▼ This research project examined the synthesis of tris-heteroleptic ruthenium polypyridyl solar dyes that incorporate the OS or 2-(Methylthio)benzoic acid ligand. The literature is lacking in robust and facile tris-heteroleptic ruthenium polpyridine, therefore many synthetic reaction conditions and product isolation techniques were explored and optimized. Furthermore, a ruthenium complex with terminal thiol linkers was synthesized and adsorbed onto the surface of a nanocrystal quantum dot. The interfacial electron transfer of this coupled system was explored via steady state photoluminescence and absorbance spectroscopy experiments. All projects were built upon the idea of exploring novel solar light capturing molecular systems for applications in photovoltaic devices. Advisors/Committee Members: Rack, Jeffrey J.

▼ A molecular optoelectronic transducer based on [Ru(bpy)2(pySO)]2+ was developed and is capable of utilizing light as an input to trigger two-color reversible photochromism in the molecule which can be read electrochemically. The devices are constructed and operated in ambient environmental conditions making them simple to create and use. Advisors/Committee Members: Rack, Jeffre.

▼ Synthesis, characterization, and photochemistry of [Ru(bpy)(biq)PYSO]2+ (where bpy=2,2’-bipyridine, biq=2,2’-biquinoline, and PYSO=2-[(propan-2-sulfnyl)methyl]pyridine). This complex was found to have selective photoisomerization between the S- and O- bonded states. In methanol, the complex was found to revert from the O-bonded state to the S-bonded state by irradiation, while in propylene carbonate the complex did not revert. Advisors/Committee Members: Rack, Jeffrey J.

▼ The human health threat from marine algal toxins is increasing with expanding human population, increased seaside populations, and the concomitant increase in aquaculture operations and demand for seafood. As humans increase demand for seafood, they create waste and activity that may increase the likelihood of harmful algal blooms (HABs) and phycotoxin production by some of these blooms, notably the production of the causative toxins for ciguatera fish poisoning (CFP), paralytic shellfish poisoning (PSP), amnesic shellfish poisoning (ASP), neurotoxic shellfish poisoning (NSP) and diarrhretic shellfish poisoning (DSP). The mainstay for regulatory detection of these toxins has long been the mouse bioassay (MBA), with intraperitoneal (i.p.) injection of suspect extracts and subsequent monitoring for symptoms and time of death. The general sentiment in the research community is that there is a need to eliminate, or at least reduce, the use of the mouse bioassay in testing for algal toxins, due to technical limitations of the procedure and its ethical drawbacks. A number of functional and analytical methods have been developed to this end. This paper reviews the rise of harmful algal blooms, toxin syndromes, historical use of and the subsequent need to find an alternative to the mouse bioassay in detection of algal toxins and obstacles to the development of these alternative methods. The role of large importing countries in this process is then considered; particular attention is paid to the United States, as there is little discussion of their efforts in the literature. Advisors/Committee Members: Chen, Hao.

▼ Obesity is characterized by a constant state of low-grade inflammation accompanied by elevated levels of macrophages in the adipose tissue itself. This phenomenon appears to be dependent on the anatomical location of the adipose depot. Previously our laboratory has demonstrated that growth hormone (GH) has the ability to decrease fat mass in a depot specific manner; however, its role in adipose tissue inflammation or macrophage infiltration has not been evaluated. Using a diet-induced obese mouse model, the purpose of this study was to determine the effects of GH or IGF-1 administration on gene expression of macrophage and inflammation markers in different depots of adipose tissue. Eighty-four C57BL/6J mice were placed on a high fat diet for 16 weeks to induce obesity. Mice were then separated into 4 groups (n=7), based on experimental treatment and length of treatment. The four experimental treatments included a control, a GH treated, an IGF-1 treated, and a diet reversal group. The control group and the diet reversal group received twice daily injections of phosphate buffered saline (PBS), and the experimental groups received twice daily injections of either GH (5.0 μg/g body weight) or IGF-1 (2.5 μg/g body weight). Groups were treated for 2, 7, or 21 days, and at the end of each time period, the mice were sacrificed and dissected. The fat pads collected and analyzed include subcutaneous, retroperitoneal, mesenteric, and epididymal depots. There was no difference in depot mass among the experimental groups following 2 days of treatment. After 7 days of treatment, significant differences were present among the diet reversal group and either the control or IGF-1 treated groups within the retroperitoneal and brown adipose depots. Finally, 21 days of treatment resulted in significantly lower fat masses in the GH and diet reversal treatments as compared to the control and IGF-1 treated group. Expression levels of the macrophage F4/80 were determined by real-time PCR. Results for relative F4/80 expression among the subcutaneous inguinal and epididymal depots showed depot specific differences, agreeing with previous studies. However, these results showed no clear trend of how macrophage infiltration alters in response to GH and IGF-1 treatment. Advisors/Committee Members: Berryman, Darlene.

▼ There were over 207,000 new cases of invasive breast cancer and nearly 40,000 deaths from the disease in the U.S. in 2010. It is, therefore, critical to develop a better understanding of the disease process. Invasive cancer is marked by the loss of integrity of the basement membrane of a tissue, a specialized form of extracellular matrix (ECM) that normally separates a tissue from its surroundings; however, a complex, dynamic interaction involving many overlapping signaling pathways exists between breast tissue and its neighboring ECM. Invasion is initiated when the tumor cells have increased adhesion to the ECM, which is mainly modulated by interactions with the integrin family of adhesion proteins on the surface of the tumor cells. Each integrin heterodimer has a different adhesive affinity for each of the ECM proteins, namely fibronectin, vitronectin, collagen I, and collagen IV. This project examined the relative expression of integrins following exposure to ionizing radiation, which is commonly used for cancer therapy. Ionizing radiation forms free radicals and reactive oxygen species, which then cause damage within the cell. Although the exact mechanism is unknown, the hypothesis of this study was that exposure to high dose ionizing radiation would change the expression of the integrins and change integrin-mediated adhesion to the ECM proteins. Results showed that in the MDA-MB-231 cell line, ionizing radiation induces significant changes in both integrin expression and integrin-mediated adhesion to fibronectin, laminin, and collagens I and IV. After gathering further evidence from this and other cell lines, this information could potentially be used to optimize treatment for patients with invasive cancers. Advisors/Committee Members: Wu, Shiyong.