Tuning the Properties of Metal-Ligand Complexes to Modify the Properties of Supramolecular Materials

Supramolecular chemistry is the study of discreet molecules assembled into more complex structures though non-covalent interactions such as host-guest effects, pi-pi stacking, electrostatic effects, hydrogen bonding, and metal-ligand interactions. Using these interactions, complex hierarchical assembles can be created from relatively simple precursors. Of the supramolecular interactions listed above, metal-ligand interactions are of particular interest due to the wide possible properties which they present. Factors such as the denticity, polarizability, steric hindrance, ligand structure, and the metal used (among others) contribute to a dramatic range in the physical properties of the metal-ligand complexes. Particularly affected by these factors are the kinetic and thermodynamic properties of the complexes. As a result metal-ligand interactions can vary from inert to extremely transient. Of the vast number of ligands available for study, this dissertation will center on substituted terpyridine ligands, with a particular focus on terpyridine-functionalized polymers. While polymer-functionalized terpyridine ligands and their complexes with transition metals have been heavily studied, the physical properties, particularly the effects of polymer functionalization on the stability of bis complexes of terpyridines, remain unexplored. In the course of investigating the kinetic stability of these complexes, polymer functionalization techniques were developed which were found to increase the stability of the metal-ligand interactions compared to conventional techniques. In addition to studying the effect of terpyridine substituents, the effects of solvent on the stability of the complexes was studied as well. As polymer-bound terpyridine complexes are often studied in solvents other than water, knowledge of the stability of the complexes in organic solvents is important to create supramolecular structures with more precisely controlled properties. It was found that, for unsubstituted terpyridyl complexes, the stability of the complexes varied by as many as five orders of magnitude in common solvents. It is believed that this decrease in stability is the result of the ability of the solvent to facilitate the movement of the ligands from the first and second coordination spheres. Although a large part of this dissertation is dedicated to the study of the kinetic stability of terpyridine complexes, synthetic techniques involving terpyridine and its complexes were investigated as well. It was found that terpyridine functionalized polystyrene could be produced by direction functionalization of terpyridine with polystyryllithium. Additionally heterloleptic terpyridine-based iron complexes were produced with high purity by reduction of the mono terpyridine complex of iron(III) in the presence of a second, functionalized terpyridine ligand. The culmination of these studies was the synthesis of supramolecular organogels, which were crosslinked using metal-terpyridine complexes, yielding dynamic mechanical properties could be broadly tuned by varying the metal used to form the crosslinks

Transportation of the sense of place (Genius loci) : the development of ideas associated with the transportation of the sense of place \u27Genius loci\u27 with particular reference to works of \u27poetical nature\u27 within British romantic art and a brief consideration of aspects of Australian art where both are implicit in an understanding of the nature and characteristics of \u27place\u27

The written and illustrative material contained herein is confirmation of the work carried out through exhibitions and associated Visual Arts work which forms the basis of the submission. The written document, covers historical, thematic, technical, philosophical and creative aspects of work based on four exhibitions of paintings and associated written, illustrative, photographic and visual research work. Exhibitions of paintings were held at: * The Town Gallery, Brisbane, Queensland Paintings on the theme Genius Loci (Sense of Place) Nov/Dec 1990 * The Solander Gallery, Deakin, ACT Sense of Place paintings Feb/March 1991 * Wright College, UNE-Armidale, NSW Paintings and poetry defining A sense of Place Jan/Feb 1992 * The Town Gallery, Brisbane, Queensland Symbiosis of time and place Nov/Dec 1992 In total, approximately 100 paintings and connected items on the theme of the \u27transportation of the sense of place\u27 were exhibited. In the final exhibition seven major works contained ideas and important and original aspects of the project researched. The illustrations, in the form of scanned and coloured photographic images, are in part a record of the major painted works themselves as well as parallel ideas concerned with re-defined characteristics of the sense of place transported between the United Kingdom and Australia. Painting commenced in 1990. It has been necessary in this documentation to refer to earlier articulations of place concepts in order that the relationships between past and present thematic interpretations are identified. References to works of \u27poetical nature\u27 (Nash 1938, p.526) come from research into British Romantic painting and literature especially of the nineteenth and early twentieth centuries and subsequently a crossover has developed in the linkage between painting concepts and developing work carried out into visual aspects of environmental design. Early activities as artist to an English new town development corporation, as a designer, and later on as an art consultant to the re-development of an important Australian urban site, have played their part in helping to discover new expressions of the characteristics of place. Ideas concerned with the \u27transportation of place\u27 have grown from personal experiences of migration and developing understandings of crosscultural activity in the United Kingdom and in Australia. Generally the thesis is concerned with place experienced in parts of Southern England and the Eastern States of Australia. There is no formal reference to Aboriginal art only to art in the Euro/British tradition

