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Solid composite propellants are used widely in the aerospace industry due to their desirable mechanical and performance characteristics, including their simplicity, high initial thrust and volume specific impulse. Knowledge of the mechanical properties is needed due to the stresses encountered by a solid rocket motor propellant during thermal cycling while in storage, during rapid ignition transients, and dynamic launch and flight phases. These stresses could damage the propellant grain, leading to an unplanned increase in burning surface area and subsequent catastrophic disassembly. Tensile testing with the conventionally used JANNAF Type C “dogbones” can be material-expensive and time-consuming, particularly if determining the propellant’s response to different strain rates and temperatures. The rapid development of propellants with novel ingredients or formulations is especially hampered by material and time constraints. Using small-scale tests, typically using “micro-dogbone” samples, tensile properties can be characterized with a strong correlation to standard JANNAF Type C samples and only use a fraction of the normally required material. The correlation between the two sample sizes can be demonstrated for a wide range of propellant formulations and environmental conditions, such as extreme temperatures used in test conditions. Propellant characterization can also be relatively slow due to the data analysis time required to ensure that samples did not contain voids or other defects. Using 2-D Digital Image Correlation (DIC) technology, a baseline behavior can be established for propellant samples that contain voids to help screen data faster, leading to a faster characterization time for propellants and reduced cost of the program. Overall, the DIC system is a promising method of non-contact strain measurement that can help characterize and screen solid composite propellants, while micro-dogbones show great promise in being able to reduce the time and cost required for characterizing novel solid propellants.

Despite the vast array of enzymatic activities available to metabolic engineers, many biosyntheses are impractical due to the production of toxic intermediates and off-target products, poor kinetic performance, and cofactor imbalances. We aim to address these roadblocks by organizing biosynthetic pathways inside custom organelles within cells. Bacterial microcompartments, porous proteinaceous organelles found in Salmonella and other bacteria, provide an ideal starting point for the engineering of subcellular bacterial organelles. To this end, we develop tools for the control of microcompartment formation, enzyme encapsulation, and small molecule transport across the compartment shell. Of particular interest is the encapsulation of enzymatic pathways that synthesize fuels, pharmaceuticals, and other products which are challenging to produce in the cytosol.In order to tune the catalytic activity of the microcompartments, we orchestrate microcompartment formation at the transcriptional level to control when the organelles are formed and how much heterologous cargo is encapsulated. We also create new localization signals that allow fine control over the loading of multiple enzymes to the compartments simultaneously. We are investigating the role of pore residues in small molecule transport across the shells of virus-like particles and the microcompartments themselves. Lastly, we use computational tools to model microcompartment function in order to facilitate the selection of pathways for encapsulation. Together, these tools allow the creation of custom biosynthetic organelles with user-defined enzyme content and transport properties, enabling the use of biosynthetic pathways which otherwise fail to function.

