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Photocleavable junctions in complex polymer architectures and photoetchable thermoplastics
Polymer materials have become important tools in nanomanufacturing due to their facile processing and ready attainment of the necessary feature sizes. The development of cleavable junctions has led to advances in the production of polymer nanotemplates. Photocleavage strategies have come to the forefront of the field because photons, as a cleavage stimulus, do not have the mass-transport limitations of chemical methods, and provide for targeted two- and three-dimensional feature control. This dissertation presents a method for producing photocleavable materials by one-pot copper-catalyzed azide-alkyne "click" chemistry (CuAAC), activator regenerated by electron transfer atom transfer radical polymerization (ARGET ATRP) and activated ester substitution methods that have each block labeled with a fluorescent dye, enabling exploration of the polymer physics of these systems by correlation fluorescence spectroscopy. It also introduces a novel photocleavable linker, the o-nitrobenzyl-1,2,3-triazole, its behavior on photocleavage, and a facile method for the production of the o-nitrobenzyl azides necessary for their synthesis. The synthesis and properties of a bulk photodegradable polytriazole are reported, as are proof of concept experiments demonstrating its potential as a directly photoetchable material. Lastly, this dissertation contains a perspective on possible avenues of new research on the topics presented.^
Sterner, Elizabeth Surles, "Photocleavable junctions in complex polymer architectures and photoetchable thermoplastics" (2014). Doctoral Dissertations Available from Proquest. AAI3615451.