Physical Chemistry Commons^™

Electrochemical Gelation Of Metal Chalcogenide Quantum Dots, Chathuranga Chinthana Hewa Rahinduwage

Wayne State University Dissertations

Quantum dots (QDs) are attractive because of their unique size-dependent optical and electronic properties and high surface area. They are tested in research for diverse applications, including energy conversion, catalysis, and sensing. Assembling QDs into functional solid-state devices while preserving their attractive properties is a challenge. Methods currently under the research are not effective in directly fabricating QDs onto devices, making large area assemblies, maintaining the high surface area by forming 3D porous structures, and conducting electricity for applications such as sensing. QD gels are an example of QD assemblies that consist of a 3D porous interconnected QD network. They …

Analyzing The Free Energy Of Ions Sampling A Voltage Gated Sodium Ion Channel, Isabel Varghese

Honors Theses

Voltage gated sodium ion channels are implicated in cardiac diseases, seizures, etc., and they play a role in maintaining ionic homeostasis in cells. Computational studies use prokaryotic model because they are simpler but function similarly to human voltage gated sodium ion channels. This study uses molecular dynamics (MD) to study three specific questions regarding voltage gated sodium ion channels of Magnetococcus marinus. The first question in this study is how the free energy of sodium diffusion compares to that of calcium ion diffusion. We were not able to find any physically significant information due to poor sampling and a lack …

Visible Opacity Of M Dwarfs And Hot Jupiters: The Tio B³Π-X³Δ Band System, W. Doug Cameron, Peter Bernath

Chemistry & Biochemistry Faculty Publications

The TiO B³Π−X³Δ electronic transition (𝛾' system) is an important opacity source in the atmospheres of M dwarfs and hot Jupiter exoplanets. The 0–0, 1–0, and 2–1 bands of the B³Π−X³Δ band system have been analyzed using a TiO emission spectrum recorded at the McMath-Pierce Solar Telescope, operated by the National Solar Observatory at Kitt Peak, Arizona. Improved spectroscopic and equilibrium constants were determined. Line strengths were calculated from an ab initio transition-dipole moment function scaled using an experimental lifetime. A new line list for v' = 0–2 and v′′ = 0–4 …

Applying Intensity-Based Methods To Disentangle Microwave Spectra Of Complex Mixtures: Analysis Of Weakly Bound Clusters Of 1,1-Difluoroethylene/Co2, Hannah Fino

Masters Theses

Microwave spectroscopy is used to study the solvent-solute interactions between molecules of CO₂ and fluoroethylenes by analyzing the formation of weakly-bound clusters in a gaseous mixture. One of the challenges to analyzing microwave spectra obtained for these weakly-bound species is that spectra for individual clusters are mixed together in an original complex spectrum. This prompts development of automated techniques that could separate complex data into subsets of related data to be more easily analyzed.

The techniques developed in this work are founded on intensity-based analyses, following the work of Dr. Robert Field on Extended Cross Correlation (XCC). The XCC …

The Photo-Transformation Of Free Methionine In The Presence Of Surrogate And Standard Isolate Dissolved Organic Matter Under Sunlit Irradiation, Benjamin J. Mohrhardt

Dissertations, Master's Theses and Master's Reports

Sulfur (S)-containing amino acids are key sources of carbon, nitrogen, and sulfur involved in protein synthesis, protein function, and providing energy for microbial growth. Dissolved free and combined methionine is one of two S-containing amino acids incorporated into proteins and has been attributed to their stability and function. The oxidation of methionine has received considerable attention given its ubiquitous presence in most biological systems and has been associated with losses in protein function and pathological disorders. In natural waters, methionine is rapidly and selectively taken up by microorganisms to achieve cellular requirements of carbon, nitrogen, and sulfur. The abiotic transformation …

Investigating The Physical Stability Of Amorphous Pharmaceutical Formulations, Travis W. Jarrells

Theses and Dissertations--Pharmacy

Amorphous formulations, including amorphous solid dispersions (ASDs), consisting of the active pharmaceutical ingredient (API) intimately mixed in a polymeric matrix, are an attractive formulation approach to improve drug delivery, dissolution, and solubility. However, an amorphous API in an ASD is in a higher energy state compared to the crystalline drug and results in most ASDs being inherently unstable. The polymer helps to stabilize the amorphous drug against crystallization such that the resulting homogenous mixture maintains its solubility advantage relative to the crystalline form. One challenge of ASDs is that the presence of impurities including crystals or residual solvent, variations in …

Molecular Engineering Of Self-Immolative Polymers As Chemically Responsive Temporary Adhesives For Protective Garments, Hana J. Yarbrough

Dartmouth College Master’s Theses

The long-term goal of this thesis is to design novel chemical protective garments that both shield and sense for chemical warfare agents. The overarching hypothesis of this work is that joining textiles with a chemically responsive temporary adhesive will reduce the permeability of and detect hazardous analytes across fabric boundaries. Work towards achieving this goal and testing this hypothesis is separated into two chapters. The first chapter reports the development of a self-immolative polymer, poly(phthalaldehyde), into a stimuli-responsive temporary adhesive. Developing poly(phthalaldehyde) as a robust adhesive that rapidly releases substrates would be a significant and novel contribution to the fields …

Using Powder Diffraction To Give Insight Into Structures Of Ir2(Diisocyanomenthane)4x2 [Dimen] (X = Cl; Pf6; Bph4), Mairead Brownell

