Following the successes obtained with using lasers to cool and trap atoms, the same principles are being applied to molecules. Finding a molecule that is amenable to laser-cooling is not trivial. Aluminum monochloride (AlCl) has been proposed as a viable candidate for laser-cooling and trapping due to predicted large Franck-Condon factors and short excited state lifetime, allowing for efficient imparting of momentum from photons. To be efficiently slowed, multiple electrons must be cycled between the ground and excited states. This thesis presents a detailed derivation of the hamiltonian terms that must be understood for the X1Σ+ ↔ A1Π transition in AlCl. Initial absorption spectroscopy measurements are performed on the transition, yielding measurements of molecular constants. From these constants, the Franck-Condon factor for the cycling transition is determined to be 0.9988, which is ideal for cycling. The choice chemical compound that is ablated to produce AlCl for these experiments is not trivial. It is found that a mixing aluminum and potassium chloride with a molar ratio of 1:1.55 produces the optimal yield of AlCl. Additionally, a magneto-optical-trap apparatus is discussed and tested here on ytterbium. This test resulted in the successful trapping of neutral ytterbium, marking the creation of the first magneto-optical-trap at the University of California, Riverside. The vibrational and rotational properties of AlCl clearly make it a strong candidate for laser-cooling and trapping, however there are still many challenges that must be overcome before such experiments can be successful.

Lithium-ion batteries are prone to severe, mechanically-induced short circuit events that can lead to thermal runaway. Risk mitigating components commonly include primary protection structures and thermally-triggered failsafe mechanisms active at high temperatures, but features taking effect in the early stages of the joule heating regime are uncommon. To bridge this gap, the nature of the rate-limiting resistance dynamics is examined experimentally to clarify the progression of discharge events, and how to effectively address them upon short circuit initiation. Direct current internal resistance, external shorting, and nail penetration experiments are performed on LIR2450 format 120 mAh LiCoO2 / graphite coin cells to probe resistance and consequent heat generation dynamics over resolute temperature and time scales. The study reveals a low-resistance, electrically-controlled capacitive discharge event occurs immediately upon shorting which is subsequently throttled by increasing ionic resistances. An electrolyte resistance model is postulated and validated experimentally in terms of concentration, temperature, permittivity, and viscosity, to show how charge carriers polarize and reallocate within a cell when operated under stress.

The information attained identifies the need to exacerbate electrical resistance via mechanical response to suppress the powerful capacitive discharge feature immediately upon impact and suppress ion transport through electrolyte to halt continued discharge thereafter. Forming thick interpenetrating phase composite electrodes within brittle porous metal current collectors are shown to curb discharge power by preventing the formation of electrically conductive pathways between current collectors, as well as increasing the distance charge carriers must travel to liberate joule heat. Poisons capable of hindering ion transport to halt continued discharge are identified consulting the postulated electrolyte resistance model and tested via simultaneous injection and nail penetration testing of LIR2450 coin cells. Multifunctional design strategies are discussed for imparting greater degrees of integration within electronics by the lithium-ion batteries to reduce overall weight and volume upon further development of safe-cell technologies.

Louisiana’s coastal wetlands are continually threatened by anthropogenic disturbances and relative sea level rise (RSLR), factors which have caused widespread degradation and loss. This region has historically been a productive ecosystem with high carbon sequestration capacity that offers important ecological benefits to neighboring communities. The region’s “blue carbon” stocks and ecosystem services are now severely degrading with the coastal wetlands’ ongoing submergence resulting from RSLR. Accretion is the trapping of sediments and deposition of organic matter resulting in the buildup of the soil surface, and wetlands will submerge if the factors governing accretion do not sufficiently account for RSLR. Remote sensing offers data that can be applied to wetland ecology to assess ecological processes relating to RSLR and accretion at a regional scale. Imaging spectroscopy, specifically, enables sophisticated modeling techniques that may improve remote sensing applications in wetland regions. This project applies imaging spectroscopy to Louisiana’s coastal wetlands, developing applications for Airborne Visible/Infrared Imaging Spectrometer-Next Generation (AVIRIS-NG) data that include image processing algorithms, environmental parameter retrievals, and assessment of vegetation growth patterns and changes. The study’s first chapter addresses image processing methods for correcting bidirectional reflectance distribution function (BRDF) effects that inhibit image mosaicking. We developed a new empirical algorithm—the adaptive reflectance geometric correction—and applied it to imagery collected around the Atchafalaya and Wax Lake deltas to produce optimized surface reflectance mosaics. The second chapter sees the estimation and mapping of hydrologic suspended solids in from those AVIRIS-NG mosaics with an independently validated and transferable algorithm. The third chapter integrates the AVIRIS-NG data with simultaneously collected data from the Uninhabited Airborne Vehicle Synthetic Aperture Radar (UAVSAR) to estimate aboveground biomass (AGB) in Louisiana’s Wax Lake Delta (WLD). The fourth chapter uses the AVIRIS-NG data to map the WLD’s vegetation species distribution, then compares the results to published data from five years prior to assess extent changes for key vegetation types. It further employs the AGB dataset to examine key species’ growth patterns across elevational gradients and zones. The methods and results developed herein will enable future efforts to model accretion and predict wetland loss at regional scales.

