Thesis (Ph. D.)--University of Texas at Austin, 2004. / Supervisor: Brent L. Iverson. Vita. Includes bibliographical references. Also available from UMI.

Thesis (MTech (Chemistry))--Cape Peninsula University of Technology, 2008. / Includes bibliographical references (leaves 77-79). Also available online.

Porphyrins offer a very synthetically flexible template which can be modified in numerous ways to synthesize molecules with very useful properties applicable in areas such as non-linear optical properties, photodynamic therapy, dye-sensitized solar cells, chemical sensors and organic electronic devices. β-Substituted π-extended porphyrins offer unique capabilities in tuning the properties of the molecule towards practical applications. Increased π-conjugation allows the HOMO-LUMO gap to decrease and hence to redshift the absorption into the near-IR region. β-Fused benzoporphyrins offer additional benefits in which the benzene ring itself can be further modified using electron donating substituents and electron donating substituents to electronically tune these porphyrins for various uses. The goal of the research pursued in this dissertation was to develop new methods for the development of β-Substituted π-extended porphyrins and to study their optical and electronic properties. To accomplish this goal, we developed new method to synthesize A2B2 type tetrabenzoporphyrins and we studied the electron transfer in such systems. We also studied the effectiveness of such systems in dye sensitized solar cells. A new method to synthesize functionalized naphthalene fused porphyrins was also developed and we were also able to use this method to synthesize a push-pull naphthalene fused porphyrin.

Fireworks on Independence Day have been identified as a nationwide but short-term source of particulate matter in the U.S. No study has specifically examined their impacts on ambient polycyclic aromatic hydrocarbons (PAHs). Based on data between 1990 and 2019 in the Air Quality System, we identified 76 unique events that had PAH measurements on both July 4th days and control days (within 15 days before and after July 4th). We compared concentrations and diagnostic ratios of 16 priority PAHs between event and control days using Wilcoxon signed-rank tests and multivariable regressions. A local PAH monitoring campaign was conducted at eight sites in Memphis, Tennessee, to obtain a close observation of PAH changes. The national geometric mean (GM) concentrations of summed 16 PAHs (ΣPAHs) were similar between event and control days (48.1 ng/m3 vs. 52.8 ng/m3, p = 0.98). About a quarter of events had elevated PAH concentrations compared with control days. Higher diagnostic ratios were found on event days, suggesting more contributions from fireworks sources. PAHs on July 4th were unlikely to cause acute or chronic health effects. While the local monitoring showed a 15% increase of ΣPAHs on July 4th, the difference was not significant (p = 0.62). Elevated PAH concentrations occurred at sites near fireworks sources and without major traffics, but did not occur at those in remote areas or near major interstate highways. In conclusion, this study finds that Independence Day fireworks have negligible impacts on atmospheric PAHs at the national level, and are unlikely to pose significant health risks. The firework effect is localized within a limited geographic scale, suggesting potential needs for local monitoring and control programs.

No description available.

This study explores the potential of the naphthalene sublimation technique to be used to analyze the manner in which surfaces regress, specifically focusing on the effect that skin friction has on regression and vice versa. For this experimentation, a flat steel plate installed with three skin friction sensors was coated with naphthalene via a mechanized sprayer and was installed in the wall of the Ahmic Aerospace Turbulent Boundary Layer Research supersonic wind tunnel. The plate and sensor configuration was subjected to three subsequent tunnel runs at Mach 2.31. This process was repeated at plenum pressures of 0.35 MPa and 0.69 MPa, which correspond to Reynolds Numbers of 1.4x10^7/m and 2.8x10^7/m. Between the first and final run, a -4.7% and -3.7% percent change in the coefficient of friction was seen at the 0.35 MPa and 0.69 MPa plenum conditions, respectively. Images of the plate taken before and after each run qualitatively indicate continual naphthalene regression with each subsequent tunnel run. This decrease in the coefficient of friction was attributed in part to the regression of the naphthalene coating, indicating that this method has the potential to be used to study the interaction between skin friction and regressing surfaces. Additionally, this study showed that it is certainly possible to measure skin friction with sensors where both the head of the movable sensor element and the surrounding wall is coated with sprayed naphthalene. / Master of Science / This study explores the potential of using an experimental method to better understand how surfaces recede when subjected to moving air. A chemical called naphthalene was used because naphthalene naturally recedes very easily, unlike many other materials which a researcher would want to study the receding behavior of, making it an ideal choice for this study. Sensors made to detect the amount of force generated by flowing air over a surface were installed into a flat metal plate. The plate was coated with naphthalene and installed into the wall of a wind tunnel, which generates airflow over the plate to simulate flight conditions. Three separate and sequential airflow runs over the plate were conducted. This process was repeated under two different air conditions. In both conditions, a decrease in the amount of force due to the air moving over the plate was detected as subsequent runs were conducted and the naphthalene receded. This indicates the method has the potential to be used to study how other surfaces recede when subjected to moving air.

