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Description
The addition of aminoalkyl-substituted 2,6-bis(imino)pyridine (or pyridine diimine, PDI) ligands to [(COD)RhCl]2 (COD = 1,5-cyclooctadiene) resulted in the formation of rhodium monochloride complexes with the general formula (NPDI)RhCl (NPDI = iPr2NEtPDI or Me2NPrPDI). The investigation of (iPr2NEtPDI)RhCl and (Me2NPrPDI)RhCl by single crystal X-ray diffraction verified the absence of amine arm coordination and a pseudo square planar geometry about rhodium. Replacement of the chloride ligand with an outer-sphere anion was achieved by adding AgBF4 directly to (iPr2NEtPDI)RhCl to form [(iPr2NEtPDI)Rh][BF4]. Alternatively, this complex was prepared upon chelate addition following the salt metathesis reaction between AgBF4 and [(COD)RhCl]2. Using the latter method, both [(NPDI)Rh][BF4] complexes were isolated and found to exhibit κ4-N,N,N,N-PDI coordination regardless of arm length or steric bulk. In contrast, the metallation of PPDI chelates featuring alkylphosphine imine substituents (PPDI = Ph2PEtPDI or Ph2PPrPDI) resulted in the formation of cationic complexes featuring κ5-N,N,N,P,P-PDI coordination in all instances, [(PPDI)Rh][X] (X = Cl, BF4). Adjusting the metallation stoichiometry allowed the preparation of [(Ph2PPrPDI)Rh][(COD)RhCl2], which was characterized by multinuclear NMR spectroscopy and single crystal X-ray diffraction.
ContributorsLevin, Hagit Ben-Daat (Author) / Trovitch, Ryan J (Thesis advisor) / Gould, Ian R (Committee member) / Ghirlanda, Giovanna (Committee member) / Arizona State University (Publisher)
Created2016
Description
This thesis develops molecular models for electron transport in molecular junctions and intra-molecular electron transfer. The goal is to identify molecular descriptors that afford a substantial simplification of these electronic processes.
First, the connection between static molecular polarizability and the molecular conductance is examined. A correlation emerges whereby the measured conductance of a tunneling junction decreases as a function of the calculated molecular polarizability for several systems, a result consistent with the idea of a molecule as a polarizable dielectric. A model based on a macroscopic extension of the Clausius-Mossotti equation to the molecular domain and Simmon’s tunneling model is developed to explain this correlation. Despite the simplicity of the theory, it paves the way for further experimental, conceptual and theoretical developments in the use of molecular descriptors to describe both conductance and electron transfer.
Second, the conductance of several biologically relevant, weakly bonded, hydrogen-bonded systems is systematically investigated. While there is no correlation between hydrogen bond strength and conductance, the results indicate a relation between the conductance and atomic polarizability of the hydrogen bond acceptor atom. The relevance of these results to electron transfer in biological systems is discussed.
Hydrogen production and oxidation using catalysts inspired by hydrogenases provides a more sustainable alternative to the use of precious metals. To understand electrochemical and spectroscopic properties of a collection of Fe and Ni mimics of hydrogenases, high-level density functional theory calculations are described. The results, based on a detailed analysis of the energies, charges and molecular orbitals of these metal complexes, indicate the importance of geometric constraints imposed by the ligand on molecular properties such as acidity and electrocatalytic activity. Based on model calculations of several intermediates in the catalytic cycle of a model NiFe complex, a hypothetical reaction mechanism, which very well agrees with the observed experimental results, is proffered.
Future work related to this thesis may involve the systematic analysis of chemical reactivity in constrained geometries, a subject of importance if the context of enzymatic activity. Another, more intriguing direction is related to the fundamental issue of reformulating Marcus theory in terms of the molecular dielectric response function.
First, the connection between static molecular polarizability and the molecular conductance is examined. A correlation emerges whereby the measured conductance of a tunneling junction decreases as a function of the calculated molecular polarizability for several systems, a result consistent with the idea of a molecule as a polarizable dielectric. A model based on a macroscopic extension of the Clausius-Mossotti equation to the molecular domain and Simmon’s tunneling model is developed to explain this correlation. Despite the simplicity of the theory, it paves the way for further experimental, conceptual and theoretical developments in the use of molecular descriptors to describe both conductance and electron transfer.
