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- All Subjects: Chemistry
- Creators: School of Molecular Sciences
- Creators: Moore, Ana L
- Member of: Theses and Dissertations
- Resource Type: Text
Description
Photosynthesis, one of the most important processes in nature, has provided an energy basis for nearly all life on Earth, as well as the fossil fuels we use today to power modern society. This research aims to mimic the photosynthetic process of converting incident solar energy into chemical potential energy in the form of a fuel via systems capable of carrying out photo-induced electron transfer to drive the production of hydrogen from water. Herein is detailed progress in using photo-induced stepwise electron transfer to drive the oxidation of water and reduction of protons to hydrogen. In the design, use of more blue absorbing porphyrin dyes to generate high-potential intermediates for oxidizing water and more red absorbing phthalocyanine dyes for forming the low potential charge needed for the production of hydrogen have been utilized. For investigating water oxidation at the photoanode, high potential porphyrins such as, bis-pyridyl porphyrins and pentafluorophenyl porphyrins have been synthesized and experiments have aimed at the co-immobilization of this dye with an IrO2-nH2O catalyst on TiO2. To drive the cathodic reaction of the water splitting photoelectrochemical cell, utilization of silicon octabutoxy-phthalocyanines have been explored, as they offer good absorption in the red to near infrared, coupled with low potential photo-excited states. Axially and peripherally substituted phthalocyanines bearing carboxylic anchoring groups for the immobilization on semiconductors such as TiO2 has been investigated. Ultimately, this work should culminate in a photoelectrochemical cell capable of splitting water to oxygen and hydrogen with the only energy input from light. A series of perylene dyes bearing multiple semi-conducting metal oxide anchoring groups have been synthesized and studied. Results have shown interfacial electron transfer between these perylenes and TiO2 nanoparticles encapsulated within reverse micelles and naked nanoparticles. The binding process was followed by monitoring the hypsochromic shift of the dye absorption spectra over time. Photoinduced electron transfer from the singlet excited state of the perylenes to the TiO2 conduction band is indicated by emission quenching of the TiO2-bound form of the dyes and confirmed by transient absorption measurements of the radical cation of the dyes and free carriers (injected electrons) in the TiO2.
ContributorsBergkamp, Jesse J (Author) / Moore, Ana L (Thesis advisor) / Mariño-Ochoa, Ernesto (Thesis advisor) / Gust, Devens J (Committee member) / Gould, Ian (Committee member) / Arizona State University (Publisher)
Created2013
Description
Solar energy is a promising alternative for addressing the world's current and future energy requirements in a sustainable way. Because solar irradiation is intermittent, it is necessary to store this energy in the form of a fuel so it can be used when required. The light-driven splitting of water into oxygen and hydrogen (a useful chemical fuel) is a fascinating theoretical and experimental challenge that is worth pursuing because the advance of the knowledge that it implies and the availability of water and sunlight. Inspired by natural photosynthesis and building on previous work from our laboratory, this dissertation focuses on the development of water-splitting dye-sensitized photoelectrochemical tandem cells (WSDSPETCs). The design, synthesis, and characterization of high-potential porphyrins and metal-free phthalocyanines with phosphonic anchoring groups are reported. Photocurrents measured for WSDSPETCs made with some of these dyes co-adsorbed with molecular or colloidal catalysts on TiO2 electrodes are reported as well. To guide in the design of new molecules we have used computational quantum chemistry extensively. Linear correlations between calculated frontier molecular orbital energies and redox potentials were built and tested at multiple levels of theory (from semi-empirical methods to density functional theory). Strong correlations (with r2 values > 0.99) with very good predictive abilities (rmsd < 50 mV) were found when using density functional theory (DFT) combined with a continuum solvent model. DFT was also used to aid in the elucidation of the mechanism of the thermal relaxation observed for the charge-separated state of a molecular triad that mimics the photo-induced proton coupled electron transfer of the tyrosine-histidine redox relay in the reaction center of Photosystem II. It was found that the inclusion of explicit solvent molecules, hydrogen bonded to specific sites within the molecular triad, was essential to explain the observed thermal relaxation. These results are relevant for both advancing the knowledge about natural photosynthesis and for the future design of new molecules for WSDSPETCs.
