Shpol'skii spectroscopy; fluorescence spectroscopy; luminescence; synchronous fluorescence spectroscopy; excitation emission matrix; polycyclic aromatic hydrocarbons; benzo[a]pyrene; dibenzo[a, l]pyrene; chemometrics; multivariate calibration; parafac; analytical instrumentation; fiber optic probe
This dissertation presents experimental and instrumentation developments that take full advantage of the multidimensional nature of line narrowing spectroscopy at liquid nitrogen (77 K) and liquid helium (4.2 K) temperatures. The inconvenience of sample freezing procedures is eliminated with the aid of cryogenic fiber optic probes. Rapid collection of multidimensional data formats such as wavelength time matrices, excitation emission matrices, time-resolved excitation emission matrices and time resolved excitation emission cubes is made possible with the combination of a pulsed tunable dye laser, a spectrograph and an intensifier-charged coupled device. These data formats provide unique opportunities for processing vibrational luminescence data with second order multivariate calibration algorithms. The use of cryogenic fiber optic probes is extended to commercial instrumentation. An attractive feature of spectrofluorimeters with excitation and emission monochromators is the possibility to record synchronous spectra. The advantages of this approach, which include narrowing of spectral bandwidth and simplification of emission spectra, were demonstrated with the direct analysis of highly toxic dibenzopyrene isomers. The same is true for the collection of steady-state fluorescence excitation-emission matrices. These approaches provide a general solution to unpredictable spectral interference, a ubiquitous problem for the analysis of organic pollutants in environmental samples of unknown composition. Since commercial spectrofluorimeters are readily available in most academic institutions, industrial settings and research institutes, the developments presented here should facilitate the widespread application of line-narrowing spectroscopic techniques to the direct determination, no chromatographic separation, of highly toxic compounds in complex environmental matrixes of unknown composition.
Doctor of Philosophy (Ph.D.)
College of Sciences
Length of Campus-only Access
Doctoral Dissertation (Open Access)
Dissertations, Academic -- Sciences; Sciences -- Dissertations, Academic
Moore, Anthony, "Improvements on Instrumentation to Explore the Multidimensionality of Luminescence Spectroscopy" (2015). Electronic Theses and Dissertations. 699.