Second, the conductance of several biologically relevant, weakly bonded, hydrogen-bonded systems is systematically investigated. While there is no correlation between hydrogen bond strength and conductance, the results indicate a relation between the conductance and atomic polarizability of the hydrogen bond acceptor atom. The relevance of these results to electron transfer in biological systems is discussed.
Hydrogen production and oxidation using catalysts inspired by hydrogenases provides a more sustainable alternative to the use of precious metals. To understand electrochemical and spectroscopic properties of a collection of Fe and Ni mimics of hydrogenases, high-level density functional theory calculations are described. The results, based on a detailed analysis of the energies, charges and molecular orbitals of these metal complexes, indicate the importance of geometric constraints imposed by the ligand on molecular properties such as acidity and electrocatalytic activity. Based on model calculations of several intermediates in the catalytic cycle of a model NiFe complex, a hypothetical reaction mechanism, which very well agrees with the observed experimental results, is proffered.
Future work related to this thesis may involve the systematic analysis of chemical reactivity in constrained geometries, a subject of importance if the context of enzymatic activity. Another, more intriguing direction is related to the fundamental issue of reformulating Marcus theory in terms of the molecular dielectric response function.
ContributorsKhezr Seddigh Mazinani, Shobeir (Author) / Mujica, Vladimiro (Thesis advisor) / Pilarisetty, Tarakeshwar (Committee member) / Angell, Charles A (Committee member) / Jones, Anne K (Committee member) / Arizona State University (Publisher)
Created2015
Description
Continuing and increasing reliance on fossil fuels to satisfy our population’s energy demands has encouraged the search for renewable carbon-free and carbon-neutral sources, such as hydrogen gas or CO2 reduction products. Inspired by nature, one of the objectives of this dissertation was to develop protein-based strategies that can be applied in the production of green fuels. The first project of this dissertation aimed at developing a controllable strategy to incorporate domains with different functions (e. g. catalytic sites, electron transfer modules, light absorbing subunits) into a single multicomponent system. This was accomplished through the rational design of 2,2’-bipyridine modified dimeric peptides that allowed their metal-directed oligomerization by forming tris(bipyridine) complexes, thus resulting in the formation of a hexameric assembly.
Additionally, two different approaches to incorporate non-natural organometallic catalysts into protein matrix are discussed. First, cobalt protoporphyrin IX was incorporated into cytochrome b562 to produce a water-soluble proton and CO2 reduction catalyst that is active upon irradiation in the presence of a photosensitizer. The effect of the porphyrin axial ligands provided by the protein environment has been investigated by introducing mutations into the native scaffold, indicating that catalytic activity of proton reduction is dependent on axial coordination to the porphyrin. It is also shown that effects of the protein environment are not directly transferred when applied to other reactions, such as CO2 reduction.
Inspired by the active site of [FeFe]-hydrogenases, the second approach is based on the stereoselective preparation of a novel amino acid bearing a 1,2-benzenedithiol side chain. This moiety can serve as an anchoring point for the introduction of metal complexes into protein matrices. By doing so, this strategy enables the study of protein interactions with non-natural cofactors and the effects that it may have on catalysis. The work developed herein lays a foundation for furthering the study of the use of proteins as suitable environments for tuning the activity of organometallic catalysts in aqueous conditions, and interfacing these systems with other supporting units into supramolecular assemblies.
Additionally, two different approaches to incorporate non-natural organometallic catalysts into protein matrix are discussed. First, cobalt protoporphyrin IX was incorporated into cytochrome b562 to produce a water-soluble proton and CO2 reduction catalyst that is active upon irradiation in the presence of a photosensitizer. The effect of the porphyrin axial ligands provided by the protein environment has been investigated by introducing mutations into the native scaffold, indicating that catalytic activity of proton reduction is dependent on axial coordination to the porphyrin. It is also shown that effects of the protein environment are not directly transferred when applied to other reactions, such as CO2 reduction.
