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Description
This work focuses on a novel approach to combine electrical current with cyanobacterial technology, called microbial electrophotosynthesis (MEPS). It involves using genetically modified PSII-less Synechocystis PCC 6803 cells to avoid photoinhibition, a problem that hinders green energy. In the work, a cathodic electron delivery system is employed for growth and

This work focuses on a novel approach to combine electrical current with cyanobacterial technology, called microbial electrophotosynthesis (MEPS). It involves using genetically modified PSII-less Synechocystis PCC 6803 cells to avoid photoinhibition, a problem that hinders green energy. In the work, a cathodic electron delivery system is employed for growth and synthesis. Photoinhibition leads to the dissipation energy and lower yield, and is a major obstacle to preventing green energy from competing with fossil fuels. However, the urgent need for alternative energy sources is driven by soaring energy consumption and rising atmospheric carbon dioxide levels. When developed, MEPS can contribute to a carbon capture technology while helping with energy demands. It is thought that if PSII electron flux can be replaced with an alternative source photosynthesis could be enhanced for more effective production. MEPS has the potential to address these challenges by serving as a carbon capture technology while meeting energy demands. The idea is to replace PSII electron flux with an alternative source, which can be enhanced for higher yields in light intensities not tolerated with PSII. This research specifically focuses on creating the initiation of electron flux between the cathode and the MEPS cells while controlling and measuring the system in real time. The successful proof-of-concept work shows that MEPS can indeed generate high-light-dependent current at intensities up to 2050 µmol photons m^‒2 s^‒1, delivering 113 µmol electrons h^‒1 mg-chl^‒1. The results were further developed to characterize redox tuning for electron delivery of flux to the photosynthetic electron transport chain and redox-based kinetic analysis to model the limitations of the MEPS system.
ContributorsLewis, Christine Michelle (Author) / Torres, César I (Thesis advisor) / Fromme, Petra (Thesis advisor) / Woodbury, Neal (Committee member) / Hayes, Mark (Committee member) / Arizona State University (Publisher)
Created2023
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Description
Earth-system models describe the interacting components of the climate system and

technological systems that affect society, such as communication infrastructures. Data

assimilation addresses the challenge of state specification by incorporating system

observations into the model estimates. In this research, a particular data

assimilation technique called the Local Ensemble Transform Kalman Filter (LETKF) is

applied

Earth-system models describe the interacting components of the climate system and

technological systems that affect society, such as communication infrastructures. Data

assimilation addresses the challenge of state specification by incorporating system

observations into the model estimates. In this research, a particular data

assimilation technique called the Local Ensemble Transform Kalman Filter (LETKF) is

applied to the ionosphere, which is a domain of practical interest due to its effects

on infrastructures that depend on satellite communication and remote sensing. This

dissertation consists of three main studies that propose strategies to improve space-

weather specification during ionospheric extreme events, but are generally applicable

to Earth-system models:

Topic I applies the LETKF to estimate ion density with an idealized model of

the ionosphere, given noisy synthetic observations of varying sparsity. Results show

that the LETKF yields accurate estimates of the ion density field and unobserved

components of neutral winds even when the observation density is spatially sparse

(2% of grid points) and there is large levels (40%) of Gaussian observation noise.

Topic II proposes a targeted observing strategy for data assimilation, which uses

the influence matrix diagnostic to target errors in chosen state variables. This

strategy is applied in observing system experiments, in which synthetic electron density

observations are assimilated with the LETKF into the Thermosphere-Ionosphere-

Electrodynamics Global Circulation Model (TIEGCM) during a geomagnetic storm.

Results show that assimilating targeted electron density observations yields on

average about 60%–80% reduction in electron density error within a 600 km radius of

the observed location, compared to 15% reduction obtained with randomly placed

vertical profiles.

