Engineering Commons^™

Effects Of Hole Transporting Layers And Surface Ligands On Interface Energetics And Photovoltaic Performance Of Methylammonium Lead Iodide Perovskites, So Min Park

Theses and Dissertations--Chemical and Materials Engineering

Organic metal halide perovskites are promising materials for various optoelectronic device applications such as light emitting diodes (LED) and photovoltaic (PV) cells. Perovskite solar cells (PSCs) have shown dramatic increases in power conversion efficiency over the previous ten years, far exceeding the rate of improvement of all other PV technologies. PSCs have attracted significant attention due to their strong absorbance throughout the visible region, high charge carrier mobilities, color tunability, and ability to make ultralight weight devices. However, organic metal halide perovskites still face several challenges. For example, their environmental stability issue must be overcome to enable widespread commercialization. Meeting …

Carbon Oxidation At The Atomic Level: A Computational Study On Oxidative Graphene Etching And Pitting Of Graphitic Carbon Surfaces, Simon Schmitt

Theses and Dissertations--Mechanical Engineering

In order to understand the oxidation of solid carbon materials by oxygen-containing gases, carbon oxidation has to be studied on the atomic level where the surface reactions occur. Graphene and graphite are etched by oxygen to form characteristic pits that are scattered across the material surface, and pitting in turn leads to microstructural changes that determine the macroscopic oxidation behavior. While this is a well-documented phenomenon, it is heretofore poorly understood due to the notorious difficulty of experiments and a lack of comprehensive computational studies. The main objective of the present work is the development of a computational framework from …

A Theoretical And Experimental Study Of Charge Transport In Organic Thermoelectric Materials And Charge Transfer States In Organic Photovoltaics, Ashkan Abtahi

Theses and Dissertations--Physics and Astronomy

Applications of organic electronics have increased significantly over the past two decades. Organic semiconductors (OSC) can be used in mechanically flexible devices with potentially lower cost of fabrication than their inorganic counterparts, yet in many cases organic semiconductor-based devices suffer from lower performance and stability. Investigating the doping mechanism, charge transport, and charge transfer in such materials will allow us to address the parameters that limit performance and potentially resolve them. In this dissertation, organic materials are used in three different device structures to investigate charge transport and charge transfer. Chemically doped π-conjugated polymers are promising materials to be used …

Correlating The Physicochemical Properties Of Magnesium Stearate With Tablet Dissolution And Lubrication, Julie L. Calahan

Theses and Dissertations--Pharmacy

Magnesium stearate (MgSt) is the most commonly used pharmaceutical excipient and is present in over half the tablet formulations on the market. In spite of its popularity as an effective lubricant, it has been repeatedly recognized that there is significant variability between MgSt samples, which can cause inconsistent lubrication between batches of MgSt. The hypothesis of this research is that the batch-to-batch variability in tablet lubrication and dissolution observed in tablet formulations containing different MgSt samples can be correlated with differences in MgSt physicochemical properties (fatty acid salt composition, crystal hydrate form, particle size and surface area). Developing correlations between …

The Effects Of Reactant Concentration And Air Flow Rate In The Consumption Of Dissolved O2 During The Photochemistry Of Aqueous Pyruvic Acid, Alexis J. Eugene, Marcelo I. Guzman

Chemistry Faculty Publications

The sunlight photochemistry of the organic chromophore pyruvic acid (PA) in water generates ketyl and acetyl radicals that contribute to the production and processing of atmospheric aerosols. The photochemical mechanism is highly sensitive to dissolved oxygen content, [O₂(aq)], among other environmental conditions. Thus, herein we investigate the photolysis (λ ≥ 305 nm) of 10–200 mM PA at pH 1.0 in water covering the relevant range 0 ≤ [O₂(aq)] ≤ 1.3 mM. The rapid consumption of dissolved oxygen by the intermediate photolytic radicals is monitored in real time with a dissolved oxygen electrode. …

