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Acetylacetone Oxidation At Room Temperature: A Multiplexed Photoionization Mass Spectrometric Investigation, Study Of The Russell Intermediates In Gas Phase Reactions, And The Investigation Of Oxidation Reaction Products Of Ethanol At Room Temperature, Sara Gallarati

Master's Theses

This thesis presents the combustion study of acetyl acetone using synchrotron radiation coupled with multiplexed photoionization mass spectrometry at 298 K. The experiments were performed at the Chemical Dynamics Beamline 9.0.2 at the Advanced Light Source of the Lawrence Berkeley National Laboratory. The reaction of acetyl acetone with chlorine (Cl) radicals was analyzed based on their photoionization spectra and reaction kinetic profiles.

Additionally, a study of the Russell intermediate has been performed. Previous to experimentation at the Advanced Light Source, computational analysis has been investigated to evaluate compounds that could possibly lead to the formation of a stable species. The …

Steric Effect On Benzyl Ether Olefines Under Sadmet Polymerization, Su Hu

Master's Theses

Acyclic diene metathesis (ADMET) polymerization, a type of olefin cross metathesis, is a step-growth and condensation polymerization that can be used to synthesize hydrocarbon polymers with diverse functional groups. Traditional ADMET with symmetric α,ω-dienes is not selective and can only form homopolymers or statistical copolymers. Changing to monomers with acrylate functional groups allows selective reactivity to form block and alternating polymers. In this project, we want to explore other functional groups that result in selective reactivity to form advanced polymer architectures via what we have termed selective acyclic diene metathesis (SADMET) polymerization. Developing new functionalized monomers for SADMET polymerization allows …

Exploration Of Novel Nickel Metal Organic Decomposition Inks, Ivy Tran

Master's Theses

In the growing and ever-evolving world of technology, the prospect of printable and flexible electronics has become prominent. Printable metal inks are of significant interest as they can be used to fabricate metal films efficiently, with greener materials, at lower-cost, and with low-waste as compared to conventional metal film deposition techniques. They also allow the utilization of a wider range of materials, giving way to flexible technologies in the future. Here, we introduce the formulation of novel nickel-precursor based liquid organometallic decomposing (MOD) inks that sinter at relatively low temperatures and thermally decompose into a conductive layer. In this work, …

Novel Thermally Decomposable Cobalt Materials, Yu-Jui Chang

Master's Theses

Developing suitable material precursors of reduced metal films plays an important role inflexible electronics. We introduce a relatively low-temperature sintering liquid material that may be used to pattern a conductive layer. The liquid material is made of oxidized metal carboxylate salts along with liquid amines or carboxylic acids. When heated above ca. 220 C, this material spontaneously decomposes into reduced metal and various gas-phase products. Inideal (albeit not this) cases, this yields an adherent, electrically conducting perfect metal mirror.Such materials, inks if you will, conserve metal and plate only where deposited, thus meeting an important ecological goal of metal conservation. …

Lc-Ms/Ms Method Development For The Quantitation Of Methylmalonic Acid Using Aqueous Normal Phase Chromatography, Daniel Joseph Biocini

Master's Theses

The aim of the study was to develop a quantitative assay for methylmalonic acid (MMA), an important biomarker for clinical diagnosis of vitamin B12 (B12) deficiency. The techniques of liquid chromatography and tandem mass spectrometry (LC-MS/MS) are used for separation and quantitation of MMA, as well as its endogenous isomer succinic acid. The MS/MS method was developed using an infusion set-up and manual tuning experiments. Relevant transitions were detected for the two analytes and MMA-d3, then a preliminary MS/MS method was developed. The preliminary LC method was further optimized. Various gradients, mobile phases (MPs), and additive combinations were used across …