ContributorsMéndez-Hernández, Dalvin D (Author) / Moore, Ana L (Thesis advisor) / Mujica, Vladimiro (Thesis advisor) / Gust, Devens J. (Committee member) / Gould, Ian (Committee member) / Arizona State University (Publisher)
Created2014
Description
Natural photosynthesis dedicates specific proteins to achieve the modular division of the essential roles of solar energy harvesting, charge separation and carrier transport within natural photosynthesis. The modern understanding of the fundamental photochemistry by which natural photosynthesis operates is well advanced and solution state mimics of the key photochemical processes have been reported previously. All of the early events in natural photosynthesis responsible for the conversion of solar energy to electric potential energy occur within proteins and phospholipid membranes that act as scaffolds for arranging the active chromophores. Accordingly, for creating artificial photovoltaic (PV) systems, scaffolds are required to imbue structure to the systems. An approach to incorporating modular design into solid-state organic mimics of the natural system is presented together with how conductive scaffolds can be utilized in organic PV systems. To support the chromophore arrays present within this design and to extract separated charges from within the structure, linear pyrazine-containing molecular ribbons were chosen as candidates for forming conductive linear scaffolds that could be functionalized orthogonally to the linear axis. A series of donor-wire-acceptor (D-W-A) compounds employing porphyrins as the donors and a C60 fullerene adduct as the acceptors have been synthesized for studying the ability of the pyrazine-containing hetero-aromatic wires to mediate photoinduced electron transfer between the porphyrin donor and fullerene acceptor. Appropriate substitutions were made and the necessary model compounds useful for dissecting the complex photochemistry that the series is expected to display were also synthesized. A dye was synthesized using a pyrazine-containing heteroaromatic spacer that features two porphyrin chromophores. The dye dramatically outperforms the control dye featuring the same porphyrin and a simple benzoic acid linker. A novel, highly soluble 6+kDa extended phthalocyanine was also synthesized and exhibits absorption out to 900nm. The extensive functionalization of the extended phthalocyanine core with dodecyl groups enabled purification and characterization of an otherwise insoluble entity. Finally, in the interest of incorporating modular design into plastic solar cells, a series of porphyrin-containing monomers have been synthesized that are intended to form dyadic and triadic molecular-heterojunction polymers with dedicated hole and electron transport pathways during electrochemical polymerization.
ContributorsWatson, Brian Lyndon (Author) / Gust, Devens (Thesis advisor) / Gould, Ian (Committee member) / Moore, Ana L (Committee member) / Arizona State University (Publisher)
Created2013
Description
The first chapter reviews three decades of artificial photosynthetic research conducted by the A. Moore, T. Moore, and D. Gust research group. Several carotenoid (Car) and tetrapyrrole containing molecules were synthesized and investigated for excitation energy transfer (EET), photoregulation, and photoprotective functions. These artificial photosynthetic compounds mimicked known processes and investigated proposed mechanisms in natural systems. This research leads to a greater understanding of photosynthesis and design concepts for organic based solar energy conversion devices. The second and third chapters analyze the triplet energy transfer in carotenoid containing dyads. Transient absorption, time-resolved FTIR and resonance Raman spectra revealed that in a 4-amide linked carotenophthalocyanine dyads the Car triplet state is shared across the larger conjugated system, which is similar to protein complexes in oxygenic photosynthetic organisms. In a carotenopurpurin dyad (CarPur) a methylene ester covalent bond prevents the purpurin (Pur) from influencing the Car triplet based on the transient absorption, time-resolved FTIR and resonance Raman spectra. Thus CarPur resembles the antenna proteins from anoxygenic photosynthetic bacteria. Additional examples of carotenoporphyrin dyads further demonstrates the need for orbital overlap for ultrafast triplet energy transfer and the formations of possible intramolecular charge transfer state. The fourth chapter studies a 4-amino phenyl carotenophthalocyanine and its model compounds using high temporal resolution transient absorption spectroscopy techniques. EET from the Car second excited (S2) state to the phthalocyanine (Pc) was determined to be 37% and a coupled hot ground state (S*)/Pc excited state spectrum was observed. Excitation of the tetrapyrrole portion of the dyad did not yield any kinetic differences, but there was an S* signal during the excited states of the dyad. This demonstrates the EET and photoregulating properties of this artificial photosynthetic compound are similar to those of natural photosynthesis. The last chapter covers the synthesis of silicon Pc (SiPc) dyes and the methods for attaching them to gold nanoparticles and flat gold surfaces. SiPc attached to patterned gold surfaces had unperturbed fluorescence, however the selectivity for the gold was low, so alternative materials are under investigation to improve the dye's selectivity for the gold surface.
