Resorcinarenes are cyclic tetramers that are synthesized by the condensation of resorcinol and various aldehydes. The upper and lower rims can be modified with substituents that provide specific selectivity and other chemical features. In this work, resorcinarene-based macrocyclic ligands with specific selectivities have been designed, synthesized and applied to chiral amine discrimination and transition metal ion separations.These resorcinarenes fall into two categories. In the first type, the upper rims of resorcinarenes were modified with amino acid groups, including chiral alanine groups. The lower rims were modified with --CH3, or --C11H23 groups. The structures were studied by nuclear magnetic resonance (NMR), mass spectrometry (MS), dynamic light scattering (DLS), and sustained off-resonance irradiation collision induced dissociation (SORI-CID) techniques in Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). The binding strength between the resorcinarenes with amines was studied by 1H NMR titration. Among these new resorcinarenes, the chiral alanine undecyl resorcinarenes acid (AUA) showed chiral discrimination among chiral secondary amines. The AUA ligands were adsorbed onto 55% cross-linked styrene-divinylbenzene resin and used as cation-exchangers in ion chromatography (IC) for transition metal ion separations. The AUA IC column showed selectivity for Cu2+ when no chelating eluent was used in the eluent, a selectivity which was not observed with a commercial column containing standard cation-exchangers. Six metal ions (Cu2+, Mn2+, Co2+, Ni2+, Cd2+, and Zn2+) were separated on the AUA column within a reasonable time with a simple oxalic acid gradient eluent. The second type of resorcinarene-based ligand, cyclenbowl, contains four cyclen units on the upper rim and four --C11H23 chains on the lower rim. The column packed with cyclenbowl adsorbed onto polystyrene showed selectivity for Cu2+ over five other transition metal ions including Mn2+, Co2+, Ni2+, Cd2+, and Zn2+ ions. The preconcentration of Cu2+ at the parts per billion level from a high concentration matrix of Mn2+, Co2+, Ni2+, Cd2+, and Zn2+ ions was achieved using HNO3 eluent. Recovery of Cu2+ was greater than 98%. Furthermore, the other five transition metal ions were well separated on the cyclenbowl column with an oxalic acid eluent gradient.

For the endangered green turtle, Chelonia mydas, a fundamental component of recovery and conservation is an understanding of its foraging ecology. Foraging optimality models suggest animals will select resources of high quality over those of low quality. For green turtles, this behavior is important, as sufficient quantities of nutritionally adequate forage items are necessary for growth and reproduction. One intrinsic element in the understanding of green turtle foraging ecology is to identify and document the availability and quality of forage resources preferred by green turtles. The objectives of this study were: 1) determine whether juvenile green turtles showed a feeding preference by comparing prey items in the diet to the availability of those items in the habitat, 2) identify species for which there was selection or avoidance, 3) identify nutritional factors determining selection or avoidance of prey items, and 4) evaluate the nutritional content of the diet. This research was conducted by comparing lavage samples from juvenile green turtles to samples from benthic surveys within the habitat. To determine feeding preference, Ivlev's Electivity Index was used to compare ingested species of algae with those available in the habitat. Nutritional analysis of forage was conducted to identify possible nutrients relating to feeding preference. Juvenile green turtles selectively foraged on Chlorophyta and Rhodophyta. Results indicate that diet selection was based on nutritional content. Both the composite diet and the main diet item, Hypnea spp, had a higher gross energy value, were higher in protein, and lower in fiber than prey items that were avoided. Conservation of green turtles requires effective habitat management, which must be informed by an understanding and evaluation of the habitat. For juvenile green turtles, this study indicates that habitats dominated by Chlorophyta and Rhodophyta may be more important for the health of green turtle populations than habitats dominated by Phaeophyta.