Electrostatic Denaturation Of Dna-Cisplatin Adducts, Eddie Madrigal

Master's Theses

In this thesis, electrochemical approaches are used to determine the properties of deoxyribonucleic acid (DNA) by electrostatic denaturation. The electrochemical routine involves an application of a destabilization potential, an equilibration potential, and a square wave voltammogram (SWV) to monitor the extent of melting. Our method uses a monolayer consisting of thiol modified DNA and mercaptohexanol on a gold electrode. These electrodes are then incubated in a complementary sequence tagged with methylene blue. By using our electrostatic denaturation technique, different parameters are explored, such as surface densities, surface coverages, and ionic strengths. As proof of concept, these techniques were applied toward …

Evaluation Of Silica Hydride Based Amide Stationary Phase For High Performance Liquid Chromatography And Aqueous Normal Phase Separations, Emma Tardiff

Master's Theses

With many modern chromatographic advancements, silica hydride based columns (also known commercially as Type-C) represent yet another evolutionary step in stationary phase development. Type-C silica hydride columns have the ability to retain both polar and nonpolar analytes and have the ability to behave in either RP or ANP modes of separation depending on mobile phase composition. A consequence of this increased stability is that Type-C columns can be used over a wide range of mobile phase compositions, from purely aqueous to purely nonpolar organic solvents, and any combination of the two. While the retention behavior of Type-C columns depends highly …

Synthesis And Study Of Verdazyl Stable Free Radical Substituted Oligothiophenes For Magnetoresistive And Spintronic Properties, Amir Shakouri Mansouri

Master's Theses

Interest in spin polarizing materials and their application in electronic devices in the field of spintronics has been steadily growing in recent years. The development of wholly organic spin polarizing materials has been of particular interest due to the material flexibility, solution processing, synthetic modifiability, and longer spin lifetimes of organics compared to inorganic analogs. One class of organic compounds with significant room for exploration is polyconjugated π systems coupled with stable radicals. We have explored the synthesis of oligothiophenes substituted with verdazyl stable free radicals with differing thiophene chain lengths, through a series of halogenation, borylation, and palladium catalyzed …

Synthesis And Evaluation Of Novel Silica Hydride-Based Stationary Phases For Bioanalytical Applications, Seiichiro Watanabe

Master's Theses

Most HPLC columns are packed with silanol (Si-OH)-rich type-B silica that often participates in undesired electrostatic interactions with sample solutes and produces a poor analyte peak shape. These silanols are also known to facilitate the surface hydration required for HILIC mode to retain polar analytes. However, the hydrated surface composition can easily fluctuate, which results in poor reproducibility and requires a lengthy equilibration step. In this study, four novel stationary phases have been developed by using the TYPE-C™ silica material, in which up to 95% of the surface silanols have been replaced with Si-H group. One of the advantages of …

Computational Models Exploring The Role Of Flexibility In Binding Tat Peptide To Tar Rna, Thanh Quoc Le

Master's Theses

Viral-encoded regulatory proteins interacting with RNA target sequences control the gene expression of lentiviruses, notably the human immunodeficiency virus (HIV) and bovine immunodeficiency virus (BIV). The latter provides a simpler interaction model between the viral trans-activator protein (Tat) and trans-activation response RNA element (TAR), including Tat peptides binding to TAR RNA fragments. This model may offer insights into clinical approaches for treatment, initially through theoretical consideration of the role of peptide flexibility in binding as evidenced by literature-based binding assays and NMR. It has more recently been suggested that DNA-protein binding may also be enhanced by increases in conformational entropy. …

Biophysical Approaches For Studying Desolvation Energy In Dna:Dna Binding Systems, Caroline Rose Harmon

Master's Theses

Hydration spheres have unique water behavior compared to the disorder of the bulk water phase. These hydration spheres have been shown to be crucial for structural and conformational stability, yet their effect on binding association has been largely mistreated. For a one-to-one binding system, we propose to append the classical Gibbs-free energy equation as follows: ΔG^0=-RT ln⁡(K_i )-[AB]ΔG_i^(H_2 O). Having a stronger grasp on how desolvation energy affects binding will ultimately aid studies from drug development and metabolism, to interpretation of structural models. To test our equation, we studied two small oligonucleotides that follow Watson-Crick base pairing using two different …

