much attention due to the cell recognition processes they can mediate. Carbohydrates are thus incorporated in polymer backbones to mimic the naturally occurring substrate for the adapted cell receptors. The originality of this thesis is based on the use of sugar moieties as potential multi-hydroxylated initiators for the polymerization of various lactones. This leads to well-defined amphiphilic polymer architectures along with the development of a more facile route for the incorporation of carbohydrates in polymer chains to promote active cell-targeting of the as-obtained nano-structures. The first part of the thesis aims at describing the synthesis of novel amphiphilic brush-like polymers via two pathways. A first approach relies upon the synthesis of polyester arms initiated from the alcohol groups of pending sugars distributed along a preformed hydrophilic polymethacrylate backbone obtained by controlled radical polymerization (via ATRP). Various metal-based and organic catalysts/activators have been studied to lead to the desired architectures using this “grafting from” technique. In another synthetic strategy, the lactone polymerization using a carbohydrate initiator has been carried out, followed by end-chain derivatization reactions yielding brush-like copolymers via a “grafting through” technique. Slight modifications of the end-chain functionalities have also afforded the possibility to synthesize amphiphilic mikto-arm copolymers which self-assemble in aqueous medium in micelles characterized by interesting size features affording promising applications as new drug delivery systems. On the other hand this thesis also focuses on the use of carbohydrate moieties in amphiphilic diblock copolymers such as poly(ε-caprolactone)-b-poly(methacrylate-graft-poly(ethylene oxide)-co-6-O-methacryloyl-D-galactopyranose) or poly(ε-caprolactone)-b-poly(methacrylate-graft-poly(ethylene oxide)-co-1-O-methacryloyl-D-mannofuranose), using the combination of lactone ring-opening polymerization with ATRP of the respective functionalized comonomers, followed by selective post-polymerization sugar deprotection. Next to these copolymers based on polylactones and polymethacrylates, fully degradable amphiphilic block copolymers composed of a polycarbonate backbone have been originally designed. To that end, a multi-step procedure involving the synthesis of sugar-substituted cyclic carbonates, block copolymerization reactions and ultimate selective sugar deprotection, has been investigated. The self-organization of the resulting copolymers, e.g., poly(trimethylene carbonate)-b-poly(3-O-(5’-methyl,5’-carboxy-1’,3’-dioxan-2’-one)-D-glucopyranose), has been studied in aqueous medium. Interestingly, the so-formed polymeric micelles proved to display remarkable living cell-targeting properties. Fabian Suriano

This project explores democracy as a way of life (radical democracy) by drawing from both North and Latin American philosophers. I work with ideas from Paulo Freire (Brazil) and Luis Villoro (Mexico) to develop (a) a criticism of mainstream liberal assumptions regarding freedom, tolerance and the nature of the relationship between the individual and the community as well as (b) a criticism of liberal democracy as a political system, and (c) a formulation of democracy as a way of life. This is relevant because the experiences in Freire's and Villoro?s historical background (colonialism, feudalism, dictatorships) have been neglected from the Western liberal approach which emphasizes property rights, individual rights and community obligations towards the individual. Working with philosophers whose theories have been informed by the liberal tradition but whose work was developed in response to living in environments of dehumanizing oppression and corruption provides us with relevant criticisms of the Western liberal tradition as well as its assumptions regarding central concepts such as freedom, tolerance and community.

Free radical cyclization methodology has been used extensively in synthesis for manipulation of complex molecules such as alkaloids, terpenes, carbohydrates, peptides and nucleic acids. The methodology has emerged as a result of work by physical organic chemists who determined rate constants for the most common radical reactions used in organic synthesis. A novel route to cyclic imines based on 5-exo radical cyclization was explored. The radical precursors were imines prepared from allylamine and readily available a-phenylselenenyl ketones. The synthesis of conformationally constrained bicyclic nucleosides is also reported using 5-exo and 6-exo cyclizations of hexenyl and heptenyl radicals in thymidine nucleosides. The nucleosides were incorporated in a 15mer antisense oligonucleotide via solid-phase oligonucleotide synthesis. The AONs with the modifications were tested for target affinity and stability and compared with the well known LNA modified AONs. The thesis discusses the unique qualities of these novel molecules and presents them as potential candidates for antisense therapeutic agents. Keeping up with the theme of intramolecular carbon-carbon bond formation, microwave induced carbodechalcogenation of chalcogenoanhydrides was explored. Poor generality in these reactions made us turn to transition metal catalysis for Sonogashira cross-coupling reactions using alkyl aryl and diaryl tellurides as coupling partners.

