Date of Award

8-14-2024

Author's School

Graduate School of Arts and Sciences

Author's Department

Chemistry

Degree Name

Doctor of Philosophy (PhD)

Degree Type

Dissertation

Abstract

The Moeller group has been developing synthetic tools for building molecular libraries on microelectrode arrays since 2004. Such a library is intriguing because one can take advantage of the library for biological signaling studies. Microelectrode arrays can serve as a powerful platform for those experiments since every electrode in the array can be addressed individually. Unique members of the library targeting biological receptors that one is interested in can be restricted only above unique electrodes in an array. Thus, high-affinity ligands for those receptors can be identified with this strategy. To make this method work, one has to make sure that the placement of the members is successful. While fluorescence-labelling the polymer coated surface above those selected electrodes is the “go-to” method for characterizing an array-based reaction, the fluorescence pattern provides little information about the desired reaction itself. To solve this problem, our effort started with the discovery of background reactions that also led to fluorescence pattern at selected electrodes. A series of negative controls of two of the most used array-based reactions, the Cu(I)-catalyzed cross-coupling reaction between an aryl bromide and an alcohol and the Cu(II)-mediated Chan-Lam cross-coupling reaction, was performed. We found that there would be fluorescence above electrodes used for negative controls in both cases. Fortunately, after introducing the “safety-catch” linker strategy, we managed to show that the background reaction for the Chan-Lam cross-coupling reaction was always minimal with the presence of Cu(II)-mediator. Additionally, we learned that the background reaction for the Cu(I)-catalyzed cross-coupling reaction would not be an issue with the use of an undivided cell. Therefore, these two reactions can both be effective methods for site-selectively placing molecules to the surface of an array for biological signaling studies.

Language

English (en)

Chair and Committee

Kevin Moeller

Committee Members

John-Stephen Taylor; Jonathan Barnes; Marcus Foston; Vladimir Birman

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