Preparation And Characterization Of A (Viologen) Containing Main Chain Peg-Carbon Nanotubes Phase For Hybrid Supercapacitor Application, Kanishka Rana

Master's Theses

Supercapacitors (SCs) and batteries are recognized as the two most important electrical energy storage devices. SCs have some distinct advantages such as high-power density and long cycle life when compared to batteries. However, they have yet to match the energy densities of batteries. In an effort to improve the energy density of SCs, a hybrid supercapacitor was developed using a pair of single-walled carbon nanotube electrodes and two polyethylene glycol (PEG-400) gel-polymer electrolytes (GPEs) containing redox additives of viologen (V) and ferrocene dicarboxylic acid (Fc), respectively. The introduction of V and Fc, was expected to improve the energy performance of …

Multi-Scale Assembly Methodologies Of Poly(3-Hexylthiophene) Derivative Systems For Enhanced Optoelectronic Anisotropy, David William Bilger

Master's Theses

Conjugated polymers represent a class of semi-conducting materials with numerous applications in optoelectronic devices, including organic light-emitting diodes, field-effect transistors, and photovoltaics. Because of the numerous advantages of macromolecular systems, including solution processing and mechanical flexibility, conjugated polymers have become a burgeoning field of research with the hopes of producing cost-effective solution-based electronics. Importantly, optoelectronic device performance is heavily influenced by conjugated polymer backbone orientation and overall thin film morphology. As such, the processing conditions of these systems are important to the construction of high- performance optoelectronics. Polythiophenes are model conjugated polymers that have been studied extensively in halogenated organic …

Sers Intensity Correlations To Lspr On Aggregated Au@Ag Systems, Caesar Alexander Munera

Master's Theses

The optimal surface enhanced Raman scattering (SERS) intensity was correlated to the localized surface plasmon resonance (LSPR) of individual and aggregated gold core/silver shell (Au@Ag) nanoparticles (NPs) in titrations involving the addition of both SERS label (e.g., rhodamine 6G, R6G) and the non-SERS active aggregant (chemical species that triggers the aggregation of NPs) potassium chloride (KCl). Titrating NP solutions with pure SERS label has often resulted in highly non-linear calibrations. In some cases, addition of non-SERS active aggregating agents such as KCl has also resulted in a large increase in SERS signals. An order of initial addition was followed in …

Evaluation Of A Silica Hydride-Based Undecynoic Acid Stationary Phase For High Performance Liquid Chromatography, Veena Menon Kozhikote

Master's Theses

Undecynoic acid (UDA) attached to a silica hydride surface has been found to exhibit weak cationic exchange properties and an aqueous normal phase (ANP) type of retention. ANP is a mechanism similar to normal phase chromatographic retention, except for the use of a polar solvent such as water in the mobile phase. In ANP, the retention of a polar molecule is increased with a higher concentration of the non-polar mobile phase solvent (usually acetonitrile). Non-polar molecules exhibit retention behavior as in reverse phase (RP) chromatography. The goal of this research was to characterize the chromatographic retention pattern of an undecynoic …

Synthesis, Structural Characterization And Chromatographic Evaluation Of Silica Hydride-Based Perfluorinated Stationary Phase, Harshada Suyog Natekar

Master's Theses

Silica hydride based stationary phases have demonstrated unique selectivity and specificity for small sized polar molecules. The weakly hydrophobic nature of silica hydride is thought to be the key reason for its remarkable retention capabilities. Traditional stationary phases bonded with fluorine moieties have also exhibited enhanced retention of small polar molecules. In this research, a perfluorinated silica hydride stationary phase was synthesized by hydrosilation and silanization procedures. Chromatographic characterization of the newly packed column was carried out by a large number of retention studies. The separation capabilities of the column were evaluated in both the aqueous normal-phase (ANP) and reversed-phase …

