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Spectroelectrochemical characterization of self-assembled monolayers on a single crystal Au bead electrode : the influence of surface crystallography Yu, Zhinan


Self-assembled monolayers (SAMs) are important structures commonly employed to functionalize metal surfaces. To optimize a metal-SAM construct, it is important to characterize the influence of the surface crystallography. In this thesis, a single crystal Au bead electrode was employed to investigate different types of SAMs, enabling studies on a variety of surfaces under identical conditions and avoiding laborious experimental replicates on a large number of crystal orientations. The application of a single crystal Au bead electrode was demonstrated by investigating the reductive desorption process for two types of SAM: the alkanethiolate SAM and the α-aminoisobutyric acid (Aib) peptide thiolate SAM. Using in situ fluorescence imaging, the influence of surface crystallography on reductive desorption was observed, reflected as a correlation between the density of broken bonds of a surface and the reductive desorption potential of a SAM deposited on the surface. Besides the surface crystallography, intermolecular interactions also had a significant impact on determining the desorption potential. Aib peptide thiolate SAMs on a Au(111) facet were further investigated. It was found that the low packing density Aib peptide thiolate SAMs exhibited a potential-modulated fluorescence response which was believed to be due to the orientational or structural change of the peptide molecules in response to the applied potential. The potential-driven reorientation effect of the DNA SAMs has been intensively explored due to its application in biosensing. Characterization of the DNA SAMs with in situ fluorescence methods suggested that surface crystallography exerts an influence not only on the formation of the DNA SAMs but also on the efficiency of the potential-driven response. Moreover, a spectroelectrochemical technique that couples electrochemistry, fluorescence microscopy and harmonic analysis was developed to explore the non-linearity of the fluorescence response to an applied AC potential. This technique could be potentially applied to detect changes in DNA hybridization state. The experimental results demonstrate the convenience and wide applicability of using a single crystal Au bead electrode to investigate SAMs. On the other hand, applying existing and developing new spectroelectrochemical techniques give insights into creating SAMs with desirable properties.

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