Waveguide Sensor Platforms: A) Development of the Electroactive Fiber-Optic Chip and B) Attenuated Total Reflectance Spectroscopy of New Molecular Materials

Abstract

The work embodied in this dissertation is specifically focused on the evanescent interaction of light with thin-films which has lead to two related instrument based projects: i) the Electroactive Fiber-Optic Chip (EA-FOC) and ii) Attenuated Total Reflectance (ATR) spectroscopy of novel materials. The EA-FOC combines the sensitivity of an electroactive total internal reflection element (20 to 50 times more sensitive than a transmission experiment) with the ease of use of fiber-optic based CCD spectrometers. A side-polished optical fiber, in a V-groove glass mount, forms the planar platform, which allows access to the evanescent field escaping from the fiber core. The exposed evanescent field, which was used to probe molecules or molecular assemblies supported by the platform, has an interaction area ca. 0.05 cm squared. Thin-film and bulk absorbing samples, and waveguide modeling calculations were initially used to evaluate the sensitivity of the FOC platform, which was found to be analogous to ATR instrumentation. The wavelength range of the FOC platform was increased to include the near-UV and applied to monitor adsorption of a protein film. Fluorescence applications of the FOC were demonstrated using a fluorescence bioassay and a drop cast nanoparticle film. Finally, a transparent conducting oxide film, ITO, was added to the surface of the platform to complete the EA-FOC for spectroelectrochemical applications. A methylene blue redox couple and an electrodeposited ultra-thin PEDOT film were used to probe the capabilities of the EA-FOC. The EA-FOC was shown to be a multifunctional platform for advanced sensor technologies requiring absorbance, fluorescence, and electrochemical detection or a combination thereof.ATR spectroscopy of novel materials included the evaluation of two architectures: i) a pH sensitive polyelectrolyte film and ii) surface capture of a nanoparticle film. Absorbance spectra of a polyaniline/polyacetic acid self-assembled bilayer were evaluated with respect to pH and potential using ATR spectroscopy; the ultimate application of the polymer signal transduction layer was to monitor proton transport across a lipid-bilayer. Additionally, ATR spectroscopy was used to monitor adsorption of pyridine capped nanoparticles on a silyl-propyl-thiol modified surface.