This qualitative study looks at the learning that takes place during activism. Throughout this work, learning is conceptualized as the ongoing formation of critical consciousness rather than the acuqisition of skills for the purpose of securing menial employment. Furthermore, critical consciousness is seen to develop through the nonlinear interplay of thoughts and actions. This investigation uses the life history method to explore the learning of five Iranian women throughout decades of struggle against repressive social structures. It focuses on questions of motivation for activism, formation of critical consciousness, and activism in diaspora. At the theoretical level, this study criticizes current learning theories while its educational implications place critical consciousness as the goal of radical adult education. On a practical level, this investigation records successful political study groups and suggests such groups as models for sites of radical adult education.

This qualitative study looks at the learning that takes place during activism. Throughout this work, learning is conceptualized as the ongoing formation of critical consciousness rather than the acuqisition of skills for the purpose of securing menial employment. Furthermore, critical consciousness is seen to develop through the nonlinear interplay of thoughts and actions. This investigation uses the life history method to explore the learning of five Iranian women throughout decades of struggle against repressive social structures. It focuses on questions of motivation for activism, formation of critical consciousness, and activism in diaspora. At the theoretical level, this study criticizes current learning theories while its educational implications place critical consciousness as the goal of radical adult education. On a practical level, this investigation records successful political study groups and suggests such groups as models for sites of radical adult education.

The construction of nanoscale polymeric objects with complex, well-defined structures and regiochemical functionalities is of great importance, because it enables the fabrication of soft materials with tunable properties. Direct polymerization of macromonomers through covalent bond formation and self-assembly of block copolymers via non-covalent interactions are two typical strategies to afford nanoscopic structures. Molecular brush polymers are composed of densely-grafted side chains along a polymeric backbone. Due to the significant steric repulsion from the side chains, they tend to adopt bottle-brush like conformations, as opposed to linear polymers. "Grafting through" synthesis of molecular brush polymers can provide precise control over the dimensions and functionalities of brush polymers. Shell crosslinked knedel-like nanoparticles (SCKs) are constructed by assembling from amphiphilic block copolymers into micelles, followed by covalent shell crosslinking to further stabilize the nanoparticles and introduce additional functional moieties. SCKs are attractive nanocarriers because of their variable morphologies, compositions and functionalities, which allow for the development of platforms for therapeutic or diagnostic purposes. By utilizing the orthogonal reactivity of the norbornene group and methacrylate group, two distinctly different reactive well-defined linear polymers, and a facile, one-pot synthesis of well-defined molecular brush polymers were studied by selective, orthogonal controlled radical polymerizations (CRPs) and ring-opening metathesis polymerization (ROMP). The living and high efficient characteristics of "grafting-through" strategy were further investigated for the preparation of topology-controlled brush polymers with tunable dimensions of both backbone and side chain lengths. Apart from the fundamental investigation of molecular brush polymers, a series of poly(carboxybetaine) (PCB)- and poly(ethylene glycol) (PEG)-grafted degradable SCKs were developed to evaluate their in vivo pharmacokinetics and biodistributions, aiming to achieve novel therapeutic and diagnostic platforms that may surpass the performance of the conventional PEGylated analogs.

If a1, a2, . . . , an are nonnegative real numbers and fj(x) = paj + x, then f1o f2o· · · fn(0) is a nested radical with terms a1, . . . , an. If it exists, the limit as n ! 1 of such an expression is a continued radical. We consider the set of real numbers S(M) representable as an infinite nested radical whose terms a1, a2, . . . are all from a finite set M. We give conditions on the set M for S(M) to be (a) an interval, and (b) homeomorphic to the Cantor set.