Topic III proposes a methodology to account for systematic model bias arising

ifrom errors in parametrized solar and magnetospheric inputs. This strategy is ap-

plied with the TIEGCM during a geomagnetic storm, and is used to estimate the

spatiotemporal variations of bias in electron density predictions during the

transitionary phases of the geomagnetic storm. Results show that this strategy reduces

error in 1-hour predictions of electron density by about 35% and 30% in polar regions

during the main and relaxation phases of the geomagnetic storm, respectively.
ContributorsDurazo, Juan, Ph.D (Author) / Kostelich, Eric J. (Thesis advisor) / Mahalov, Alex (Thesis advisor) / Tang, Wenbo (Committee member) / Moustaoui, Mohamed (Committee member) / Platte, Rodrigo (Committee member) / Arizona State University (Publisher)
Created2018
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Description
The fundamental photophysics of fluorescent probes must be understood when the probes are used in biological applications. The photophysics of BODIPY dyes inside polymeric micelles and rhodamine dyes covalently linked to proteins were studied. Hydrophobic boron-dipyrromethene (BODIPY) dyes were noncovalently encapsulated inside polymeric micelles. Absorbance and fluorescence measurements were employed

The fundamental photophysics of fluorescent probes must be understood when the probes are used in biological applications. The photophysics of BODIPY dyes inside polymeric micelles and rhodamine dyes covalently linked to proteins were studied. Hydrophobic boron-dipyrromethene (BODIPY) dyes were noncovalently encapsulated inside polymeric micelles. Absorbance and fluorescence measurements were employed to study the photophysics of these BODIPY dyes in the micellar environments. Amphiphilic polymers with a hydrophobic character and low Critical Micelle Concentration (CMC) protected BODIPYS from the aqueous environment. Moderate dye loading conditions did not result in ground-state dimerization, and only fluorescence lifetimes and brightnesses were affected. However, amphiphilic polymers with a hydrophilic character and high CMC did not protect the BODIPYS from the aqueous environment with concomitant ground-state dimerization and quenching of the fluorescence intensity, lifetime, and brightnesses even at low dye loading conditions. At the doubly-labeled interfaces of Escherichia coli (E. coli) DNA processivity β clamps, the interchromophric interactions of four rhodamine dyes were studied: tetramethylrhodamine (TMR), TMR C6, Alexa Fluor 488, and Alexa Fluor 546. Absorbance and fluorescence measurements were performed on doubly-labeled β clamps with singly-labeled β clamps and free dyes as controls. The absorbance measurements revealed that both TMR and TMR C6 readily formed H-dimers (static quenching) at the doubly-labeled interfaces of the β clamps. However, the TMR with a longer linker (TMR C6) also displayed a degree of dynamic quenching. For Alexa Fluor 546 and Alexa Fluor 488, there were no clear signs of dimerization in the absorbance scans. However, the fluorescence properties (fluorescence intensity, lifetime, and anisotropy) of the Alexa Fluor dyes significantly changed when three methodologies were employed to disrupt the doubly-labeled interfaces: 1) the addition of sodium dodecyl sulfate (SDS) detergent to denature the proteins, 2) the addition of clamp loader (γ complex) to open one of the two interfaces, and 3) the use of subunit exchange to decrease the number of dyes per interface. These fluorescence measurements indicated that for the Alexa Fluor dyes, other interchromophoric interactions were present such as dynamic quenching and homo-Förster Resonance Energy Transfer (homo-FRET).
ContributorsDonaphon, Bryan Matthew (Author) / Levitus, Marcia (Thesis advisor) / Van Horn, Wade (Committee member) / Woodbury, Neal (Committee member) / Arizona State University (Publisher)
Created2018
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Description
The highly predictable structural and thermodynamic behavior of deoxynucleic acid (DNA) and ribonucleic acid (RNA) have made them versatile tools for creating artificial nanostructures over broad range. Moreover, DNA and RNA are able to interact with biological ligand as either synthetic aptamers or natural components, conferring direct biological functions to

The highly predictable structural and thermodynamic behavior of deoxynucleic acid (DNA) and ribonucleic acid (RNA) have made them versatile tools for creating artificial nanostructures over broad range. Moreover, DNA and RNA are able to interact with biological ligand as either synthetic aptamers or natural components, conferring direct biological functions to the nucleic acid devices. The applications of nucleic acids greatly relies on the bio-reactivity and specificity when applied to highly complexed biological systems.

