Thiophene and Derivatives for Use in Pyridazines and Thiapentalenes

This thesis introduces the idea of Band Theory and how it can be used to describe a solid-state materials ability to carry an electrical charge. Next, this thesis defines what makes a material a conductor, semiconductor, or insulator. Semiconductors are attracting interest in chemistry, as well as in the manufacturing of consumer electronics, because of their ability to carry a charge, without the risk of short-circuiting like traditional conductors.1,4 Organic semiconductors, which behave differently than traditional semiconductors, are of particular interest because they offer mechanical flexibility, lowcost, simplicity, and the ability to be manufactures at low temperatures.6 Nonorganic and organic semiconductors can be enhanced by a process called doping, which is further explained within this thesis. This thesis will focus on the unique properties and advantages that heterocycles, particularly thiophene and thiophene derivative complexes, and cyclopenta[c]thiophenes offer in the manufacturing of organic semiconductors. One area of thiophene research that has showed promise in leading to mass production of semiconductors derived from thiophene complexes is the use of thiophenes with electron withdrawing groups attached to the two and five position.26-27 In a recent publication in the Journal of Sulfur Chemistry a novel approach for developing thiophene derivatives was successfully investigated.27-31 This novel approach will be explained, and a successful synthetic route using 2,5-dimethylthiophene as a starting material will be provided. This thesis also explored using 2,5-dichlorothiophene and 2,5- dibromothiophene as novel starting materials in the previously successful route utilizing 2,5-dimethylthiophene. Unfortunately, however, this area of research was unsuccessful; therefore, research shifted towards the development of the lactone 1,3-Dimethyl-7,8- dihydro-4H-thieno[3,4-c]oxepin-6-one, which is one of the many products needed for the newly proposed synthetic route of manufacturing cyclopenta[c]thiophenes utilizing a much shorter route than previously attempted. Even more importantly, the synthetic route that was attempted is filled with mostly fundamental bedrock organic chemistry that can be pulled straight from a textbook. Research stopped at the lactone due to time constraints; however, this creates an opportunity for ongoing research for future undergraduate and graduate students

Climate scenarios for California

Possible future climate changes in California are investigated from a varied set of climate change model simulations. These simulations, conducted by three state-of-the-art global climate models, provide trajectories from three greenhouse gas (GHG) emission scenarios. These scenarios and the resulting climate simulations are not “predictions,” but rather are a limited sample from among the many plausible pathways that may affect California’s climate. Future GHG concentrations are uncertain because they depend on future social, political, and technological pathways, and thus the IPCC has produced four “families” of emission scenarios. To explore some of these uncertainties, emissions scenarios A2 (a medium-high emissions) and B1 (low emissions) were selected from the current IPCC Fourth climate assessment, which provides several recent model simulations driven by A2 and B1 emissions. The global climate model simulations addressed here were from PCM1, the Parallel Climate Model from the National Center for Atmospheric Research (NCAR) and U.S. Department of Energy (DOE) group, and CM2.1 from the National Oceanic and Atmospheric Administration (NOAA) Geophysical Fluids Dynamics Laboratory (GFDL). As part of the scenarios assessment, a statistical technique using properties of historical weather data was employed to correct model biases and “downscale” the global-model simulation of future climates to a finer level of detail, onto a grid of approximately 7 miles (12 kilometers), which is more suitable for impact studies at the scales needed by California decision makers. In current climate-change simulations, temperatures over California warm significantly during the twenty-first century, with temperature increases from approximately +3ºF (1.5ºC) in the lower emissions scenario (B1) within the less responsive model (PCM1) to +8ºF (4.5ºC) in the higher emissions scenario (A2) within the more responsive model (CM2.1). Three of the simulations (all except the low-emission scenario run of the low-response model) exhibit more warming in summer than in winter. In all of the simulations, most precipitation continues to occur in winter, with virtually all derived from North Pacific winter storms. Relatively little change in overall precipitation is projected. Climate warming has a profound influence in diminishing snow accumulations, because there is more rain and less snow, and earlier snowmelt. These snow losses increase as the warming increases, so that they are most severe under climate changes projected by the more sensitive model with the higher GHG emissions

Surgical techniques for evacuation of chronic subdural hematoma: a mini-review

Chronic subdural hematoma is one of the most common neurosurgical pathologies with over 160,000 cases in the United States and Europe each year. The current standard of care involves surgically evacuating the hematoma through a cranial opening, however, varied patient risk profiles, a significant recurrence rate, and increasing financial burden have sparked innovation in the field. This mini-review provides a brief overview of currently used evacuation techniques, including emerging adjuncts such as endoscopic assistance and middle meningeal artery embolization. This review synthesizes the body of available evidence on efficacy and risk profiles for each critical aspect of surgical technique in cSDH evacuation and provides insight into trends in the field and promising new technologies

Hypomethylating Agent Azacitidine Is Effective in Treating Brain Metastasis Triple-Negative Breast Cancer Through Regulation of DNA Methylation of Keratin 18 Gene.

Breast cancer patients presenting with symptomatic brain metastases have poor prognosis, and current chemotherapeutic agents are largely ineffective. In this study, we evaluated the hypomethylating agent azacitidine (AZA) for its potential as a novel therapeutic in preclinical models of brain metastasis of breast cancer. We used the parental triple-negative breast cancer MDA-MB-231 (231) cells and their brain colonizing counterpart (231Br) to ascertain phenotypic differences in response to AZA. We observed that 231Br cells have higher metastatic potential compared to 231 cells. With regard to therapeutic value, the AZA I