Design and Synthesis Strategies for Small Molecule and Polymer Amplification Reagents

Open Access
Author:
Cordes, Travis John
Graduate Program:
Chemistry
Degree:
Doctor of Philosophy
Document Type:
Dissertation
Date of Defense:
July 22, 2016
Committee Members:
  • Scott T Phillips, Dissertation Advisor
  • Scott T Phillips, Committee Chair
  • Ken S Feldman, Committee Member
  • Przemyslaw Maslak, Committee Member
  • Robert Martin Rioux Jr., Outside Member
Keywords:
  • Signal Amplification
  • Synthesis
  • Stimuli-Responsive
  • Polymers
  • Autocatalysis
Abstract:
Self-replicating and self-amplifying systems provide the foundation for the evolution of life and are an inherent component of many biological processes. For over a century, scientists have studied these reactions in an attempt to elucidate the mechanisms responsible for the origin of life, as well as to create chemical reaction systems that mimic these biological phenomena. However, relatively few synthetic amplification reactions are used in commercial applications due to their complexity, or because of limitations such as slow rates of reaction and thermal instability. Amplification reactions are currently sought after in the context of creating reagents for point-of-need assays and stimuli-responsive materials. Reactions that amplify the presence of a molecular signal are particularly attractive due to their ability to produce a large readout signal in response to trace quantities of an analyte. In particular, this dissertation will focus on the development of two approaches to signal amplification: i) autocatalytic reagents and ii) depolymerizable polymers. More specifically, this dissertation will address methods for accelerating the rate of various signal amplification reactions. This includes i) studying the effects of proximity and effective concentration on a base-mediated autocatalytic reaction; ii) designing novel polymer backbones for rapid depolymerization; iii), increasing the rate of solid-state depolymerization in aqueous environments; and iv) mechanoresponsive properties of depolymerizable polymers.