Thesis (Ph. D.)--University of Missouri-Columbia, 2001. / Typescript. Vita. Includes bibliographical references (leaves 123-128). Also available on the Internet.

Thesis (Ph. D.)--University of Washington, 2003. / Vita. Includes bibliographical references (leaves 154-161).

Thesis (Ph. D.)--Institute of Paper Chemistry, 1976. / Includes bibliographical references (p. 138-139).

published_or_final_version / Chemistry / Master / Master of Philosophy

This thesis is dedicated to the study of gain transients of discrete fiber Raman amplifiers and to the all-optical gain-clamping technique which is used to mitigate those transients. / First, we study the standing-wave and the traveling-wave gain-clamping techniques when applied to a single discrete fiber Raman amplifier in the context of WDM channel add and drop. We take into account the operational regime of the amplifier and the location of the surviving channel in the amplification band. We demonstrate that the gain-clamped amplifier has to be operated in a regime below the critical regime to ensure that gain-clamping will be in effect. The efficiency of gain-clamping also depends on the feedback level of the lasing signal and on the implementation. / Next, we investigate the dynamic behaviour of a single discrete fiber Raman amplifier fed by multi-channel packet traffic. Our study shows that the efficiency of the gain-clamping technique to reduce the gain transients is dependent upon the operational regime of the amplifier and the packet duration. However, we also demonstrate that gain-clamping is not required to control the gain transients as the gain variations of the unclamped amplifier are small enough to be neglected. / We then theoretically analyse the dynamic response of cascades of discrete fiber Raman amplifiers subject to WDM channel add and drop. We consider cascades of mixed unclamped and gain-clamped amplifiers, varying the number and the position of the gain-clamped amplifiers in the cascade and taking into account the location of the surviving channel and the operational regime of the amplifiers. Our results show that the location of the gain-clamped amplifiers in a mixed cascade affects the transient characteristics and that it is possible to control the transients within tolerable limits. / Finally, we investigate the gain transients that occur in hybrid amplifiers in the presence of channel add and drop. We demonstrate that the gain-clamping technique can be used to mitigate the gain transients in hybrid amplifiers and that the surviving channel location does not influence the transient characteristics, contrary to the case of single and cascaded fiber Raman amplifiers.

To truly realize and exploit the extremely powerful information given from surface-enhanced Raman scattering (SERS) spectroscopy, it is critical to develop an understanding of how to design highly sensitive and selective substrates, produce specific and label-free spectra of target analytes, and fabricate long-lasting and in-the-field ready platforms for trace detection applications. The study presented in this dissertation investigated the application of two- and three-dimensional substrates composed of highly-ordered metal nanostructures. These systems were designed to specifically detect target analytes that would enable the trace, label-free, and real-time detection of chemicals and biomolecules. Specifically, this work provides new insight into the required properties for maximizing electromagnetic and chemical Raman enhancement in three-dimensional porous alumina substrates by designing metal nanostructure shape, density, aggregated state, and most importantly aligning the substrate pore size with the excitation wavelength used for plasmonic enhancement leading to the ppb detection of vapor phase hazardous chemicals. A new micropatterned silver nanoparticle substrate fabricated via soft lithography with specific functionalization was developed, which allows the simultaneous analyte and background detection for trace concentrations of the target biomolecule, immunoglobulin G. Also, a novel functionalized SERS hot spot fabrication technique, which utilizes highly specific aptamers as both the mediator for electrostatic assembly of gold nanoframe dimers as well as the biorecognition element for the target, riboflavin, to properly locate the tethered biomolecule within the enhanced region for trace detection, was demonstrated. We suggest that the understanding of SERS phenomena that occur at the interface of nanostructures and target molecules combined with the active functionalization and organization of metal nanostructures and trace detection of analytes discussed in this study can provide important insight for addressing some of the challenges facing the field of SERS sensor design such as high sensitivity and selectivity, reliable and repeatable label-free identification of spectral peaks, and the well-controlled assembly of functional metal nanostructures. This research will have a direct impact on the future application of SERS sensors for the trace detection of target species in chemical, environmental, and biomedical fields through the development of specific design criteria and fabrication processes.

Electrochemical and spectroelectrochemical data was obtained for a silver electrode modified with oxazine 720. A quasi-reversible redox behaviour was observed for the modified electrode. Surface adsorption density, calculated from the measured electrochemical charge transfer, is higher than would be expected for a monolayer of flat-adsorbed ox¬azine 720. Surface-enhanced Raman scattering (SERS) data, in conjunction with results of a density functional theory (DFT) calculation, suggest that the molecule is adsorbed with its rings perpendicular to the electrode surface, consistent with the electrochemically estimated adsorption density. SERS was recorded in situ at different applied potentials. The SERS intensity remains relatively stable between -200 and -500 mV (versus AglAgCl Cl-sat), but decreases dramatically as the applied potential is made more negative than -500 mV. Ths is consistent with the onset of oxazine 720 reduction observed during cyclic voltammetry. The spectroelectrochemical data indicates that oxazine 720 remains adsorbed at the SERS-active sites even in its reduced form. Similar in situ SERS data was collected for rhodamine 6G and pyridine. Spectra in the Stokes and anti-Stokes regions were obtained at several applied potentials using two different laser excitation energies. Normalized ratios of the anti-Stokes to Stokes intensities were calculated for various vibrational bands of the three molecules. The measured ratios vary with changes in the excitation energy, the applied voltage and the energy of the vibrational mode being investigated. The ratios for oxazine 720 show a preferential enhancement of the Stokes scattering while the ratios for rhodamine 6G indicate an enhancement of the anti-Stokes scattering. For pyridine, the preferential enhancement changes between Stokes and anti-Stokes depending on the excitation wavelength used, the applied voltage and the vibrational band being examined. The main trends of the anti-Stokes to Stokes ratios can be satisfactorily explained using resonance models based on standard SERS theories. No evidence of a SERS-induced non-thermal population distribution among the vibrational states of the adsorbed molecules (vibrational optical pumping) was observed.

Thesis (M. Phil.)--University of Hong Kong, 2008. / Includes bibliographical references (leaf 76-77) Also available in print.

Thesis (Ph. D.)--University of Hong Kong, 2008. / Includes bibliographical references (leaves 140-147) Also available in print.

Dissertation (Ph.D.)--Auburn University, 2008. / Abstract. Vita. Includes bibliographic references.