ContributorsWongCarter, Katherine (Author) / Moore, Ana L (Thesis advisor) / Gust, Devens (Committee member) / Gould, Ian (Committee member) / Arizona State University (Publisher)
Created2014
Description
Increasing concentrations of carbon dioxide in the atmosphere will inevitably lead to long-term changes in climate that can have serious consequences. Controlling anthropogenic emission of carbon dioxide into the atmosphere, however, represents a significant technological challenge. Various chemical approaches have been suggested, perhaps the most promising of these is based on electrochemical trapping of carbon dioxide using pyridine and derivatives. Optimization of this process requires a detailed understanding of the mechanisms of the reactions of reduced pyridines with carbon dioxide, which are not currently well known. This thesis describes a detailed mechanistic study of the nucleophilic and Bronsted basic properties of the radical anion of bipyridine as a model pyridine derivative, formed by one-electron reduction, with particular emphasis on the reactions with carbon dioxide. A time-resolved spectroscopic method was used to characterize the key intermediates and determine the kinetics of the reactions of the radical anion and its protonated radical form. Using a pulsed nanosecond laser, the bipyridine radical anion could be generated in-situ in less than 100 ns, which allows fast reactions to be monitored in real time. The bipyridine radical anion was found to be a very powerful one-electron donor, Bronsted base and nucleophile. It reacts by addition to the C=O bonds of ketones with a bimolecular rate constant around 1* 107 M-1 s-1. These are among the fastest nucleophilic additions that have been reported in literature. Temperature dependence studies demonstrate very low activation energies and large Arrhenius pre-exponential parameters, consistent with very high reactivity. The kinetics of E2 elimination, where the radical anion acts as a base, and SN2 substitution, where the radical anion acts as a nucleophile, are also characterized by large bimolecular rate constants in the range ca. 106 - 107 M-1 s-1. The pKa of the bipyridine radical anion was measured using a kinetic method and analysis of the data using a Marcus theory model for proton transfer. The bipyridine radical anion is found to have a pKa of 40±5 in DMSO. The reorganization energy for the proton transfer reaction was found to be 70±5 kJ/mol. The bipyridine radical anion was found to react very rapidly with carbon dioxide, with a bimolecular rate constant of 1* 108 M-1 s-1 and a small activation energy, whereas the protonated radical reacted with carbon dioxide with a rate constant that was too small to measure. The kinetic and thermodynamic data obtained in this work can be used to understand the mechanisms of the reactions of pyridines with carbon dioxide under reducing conditions.