Amsinckiinae is a diverse and ecologically important subtribe of annual herbaceous or perennial suffrutescent taxa with centers of distribution in western North America and southern South America. Taxa in the subtribe occur in all major ecosystems in California and more broadly in western North America, from the deserts of Baja California in the south where Johnstonella and Pectocarya are common, north to the ephemeral wetland ecosystems of the California Floristic Province where a majority of Plagiobothrys sect. Allocarya taxa occur, and east to the Basin and Range Province of western North America, where Cryptantha sensu stricto (s.s.) and Oreocarya are well represented. The subtribe minimally includes 9 genera: Amsinckia, Cryptantha s.s., Eremocarya, Greeneocharis, Harpagonella, Johnstonella, Oreocarya, Pectocarya, and Plagiobothrys; overall minimum-rank taxonomic diversity in the subtribe is ca. 330-342 taxa, with ca. 245--257 taxa occurring in North America, 86 in South America, and 4 in Australia.Despite their prevalence on the landscape and a history of active botanical research for well over a century, considerable research needs remain in Amsinckiinae, especially in one of the two largest genera, Plagiobothrys. Taxonomic concepts in the genus have fluctuated through the 1900s and to date no critical reappraisal of the accepted taxonomy in Plagiobothrys has been performed using modern molecular phylogenetic methods; evolutionary patterns have been neglected as well. This dissertation focuses on evaluating patterns of diversification in the subtribe with an emphasis on Plagiobothrys. The objectives of the dissertation were three-fold: (1) to generate a hypothesis of evolutionary relationships among target Amsinckiinae and if necessary, revise classification in Plagiobothrys so that only monophyletic groups are recognized taxonomically; (2) to evaluate patterns and processes involved with the American Amphitropical Disjunction (AAD) biogeographic pattern in Amsinckiinae; and (3) to examine patterns of diversification within Plagiobothrys with respect to habitat affinity.Chapter 1 examines evolutionary relationships and classification in Amsinckiinae with a focus on Plagiobothrys. Molecular sequence data were used to estimate a hypothesis of evolutionary relationships. Plagiobothrys was found to be non-monophyletic, with some members more closely related to Amsinckia or Cryptantha s.l. than to Plagiobothrys in the strict sense. Two new genera were established and one older genus name was recommended for usage so that only monophyletic groups are recognized taxonomically. Morphology was examined in light of the new estimate of phylogenetic relationships. These analyses demonstrate that the trait traditionally used to delimit the large genus Cryptantha s.l., a grooved adaxial surface, is a shared ancestral feature and is in conflict with the evolutionary history inferred in this study.Chapter 2 focuses on AAD, an interesting but understudied New World biogeographic pattern wherein close relatives grow in temperate North America and temperate South America, but are lacking in the intervening New World tropics. Molecular sequence data and fossil and secondary calibrations were used to generate a time-calibrated phylogram on which biogeographic patterns could be assessed using maximum likelihood and Bayesian inference approaches. This study shows that sampled members of Amsinckiinae have moved between North America and South America over 10 times, and always from north to south. Timing of inferred dispersals ranges from Plio-Pleistocene to near to the present. Statistical models suggest that taxa that dispersed from North America to other continents had smaller fruits and more highly ornamented fruits, a pattern that supports birds as the probable dispersal vector.Chapter 3 evaluates diversification in Plagiobothrys with an emphasis on examining the role of habitat and ecological opportunity in promoting increased net diversification rates. Once again, molecular sequence data and fossils calibrations were used to generate a time-calibrated phylogeny of Plagiobothrys and the subtribe. Likelihood-based methods were used to reconstruct the ancestral habitat in the genus, in particular to assess the number of times that vernal pools and other ephemeral aquatic ecosystems were invaded. This analysis was unequivocal in estimating a single transition to ephemerally aquatic ecosystems. A character (habitat) independent diversification analysis identified a major net diversification rate shift following the invasion of vernal pools and other ephemeral aquatic ecosystems. A character dependent analysis of diversification with respect to habitat resulted in an estimate of diversification rates over three times greater in ephemeral aquatic lineages than in terrestrial lineages. These findings support the hypothesis that increased rates of diversification accompanied the invasion of vernal pool and ephemeral aquatic ecosystems in the Mediterranean-type climate regions of western North America and western South America. Diversification did not begin until these systems formed ca. 4-3 Ma, suggesting that the evolution of these ephemeral water bodies over millions of acres presented an ecological opportunity that was exploited by members of Plagiobothrys from the Plio-Pleistocene to the present day.