Morphology-Property Relationship For Binary Organic Thin Films, Alyssa Lynn Griffin

Master's Theses

Organic thin films can be readily mass-produced through solution-based fabrication methods including ink-printing and solution-casting because their light weight, flexibility, and inexpensive sources. Their applications range from organic field-effect transistors (OFET), organic solar cells (OSC), to organic light emitting diodes (OLEDs). Compared with pure component films, binary organic thin films (BOTF) allows for novel characteristics and specialized features to handle more demanding tasks. Due to the complex intermolecular interactions in BOTF, various microscopic phases with different morphological and electronic properties may be formed and this information is difficult to extract through conventional bulk measurements.

Organic thin films can be readily …

Synthesis Of A Ditopic Verdazyl Ligand And Investigation Of Its Coordination To Transition Metals, Erik Charles Johnson

Master's Theses

The goal of this research project was to prepare a self-assembled grid complex with a ditopic bis-verdazyl ligand and nickel(II) ions. A verdazyl is a relatively stable type of organic free radical in which the unpaired electron is delocalized over four nitrogen atoms. The ditopic verdazyl ligand was synthesized in six steps, and its coordination to metal ions, in particular Ni2+, was investigated. The hypothesized complex of the ligand with Ni2+ is potentially functional as a molecular magnet due to the free radical nature of the ligand; hence, the complex could be useful for information storage. The ligand was definitively …

Computational Fluid Dynamics Modeling Of Two-Dimensional And Three-Dimensional Segmented Flow In Microfluidic Chips, Katrina Jolene Donovan

Master's Theses

Microfluidics is a rapidly growing topic of interest for scientists, engineers, and medical researchers. The micrometer length scale constrains flow to a laminar behavior, allowing for a more predictable system. High-throughput experimentation is possible with laminar multiphase flow, specifically microdroplets. Manipulating microdroplets by generating, splitting, separating, and fusing provides a versatile environment for analysis in a variety of biological and chemical systems.

The process of design, fabrication, and testing of microfluidic systems is an iterative and tedious procedure. The purpose of this research was to utilize computational fluid dynamics software to expedite the fabrication and design process by simulating time-dependent …

Synthesis Of Hybrid Inositol Glycan Analogues, Sudi Sabet

Master's Theses

A 2010 study by Centers for Disease Control and Prevention has projected that one of three US adults could have diabetes by the year 2050. More than 90% of the diagnosed cases are Type II diabetes, a condition characterized by insulin resistance. In search of new antidiabetic drugs, a class of natural, phosphorylated, inositol-containing pseudosaccharides called inositol glycans (IGs) has been studied for years. These compounds have insulin-mimetic activity in insulin-sensitive cells and can stimulate processes such as lipogenesis and glucose transport. Due to the heterogeneity of IGs, it is very difficult to isolate them from their natural sources, and …

Nanoparticles And Polymer Crystallization Kinetics In Hybrid Electronic Devices, Taylor William Wagner

Master's Theses

Conjugated semi-conducting polymers have become well known for their potential applications in hybrid electronic devices like solar cells, LEDs, and organic displays. These hybrid devices also contain inorganic nanoparticles, which complement the polymer when they are combined into the same layer. Control over the conformation and crystallinity of the polymer is critical for device performance, yet not much is known about the effect that these nanoparticles have on the polymer. Here, zinc oxide nanowire was surface modified with mono-substituted-carboxylic acid tetraphenylporphyrin and dodecanethiol, and introduced to poly(3-hexyl thiophene) in solution. The electron transfer, kinetics, and thermodynamics of this system were …

Material Characterization Of Ultra-High Performance Fiber Reinforced Concrete At Elevated Temperatures, Richard T. Way

