Date of Award

12-31-2013

Document Type

Campus Access Dissertation

Degree Name

Doctor of Philosophy (PhD)

Department

Chemistry/Green Chemistry

First Advisor

Jason Evans

Second Advisor

Bela Torok

Third Advisor

Michelle Foster

Abstract

Photoreactive polymers have become increasingly appealing due to the possibility of their application as photoresists. The three projects presented in this dissertation are all inspired by nature and successfully use the properties of the polymers as a photoresist to photochemically crosslink under mild aqueous conditions. Inspiration was found in the photocrosslinking mechanism of thymine bases found within DNA. The second chapter compares five terpolymer systems composed of vinylbenzyltriethyl-ammonium chloride (VBA), N-butyl-N,N-dimethyl-(4-vinylbenzyl)-ammonium chloride (BDMQ) and vinylbenzyl thymine (VBT). It was found that increasing the ratio of BDMQ within the terpolymer system also increases the hydrophobic properties of the system along with an increase in thermal stability. While VBT copolymers are bio-reusable, via enzymatic cleavage of the VBT photodimer, due to the styrene backbone, they are not biodegradable. Chapter three addresses this issue with the successful functionalization of pullulan with 1-(2'-chloroethyl)thymine (ClET). Chapter four examines a new photo-response system prepared by the polymerization of 7-(4-vinyl-benzyloxyl)-4-methylcoumarin (VBMC) with either VBA or (4-vinylbenzyl) sulfonic acid (SSA).

The main point of interest and driving force behind the three research projects presented in this dissertation has been Green Chemistry. Strategic pathways developed for each step along the way chose the greenest option with the highest likelihood of success-initially. Even though the greenest method does not always work, best efforts were made to stay within these guidelines; however, alternative pathways were sometimes required. The end result of this body of work is three novel photodimerized polymeric systems that were developed and synthesized based off of their environmental impact and principles of Green Chemistry.

Comments

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