This dissertation aims to 1) develop new strategy to identify high affinity nucleic acid aptamers against biological ligand; and 2) explore highly orthogonal RNA riboregulators in vivo for constructing multi-input gene circuits with NOT logic. With the aid of a DNA nanoscaffold, pairs of hetero-bivalent aptamers for human alpha thrombin were identified with ultra-high binding affinity in femtomolar range with displaying potent biological modulations for the enzyme activity. The newly identified bivalent aptamers enriched the aptamer tool box for future therapeutic applications in hemostasis, and also the strategy can be potentially developed for other target molecules. Secondly, by employing a three-way junction structure in the riboregulator structure through de-novo design, we identified a family of high-performance RNA-sensing translational repressors that down-regulates gene translation in response to cognate RNAs with remarkable dynamic range and orthogonality. Harnessing the 3WJ repressors as modular parts, we integrate them into biological circuits that execute universal NAND and NOR logic with up to four independent RNA inputs in Escherichia coli.
ContributorsZhou, Yu (Ph.D.) (Author) / Yan, Hao (Thesis advisor) / Green, Alexander (Thesis advisor) / Woodbury, Neal (Committee member) / Ros, Alexandra (Committee member) / Arizona State University (Publisher)
Created2019
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Description
Two urban flows are analyzed, one concerned with pollutant transport in a Phoenix, Arizona neighborhood and the other with windshear detection at the Hong Kong International Airport (HKIA).

Lagrangian measures, identified with finite-time Lyapunov exponents, are first used to characterize transport patterns of inertial pollutant particles. Motivated by actual events the

Two urban flows are analyzed, one concerned with pollutant transport in a Phoenix, Arizona neighborhood and the other with windshear detection at the Hong Kong International Airport (HKIA).

Lagrangian measures, identified with finite-time Lyapunov exponents, are first used to characterize transport patterns of inertial pollutant particles. Motivated by actual events the focus is on flows in realistic urban geometry. Both deterministic and stochastic transport patterns are identified, as inertial Lagrangian coherent structures. For the deterministic case, the organizing structures are well defined and are extracted at different hours of a day to reveal the variability of coherent patterns. For the stochastic case, a random displacement model for fluid particles is formulated, and used to derive the governing equations for inertial particles to examine the change in organizing structures due to ``zeroth-order'' random noise. It is found that, (1) the Langevin equation for inertial particles can be reduced to a random displacement model; (2) using random noise based on inhomogeneous turbulence, whose diffusivity is derived from $k$-$\epsilon$ models, major coherent structures survive to organize local flow patterns and weaker structures are smoothed out due to random motion.

A study of three-dimensional Lagrangian coherent structures (LCS) near HKIA is then presented and related to previous developments of two-dimensional (2D) LCS analyses in detecting windshear experienced by landing aircraft. The LCS are contrasted among three independent models and against 2D coherent Doppler light detection and ranging (LIDAR) data. Addition of the velocity information perpendicular to the lidar scanning cone helps solidify flow structures inferred from previous studies; contrast among models reveals the intramodel variability; and comparison with flight data evaluates the performance among models in terms of Lagrangian analyses. It is found that, while the three models and the LIDAR do recover similar features of the windshear experienced by a landing aircraft (along the landing trajectory), their Lagrangian signatures over the entire domain are quite different - a portion of each numerical model captures certain features resembling those LCS extracted from independent 2D LIDAR analyses based on observations. Overall, it was found that the Weather Research and Forecast (WRF) model provides the best agreement with the LIDAR data.

