Synthesis and Applications of Novel Responsive Materials

This thesis describes the synthesis of responsive organic polymers which show potential for use in a variety of applications. A series of pyridine terminated m-phenylene ethynylene oligomers were synthesized. When trans-dichlorobis(acetonitrile)palladium was added to a solution of these oligomers, they were found to undergo cooperative nucleation-elongation polymerization or macrocyclization and pi-stacking depending on the length of the oligomer. The supramolecular properties of these responsive polymers are attributed to the palladium-pyridine coordination and pi-pi stacking. A responsive hydrogel, sensitive to changes in pH, was coupled with a plasmonic crystal (PC). This hydrogel contained a small amount of acrylic acid which, when polymerized into the hydrogel, caused an expansion of the hydrogel due to electrostatic repulsion when the pH of the solution was raised above the pKa of the acrylic acid group. The hydrogel was covalently linked to surface of a PC for reversible and quantifiable spectroscopic analysis. Changes in the pH of the solution cause the hydrogel swell to different extents which changes the refractive index at the surface of the PC. Refractive index changes can be measured spectroscopically in the visible and near infra-red regions with this PC due to its nanostructure. The spectroscopic response was found to be enhanced when protected gold nanoparticles (Au NPs) were added to the hydrogel. The increase in response is presumably due to the plasmonic coupling between the Au NPs and the PC.

Name thesis:degree_name

Ph.D.

Level thesis:degree_level

Dissertation

Discipline thesis:degree_discipline

Chemistry

Grantor

University of Illinois at Urbana-Champaign

Year dc:date

2015

Author dc:creator

• Wackerly, Jay

Contributors dc:contributor

• Moore, Jeffrey S.

• Chemistry, Physical

Language dc:language

eng

Identifier

(MiAaPQ)AAI3337952

OAI identifier oai:identifier

oai:www.ideals.illinois.edu:2142/84323