ContributorsRanjan, Rajeev (Author) / Gould, Ian R (Thesis advisor) / Buttry, Daniel A (Thesis advisor) / Yarger, Jeff (Committee member) / Seo, Dong-Kyun (Committee member) / Arizona State University (Publisher)
Created2015
Description
The work described in the thesis involves the synthesis of a molecular triad which is designed to undergo proton coupled electron transfer (PCET) upon irradiation with light. Photoinduced PCET is an important process that many organisms use and the elucidation of its mechanism will allow further understanding of this process and its potential applications. The target compound designed for PCET studies consists of a porphyrin chromophore (also a primary electron donor), covalently linked to a phenol-imidazole (secondary electron donor), and a C60 (primary electron acceptor). The phenol-imidazole moiety of this system is modeled after the TyrZ His-190 residues in the reaction center of Photosystem II (PS II). These residues participate in an intermolecular H-bond between the phenol side chain of TyrZ and the imidazole side chain of His-190. The phenol side chain of TyrZ is the electron transfer mediator between the oxygen evolving complex (OEC) and P680 (primary electron donor) in PSII. During electron transfer from TyrZ to P680*+, the phenolic proton of TyrZ becomes highly acidic (pKa~-2) and the hydrogen is preferentially transferred to the relatively basic imidazole of His-190 through a pre-existing hydrogen bond. This PCET process avoids a charged intermediate, on TyrZ, and results in a neutral phenolic radical (TyrZ*). The current research consists of building a molecular triad, which can mimic the photoinduced PCET process of PSII. The following, documents the synthetic progress in the synthesis of a molecular triad designed to investigate the mechanism of PCET as well as gain further insight on how this process can be applied in artificial photosynthetic devices.
ContributorsPatterson, Dustin (Author) / Moore, Ana L (Thesis advisor) / Gust, Devens (Committee member) / Skibo, Edward B (Committee member) / Arizona State University (Publisher)
Created2011
Description
Understanding the mechanisms of metalloproteins at the level necessary to engineer new functionalities is complicated by the need to parse the complex overlapping functions played by each amino acid without negatively impacting the host organism. Artificial or designed metallopeptides offer a convenient and simpler platform to explore metal-ligand interactions in an aqueous, biologically relevant coordination context. In this dissertation, the peptide SODA (ACDLPCG), a synthetic derivative of the nickel-binding pocket of nickel superoxide dismutase, is used as a scaffold to construct a variety of novel metallopeptides and explore their reactivity. In Chapter 2, I show that SODA binds Co(II) and the resulting peptide, CoSODA, reacts with oxygen in an unexpected two step process that models the biosynthesis of Co nitrile hydratase. First, the thiolate sulfur is oxidized and then the metallocenter is oxidized to Co(III). In Chapter 3, I show that both CoSODA and CuSODA form CN- adducts. Spectroscopic investigations of these metallopeptides are compared with data from NiSODA and Ni(CN)SODA to show the remarkable geometric versatility of SODA with respect to interactions with metallocenters. In Chapter 4, exploiting the propensity of sulfur ligands to form bridging structures, NiSODA is used as a metallosynthon to direct synthesis of hetero bi- and tri-metallic peptides as models for [NiFe]-hydrogenases and the A cluster of acetyl-CoA synthase carbon monoxide dehydrogenase. Building on this synthetic strategy, in Chapter 5, I demonstrate synthesis of NiRu complexes including a Ru(bipyridine)2 moiety and characterize their photochemistry.
ContributorsDutta, Arnab (Author) / Jones, Anne K (Thesis advisor) / Moore, Ana L (Committee member) / Vermass, Willem (Committee member) / Arizona State University (Publisher)
Created2012
Description
The free-base tetra-tolyl-porphyrin and the corresponding cobalt and iron porphyrin complexes were synthesized and characterized to show that this class of compound can be promising, tunable catalysts for carbon dioxide reduction. During cyclic voltammetry experiments, the iron porphyrin showed an on-set of ‘catalytic current’ at an earlier potential than the cobalt porphyrin’s in organic solutions gassed with carbon dioxide. The cobalt porphyrin yielded larger catalytic currents, but at the same potential as the electrode. This difference, along with the significant changes in the porphyrin’s electronic, optical and redox properties, showed that its capabilities for carbon dioxide reduction can be controlled by metal ions, allotting it unique opportunities for applications in solar fuels catalysis and photochemical reactions.
