Chemical Reactions at Metal Surfaces: Functionalization Strategies and Spectroscopic Characterization
Abstract
Tremendous interest in increasing the control over surface properties has led to high demand for new efficient methods for chemical surface modifications. In this work, several approaches toward surface functionalization are explored, and modified surfaces are subsequently characterized using uniquely suited spectroscopic techniques. In the first part of this thesis, strain-promoted alkyne-azide cycloaddition (SPAAC) reactions are investigated for their potential to precisely tune the surface properties of gold substrates at the monolayer level. The utility of SPAAC reactions in preparing biorecognition interfaces for cell adhesion is then examined. Polarization modulation infrared reflection-absorption spectroscopy is used to characterize adsorbed monolayers and probe the progress of surface SPAAC reactions. In the second section of this thesis, novel plasmonically active metallic substrates are fabricated. These substrates are used to catalyze the plasmon-mediated grafting of diazonium salts onto gold nanoparticle surfaces and are also employed as platforms for surface-enhanced Raman spectroscopy.