Inspired by the active site of [FeFe]-hydrogenases, the second approach is based on the stereoselective preparation of a novel amino acid bearing a 1,2-benzenedithiol side chain. This moiety can serve as an anchoring point for the introduction of metal complexes into protein matrices. By doing so, this strategy enables the study of protein interactions with non-natural cofactors and the effects that it may have on catalysis. The work developed herein lays a foundation for furthering the study of the use of proteins as suitable environments for tuning the activity of organometallic catalysts in aqueous conditions, and interfacing these systems with other supporting units into supramolecular assemblies.
ContributorsAlcala-Torano, Rafael de Jesus (Author) / Ghirlanda, Giovanna (Thesis advisor) / Moore, Ana L (Committee member) / Mills, Jeremy H (Committee member) / Arizona State University (Publisher)
Created2019
Description
The fuel cell is a promising device that converts the chemical energy directly into the electrical energy without combustion process. However, the slow reaction rate of the oxygen reduction reaction (ORR) necessitates the development of cathode catalysts for low-temperature fuel cells. After a thorough literature review in Chapter 1, the thesis is divided into three parts as given below in Chapters 2-4.
Chapter 2 describes the study on the Pt and Pt-Me (Me: Co, Ni) alloy nanoparticles supported on the pyrolyzed zeolitic imidazolate framework (ZIF) towards ORR. The Co-ZIF and NiCo-ZIF were synthesized by the solvothermal method and then mixed with Pt precursor. After pyrolysis and acid leaching, the PtCo/NC and PtNiCo/NC were evaluated in proton exchange membrane fuel cells (PEMFC). The peak power density exhibited > 10% and 15% for PtCo/NC and PtNiCo/NC, respectively, compared to that with commercial Pt/C catalyst under identical test conditions.
Chapter 3 is the investigation of the oxygen vacancy (OV) effect in a-MnO2 as a cathode catalyst for alkaline membrane fuel cells (AMFC). The a-MnO2 nanorods were synthesized by hydrothermal method and heated at 300, 400 and 500 ℃ in the air to introduce the OV. The 400 ℃ treated material showed the best ORR performance among all other samples due to more OV in pure a-MnO2 phase. The optimized AMFC electrode showed ~ 45 mW.cm-2, which was slightly lower than that with commercial Pt/C (~60 mW.cm-2).
Chapter 4 is the density functional theory (DFT) study of the protonation effect and active sites towards ORR on a-MnO2 (211) plane. The theoretically optimized oxygen adsorption and hydroxyl ion desorption energies were ~ 1.55-1.95 eV and ~ 0.98-1.45 eV, respectively, by Nørskov et al.’s calculations. All the configurations showed oxygen adsorption and hydroxyl ion desorption energies were ranging from 0.27 to 1.76 eV and 1.59 to 15.0 eV, respectively. The site which was close to two Mn ions showed the best oxygen adsorption and hydroxyl ion desorption energies improvement with the surface protonation.
Based on the results given in Chapters 1-4, the major findings are summarized in Chapter 5.
Chapter 2 describes the study on the Pt and Pt-Me (Me: Co, Ni) alloy nanoparticles supported on the pyrolyzed zeolitic imidazolate framework (ZIF) towards ORR. The Co-ZIF and NiCo-ZIF were synthesized by the solvothermal method and then mixed with Pt precursor. After pyrolysis and acid leaching, the PtCo/NC and PtNiCo/NC were evaluated in proton exchange membrane fuel cells (PEMFC). The peak power density exhibited > 10% and 15% for PtCo/NC and PtNiCo/NC, respectively, compared to that with commercial Pt/C catalyst under identical test conditions.
Chapter 3 is the investigation of the oxygen vacancy (OV) effect in a-MnO2 as a cathode catalyst for alkaline membrane fuel cells (AMFC). The a-MnO2 nanorods were synthesized by hydrothermal method and heated at 300, 400 and 500 ℃ in the air to introduce the OV. The 400 ℃ treated material showed the best ORR performance among all other samples due to more OV in pure a-MnO2 phase. The optimized AMFC electrode showed ~ 45 mW.cm-2, which was slightly lower than that with commercial Pt/C (~60 mW.cm-2).
