Date of Award

12-2026

Document Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

Department

Chemistry and Chemical Engineering

First Advisor

Yi Liao

Second Advisor

Jessica Smeltz

Third Advisor

Toufiq Reza

Fourth Advisor

Robert Usselman

Abstract

Metastable-state photoacid (mPAH) has become a common tool for controlling and driving chemical processes with light. mPAHs with fast reverse reactions are desirable for precise temporal control or generating quick pulses of proton concentration. In this work, different approaches towards fast reversing mPAHs are studied. Experimental and computational results showed that stabilizing the charge–transfer intermediate is an effective way to increase the rate. A novel mPAH with a reverse reaction ≈500 times faster than the most widely used mPAH in methanol has been developed. Another water-soluble mPAH exhibited a reverse reaction with a rate constant of 7.8 s−1, the fastest ever reported. The half-life of the acidic state is calculated to be 89 ms, which allowed to demonstrate sub-second switching using this mPAH. Another project, Poly(caprolactone) (PCL) films and microtubes were covalently functionalized via aminolysis, followed by attachment of a dialdehyde linker and L-tryptophan ethyl ester as a model drug. The release profiles of both tryptophan and the linker were monitored by UV-Vis absorption spectroscopy. Tryptophan displayed a distinct initial burst release prior to stabilization, and the dialdehyde linker exhibited slower release. Overall, this linker-mediated modification strategy provides a versatile tool for controlling the retention and release of biomolecules from biodegradable vascular scaffolds.

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