Finally, the three-dimensional variational (3DVAR) data assimilation scheme in WRF is used to incorporate the LIDAR line of sight velocity observations into the WRF model forecast at HKIA. Using two different days as test cases, it is found that the LIDAR data can be successfully and consistently assimilated into WRF. Using the updated model forecast LCS are extracted along the LIDAR scanning cone and compare to onboard flight data. It is found that the LCS generated from the updated WRF forecasts are generally better correlated with the windshear experienced by landing aircraft as compared to the LIDAR extracted LCS alone, which suggests that such a data assimilation scheme could be used for the prediction of windshear events.
ContributorsKnutson, Brent (Author) / Tang, Wenbo (Thesis advisor) / Calhoun, Ronald (Committee member) / Huang, Huei-Ping (Committee member) / Kostelich, Eric (Committee member) / Mahalov, Alex (Committee member) / Arizona State University (Publisher)
Created2018
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Description
Humanity’s demand for energy is increasing exponentially and the dependence on fossil fuels is both unsustainable and detrimental to the environment. To provide a solution to the impending energy crisis, it is reasonable to look toward utilizing solar energy, which is abundant and renewable. One approach to harvesting solar irradiation

Humanity’s demand for energy is increasing exponentially and the dependence on fossil fuels is both unsustainable and detrimental to the environment. To provide a solution to the impending energy crisis, it is reasonable to look toward utilizing solar energy, which is abundant and renewable. One approach to harvesting solar irradiation for fuel purposes is through mimicking the processes of natural photosynthesis in an artificial design to use sunlight and water to store energy in chemical bonds for later use. Thus, in order to design an efficient energy conversion device, the underlying processes of the natural system must be understood. An artificial photosynthetic device has many components and each can be optimized separately. This work deals with the design, construction and study of some of those components. The first chapter provides an introduction to this work. The second chapter shows a proof of concept for a water splitting dye sensitized photoelectrochemical cell followed by the presentation of a new p-type semiconductor, the design of a modular cluster binding protein that can be used for incorporating catalysts, and a new anchoring group for semiconducting oxides with high electron injection efficiency. The third chapter investigates the role of electronic coupling and thermodynamics for photoprotection in artificial systems by triplet-triplet energy transfer from tetrapyrroles to carotenoids. The fourth chapter describes a mimic of the proton-coupled electron transfer in photosystem II and confirms that in the artificial system a concerted mechanism operates. In the fifth chapter, a microbial system is designed to work in tandem with a photovoltaic device to produce high energy fuels. A variety of quinone redox mediators have been synthesized to shuttle electrons from an electron donor to the microbial system. Lastly, the synthesis of a variety of photosensitizers is detailed for possible future use in artificial systems. The results of this work helps with the understanding of the processes of natural photosynthesis and suggests ways to design artificial photosynthetic devices that can contribute to solving the renewable energy challenge.
ContributorsBrown, Chelsea L (Author) / Moore, Ana L (Thesis advisor) / Gust, Devens (Committee member) / Woodbury, Neal (Committee member) / Arizona State University (Publisher)
Created2015
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Description
The manipulation of biological targets using synthetic compounds has been the focal point of medicinal chemistry. The work described herein centers on the synthesis of organic small molecules that act either as probes for studying protein conformational changes or DNA–protein interaction, or as multifunctional radical quenchers.

Fluorescent labeling is of paramount

The manipulation of biological targets using synthetic compounds has been the focal point of medicinal chemistry. The work described herein centers on the synthesis of organic small molecules that act either as probes for studying protein conformational changes or DNA–protein interaction, or as multifunctional radical quenchers.

Fluorescent labeling is of paramount importance to biological studies of proteins. For the development of new extrinsic small fluorophores, a series of tryptophan analogues has been designed and synthesized. Their pdCpA derivatives have been synthesized for tRNA activation and in vitro protein synthesis. The photophysical properties of the tryptophan (Trp) analogues have been examined, some of which can be selectively monitored even in the presence of multiple native tryptophan residues. Further, some of the Trp analogues form efficient FRET pairs with acceptors such as acridon-2-ylalanine (Acd) or L-(7-hydroxycoumarin-4-yl)ethylglycine (HCO) for the selective study of conformational changes in proteins.