Photocatalytic Activity: Experimental Features To Report In Heterogeneous Photocatalysis, Md. Ariful Hoque, Marcelo I. Guzman

Chemistry Faculty Publications

Heterogeneous photocatalysis is a prominent area of research with major applications in solar energy conversion, air pollution mitigation, and removal of contaminants from water. A large number of scientific papers related to the photocatalysis field and its environmental applications are published in different journals specializing in materials and nanomaterials. However, many problems exist in the conception of papers by authors unfamiliar with standard characterization methods of photocatalysts as well as with the procedures needed to determine photocatalytic activities based on the determination of “apparent quantum efficiencies” within a wavelength interval or “apparent quantum yields” in the case of using monochromatic …

Cross Photoreaction Of Glyoxylic And Pyruvic Acids In Model Aqueous Aerosol, Sha-Sha Xia, Alexis J. Eugene, Marcelo I. Guzman

Chemistry Faculty Publications

Aerosols of variable composition, size, and shape are associated with public health concerns as well as with light-particle interactions that play a role in the energy balance of the atmosphere. Photochemical reactions of 2-oxocarboxylic acids in the aqueous phase are now known to contribute to the total secondary organic aerosol (SOA) budget. This work explores the cross reaction of glyoxylic acid (GA) and pyruvic acid (PA) in water, the two most abundant 2-oxocarboxylic acids in the atmosphere, under solar irradiation and dark thermal aging steps. During irradiation, PA and GA are excited and initiate proton-coupled electron transfer or hydrogen abstraction …

Oxidation Of Substituted Catechols At The Air-Water Interface: Production Of Carboxylic Acids, Quinones, And Polyphenols, Elizabeth A. Pillar, Marcelo I. Guzman

Chemistry Faculty Publications

Anthropogenic activities contribute benzene, toluene, and anisole to the environment, which in the atmosphere are converted into the respective phenols, cresols, and methoxyphenols by fast gas-phase reaction with hydroxyl radicals (HO(•)). Further processing of the latter species by HO(•) decreases their vapor pressure as a second hydroxyl group is incorporated to accelerate their oxidative aging at interfaces and in aqueous particles. This work shows how catechol, pyrogallol, 3-methylcatechol, 4-methylcatechol, and 3-methoxycatechol (all proxies for oxygenated aromatics derived from benzene, toluene, and anisole) react at the air-water interface with increasing O3(g) during τc ≈ 1 μs contact time and contrasts their …

Nitrate Radicals And Biogenic Volatile Organic Compounds: Oxidation, Mechanisms And Organic Aerosol, Nga Lee Ng, Steven S. Brown, Alexander T. Archibald, Elliot Atlas, Ronald C. Cohen, John N. Crowley, Douglas A. Day, Neil M. Donahue, Juliane L. Fry, Hendrik Fuchs, Robert J. Griffin, Marcelo I. Guzman, Hartmut Hermann, Alma Hodzic, Yoshiteru Iinuma, José L. Jimenez, Astrid Kiendler-Scharr, Ben H. Lee, Deborah J. Luecken, Jingqiu Mao, Robert Mclaren, Anke Mutzel, Hans D. Osthoff, Bin Ouyang, Benedicte Picquet-Varrault, Ulrich Platt, Havala O. T. Pye, Yinon Rudich, Rebecca H. Schwantes, Manabu Shiraiwa, Jochen Stutz, Joel A. Thornton, Andreas Tilgner, Brent J. Williams, Rahul A. Zaveri

Chemistry Faculty Publications

Oxidation of biogenic volatile organic compounds (BVOC) by the nitrate radical (NO₃) represents one of the important interactions between anthropogenic emissions related to combustion and natural emissions from the biosphere. This interaction has been recognized for more than 3 decades, during which time a large body of research has emerged from laboratory, field, and modeling studies. NO₃-BVOC reactions influence air quality, climate and visibility through regional and global budgets for reactive nitrogen (particularly organic nitrates), ozone, and organic aerosol. Despite its long history of research and the significance of this topic in atmospheric chemistry, a number …