Contextualization of Protestant church liturgical gestures, among the Kankana-ey people, Benguet, Northern Philippines

A field-survey indicated that gesture forms used in Protestant Church liturgy arc not identified with the general culture among Kankana-ey, Northern Philippines. Based on an open-system approach to communication, the project identified two categories of gestures, ceremonial and spontaneous, within which eighteen gestures were compared between their use in Sunday church services and the general culture. In a sample of respondents, quantified data was obtained through in-depth interviews and photo-elicitation conducted in four selected congregations, within two denominations: the Episcopal Church and the Assemblies of God. These denominations represent two end points in the Protestant Church liturgical spectrum and results indicate that a difference exists in the forms used in both categories of gestures by both denominations between church and culture.Two reasons are offered to account for this difference in findings between gestures used in the liturgy and their use in culture: the slow pace adopted by Protestant missions to contextualize the church in the Philippines; and a "culture of dependence" that still existed in Protestant churches after independence from their parent body. Further research is needed to determine the level of contextualization on other forms of communication in the church such as preaching, teaching, counselling.The study findings indicate: that an emphasis on contextualization by Protestant misions at church planting level will help to avoid possible conflict between liturgical church forms and culture; that local church bodies must continually adapt forms of communication to the cultural context where they are located, while avoiding blandness, or the alienation of followers who are used to particular forms

On The evolution of phase separation in polymer blends

An investigation is undertaken into the dynamics of phase separation in polymer blends in order to try to understand the morphologies produced via spinodal decomposition and to identify ways to target beneficial morphologies. Cahn-Hilliard theory is used with the Flory-Huggins free energy to model phase separating systems undergoing spinodal decomposition for a number of different systems. Initially a simple two component blend is studied undergoing spinodal decomposition via a temperature quench from the one phase to the two-phase region. The model is then used to study the process of secondary phase separation via a two-step quench process. A temperature quench from the one phase to the two phase region is undertaken and then the system is left to equilibrate for two different time periods before a quench further into the two phase region is carried out. The model is then extended to focus on the technologically useful process of reaction induced phase separation. In this case a two component polydisperse blend is quenched from the one phase to the two phase region via polymerisation of one component of the blend. The phase separation process is followed for selected reaction rates and the consequences of changing the final degree of polymerisation are studied both with and without the formation of a network in the reacting component of the blend. Finally a study of the effect of adding a surface into the blend is undertaken to show the development of a phase separated morphology at and near to the surface, we also present a method to overcome inconsistencies found in the Cahn-Hilliard model. The model is then used to target specific phase separated morphologies on a chemically patterned surface and to try and understand the processes involved in the phase separation of a three component, A B C, blend at a surface

Mobilizing learning: mobile Web 2.0 scenarios in tertiary education

Based upon three years of mobile learning (mlearning) projects, a major implementation project has been developed for integrating the use of mobile web 2.0 tools across a variety of departments and courses in a tertiary education environment. A participatory action research methodology guides and informs the project. The project is based upon an explicit social constuctivist pedagogy, focusing on student collaboration, and the sharing and critique of student-generated content using freely available web 2.0 services. These include blogs, social networks, location aware (geotagged) image and video sharing, instant messaging, microblogging etc… Students and lecturers are provided with either an appropriate smartphone and/or a 3G capable netbook to use as their own for the duration of the project. Keys to the projects success are the level of pedagogical and technical support, and the level of integration of the tools into the courses – including assessment and lecturer modelling of the use of the tools. The projects are supported by an intentional community of practice model, with the researcher taking on the role of the “technology steward”. The paper outlines three different scenarios illustrating how this course integration is being achieved, establishing a transferable model of mobile web 2.0 integration and implementation. The goal is to facilitate a student-centred, collaborative, flexible, context-bridging learning environment that empowers students as content producers and learning context generators, guided by lecturers who effectively model th