Ten strategically placed push-pull wells were installed to determine in-situ degradation rates at a creosote contaminated site and to assess the contribution of hybrid poplar trees to polynuclear aromatic hydrocarbon (PAH) remediation. Well positioning enabled comparison between contaminated and non-contaminated locations, as well as comparisons between locations with and without trees. Comparison of areas with and without trees enabled an improved understanding of the role that the phytoremediation system has on the overall degradation of PAHs at the site. Bromide, a conservative, non-reactive tracer, was injected in solution along with dissolved oxygen. Twelve push-pull tests (PPTs) were performed, of which three did not include naphthalene in the injection solution, so that the developed method could be evaluated, tested, and yield an initial set of rates to make seasonal and spatial varying in-situ comparisons. Method comparison used for rate analysis found the highest confidence in the method of Snodgrass and Kitanidis (1998) for zero order rates and the method of Haggerty et al. (1998) for first order rates. The largest zero and first order rates, 2.43 mgnaphthalene/L-hr and 1.25 1/hr, respectively, occurred at treed regions in June. Zero and first order winter rates at treed regions were greater by a factor of at least 2.5 when compared to non-treed regions. Degradation rates at treed regions were found to steadily increase by over four times from winter to summer. Results validate that decay variations attributed to phytoremediation can be detected with the push-pull method. PPTs performed at the Oneida site verified observed trends determined from six years of monitoring data, microbial characterization, and microcosm studies. / Master of Science

Direct transpiration rates and plant uptake of naphthalene by a hybrid poplar phytoremediation system located in Oneida, Tennessee were determined using hydrologic and groundwater concentration data. Water table recession analysis techniques were employed to determine direct transpiration rates from the saturated zone of the shallow, unconfined aquifer underlying the site. Direct transpiration rates varied over the growing season (late March to mid-October), with a maximum and mean daily direct transpiration of 0.0100 and 0.0048 feet/day, respectively. During 2004, the maximum direct transpiration rate was observed in May, and rates declined starting in June due to an associated decline in the water table. A technique was developed to estimate the volumetric transpiration rate of each tree based on the breast-height diameters and seasonally variable direct transpiration rates. During peak transpiration, the larger trees at the study site were estimated to directly transpire 4 to 13 gallons per day per tree. Plant uptake rates of naphthalene were estimated by superimposing spatial data (volumetric transpiration rates and naphthalene concentration in groundwater). The mass loss rate of naphthalene from the aquifer as a result of plant uptake during July 2004 was 335 mg/day which only represents 0.117% of the aqueous mass plume. Monthly groundwater profiles showed a decrease of the saturated thickness beneath the system of hybrid poplars between the dormant and active season. This study suggests direct transpiration rates and plant uptake of naphthalene are dependent on variables including climatic parameters, magnitude of the saturated thickness, and the concentration of naphthalene in groundwater. / Master of Science

Understanding how atoms interact is a fundamental aspect of chemistry, biology and materials science. There have been great advances in the knowledge of covalent and ionic bonding over the past twenty years but one of the major challenges for chemistry is to develop full understanding of weak interatomic/intermolecular forces. This thesis describes fundamental studies that develop the basic understanding of weak interactions between heavier polarisable elements. The chosen methodology is to constrain heavy atoms using a rigid naphthalene backbone. When substituents larger than hydrogen, are positioned at close proximity at the peri-positions of a naphthalene molecule they experience steric strain; the extent of which is dictated by intramolecular interactions. These interactions can be repulsive due to steric hindrance or attractive due to weak or strong bonding. In efforts to understand the factors which influence distortion in sterically crowded naphthalenes and study possible weak intramolecular interactions between peri-atoms, investigations focussed on previously unknown mixed 1,8-disubstituted naphthalene systems. Mixed phosphorus-chalcogenide species were initially studied; three mixed phosphine compounds of the type Nap[ER][PPh2] were prepared along with their chalcogenides and a series of metal complexes. The study of interactions between heavy atoms was progressed by investigations into a series of mixed chalcogenide compounds of the type Nap[EPh][E’Ph] (E = S, Se, Te). Subsequent reaction of the chalcogenide systems with the di-halogens, dibromine and diiodine, afforded a mixture of charge transfer and insertion adducts displaying an array of different geometries around the chalcogen atom. From molecular structural studies, a collection of intramolecular peri-interactions were found, extending from no interaction due to repulsive effects, weak attractive 3c-4e type interactions and one example containing a strong covalent peri-bond. Further weak intramolecular interactions observed include CH-π and E•••E’ type interactions plus π-π stacking between adjacent phenyl rings. It was discovered that the bulk of the peri-atoms is influential on the distance between them, but this is not the only factor determining the naphthalene geometry. Inter- and intramolecular interactions can also have an impact and furthermore the number, size and electronic properties of substituents attached to the peri-atoms can determine molecular distortion.

Biotransformation and biodegradation rate constants were determined for naphthalene, lindane, and phenol in water samples from three different sources. Rate constants produced from monitoring disappearance of the parent chemical (biotransformation) were compared to those obtained from mineralization of the chemical (ultimate biodegradation) by ¹⁴CO₂ evolution as well as acidification of the residual ¹⁴C-labeled compound (primary biodegradation). Rate constants were statistically different for the three chemicals. The water source affected the rate constants. When biomass measurements of the waters were considered and second-order rate constants were derived, there was no statistical evidence that this parameter gave a reliable rate constant statistic that could be useful in predicting the fate of any of naphthalene, lindane, and phenol in these waters.