Applications of Photoinduced Electron Transfer Chemistry: Photoremovable Protecting Groups and Carbon Dioxide Conversion

Traditional organic chemistry has long been dominated by ground state thermal reactions. The alternative to this is excited state chemistry, which uses light to drive chemical transformations. There is considerable interest in using this clean renewable energy source due to concerns surrounding the combustion byproducts associated with the consumption of fossil fuels. The work presented in this text will focus on the use of light (both ultraviolet and visible) for the following quantitative chemical transformations: (1) the release of compounds containing carboxylic acid and alcohol functional groups and (2) the conversion of carbon dioxide into other useable chemicals. Chapters 1-3 will introduce and explore the use of photoremovable protecting groups (PPGs) for the spatiotemporal control of molecular concentrations. Two new PPGs are discussed, the 2,2,2-tribromoethoxy group for the protection of carboxylic acids and the 9-phenyl-9-tritylone group for the protection of alcohols. Fundamental interest in the factors that affect C–X bond breaking has driven the work presented in this text for the release of carboxylic acid substrates. Product analysis from the UV photolysis of 2,2,2-tribromoethyl-(2′-phenylacetate) in various solvents results in the formation of H–atom abstraction products as well as the release of phenylacetic acid. The deprotection of alcohols is realized through the use of UV or visible light photolysis of 9-phenyl-9-tritylone ethers. Central to this study is the use of photoinduced electron transfer chemistry for the generation of ion diradicals capable of undergoing bond-breaking chemistry leading to the release of the alcohol substrates. Chapters 4 and 5 will explore the use of N-heterocyclic carbenes (NHCs) as a catalyst for the photochemical reduction of carbon dioxide. Previous experiments have demonstrated that NHCs can add to CO2 to form stable zwitterionic species known as N-heterocylic-2-carboxylates (NHC–CO2). Work presented in this text illustrate that the stability of these species is highly dependent on solvent polarity, consistent with a lengthening of the imidazolium to carbon dioxide bond (CNHC–CCO2). Furthermore, these adducts interact with excited state electron donors resulting in the generation of ion diradicals capable of converting carbon dioxide into formic acid.

Plant Migrations Impact on Potential Vegetation and Carbon Redistribution in Northern North America from Climate Change

Forests have a prominent role in carbon storage and sequestration. Anthropogenic forcing has the potential to accelerate climate change and alter the distribution of forests. How forests redistribute spatially and temporally in response to climate change can alter their carbon sequestration potential. The driving question for this research was: How does plant migration from climate change impact vegetation distribution and carbon sequestration potential over continental scales? Large-scale simulation of the equilibrium response of vegetation and carbon from future climate change has shown relatively modest net gains in sequestration potential, but studies of the transient response has been limited to the sub-continent or landscape scale. The transient response depends on fine scale processes such as competition, disturbance, landscape characteristics, dispersal, and other factors, which makes it computational prohibitive at large domain sizes. To address this, this research used an advanced mechanistic model (Ecosystem Demography Model, ED) that is individually based, but pseudo-spatial, that reduces computational intensity while maintaining the fine scale processes that drive the transient response. First, the model was validated against remote sensing data for current plant functional type distribution in northern North America with a current climatology, and then a future climatology was used to predict the potential equilibrium redistribution of vegetation and carbon from future climate change. Next, to enable transient calculations, a method was developed to simulate the spatially explicit process of dispersal in pseudo-spatial modeling frameworks. Finally, the new dispersal sub-model was implemented in the mechanistic ecosystem model, and a model experimental design was designed and completed to estimate the transient response of vegetation and carbon to climate change. The potential equilibrium forest response to future climate change was found to be large, with large gross changes in distribution of plant functional types and comparatively smaller changes in net carbon sequestration potential for the region. However, the transient response was found to be on the order of centuries, and to depend strongly on disturbance rates and dispersal distances. Future work should explore the impact of species-specific disturbance and dispersal rates, landscape fragmentation, and other processes that influence migration rates and have been simulated at the sub-continent scale, but now at continental scales, and explore a range of alternative future climate scenarios as they continue to be developed.