A major contribution to global warming is CO2 emitted from the combustion of fossil fuels. Electrochemical processes can help to mitigate the elevated CO2 emissions through either the conversion of CO2 into value-added chemicals or the replacement of fossil fuels with clean fuels such as hydrogen produced from water oxidation. The present dissertation focuses on the mechanistic aspects of electrochemical processes. Electrochemical water oxidation is hindered by the low efficiency of oxygen evolution reaction (OER) at the anode whereas electrochemical reduction of CO2 (ERCO2) is hampered by high overpotentials and poor product selectivity. In this dissertation, we studied the catalytic activity of transition metal-based catalysts, including FeNi spinels, metal-oxide/copper, and d metal cyclam complexes, for both OER and ERCO2 using the density functional theory (DFT) computational approach.We report a combined effort of fabricating FeNi oxide catalysts and identifying the active component of the catalyst for OER. Our collaborators at the University of California, Santa Cruze fabricated a series of FeNi spinels-based materials including Ni(OH)Fe2O4(Cl), Ni(OH)Fe2O4, Fe(OH)Fe2O4(Cl), Fe(OH)Fe2O4, Ni(OH)O(Cl), Ni(OH)O and some show exceptional activity for OER. Combined experimental characterization and computational mechanistic study based on the computational hydrogen electrode (CHE) model revealed that Ni(OH)Fe2O4(Cl) is the active ensemble for exceptional OER performance. We also investigated CO2 reduction to C1 products at the metal-oxide/copper interfaces ((MO)4/Cu(100), M = Fe, Co and Ni) based on the CHE model. The effect of tuning metal-oxide/copper interfaces on product selectivity and limiting potential was clearly demonstrated. This study showed that the catalyst/electrode interface and solvent can be regulated to optimize product selectivity and lower the limiting potential for ERCO2. Applied potential affects the stability of species on the surface of the electrode. The proton-coupled electron transfer (PCET) equilibrium assumed in the CHE model does not capture the change in free energy under the influence of the applied potential. In contrast, the constant electrode potential (CEP) model captures changes in free energy due to applied potential, we applied the CEP model to ERCO2 and OER on (MO)4/Cu(100) and compared the results with those from the CHE model. The results demonstrate that the CHE and the CEP models predict different limiting potentials and product selectivity for ERCO2, but they predict similar limiting potentials for OER. The results demonstrate the importance of accounting for the applied potential effect in the study of more complex multi-step electrochemical processes. We also studied transition metal-based homogeneous catalysts for ERCO2. We examined the performance of transition metal(M) - cyclam(L) complexes as molecular catalysts for the reduction of CO2 to HCOO- and CO, focusing on the effect of changing the metal ions in cyclam on product selectivity (either HCOO- or CO), limiting potential and competitive hydrogen evolution reaction. Our results show that among the complexes, [LNi]2+ and [LPd]2+ can catalyze CO2 reduction to CO, and [LMo]2+ and [LW]3+ can reduce CO2 to HCOO-. Notably, [LMo]2+, [LW]3+, [LW]2+ and [LCo]2+ have a limiting potential less negative than -1.6 V and are based on earth-abundant elements, making them attractive for practical application. In summary, the dissertation demonstrates high-performance catalysts can be designed from earth-abundant transition metals for electrochemical processes that would alleviate the high CO2 level in the environment. On the other hand, completely reversing the increasing trend of CO2 level in the atmosphere requires a collective human effort.