Chapter 4 is the density functional theory (DFT) study of the protonation effect and active sites towards ORR on a-MnO2 (211) plane. The theoretically optimized oxygen adsorption and hydroxyl ion desorption energies were ~ 1.55-1.95 eV and ~ 0.98-1.45 eV, respectively, by Nørskov et al.’s calculations. All the configurations showed oxygen adsorption and hydroxyl ion desorption energies were ranging from 0.27 to 1.76 eV and 1.59 to 15.0 eV, respectively. The site which was close to two Mn ions showed the best oxygen adsorption and hydroxyl ion desorption energies improvement with the surface protonation.
Based on the results given in Chapters 1-4, the major findings are summarized in Chapter 5.
ContributorsShi, Xuan, Ph.D (Author) / Kannan, Arunachalanadar Mada (Thesis advisor) / Liu, Jingyue (Committee member) / Nam, Changho (Committee member) / Peng, Xihong (Committee member) / Arizona State University (Publisher)
Created2019
Description
Quantifying molecular interactions is pivotal for understanding biological processes at molecular scale and for screening drugs. Although various detection technologies have been developed, it is still challenging to quantify the binding kinetics of small molecules because the sensitivities of the mainstream technologies scale down with the size of the molecule. To address this problem, two different optical detection methods, charge sensitive optical detection (CSOD) and virion
ano-oscillators, are developed to measure the binding-induced charge change instead of the mass change, which enables quantification of the binding kinetics for both large and small molecules.
In particular, the nano-oscillator approach provides a unique capability to image individual nanoparticles and measure the size and charge of each nanoparticle simultaneously. This approach is applied to measure one of the smallest biological particles - single protein molecules. By tracking the oscillation of each protein molecule, the size, charge, and mobility are measured in real-time with high precision. This capability also allows to monitor the conformation and charge changes of single protein molecules upon ligand binding. Measuring the size and charge of single proteins opens a new revenue to protein analysis and disease biomarker detection at the single molecule level.
The virion
ano-oscillators and the single protein approach employ a scheme where a particle is tethered to the surface with a polymer molecule. The dynamics of the particle is governed by two important forces: One is entropic force arising from the conformational change of the molecular tether, and the other is solvent damping on the particle and the molecule. The dynamics is studied by varying the type of the tether molecule, size of the particle, and viscosity of the solvent. The findings provide insights into single molecule studies using not only tethered particles, but also other approaches, including force spectroscopy using atomic force microscopy and nanopores.
ano-oscillators, are developed to measure the binding-induced charge change instead of the mass change, which enables quantification of the binding kinetics for both large and small molecules.
In particular, the nano-oscillator approach provides a unique capability to image individual nanoparticles and measure the size and charge of each nanoparticle simultaneously. This approach is applied to measure one of the smallest biological particles - single protein molecules. By tracking the oscillation of each protein molecule, the size, charge, and mobility are measured in real-time with high precision. This capability also allows to monitor the conformation and charge changes of single protein molecules upon ligand binding. Measuring the size and charge of single proteins opens a new revenue to protein analysis and disease biomarker detection at the single molecule level.
The virion
ano-oscillators and the single protein approach employ a scheme where a particle is tethered to the surface with a polymer molecule. The dynamics of the particle is governed by two important forces: One is entropic force arising from the conformational change of the molecular tether, and the other is solvent damping on the particle and the molecule. The dynamics is studied by varying the type of the tether molecule, size of the particle, and viscosity of the solvent. The findings provide insights into single molecule studies using not only tethered particles, but also other approaches, including force spectroscopy using atomic force microscopy and nanopores.
ContributorsMa, Guangzhong, Ph.D (Author) / Tao, Nongjian (Thesis advisor) / Wang, Shaopeng (Thesis advisor) / Ros, Alexandra (Committee member) / Guo, Jia (Committee member) / Arizona State University (Publisher)
Created2019
Description
Air pollution has been linked to various health problems but how different air pollutants and exposure levels contribute to those diseases remain largely unknown. Researchers have mainly relied on data from government air monitoring stations to study the health effects of air pollution exposure. The limited information provided by sparse stations has low spatial and temporal resolution, which is not able to represent the actual exposure of individuals. A tool that can accurately monitor personal exposure provides valuable data for epidemiologists to understand the relationship between air pollution and certain diseases. It also allows individuals to be aware of any ambient air quality issues and prevent air pollution exposure. To build such a tool, sensors with features of fast response, small size, long lifetime, high sensitivity, high selectivity, and multi-analyte sensing are of great importance.
