The focus of the research presented in this thesis is the design, synthesis, and anion recognition properties of a structurally novel class of poly(amides) that incorporates the diaminocyclobutenedione (squaramide) group into the polymer backbone.
In Chapter 1, a brief overview of different anion-responsive synthetic macromolecules is presented. Emphasis is placed on the wide structural diversity of the polymers, the mechanisms of their anion-induced responses, and features such as signal amplification, multivalency, and cooperative behavior that can be exploited productively in the context of anion recognition and sensing.
Chapter 2 describes a new method for the regioselective preparation of squaramides, using Lewis acid-catalyzed condensations of diethyl squarate and different anilines. Zinc trifluoromethanesulfonate promotes efficient condensations of anilines with squarate esters, providing access to symmetrical and unsymmetrical squaramides in high yields from readily available starting materials. Colorimetric anion-sensing behavior and computational studies illustrating the enhanced hydrogen bond donor ability and acidity of squaramides in comparison to ureas are presented.
In Chapter 3, the application of the synthetic method described above to the selective preparation of polysquaramides composed of 1,2-isomeric repeat units is described. The optical, thermal and aggregation properties of these materials are also discussed.
Finally, Chapter 4 describes self-assembly properties as well as applications of these materials in the area of anion recognition and sensing. Incorporating an anion-binding squaramide group into a polymeric architecture results in drastic alterations in the selectivity and magnitude of its anion-induced response, resulting in a sensitive and discriminating turn-on fluorescence sensor for dihydrogenphosphate ions. This unusual behavior is the result of a cooperative, anion-triggered aggregation process that was further probed by dynamic light scattering (DLS), transmission electron microscopy (TEM) and laser confocal microscopy.
| Identifer | oai:union.ndltd.org:LACETR/oai:collectionscanada.gc.ca:OTU.1807/32875 |
| Date | 31 August 2012 |
| Creators | Rostami, Ali |
| Contributors | Taylor, Mark S. |
| Source Sets | Library and Archives Canada ETDs Repository / Centre d'archives des thèses électroniques de Bibliothèque et Archives Canada |
| Language | en_ca |
| Detected Language | English |
| Type | Thesis |
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