Charge Transport In Electronic-Ionic Composites, Long Zhang

Theses and Dissertations--Chemical and Materials Engineering

The goal of this thesis is to generate fundamental understandings of charge transport behaviors of composites consisting of garnet structured Al substituted Li₇La₃Zr₂O₁₂ (LLZO) electrolyte and LiCoO₂ electrode. In order to take full advantage of all-solid-state batteries, bulk type composite electrodes should be introduced to increase energy and power density. However, the charge utilization of bulk type composite electrodes is quite low. Understanding ionic conduction behavior is, therefore, important for improving the performance of all-solid-state batteries, because ion conduction within solids depends on effective pathways. Electronic conductivity can be easily compensated by …

Aqueous Photochemistry Of Glyoxylic Acid, Alexis J. Eugene, Sha-Sha Xia, Marcelo I. Guzman

Chemistry Faculty Publications

Aerosols affect climate change, the energy balance of the atmosphere, and public health due to their variable chemical composition, size, and shape. While the formation of secondary organic aerosols (SOA) from gas phase precursors is relatively well understood, studying aqueous chemical reactions contributing to the total SOA budget is the current focus of major attention. Field measurements have revealed that mono-, di-, and oxo-carboxylic acids are abundant species present in SOA and atmospheric waters. This work explores the fate of one of these 2-oxocarboxylic acids, glyoxylic acid, which can photogenerate reactive species under solar irradiation. Additionally, the dark thermal aging …

Effect Of Spalled Particles Thermal Degradation On A Hypersonic Flow Field Environment, Raghava S. C. Davuluri, Huaibao Zhang, Alexandre Martin

Mechanical Engineering Faculty Publications

Two-way coupling is performed between a spallation code and a hypersonic aerothermodynamics CFD solver to evaluate the effect of spalled particles on the flow field. Time accurate solutions are computed in argon and air flow fields. A single particle simulations and multiple particles simulations are performed and studied. The results show that the carbon vapor released by spalled particles tend to change the composition of the flow field, particularly the upstream region of the shock.

Understanding Electrical Conduction In Lithium Ion Batteries Through Multi-Scale Modeling, Jie Pan

Theses and Dissertations--Chemical and Materials Engineering

Silicon (Si) has been considered as a promising negative electrode material for lithium ion batteries (LIBs) because of its high theoretical capacity, low discharge voltage, and low cost. However, the utilization of Si electrode has been hampered by problems such as slow ionic transport, large stress/strain generation, and unstable solid electrolyte interphase (SEI). These problems severely influence the performance and cycle life of Si electrodes. In general, ionic conduction determines the rate performance of the electrode, while electron leakage through the SEI causes electrolyte decomposition and, thus, causes capacity loss. The goal of this thesis research is to design Si …

Heterogeneous Oxidation Of Catechol, Elizabeth A. Pillar, Ruixin Zhou, Marcelo I. Guzman

Chemistry Faculty Publications

Natural and anthropogenic emissions of aromatic hydrocarbons from biomass burning, agro-industrial settings, and fossil fuel combustion contribute precursors to secondary aerosol formation (SOA). How these compounds are processed under humid tropospheric conditions is the focus of current attention to understand their environmental fate. This work shows how catechol thin films, a model for oxygenated aromatic hydrocarbons present in biomass burning and combustion aerosols, undergo heterogeneous oxidation at the air–solid interface under variable relative humidity (RH = 0–90%). The maximum reactive uptake coefficient of O₃(g) by catechol γ_O3 = (7.49 ± 0.35) × 10^–6 occurs for …

Catechol Oxidation By Ozone And Hydroxyl Radicals At The Air-Water Interface, Elizabeth A. Pillar, Robert C. Camm, Marcelo I. Guzman