In order to meet these requirements, three generations of novel colorimetric sensors have been developed. The first generation is mosaic colorimetric sensors based on tiny sensor blocks and by detecting absorbance change after each air sample injection, the target analyte concentration can be measured. The second generation is a gradient-based colorimetric sensor. Lateral transport of analytes across the colorimetric sensor surface creates a color gradient that shifts along the transport direction over time, and the sensor tracks the gradient shift and converts it into analyte concentration in real-time. The third generation is gradient-based colorimetric arrays fabricated by inkjet-printing method that integrates multiple sensors on a miniaturized sensor chip. Unlike traditional colorimetric sensors, such as detection tubes and optoelectronic nose, that are typically for one-time use, the presented three generations of colorimetric sensors aim to continuously monitor multiple air pollutants and the sensor lifetime and fabrication methods have been improved over each generation. Ozone, nitrogen dioxide, formaldehyde and carbon monoxide are chosen as analytes of interest. The performance of sensors has been validated in the lab and field tests, proving the capability of the sensors to be used for personal exposure monitoring.
In order to meet these requirements, three generations of novel colorimetric sensors have been developed. The first generation is mosaic colorimetric sensors based on tiny sensor blocks and by detecting absorbance change after each air sample injection, the target analyte concentration can be measured. The second generation is a gradient-based colorimetric sensor. Lateral transport of analytes across the colorimetric sensor surface creates a color gradient that shifts along the transport direction over time, and the sensor tracks the gradient shift and converts it into analyte concentration in real-time. The third generation is gradient-based colorimetric arrays fabricated by inkjet-printing method that integrates multiple sensors on a miniaturized sensor chip. Unlike traditional colorimetric sensors, such as detection tubes and optoelectronic nose, that are typically for one-time use, the presented three generations of colorimetric sensors aim to continuously monitor multiple air pollutants and the sensor lifetime and fabrication methods have been improved over each generation. Ozone, nitrogen dioxide, formaldehyde and carbon monoxide are chosen as analytes of interest. The performance of sensors has been validated in the lab and field tests, proving the capability of the sensors to be used for personal exposure monitoring.
ContributorsLin, Chenwen (Author) / Tao, Nongjian (Thesis advisor) / Borges, Chad R (Committee member) / Hayes, Mark A. (Committee member) / Arizona State University (Publisher)
Created2019
Description
An evolving understanding of elastomeric polymer nanocomposites continues to expand commercial, defense, and industrial products and applications. This work explores the thermomechanical properties of elastomeric nanocomposites prepared from bisphenol A diglycidyl ether (BADGE) and three amine-terminated poly(propylene oxides) (Jeffamines). The Jeffamines investigated include difunctional crosslinkers with molecular weights of 2,000 and 4,000 g/mol and a trifunctional crosslinker with a molecular weight of 3,000 g/mol. Additionally, carbon nanotubes (CNTs) were added, up to 1.25 wt%, to each thermoset. The findings indicate that the Tg and storage modulus of the polymer nanocomposites can be controlled independently within narrow concentration windows, and that effects observed following CNT incorporation are dependent on the crosslinker molecular weight.
Polymer matrix composites (PMCs) offer design solutions to produce smart sensing, conductive, or high performance composites for a number of critical applications. Nanoparticle additives, in particular, carbon nanotubes and metallic quantum dots, have been investigated for their ability to improve the conductivity, thermal stability, and mechanical strength of traditional composites. Herein we report the use of quantum dots (QDs) and fluorescently labeled carbon nanotubes (CNTs) to modify the thermomechanical properties of PMCs. Additionally, we find that pronounced changes in fluorescence emerge following plastic deformation, indicating that in these polymeric materials the transduction of mechanical force into the fluorescence occurs in response to mechanical activation.
