Discovery of chemical and biochemical reactions on self-assembled monolayers

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Bibliographic Details
Author / Creator:Li, Jing.
Description:117 p.
Format: E-Resource Dissertations
Local Note:School code: 0330.
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Other authors / contributors:University of Chicago.
Notes:Advisor: Milan Mrksich.
Thesis (Ph.D.)--The University of Chicago, Division of the Physical Sciences, Department of Chemistry, 2010.
Dissertation Abstracts International, Volume: 72-02, Section: B, page: 0898.
Summary:This dissertation describes the discovery of chemical and biochemical reactions on self-assembled monolayers (SAMs) of alkanethiolates on gold. Matrix-assisted laser desorption/ionization mass spectrometry was used to rapidly characterize products and yields of reactions that occur on the SAMs. This technique is termed SAMDI MS. 16 chemical reactions for elaborating the structure of SAMs were reported. Taking advantage of the easy purification of reactions on SAMs and the label-free detection of SAMDI MS, a platform for performing arrays of reactions in parallel and analyzing the reaction outcome by SAMDI MS was developed. The discovery of two novel chemical reactions by this platform was demonstrated in this thesis. The first reaction is an interfacial condensation of surface immobilized amine with three equivalents of aldehydes to form an N-alkylpyridinium product with high efficiency. The second reaction discovered is a three-component condensation of siloxy alkynes, aldehydes, and anilines. The three-component reaction was confirmed in solution and the reaction scope was investigated. The thesis also describes using a SAM-based model system to characterize the kinetics of interfacial biochemical reactions. Rate enhancement that stems from localization of the enzyme cutinase with its substrate by way of the SH2 adaptor domain was measured by cyclic voltammetry. The work presented in this thesis demonstrated that SAMs can be designed to become an excellent platform for studying chemical and biochemical reactions.