Chemistry Faculty Publications

Anthropogenic emissions of aromatic hydrocarbons promptly react with hydroxyl radicals undergoing oxidation to form phenols and polyphenols (e.g., catechol) typically identified in the complex mixture of humic-like substances (HULIS). Because further processing of polyphenols in secondary organic aerosols (SOA) can continue mediated by a mechanism of ozonolysis at interfaces, a better understanding about how these reactions proceed at the air–water interface is needed. This work shows how catechol, a molecular probe of the oxygenated aromatic hydrocarbons present in SOA, can contribute interfacial reactive species that enhance the production of HULIS under atmospheric conditions. Reactive semiquinone radicals are quickly produced upon …

The Critical Role Of Mechanism-Based Models For Understanding And Predicting Liposomal Drug Loading, Binding And Release Kinetics, Sweta Modi

Theses and Dissertations--Pharmacy

Liposomal delivery systems hold considerable promise for improvement of cancer therapy provided that critical formulation design criteria can be met. The main objective of the current project was to enable quality by design in the formulation of liposomal delivery systems by developing comprehensive, mechanism-based mathematical models of drug loading, binding and release kinetics that take into account not only the therapeutic requirement but the physicochemical properties of the drug, the bilayer membrane, and the intraliposomal microenvironment.

Membrane binding of the drug affects both drug loading and release from liposomes. The influence of bilayer composition and phase structure on the partitioning …

Concentration Effects And Ion Properties Controlling The Fractionation Of Halides During Aerosol Formation, Marcelo I. Guzman, Richa R. Athalye, Jose M. Rodriguez

Chemistry Faculty Publications

During the aerosolization process at the sea surface, halides are incorporated into aerosol droplets, where they may play an important role in tropospheric ozone chemistry. Although this process may significantly contribute to the formation of reactive gas phase molecular halogens, little is known about the environmental factors that control how halides selectively accumulate at the air-water interface. In this study, the production of sea spray aerosol is simulated using electrospray ionization (ESI) of 100 nM equimolar solutions of NaCl, NaBr, NaI, NaNO(2), NaNO(3), NaClO(4), and NaIO(4). The microdroplets generated are analyzed by mass spectrometry to study the comparative enrichment of …

Studies On Silicon Nmr Characterization And Kinetic Modeling Of The Structural Evolution Of Siloxane-Based Materials And Their Applications In Drug Delivery And Adsorption, Jyotrhirmai Ambati

University of Kentucky Doctoral Dissertations

This dissertation presents studies of the synthetic processes and applications of siloxane-based materials. Kinetic investigations of bridged organoalkoxysilanes that are precursors to organic-inorganic hybrid polysilsesquioxanes are a primary focus. Quick gelation despite extensive cyclization is found during the polymerization of bridged silane precursors except for silanes with certain short bridges. This work is an attempt to characterize and understand some of the distinct features of bridged silanes using experimental characterization, kinetic modeling and simulation. In addition to this, the dissertation shows how the properties of siloxane- materials can be engineered for drug delivery and adsorption.

The phase behavior of polymerizing …

Evaluation Of The Physicochemical Properties And Stability Of Solid Lipid Nanoparticles Designed For The Delivery Of Dexamethasone To Tumors, Melissa Howard

University of Kentucky Doctoral Dissertations

Pre-clinical and clinical trials suggest that pre-treatment with dexamethasone (Dex) may facilitate enhanced uptake of subsequently administered chemotherapeutic agents. To reduce the side effects associated with systemic administration of Dex, solid lipid nanoparticles (SLNs) containing dexamethasone palmitate (Dex-P) were prepared as a means of achieving tumor-targeted drug delivery. These studies were aimed at evaluating the physicochemical properties and both the physiological and storage stability of the SLNs.

SLNs were prepared using nanotemplate engineering technology. Stearyl alcohol (SA) was used as the lipid phase with Brij^® 78 and Polysorbate 60 as surfactants and PEG6000 monostearate as a long-chain PEGylating agent. …