Molecules which can bind with high sequence selectivity to a chosen target in a gene sequence are of interest for the development of gene therapy, diagnostic devices for genetic analysis, and as molecular tools for nucleic acid manipulations. Stereoselective synthesis of different alanyl nucleobase amino acids is described. Their pdCpA derivatives have been synthesized for tRNA activation and site-specific incorporation into the DNA-binding protein RRM1 of hnRNP LL. It is proposed that the nucleobase moieties in the protein may specifically recognize base sequence in the i-motif DNA through H-bonding and base-stacking interactions.

The mitochondrial respiratory chain accumulates more oxidative damage than any other organelle within the cell. Dysfunction of this organelle is believed to drive the progression of many diseases, thus mitochondria are an important potential drug target. Reactive oxygen species (ROS) are generated when electrons from the respiratory chain escape and interact with oxygen. ROS can react with proteins, lipids or DNA causing cell death. For the development of effective neuroprotective drugs, a series of N-hydroxy-4-pyridones have been designed and synthesized as CoQ10 analogues. All the analogues synthesized were evaluated for their ability to quench lipid peroxidation and reactive oxygen species (ROS).
ContributorsTalukder, Poulami (Author) / Hecht, Sidney M. (Thesis advisor) / Woodbury, Neal (Committee member) / Gould, Ian (Committee member) / Arizona State University (Publisher)
Created2016
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Description
Sunlight, the most abundant source of energy available, is diffuse and intermittent; therefore it needs to be stored in chemicals bonds in order to be used any time. Photosynthesis converts sunlight into useful chemical energy that organisms can use for their functions. Artificial photosynthesis aims to use the essential chemistry

Sunlight, the most abundant source of energy available, is diffuse and intermittent; therefore it needs to be stored in chemicals bonds in order to be used any time. Photosynthesis converts sunlight into useful chemical energy that organisms can use for their functions. Artificial photosynthesis aims to use the essential chemistry of natural photosynthesis to harvest solar energy and convert it into fuels such as hydrogen gas. By splitting water, tandem photoelectrochemical solar cells (PESC) can produce hydrogen gas, which can be stored and used as fuel. Understanding the mechanisms of photosynthesis, such as photoinduced electron transfer, proton-coupled electron transfer (PCET) and energy transfer (singlet-singlet and triplet-triplet) can provide a detailed knowledge of those processes which can later be applied to the design of artificial photosynthetic systems. This dissertation has three main research projects. The first part focuses on design, synthesis and characterization of suitable photosensitizers for tandem cells. Different factors that can influence the performance of the photosensitizers in PESC and the attachment and use of a biomimetic electron relay to a water oxidation catalyst are explored. The second part studies PCET, using Nuclear Magnetic Resonance and computational chemistry to elucidate the structure and stability of tautomers that comprise biomimetic electron relays, focusing on the formation of intramolecular hydrogen bonds. The third part of this dissertation uses computational calculations to understand triplet-triplet energy transfer and the mechanism of quenching of the excited singlet state of phthalocyanines in antenna models by covalently attached carotenoids.
ContributorsTejeda Ferrari, Marely (Author) / Moore, Ana (Thesis advisor) / Mujica, Vladimiro (Thesis advisor) / Gust, John (Committee member) / Woodbury, Neal (Committee member) / Arizona State University (Publisher)
Created2016
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Description
The role of environmental factors that influence atmospheric propagation of sound originating from freeway noise sources is studied with a combination of field experiments and numerical simulations. Acoustic propagation models are developed and adapted for refractive index depending upon meteorological conditions. A high-resolution multi-nested environmental forecasting model forced by coarse

The role of environmental factors that influence atmospheric propagation of sound originating from freeway noise sources is studied with a combination of field experiments and numerical simulations. Acoustic propagation models are developed and adapted for refractive index depending upon meteorological conditions. A high-resolution multi-nested environmental forecasting model forced by coarse global analysis is applied to predict real meteorological profiles at fine scales. These profiles are then used as input for the acoustic models. Numerical methods for producing higher resolution acoustic refractive index fields are proposed. These include spatial and temporal nested meteorological simulations with vertical grid refinement. It is shown that vertical nesting can improve the prediction of finer structures in near-ground temperature and velocity profiles, such as morning temperature inversions and low level jet-like features. Accurate representation of these features is shown to be important for modeling sound refraction phenomena and for enabling accurate noise assessment. Comparisons are made using the acoustic model for predictions with profiles derived from meteorological simulations and from field experiment observations in Phoenix, Arizona. The challenges faced in simulating accurate meteorological profiles at high resolution for sound propagation applications are highlighted and areas for possible improvement are discussed.



