Date of Award

Spring 2020

Degree Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

School

Polymer Science and Engineering

Committee Chair

Dr. Jason D. Azoulay

Committee Chair School

Polymer Science and Engineering

Committee Member 2

Dr. Robson F. Storey

Committee Member 2 School

Polymer Science and Engineering

Committee Member 3

Dr. Derek L. Patton

Committee Member 3 School

Polymer Science and Engineering

Committee Member 4

Dr. Charles L. McCormick

Committee Member 4 School

Polymer Science and Engineering

Committee Member 5

Dr. Xiaodan Gu

Committee Member 5 School

Polymer Science and Engineering

Abstract

The food, energy, and water (FEW) nexus has emerged as a new paradigm to guide scientists, policy makers, and businesses in making a conscious effort toward a sustainable future. The goal of the nexus approach is to transition to a Green Economy, aiming at efficiency, a reduction of negative externalities, and an increased quality of life. The lack of available information regarding the quality of our water resources persists as a major challenge to these efforts. The last few decades have demonstrated the rise of soft condensed matter sensing technologies in the form of solution-processed organic semiconductors based on conjugated polymeric (CP) materials. The delocalized electronic structures, large extinction coefficients, highly emissive properties, and synthetic tunability of CPs have popularized them for the detection of a wide range of analytes. Despite the achievement of significant technological milestones, clear design guidelines by which to tailor CP-based sensors for the detection of environmentally relevant analytes such as nitrates, phosphates, polycyclic aromatic hydrocarbons (PAHs), etc. in seawater remain absent.

Chapter I introduces concepts that are the foundation of this research and frames the current limitations in the field. Chapter II demonstrates a simple post-polymerization modification protocol, based on thiol-ene click chemistry, that results in the rapid installation of ionic receptor chemistries onto a CPE scaffold. The fluorescence of the resulting water-soluble CPE is quenched by Fe3+, dequenched selectively by pyrophosphate (PPi), and accurately quantifies PPi within ±6 nM in artificial seawater.

Chapters III and IV outline an alternative approach for the detection and discrimination of classes of analytes, such as PAHs and textile dyes, which lack recognition chemistries and are therefore precluded from traditional optical sensing platforms. In these systems the inner filter effect (IFE), in combination with CP array-based sensing, offers a straightforward approach for the quantitative and qualitative profiling of diverse libraries of similar spectroscopically active analytes. Chapter V further investigates the utility of the IFE in CP-based sensing, demonstrating the solvent and spatial independence of signal transduction through a solid-state sensor design, enabling a reusable sensor with broad applicability.

ORCID ID

0000-0002-1427-1296

Available for download on Monday, May 14, 2170

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