Like impressionist art, a multitude of subtle and complex interactions determine the behavior of biological systems but a generalized perception loses significant resolution. This is true within the discipline of soft matter, where the chemical multiplicity of the involved components and their resulting physical consequences within lamellar mesophase assemblies are commonly ignored. Therefore, it is imperative to investigate the minute thermodynamic considerations between varied lipidic lamellar mesophases and biologically relevant dopants (like surface-active agents and proteinaceous content) and their resulting physical behaviors. By using various microscopy techniques and x-ray diffraction measurements, lamellar mesophase behavior can be monitored upon the addition (in real-time or post-doping event) of these surface-active and biological substances, and the resulting analyses elucidate the microscopic information others have commonly missed. Such studies can not only enlighten scientists with a higher-level understanding of amphiphilic systems but also lead to the development of unique structural assemblies for various applications.In a larger perspective, this dissertation aims to assemble structurally-diverse lamellar mesophases and expose them to surface-active molecules (also written as surfactant or detergent) and proteinaceous content in varying methods to connect macroscopic and microscopic information. Employing various methodologies like directed aqueous hydration, water vapor hydration, and electroformation, both multilamellar and unilamellar mesophases populated by common lipids and fluorescently-tagged phospholipids were assembled. Such assemblies were then perturbed by symmetric (or internalized) or asymmetric (or external) doping of the focal substances. The consequential physical and structural properties of the mixed-component systems were then investigated to understand the impacts of chemical multiplicity. This dissertation only begins to expound the subtleties of chemistry within lamellar mesophases and question the value of generalized models of membrane behavior. Through these efforts, a new, adaptable, and inclusive intellectual framework of membranes can be developed and considered.

Protein design is a challenging endeavor that attempts to harness the power of nature and engineer it to a particular task. The use of a protein enzyme over a catalyst has both economical and environmental advantages. Discussed here are the initial steps and groundwork in redesigning a metallo-enzyme with the purpose of catalyzing an intramolecular hydroarylation of a carbon-carbon triple bond in the formation of a coumarin. The initial structure scaffold was chosen by comparing structures in the Protein Database. The chosen starting protein, pdb code 1UDV, will be investigated to determine if mutations are necessary to ensure binding of palladium which is the catalyst for the coumarin formation, and folding of the protein. Palladium will be inserted into the active site of the protein and the protein stability will be compared to the corresponding native structure using ΔΔG as a metric. Experimental results will confirm the binding of palladium to the protein and the catalytic efficiency of the enzyme.

I. An environmentally responsible, mild method for the synthesis of functionalized 1,3-butadienes is presented. It utilizes allenic esters of varying substitution patterns, as well as a wide range of boron-based nucleophiles under palladium catalysis, generating sp−sp2, sp2−sp2, and sp2−sp3 bonds. Functional group tolerance measured via robustness screening, along with room temperature and aqueous reaction conditions highlight the methodology’s breadth and potential utility in synthesis.

II. A mild method for the synthesis of highly functionalized [3]–[6]dendralenes is reported, representing a general strategy to diversely substituted higher homologues of the dendralenes. The methodology utilizes allenoates bearing various substitution patterns, along with a wide range of boron and alkenyl nucleophiles that couple under palladium catalysis leading to sp-, sp2-, and sp3-substituted arrays. Regioselective transformations of the newly formed unsymmetrical dendralene derivatives are demonstrated. The use of micellar catalysis, where water is the global reaction medium, and room temperature reaction conditions, highlights the green nature of this technology.