Master's Theses

With the recent development of Ultra High Performance Fiber Reinforced Concrete (UHPFRC), there has been limited investigation into the mechanical and material properties of this composite at elevated temperatures. At elevated temperatures concrete is shown to undergo several material changes which affect the residual mechanical properties. Additionally, fast heating rates are known to cause a phenomenon called explosive spalling. This research investigates the effect of high temperature on the residual mechanical properties and chemical degradation of two types of UHPFRC. This was accomplished by casting and testing two different UHPFRC mixes and exposing them to elevated temperatures at two rates …

Application Of Query-Based Qualitative Descriptors In Conjunction With Protein Sequence Homology For Prediction Of Residue Solvent Accessibility, Reecha Nepal

Master's Theses

Characterization of relative solvent accessibility (RSA) plays a major role in classifying a given protein residue as being on the surface or buried. This information is useful for studying protein structure and protein-protein interactions, and it is usually the first approach applied in the prediction of 3-dimensional (3D) protein structures.

Various complicated and time-consuming methods, such as machine learning, have been applied in solvent-accessibility predictions. In this thesis, we presented a simple application of linear regression methods using various sequence homology values for each residue as well as query residue qualitative predictors corresponding to each of the 20 amino acids. …

Activation Of Alcohols Toward Nucleophilic Substitution: Conversion Of Alcohols To Alkyl Halides, Amani Atiyalla Abdugadar

Master's Theses

The conversion of alcohols into alkyl halides is one of the most important reactions in organic chemistry. Development of new methodology is still desirable in academic research. Unfortunately, the hydroxyl group of the alcohol is relatively difficult to replace under normal conditions. That necessitates the conversion of alcohols to a more activated functionality before nucleophilic substitution becomes viable. Under vigorous conditions, the replacement is straightforward. Procedures for the generation of halides from alcohols have been extensively examined, e.g., using HX or Mitsunobu inversion. However, these methods require time, strong acid, or catalysis to proceed. These classical methods suffer from issues …

Controlling Nanoparticle Dispersion For Nanoscopic Self-Assembly, Nathan S. Starkweather

Master's Theses

Nanotechnology is the manipulation of matter and devices on the nanometer scale. Below the critical dimension length of 100nm, materials begin to display vastly different properties than their macro- or micro- scale counterparts. The exotic properties of nanomaterials may trigger the start of a new technological revolution, similar to the electronics revolution of the late 20^th century. Current applications of nanotechnology primarily make use of nanoparticles in bulk, often being made into composites or mixtures. While these materials have fantastic properties, organization of nano and microstructures of nanoparticles may allow the development of novel devices with many unique properties. …

Luminescence Studies Of Europium (Iii) - D-Glucosamine Complexes In Water, Triny Trinh Pham

Master's Theses

LUMINESCENCE STUDIES OF EUROPIUM(III) - D-GLUCOSAMINE

COMPLEXES IN WATER

by Triny Trinh Pham

Lanthanide complexation interactions measured by luminescence have become

interesting topic in recent years. Europium is a rare earth metal and the Eu(III) ion is a hard acid; when Eu(III) and a monosaccharide ligand are present, a complex may be formed. The goal is to determine the equilibrium constant KEuL between the europium ion and a D-glucosamine ligand. At 25oC and pH ~ 7.40, a physiologically important pH, adding D-glucosamine enhanced the luminescence of 0.0025 M Eu(III). As the concentration of ligand increased, the emission intensity was also …

A Clay Modified Electrode For Ion-Exchange Voltammetry, Thaddeus S. Wielgos

Master's Theses

No abstract provided.

Nmr Study Of Na+-H+ And Na+-Li+ Exchange In Human Erythrocytes, Suilan Mo

Master's Theses

No abstract provided.

Electrochemical Studies Of Swelling And Shrinking Of Clay Films, Jia Du

Master's Theses

No abstract provided.

Reactions Of 1-Triptycyl Carbinol And Bis-(1-Triptycyl)-Carbinol, Bryce Arthur Milleville

Master's Theses

No abstract provided.