Cyclic nucleotides such as cAMP and cGMP serve as intracellular second messengers in diverse signaling pathways that control a wide range of cellular functions. Such pathways are regulated by key cyclic nucleotide receptor proteins including protein kinase A (PKA), the exchange protein directly activated by cAMP (EPAC), the hyperpolarization-activated cyclic-nucleotide-modulated (HCN) ion channels, and protein kinase G (PKG), and malfunction of these proteins has been linked to a number of pathologies. While it is known that cyclic nucleotide binding to these proteins leads to structural perturbations that promote their activation, the role played by dynamics in auto-inhibition and cyclic-nucleotide-dependent activation is not fully understood. Therefore, in this thesis we examined dynamics within the cyclic-nucleotide receptor proteins EPAC, HCN and PKG, and found that dynamics are critical for allosteric control of activation and/or autoinhibition of all three proteins. In particular, our findings for EPAC and HCN have highlighted dynamics as a key modulator of the entropic and enthalpic components, respectively, of the free-energy landscape for cAMP-dependent allostery, while our findings for PKG have highlighted dynamics as a key determinant of the cGMP-vs.-cAMP selectivity necessary to minimize cross-talk between signaling pathways. Ultimately, we envision that the methods outlined in this thesis will reveal key differences in the regulatory mechanisms of human cyclic nucleotide receptors that can eventually be exploited in the development of novel therapeutics to selectively target a single receptor, and thus treat physiological conditions/diseases linked to malfunction of the target receptor. / Thesis / Doctor of Philosophy (PhD) / In this thesis, we examined cyclic-nucleotide-responsive proteins that regulate key physiological processes, and whose malfunction has been linked to cardiovascular and neurological disorders. In particular, in three such proteins we examined dynamics, whose role in cyclic-nucleotide-responsive function is not fully understood. We found that cyclic-nucleotide-dependent variations in dynamics play a critical role in the function of these proteins, with the results for each protein highlighting a different role played by dynamics. Ultimately, we envision that the methods outlined in this thesis will reveal key functional differences among human cyclic-nucleotide-responsive proteins that can eventually lead to the development of novel therapeutics to treat certain diseases such as arrhythmias or epilepsy by selectively targeting a single cyclic-nucleotide-responsive protein.

The human visual system must quickly and accurately deploy task-and-object-specific processing to successfully navigate the environment, which suggests several interesting research questions: What is the nature of these strategies? Are they flexible? To what extent is this behaviour optimal given the natural statistics of the environment? In this thesis, I explored these questions using human faces, a complex and dynamic source of socially relevant information that we encounter throughout our lives. Specifically, I conducted several experiments examining the role of horizontally-oriented spatial frequency components in face identification. In Chapter 2, I use computational modelling to demonstrate that the structure conveyed by these components is maximally diagnostic for face identity, and show that selective processing of this structure predicts both face identification performance and the face inversion effect. In Chapter 3, I quantify the bandwidth utilized by human observers and relate this sampling strategy to the information structure of face stimuli. In Chapter 4, I show that the selective sampling described in Chapters 2 and 3 is driven by information from the eyes. Finally, in Chapter 5, I show that the impaired horizontal selectivity associated with face inversion is enhanced by practice identifying inverted faces. Together, these experiments characterize a stimulus with differentially diagnostic information sources that, through experience, becomes selectively processed in a manner associated with task performance. These results contribute to our understanding of expert object processing and may have implications for observers experiencing face perception deficits. / Thesis / Doctor of Philosophy (PhD)

A core construct in the lifespan theory of socioemotional selectivity, future time perspective (FTP) refers to individuals’ perceptions of their remaining time in life. Its adaptation to the work context, occupational future time perspective (OFTP), entails workers’ perceptions of remaining time and opportunities in their careers. Over the past decade, several quantitative studies have investigated antecedents and consequences of general FTP and OFTP in the work context (i.e., FTP at work). We systematically review and critically discuss this literature on general FTP (k = 17 studies) and OFTP (k = 16 studies) and highlight implications for future research and practice. Results of our systematic review show that, in addition to its strong negative relationship with age, FTP at work is also associated with other individual (e.g., personality traits) and contextual variables (e.g., job characteristics). Moreover, FTP at work has been shown to mediate and moderate relationships of individual and contextual antecedents with occupational well-being, as well as motivational and behavioral outcomes. As a whole, findings suggest that FTP at work is an important variable in the field of work and aging, and that future research should improve the ways in which FTP at work is measured and results on FTP at work are reported.

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