This dissertation describes the synthesis, characterization, and reactivity of organometallic complexes of yttrium and the lanthanides in an effort to more completely understand the nature of a recently-discovered class of +2 ions of these rare earth metals. The reactivity of complexes of a new set of Ln2+ ions (Ln = rare earth metal) with unprecedented 4fn5d1 electron configurations has been explored to expand the unique chemistry possible with the rare earth elements. The isolation of unexpected reaction products is described as well as the discovery of a new divalent lanthanide system and the utilization of solvent-free mechanochemical synthesis for established rare earth organometallic species.In Chapter 1, the reactivity of the highly-reducing, air-, moisture-, and temperature-sensitive divalent lanthanide complexes [K(2.2.2-cryptand)][Cp'3Ln] (Ln = Y, La, Ce, Dy) is characterized by examining reactions with aromatic organic substrates of known reduction potential. Complexes of the 4fn5d1 Ln2+ ions reduce naphthalene and biphenyl within minutes to form a new class of reduced aromatic complexes, [K(2.2.2-cryptand)][Cp'2Ln(η4-C10H8)] (Ln = Y, La, Ce, Dy) and [K(2.2.2-cryptand)][Cp'2Y(η6-C6H5Ph)], respectively. The naphthalene reactions also produced the previously unobserved ligand redistribution products [K(2.2.2-cryptand)][Cp'4Ln] (Ln = Y, La), which show the effect of the lanthanide contraction on structure as the lanthanum complex has four η5-Cp' rings while yttrium has three η5-Cp' rings and one η1-Cp' ring.Chapter 2 describes the synthesis and characterization of a new class of 4fn5d1 Ln2+ complexes in which a reduced benzene dianion bridges two metal centers: [K(2.2.2-cryptand)]2[(Cp'2Ln)2(μ-η6:η6-C6H6)] (Ln = La, Ce). In these complexes, the (C6H6)2− dianion formally takes the place of a (Cp')1− anion in the [K(2.2.2-cryptand)][Cp'3Ln] complexes above and suggests a pattern that three anionic carbocyclic rings can stabilize the new Ln2+ ions. In accordance with the presence of two metal centers of 4fn5d1 electron configurations and (C6H6)2− dianions, these complexes react as four electron reductants to reduce two equiv of naphthalene to two equiv of [K(2.2.2-cryptand)][Cp'2Ln(η4-C10H8)] (Ln = La, Ce). This constitutes a better synthesis of these complexes than the one above since no (Cp'4Ln)1− byproducts are formed.Chapter 3 describes the solvent-free synthesis of the previously established complexes (C5Me5)3Y, Cp'3Y, [Cp'2Y(μ-Cl)]2, Y[N(SiMe3)2]3, and U[N(SiMe3)2]3 by mechanochemical ball milling. Not only do these reactions show the feasibility of ball milling as an alternative method to synthesizing organometallic rare earth complexes, but these preliminary results also show promising routes that shorten reaction times and limit the generation of organic solvent waste. This new method of solid-state synthesis is especially important for the isolation of (C5Me5)3Y as the established synthetic route must avoid aromatic hydrocarbons.Chapter 4 describes a study of the reactivity of organometallic rare earth non-classical carbocation complexes (C5Me5)2Ln[(OC)2C5Me5-κ2-O,O'] (Ln = La, Sm) obtained from sterically crowded (C5Me5)3Ln and carbon monoxide. Investigation of the reactivity is consistent with DFT analysis that suggests the LUMO of the La complex is the 5dz2 orbital of the metal center rather than an orbital centered on the carbocation.Also described in this dissertation are the synthesis and structural and spectroscopic characterization of two previously unreported rare earth amide complexes, Y(NCy2)3(THF) and Y(NPh2)3(THF)2 (Chapter 5), the insertion of CO2 into a Y–C bond for the first time with the Cp' ligand to form [Cp'2Y{μ-O2C[3-(Me3Si)C5H4]-κ2O,O'}]2 (Appendix A), the synthesis and structural characterization Cp'2Ln metallocene complexes of unsubstituted phenyl ligands, Cp'2LnPh(THF) (Ln = Y, Dy) (Appendix B), and the attempted synthesis of a bimetallic bridging monoanionic benzene rare earth complexes with the aim of developing a new class of single molecule magnets (Appendix C).