Segmented ionenes are a class of thermoplastic elastomers that contain a permanent charged group within the polymer backbone and a spacer segment with a low glass transition temperature (Tg) to provide flexibility. Ionenes are of interest because of their synthetic versatility, unique morphologies, and ionic nature. Using phase changing ionene-based nanocomposites could be extended to create reversible mechanically, electrically, optically, and/or thermally responsive materials depending on constituent nanoparticles and polymers. This talk will discuss recent efforts to utilize the synthetic versatility of ionenes (e.g., spacer composition of PTMO or PEG) to prepare percolated ionic domains in microphase separated polymers that display a range of thermomechanical properties. Furthermore, by synthesizing two series of ionene copolymers with either PEG or PTMO spacers at various ratios with 1,12-dibromododecane will yield a range of ion contents (hard contents) and will impact nanoparticle dispersion.
Polymer matrix composites (PMCs) offer design solutions to produce smart sensing, conductive, or high performance composites for a number of critical applications. Nanoparticle additives, in particular, carbon nanotubes and metallic quantum dots, have been investigated for their ability to improve the conductivity, thermal stability, and mechanical strength of traditional composites. Herein we report the use of quantum dots (QDs) and fluorescently labeled carbon nanotubes (CNTs) to modify the thermomechanical properties of PMCs. Additionally, we find that pronounced changes in fluorescence emerge following plastic deformation, indicating that in these polymeric materials the transduction of mechanical force into the fluorescence occurs in response to mechanical activation.
Segmented ionenes are a class of thermoplastic elastomers that contain a permanent charged group within the polymer backbone and a spacer segment with a low glass transition temperature (Tg) to provide flexibility. Ionenes are of interest because of their synthetic versatility, unique morphologies, and ionic nature. Using phase changing ionene-based nanocomposites could be extended to create reversible mechanically, electrically, optically, and/or thermally responsive materials depending on constituent nanoparticles and polymers. This talk will discuss recent efforts to utilize the synthetic versatility of ionenes (e.g., spacer composition of PTMO or PEG) to prepare percolated ionic domains in microphase separated polymers that display a range of thermomechanical properties. Furthermore, by synthesizing two series of ionene copolymers with either PEG or PTMO spacers at various ratios with 1,12-dibromododecane will yield a range of ion contents (hard contents) and will impact nanoparticle dispersion.
ContributorsWang, Meng, Ph.D (Author) / Green, Matthew D (Thesis advisor) / Green, Alexander (Committee member) / Yarger, Jeffery (Committee member) / Arizona State University (Publisher)
Created2019
Temperature and polarizability effects on electron transfer in biology and artificial photosynthesis
Description
This study aims to address the deficiencies of the Marcus model of electron transfer
(ET) and then provide modifications to the model. A confirmation of the inverted energy
gap law, which is the cleanest verification so far, is presented for donor-acceptor complexes.
In addition to the macroscopic properties of the solvent, the physical properties of the solvent
are incorporated in the model via the microscopic solvation model. For the molecules
studied in this dissertation, the rate constant first increases with cooling, in contrast to the
prediction of the Arrhenius law, and then decreases at lower temperatures. Additionally,
the polarizability of solute, which was not considered in the original Marcus theory, is included
by the Q-model of ET. Through accounting for the polarizability of the reactants, the
Q-model offers an important design principle for achieving high performance solar energy
conversion materials. By means of the analytical Q-model of ET, it is shown that including
molecular polarizability of C60 affects the reorganization energy and the activation barrier
of ET reaction.
The theory and Electrochemistry of Ferredoxin and Cytochrome c are also investigated.
By providing a new formulation for reaction reorganization energy, a long-standing disconnect
between the results of atomistic simulations and cyclic voltametery experiments is
resolved. The significant role of polarizability of enzymes in reducing the activation energy
of ET is discussed. The binding/unbinding of waters to the active site of Ferredoxin leads
to non-Gaussian statistics of energy gap and result in a smaller activation energy of ET.
Furthermore, the dielectric constant of water at the interface of neutral and charged
C60 is studied. The dielectric constant is found to be in the range of 10 to 22 which is
remarkably smaller compared to bulk water( 80). Moreover, the interfacial structural
crossover and hydration thermodynamic of charged C60 in water is studied. Increasing the
charge of the C60 molecule result in a dramatic structural transition in the hydration shell,
which lead to increase in the population of dangling O-H bonds at the interface.
(ET) and then provide modifications to the model. A confirmation of the inverted energy
gap law, which is the cleanest verification so far, is presented for donor-acceptor complexes.
