Matching Items (101)
Filtering by
- Status: Published
Description
Organic electronics have remained a research topic of great interest over the past few decades, with organic light emitting diodes (OLEDs) emerging as a disruptive technology for lighting and display applications. While OLED performance has improved significantly over the past decade, key issues remain unsolved such as the development of stable and efficient blue devices. In order to further the development of OLEDs and increase their commercial potential, innovative device architectures, novel emissive materials and high-energy hosts are designed and reported.
OLEDs employing step-wide graded-doped emissive layers were designed to improve charge balance and center the exciton formation zone leading to improved device performance. A red OLED with a peak efficiency of 16.9% and an estimated LT97 over 2,000 hours at 1,000 cd/m2 was achieved. Employing a similar structure, a sky-blue OLED was demonstrated with a peak efficiency of 17.4% and estimated LT70 over 1,300 hours at 1,000 cd/m2. Furthermore, the sky-blue OLEDs color was improved to CIE coordinates of (0.15, 0.25) while maintaining an efficiency of 16.9% and estimated LT70 over 600 hours by incorporating a fluorescent sensitizer. These devices represent literature records at the time of publication for efficient and stable platinum phosphorescent OLEDs.
A newly developed class of emitters, metal-assisted delayed-fluorescence (MADF), are demonstrated to achieve higher-energy emission from a relatively low triplet energy. A green MADF device reaches a peak efficiency of 22% with an estimated LT95 over 350 hours at 1,000 cd/m2. Additionally, a blue charge confined OLED of PtON1a-tBu demonstrated a peak efficiency above 20%, CIE coordinated of (0.16, 0.27), and emission onset at 425 nm.
High triplet energy hosts are required for the realization of stable and efficient deep blue emission. A rigid “M”-type carbazole/fluorene hybrid called mDCzPF and a carbazole/9-silafluorene hybrid called mDCzPSiF are demonstrated to have high triplet energies ET=2.88 eV and 3.03 eV respectively. Both hosts are demonstrated to have reasonable stability and can serve as a template for future material design. The techniques presented here demonstrate alternative approaches for improving the performance of OLED devices and help to bring this technology closer to widespread commercialization.
OLEDs employing step-wide graded-doped emissive layers were designed to improve charge balance and center the exciton formation zone leading to improved device performance. A red OLED with a peak efficiency of 16.9% and an estimated LT97 over 2,000 hours at 1,000 cd/m2 was achieved. Employing a similar structure, a sky-blue OLED was demonstrated with a peak efficiency of 17.4% and estimated LT70 over 1,300 hours at 1,000 cd/m2. Furthermore, the sky-blue OLEDs color was improved to CIE coordinates of (0.15, 0.25) while maintaining an efficiency of 16.9% and estimated LT70 over 600 hours by incorporating a fluorescent sensitizer. These devices represent literature records at the time of publication for efficient and stable platinum phosphorescent OLEDs.
A newly developed class of emitters, metal-assisted delayed-fluorescence (MADF), are demonstrated to achieve higher-energy emission from a relatively low triplet energy. A green MADF device reaches a peak efficiency of 22% with an estimated LT95 over 350 hours at 1,000 cd/m2. Additionally, a blue charge confined OLED of PtON1a-tBu demonstrated a peak efficiency above 20%, CIE coordinated of (0.16, 0.27), and emission onset at 425 nm.
High triplet energy hosts are required for the realization of stable and efficient deep blue emission. A rigid “M”-type carbazole/fluorene hybrid called mDCzPF and a carbazole/9-silafluorene hybrid called mDCzPSiF are demonstrated to have high triplet energies ET=2.88 eV and 3.03 eV respectively. Both hosts are demonstrated to have reasonable stability and can serve as a template for future material design. The techniques presented here demonstrate alternative approaches for improving the performance of OLED devices and help to bring this technology closer to widespread commercialization.
ContributorsKlimes, Kody George (Author) / Li, Jian (Thesis advisor) / Adams, James (Committee member) / Wang, Liping (Committee member) / Arizona State University (Publisher)
Created2019
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 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.
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
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 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
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 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.
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
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 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.
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
Optical simulation and optimization of light extraction efficiency for organic light emitting diodes
Description
Current organic light emitting diodes (OLEDs) suffer from the low light extraction efficiency. In this thesis, novel OLED structures including photonic crystal, Fabry-Perot resonance cavity and hyperbolic metamaterials were numerically simulated and theoretically investigated. Finite-difference time-domain (FDTD) method was employed to numerically simulate the light extraction efficiency of various 3D OLED structures. With photonic crystal structures, a maximum of 30% extraction efficiency is achieved. A higher external quantum efficiency of 35% is derived after applying Fabry-Perot resonance cavity into OLEDs. Furthermore, different factors such as material properties, layer thicknesses and dipole polarizations and locations have been studied. Moreover, an upper limit for the light extraction efficiency of 80% is reached theoretically with perfect reflector and single dipole polarization and location. To elucidate the physical mechanism, transfer matrix method is introduced to calculate the spectral-hemispherical reflectance of the multilayer OLED structures. In addition, an attempt of using hyperbolic metamaterial in OLED has been made and resulted in 27% external quantum efficiency, due to the similar mechanism of wave interference as Fabry-Perot structure. The simulation and optimization methods and findings would facilitate the design of next generation, high-efficiency OLED devices.
ContributorsSu, Hang (Author) / Wang, Liping (Thesis advisor) / Li, Jian (Committee member) / Huang, Huei-Ping (Committee member) / Arizona State University (Publisher)
Created2016
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 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
Description
White organic light emitting diodes (WOLEDs) are currently being developed as the next generation of solid state lighting sources. Although, there has been considerable improvements in device efficiency from the early days up until now, there are still major drawbacks for the implementation of WOLEDs to commercial markets. These drawbacks include short lifetimes associated with highly efficient and easier to fabricate device structures. Platinum (II) complexes are been explored as emitters for single emissive layer WOLEDs, due to their higher efficiencies and stability in device configurations. These properties have been attributed to their square planar nature. Tetradentate platinum (II) complexes in particular have been shown to be more rigid and thus more stable than their other multidentate counterparts. This thesis aims to explore the different pathways via molecular design of tetradentate platinum II complexes and in particular the percipient engineering of a highly efficient and stable device structure. Previous works have been able to obtain either highly efficient devices or stable devices in different device configurations. In this work, we demonstrate a device structure employing Pt2O2 as the emitter using mCBP as a host with EQE of above 20% and lifetime values (LT80) exceeding 6000hours at practical luminance of 100cd/m2. These results open up the pathway towards the commercialization of white organic light emitting diodes as a solid state lighting source.
ContributorsOloye, Temidayo Abiola (Author) / Li, Jian (Thesis advisor) / Alford, Terry (Committee member) / Adams, James (Committee member) / Arizona State University (Publisher)
Created2016
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 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).
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
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 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