ContributorsSkibo, Edward Kim (Author) / Moore, Gary (Thesis director) / Woodbury, Neal (Committee member) / School of Molecular Sciences (Contributor) / School of Sustainability (Contributor) / Barrett, The Honors College (Contributor)
Created2016-05
Description
Iron (Fe) scarcity limits biological productivity in high-nutrient low-chlorophyll (HNLC) ocean regions. Thus, the input, output and abundance of Fe in seawater likely played a critical role in shaping the development of modern marine ecosystems and perhaps even contributed to past changes in Earth’s climate. Three sources of Fe—wind-blown dust, hydrothermal activity, and sediment dissolution—carry distinct Fe isotopic fingerprints, and can therefore be used to track Fe source variability through time. However, establishing the timing of this source variability through Earth’s history remains challenging because the major depocenters for dissolved Fe in the ocean lack well-established chronologies. This is due to the fact that they are difficult to date with traditional techniques such as biostratigraphy and radiometric dating. Here, I develop age models for sediments collected from the International Drilling Program Expedition 329 by measuring the Os (osmium) isotopic composition of the hydrogenous portion of the clays. These extractions enable dating of the clays by aligning the Os isotope patterns observed in the clays to those in a reference curve with absolute age constraints through the Cenozoic. Our preliminary data enable future development of chronologies for three sediment cores from the high-latitude South Pacific and Southern Oceans, and demonstrate a wider utility of this method to establish age constraints on pelagic sediments worldwide. Moreover, the preliminary Os isotopic data provides a critical first step needed to examine the changes in Fe (iron) sources and cycling on millions of years timescales. Fe isotopic analysis was conducted at the same sites in the South Pacific and demonstrates that there are significant changes in the sources of Fe to the Southern Ocean over the last 90 Ma. These results lay the groundwork for the exploration of basin-scale sources to Fe source changes, which will have implications for understanding how biological productivity relates to Fe source variability over geological timescales.
ContributorsTegler, Logan Ashley (Author) / Anbar, Ariel (Thesis director) / Herckes, Pierre (Committee member) / Romaniello, Stephen (Committee member) / Department of English (Contributor) / School of Molecular Sciences (Contributor) / Barrett, The Honors College (Contributor)
Created2018-05
Description
As a child passes through the birth canal, they become inoculated with vital gram positive and gram-negative bacteria, aerobes and anaerobes. Breast milk helps to support this growing microbiome by providing oligosaccharides that support its proliferation. Breast milk can be considered the most nutritious source of food available to a growing infant by providing the necessary nutrients, growth hormones and antibodies to promote digestive health, growth, and a strong immune system. The Developmental Origins of Health and Disease Theory (DOHaD) is a theory that suggests a growing fetus and nursing child's nutrients and immune system are dependent on the mother's exposure to nutrients and toxins. Studies have shown a positive correlation between the length of nursing and a child's overall health through life. In addition, consuming an enriched diet after weaning builds a strong immunological and nutritional basis from which the child can grow. This leads to improvements in a child's overall health, which has beneficial long-term effects on morbidity and mortality. This project applied the theory to two Middle Horizon (AD500-1100) individuals from Akapana, Tiwanaku, in the Lake Titicaca Basin, Bolivia. Stable nitrogen and carbon isotope analysis was applied to first molar serial samples of these two individuals to determine weaning age and early childhood diet. Both individuals were male; one male died in adolescence between the age of 9-15 years, and the other died as an elderly adult around the age of 50-59 years. The results showed that the male who died in adulthood was provisioned with supplemental and post-weaning foods high in animal protein, and received breast milk until around 37 months of age. The adolescent male was weaned between 11-12 months and consumed a diet dominated by C4 plants \u2014 most likely maize \u2014 with much less protein. The correlation between prolonged access to breast milk and a healthier and more nutritious childhood diet and longevity are consistent with the theory discussed above.
ContributorsCampbell, Sibella Sweelin (Author) / Knudson, Kelly (Thesis director) / Marsteller, Sara (Committee member) / Greenwald, Alexandra (Committee member) / School of Human Evolution & Social Change (Contributor) / School of Molecular Sciences (Contributor) / Barrett, The Honors College (Contributor)
Created2018-12