A detailed evaluation of the environmental forecast is conducted by investigating the Surface Energy Balance (SEB) obtained from observations made with an eddy-covariance flux tower compared with SEB from simulations using several physical parameterizations of urban effects and planetary boundary layer schemes. Diurnal variation in SEB constituent fluxes are examined in relation to surface layer stability and modeled diagnostic variables. Improvement is found when adapting parameterizations for Phoenix with reduced errors in the SEB components. Finer model resolution (to 333 m) is seen to have insignificant ($<1\sigma$) influence on mean absolute percent difference of 30-minute diurnal mean SEB terms. A new method of representing inhomogeneous urban development density derived from observations of impervious surfaces with sub-grid scale resolution is then proposed for mesoscale applications. This method was implemented and evaluated within the environmental modeling framework. Finally, a new semi-implicit scheme based on Leapfrog and a fourth-order implicit time-filter is developed.
ContributorsShaffer, Stephen R. (Author) / Moustaoui, Mohamed (Thesis advisor) / Mahalov, Alex (Committee member) / Fernando, Harindra J.S. (Committee member) / Ovenden, Nicholas C. (Committee member) / Huang, Huei-Ping (Committee member) / Calhoun, Ronald (Committee member) / Arizona State University (Publisher)
Created2014
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Description
The healthcare system in this country is currently unacceptable. New technologies may contribute to reducing cost and improving outcomes. Early diagnosis and treatment represents the least risky option for addressing this issue. Such a technology needs to be inexpensive, highly sensitive, highly specific, and amenable to adoption in a clinic.

The healthcare system in this country is currently unacceptable. New technologies may contribute to reducing cost and improving outcomes. Early diagnosis and treatment represents the least risky option for addressing this issue. Such a technology needs to be inexpensive, highly sensitive, highly specific, and amenable to adoption in a clinic. This thesis explores an immunodiagnostic technology based on highly scalable, non-natural sequence peptide microarrays designed to profile the humoral immune response and address the healthcare problem. The primary aim of this thesis is to explore the ability of these arrays to map continuous (linear) epitopes. I discovered that using a technique termed subsequence analysis where epitopes could be decisively mapped to an eliciting protein with high success rate. This led to the discovery of novel linear epitopes from Plasmodium falciparum (Malaria) and Treponema palladium (Syphilis), as well as validation of previously discovered epitopes in Dengue and monoclonal antibodies. Next, I developed and tested a classification scheme based on Support Vector Machines for development of a Dengue Fever diagnostic, achieving higher sensitivity and specificity than current FDA approved techniques. The software underlying this method is available for download under the BSD license. Following this, I developed a kinetic model for immunosignatures and tested it against existing data driven by previously unexplained phenomena. This model provides a framework and informs ways to optimize the platform for maximum stability and efficiency. I also explored the role of sequence composition in explaining an immunosignature binding profile, determining a strong role for charged residues that seems to have some predictive ability for disease. Finally, I developed a database, software and indexing strategy based on Apache Lucene for searching motif patterns (regular expressions) in large biological databases. These projects as a whole have advanced knowledge of how to approach high throughput immunodiagnostics and provide an example of how technology can be fused with biology in order to affect scientific and health outcomes.
ContributorsRicher, Joshua Amos (Author) / Johnston, Stephen A. (Thesis advisor) / Woodbury, Neal (Committee member) / Stafford, Phillip (Committee member) / Papandreou-Suppappola, Antonia (Committee member) / Arizona State University (Publisher)
Created2014