In addition to the macroscopic properties of the solvent, the physical properties of the solvent
are incorporated in the model via the microscopic solvation model. For the molecules
studied in this dissertation, the rate constant first increases with cooling, in contrast to the
prediction of the Arrhenius law, and then decreases at lower temperatures. Additionally,
the polarizability of solute, which was not considered in the original Marcus theory, is included
by the Q-model of ET. Through accounting for the polarizability of the reactants, the
Q-model offers an important design principle for achieving high performance solar energy
conversion materials. By means of the analytical Q-model of ET, it is shown that including
molecular polarizability of C60 affects the reorganization energy and the activation barrier
of ET reaction.
The theory and Electrochemistry of Ferredoxin and Cytochrome c are also investigated.
By providing a new formulation for reaction reorganization energy, a long-standing disconnect
between the results of atomistic simulations and cyclic voltametery experiments is
resolved. The significant role of polarizability of enzymes in reducing the activation energy
of ET is discussed. The binding/unbinding of waters to the active site of Ferredoxin leads
to non-Gaussian statistics of energy gap and result in a smaller activation energy of ET.
Furthermore, the dielectric constant of water at the interface of neutral and charged
C60 is studied. The dielectric constant is found to be in the range of 10 to 22 which is
remarkably smaller compared to bulk water( 80). Moreover, the interfacial structural
crossover and hydration thermodynamic of charged C60 in water is studied. Increasing the
charge of the C60 molecule result in a dramatic structural transition in the hydration shell,
which lead to increase in the population of dangling O-H bonds at the interface.
ContributorsWaskasi, Morteza M (Author) / Matyushov, Dmitry (Thesis advisor) / Richert, Ranko (Committee member) / Heyden, Matthias (Committee member) / Beckstein, Oliver (Committee member) / Arizona State University (Publisher)
Created2019
Description
Nanostructured zeolites, in particular nanocrystalline zeolites, are of great interest due to their efficient use in conventional catalysis, separations, and emerging applications. Despite the recent advances, fewer than 20 zeolite framework types have been synthesized in the form of nanocrystallites and their scalable synthesis has yet to be developed and understood. Geopolymers, claimed to be “amorphous cousins of zeolites”, are a class of ceramic-like aluminosilicate materials with prominent application in construction due to their unique chemical and mechanical properties. Despite the monolith form, geopolymers are fundamentally nanostructured materials and contain zeolite nanocrystallites.
Herein, a new cost-effective and scalable synthesis of various types of nanocrystalline zeolites based on geopolymer chemistry is presented. The study includes the synthesis of highly crystalline discrete nanorods of a CAN zeolite framework structure that had not been achieved hitherto, the exploration of the Na−Al−Si−H2O kinetic phase diagram of hydrogels that gives SOD, CAN and FAU nanocrystalline zeolites, and the discovery of a unique formation mechanism of highly crystalline nanostructured FAU zeolite with intermediate gel products that possess an unprecedented uniform distribution of elements. This study demonstrated the possibility of using high-concentration hydrogels for the synthesis of nanocrystalline zeolites of additional framework structures.
Moreover, a comprehensive study on nanostructured FAU zeolites ion-exchanged with Ag+, Zn2+, Cu2+ and Fe2+ for antibacterial applications is presented, which comprises metal ion release kinetics, antibacterial properties, and cytotoxicity. For the first time, superior metal ion release performance was confirmed for the nanostructured zeolites compared to their micron-sized counterparts. The metal ion-exchanged FAU nanostructured zeolites were established as new effective antibacterial materials featuring their unique physiochemical, antibacterial, and cytotoxic properties.
Herein, a new cost-effective and scalable synthesis of various types of nanocrystalline zeolites based on geopolymer chemistry is presented. The study includes the synthesis of highly crystalline discrete nanorods of a CAN zeolite framework structure that had not been achieved hitherto, the exploration of the Na−Al−Si−H2O kinetic phase diagram of hydrogels that gives SOD, CAN and FAU nanocrystalline zeolites, and the discovery of a unique formation mechanism of highly crystalline nanostructured FAU zeolite with intermediate gel products that possess an unprecedented uniform distribution of elements. This study demonstrated the possibility of using high-concentration hydrogels for the synthesis of nanocrystalline zeolites of additional framework structures.