III. A copper-catalyzed oxidative cleavage of electron-rich olefins into their corresponding carbonyl derivatives is described as an alternative to ozonolysis. The scope includes various precursors to aryl ketone derivatives, as well as oxidations of enol ethers bearing atypical alkyl and dialkyl substitution, the first of their kind among such metal catalyzed alkene cleavage reactions. The use of an inexpensive copper salt, room temperature conditions, an aerobic atmosphere, and water as the global reaction medium highlight the green features of this new method. Associated mechanistic investigations are also presented.

Wetland conservation in California faces a multitude of challenges, this is especially true in the Suisun Marsh, one of the largest tidal marshes on the west coast of North America. The marsh has historically supported large numbers of non-breeding waterfowl but the capacity of the marsh to continue to do so remains uncertain, due to drought, habitat loss, future sea level rise, and conflicting conservation needs for many species of fish and wildlife. A guiding principle for the conservation of non-breeding waterfowl is to manage for food resources, under the working hypothesis that food resources may be limiting in winter, and the decline in the abundance of waterfowl within Suisun Marsh may be due to reduced food production or availability. Non-breeding waterfowl depend on plant seeds as a primary source of food throughout winter. However, we lack information concerning what food resources may be in limited supply because there has never been a direct assessment of total seed abundance in Suisun Marsh. Efforts to recover threatened and endangered species within the marsh – through the conversion of managed wetlands to tidal marsh ¬– could further impact the carrying capacity of the marsh for waterfowl by reducing the abundance or availability of waterfowl food resources. To evaluate these concerns, I undertook a multifaceted study to evaluate the abundance, production, and depletion of food resources for wintering waterfowl in both tidal and managed wetlands. I found that seed abundance in both wetland types was much lower than previously predicted. Seed abundance in Fall was similar in tidal (172.9 kg/ha) and managed (163.8 kg/ha) wetlands, but there was considerable spatial variation. The species composition of seeds differed substantially according to wetland type; over 75% of aggregate seed mass in managed wetlands was comprised of food species that waterfowl prefer, while a non-preferred food, Schoenoplecutus sp., was the dominant seed in tidal marshes. The occurrence of several plant species within managed wetlands that produce waterfowl-preferred seeds was correlated with salinity, wetland management intensity, and disking. The best predictor of total seed abundance in managed wetlands was habitat zone, which is defined by shared physical factors known to impact vegetation growth and production in different regions in the marsh. These regional differences in seed abundance have important implications for tidal restoration efforts, as the loss of seasonal wetland acreage within more productive regions could have a disproportionate impact on total food availability. To evaluate seed dynamics at a finer scale, I used small-scale sampling sites and foraging exclosures in a managed wetland within the marsh and stratified these sampling locations according to high and low waterfowl use areas. Contrary to expectations of a “table-is-set” hypothesis, I found seed that abundance increased over three weeks post-flooding, and over seven to ten weeks in foraging exclosures. Observed declines in the abundance of seeds were substantially greater than rates of decomposition, suggesting seed removal by waterfowl was a major source of seed depletion. However, the amount of seed consumption that could be attributed to waterfowl was spatially variable and correlated with waterfowl locations – high use areas exhibited significantly higher rates of seed loss. Hydrochory (movement of seed due to water flow) was likely responsible for the changes in seed abundance observed for several weeks after the wetlands were flooded, as abundances within foraging exclosures nearly tripled over ten weeks in high waterfowl use areas. These results suggest that seed removal by waterfowl and hydrochory can impact our ability to accurately estimate peak seed abundance. Without accounting for seed removal by waterfowl, and hydrochory, bioenergetic models may produce inaccurate estimates of habitat carrying capacity. My results provide new insight and greater refinement of estimates of seed abundance to more accurately determine the carrying capacity of the Suisun Marsh for wintering waterfowl, and to assess the potential impacts of future changes.

Advances in colloidal nanocrystal chemistries have enabled more complex fabrication of nanostructured materials. Colloidal nanocrystals can be easily deposited from solution and used in a variety of optoelectronic applications such as photodetectors and photovoltaics. Colloidal nanocrystals deposited as films act as the light absorbing layer. These films can be used as-is or be sintered into polycrystalline films. Introducing dopant species as a surface species on semiconducting nanocrystals allows controlled doping profiles in sintered films where the dopant preferentially segregates at the grain boundaries. Chloride in CdTe films is one well-known example of this phenomena. The focus of this work is designing chloride-capped CdTe nanocrystal building blocks and sintering these into polycrystalline films with controlled grain structure and therefore doping profiles. Applications investigated for these films are solar cells and photodetectors.