Moreover, a comprehensive study on nanostructured FAU zeolites ion-exchanged with Ag+, Zn2+, Cu2+ and Fe2+ for antibacterial applications is presented, which comprises metal ion release kinetics, antibacterial properties, and cytotoxicity. For the first time, superior metal ion release performance was confirmed for the nanostructured zeolites compared to their micron-sized counterparts. The metal ion-exchanged FAU nanostructured zeolites were established as new effective antibacterial materials featuring their unique physiochemical, antibacterial, and cytotoxic properties.
ContributorsChen, Shaojiang (Author) / Seo, Dong Kyun (Thesis advisor) / Trovitch, Ryan (Committee member) / Thomas, MaryLaura Lind (Committee member) / Arizona State University (Publisher)
Created2019
Description
There is increasing interest and demand in biology studies for identifying and characterizing rare cells or bioparticle subtypes. These subpopulations demonstrate special function, as examples, in multipotent proliferation, immune system response, and cancer diagnosis. Current techniques for separation and identification of these targets lack the accuracy and sensitivity needed to interrogate the complex and diverse bioparticle mixtures. High resolution separations of unlabeled and unaltered cells is an emerging capability. In particular, electric field-driven punctuated microgradient separations have shown high resolution separations of bioparticles. These separations are based on biophysical properties of the un-altered bioparticles. Here, the properties of the bioparticles were identified by ratio of electrokinetic (EK) to dielectrophoretic (DEP) mobilities.
As part of this dissertation, high-resolution separations have been applied to neural stem and progenitor cells (NSPCs). The abundance of NSPCs captured with different range of ratio of EK to DEP mobilities are consistent with the final fate trends of the populations. This supports the idea of unbiased and unlabeled high-resolution separation of NSPCs to specific fates is possible. In addition, a new strategy to generate reproducible subpopulations using varied applied potential were employed for studying insulin vesicles from beta cells. The isolated subpopulations demonstrated that the insulin vesicles are heterogenous and showed different distribution of mobility ratios when compared with glucose treated insulin vesicles. This is consistent with existing vesicle density and local concentration data. Furthermore, proteins, which are accepted as challenging small bioparticles to be captured by electrophysical method, were concentrated by this technique. Proteins including IgG, lysozyme, alpha-chymotrypsinogen A were differentiated and characterized with the ratio factor. An extremely narrow bandwidth and high resolution characterization technique, which is experimentally simple and fast, has been developed for proteins. Finally, the native whole cell separation technique has also been applied for Salmonella serotype identification and differentiation for the first time. The technique generated full differentiation of four serotypes of Salmonella. These works may lead to a less expensive and more decentralized new tool and method for transplantation, proteomics, basic research, and microbiologists, working in parallel with other characterization methods.
As part of this dissertation, high-resolution separations have been applied to neural stem and progenitor cells (NSPCs). The abundance of NSPCs captured with different range of ratio of EK to DEP mobilities are consistent with the final fate trends of the populations. This supports the idea of unbiased and unlabeled high-resolution separation of NSPCs to specific fates is possible. In addition, a new strategy to generate reproducible subpopulations using varied applied potential were employed for studying insulin vesicles from beta cells. The isolated subpopulations demonstrated that the insulin vesicles are heterogenous and showed different distribution of mobility ratios when compared with glucose treated insulin vesicles. This is consistent with existing vesicle density and local concentration data. Furthermore, proteins, which are accepted as challenging small bioparticles to be captured by electrophysical method, were concentrated by this technique. Proteins including IgG, lysozyme, alpha-chymotrypsinogen A were differentiated and characterized with the ratio factor. An extremely narrow bandwidth and high resolution characterization technique, which is experimentally simple and fast, has been developed for proteins. Finally, the native whole cell separation technique has also been applied for Salmonella serotype identification and differentiation for the first time. The technique generated full differentiation of four serotypes of Salmonella. These works may lead to a less expensive and more decentralized new tool and method for transplantation, proteomics, basic research, and microbiologists, working in parallel with other characterization methods.
ContributorsLiu, Yameng (Author) / Hayes, Mark A. (Thesis advisor) / Wang, Xu (Committee member) / Borges, Chad (Committee member) / Arizona State University (Publisher)
Created2020