Scripps Senior Theses

Ir2(dimen)42+ (dimen = 1,8-diisocyanomenthane) has been studied extensively as model compound to better understand catalysis of photochemical reactions. Although Ir2(dimen)42+ has been used primarily to observe the photophysical changes of metal-metal transitions, it gives great insight into the transitions that allow other d8-d8 metal complexes to undergo photochemical processes and generate hydrogen gas. The large visible range by which Ir2(dimen)42+ (1) can be electronically excited in solution is indicative of its two solution phase ground states, which interestingly have been hypothesized to resemble two unique packing structures observed in the powder state. In this study, the powder diffraction patterns of …

Nrlmsis 2.1: An Empirical Model Of Nitric Oxide Incorporated Into Msis, J. T. Emmert, M. Jones Jr., D. E. Siskind, D. P. Drob, J. M. Picone, M. H. Stevens, S. M. Bailey, S. Bender, P. F. Bernath, B. Funke, M. E. Hervig, K. Pérot

Chemistry & Biochemistry Faculty Publications

We have developed an empirical model of nitric oxide (NO) number density at altitudes from ∼73 km to the exobase, as a function of altitude, latitude, day of year, solar zenith angle, solar activity, and geomagnetic activity. The model is part of the NRLMSIS® 2.1 empirical model of atmospheric temperature and species densities; this upgrade to NRLMSIS 2.0 consists solely of the addition of NO. MSIS 2.1 assimilates observations from six space-based instruments: UARS/HALOE, SNOE, Envisat/MIPAS, ACE/FTS, Odin/SMR, and AIM/SOFIE. We additionally evaluated the new model against independent extant NO data sets. In this paper, we describe the formulation and …

Here, There, And Everywhere: Probing Ubiquitin-Cavitand Binding Via 15n-1h Hsqc, Julia Didziulis

Scripps Senior Theses

Ubiquitination and other post-translational modifications play a major role in the proliferation of many neurodegenerative diseases, developmental disorders, and cancers, and as such are subjects of recently increased biochemical interest. Expanding upon such research, this study confirmed a robust method of ubiquitin expression and purification, then used 15N-1H HSQC to analyze ubiquitin samples containing varying concentrations of a deep cavitand with affinity for lysine and arginine side chains. In the pure ubiquitin spectrum, arginine side chain chemical shifts were detected in the nitrogen 80-85 ppm range and lysine side chain signals were undetected. However, upon introduction of the cavitand, collection …

Metal Nanoparticle Synthesis Via Laser-Induced Photochemical Reduction Of Metal Salts, Laysa M. Frias Batista

Theses and Dissertations

Significant attention has been focused on metal nanoparticles (MNPs) due to their unique optical, catalytic, and electronic properties. In the last two decades, laser synthesis techniques have emerged as versatile routes to MNPs that enable control over particle size, shape, and surface chemistry without the use of chemical reducing agents or surface-blocking capping ligands. A method gaining increasing attention is the direct laser-driven reduction of metal salts, called Laser Reduction in Liquid (LRL). LRL typically involves the use of intense laser pulses of picosecond or femtosecond duration to ionize and dissociate solvent molecules, generating plasmas with reactive chemical species such …

Biodiesel Production From Castor Oil: Mixing Optimization During Transestrification, Islam M. Al-Akraa

Chemical Engineering

No abstract provided.

Gas Phase C-H And C-C Bond Activation By Ternary Metal Complexes, Kevin Parker

Graduate Research Theses & Dissertations

The activation of relatively inert C-H bonds has remained a challenge in organic chemistry for over a century. Metal catalysts have been deployed to overcome the labile reactivity of these bonds and through gas-phase studies, detailed mechanisms can be elucidated for this important class of chemistry. The powerful combination of ion-molecule reactions, collisional activation of ions, and density functional theory calculations allows for structural elucidation, intermediate determination, and as shown throughout this work, a complete picture of catalytic processes. Modified linear ion-trap mass spectrometers were used to trap and generate reactive intermediates of the form [(L)(M)(X)]+ (L= auxiliary ligand; M= …

Novel Modes Of Synchronization And Extreme Events In Coupled Chemical Oscillators, David Allen Mersing

Graduate Theses, Dissertations, and Problem Reports (ETD)

We experimentally and computationally investigate dynamical behaviors in coupled chemical oscillators. These networks of chemical oscillators are created using catalytic Ru(bpy)₃²⁺ loaded cation exchange beads submerged in catalyst-free Belousov-Zhabotinsky (BZ) solutions. Various network structures are created by utilizing the photosensitive nature of the Ru(bpy) ₃²⁺ catalyst. The response of the oscillators due to light stimuli can be characterized by constructing a phase response curve (PRC). The PRC quantifies the excitatory and inhibitory responses of BZ oscillators due to applied light perturbations as a function of the oscillators' phase. Different initial concentrations of reactants in the BZ reaction …

Study Of Resonantly Stabilized Radicals In Combustion Environments, James H. Lee

Graduate Theses, Dissertations, and Problem Reports (ETD)

Resonantly stabilized radicals (RSRs) play an important role in combustion environments due to their high stability resulting from resonance. Many RSRs such as the propargyl, allyl, or benzyl radicals are precursors to the formation of polycyclic aromatic hydrocarbons (PAHs), which can aggregate to form soot. Due to their stability, these RSRs can accumulate in combustion environments in significant quantities. The primary way these radical species are consumed in flames or by reactions with other abundant radicals, by self-recombination of propargyl to form benzene, or in the form of other abundant radicals such as the hydroxyl radical. Experimentally determining the pathways …

Gas-Phase Acid-Base Properties And Conformations Of Oligopeptides Through Mass Spectrometry And Computational Studies, Yuntao Zhang

University of the Pacific Theses and Dissertations

This dissertation presents a comprehensive study of the peptides of interest to deeper understand the gas-phase acid-base properties in relation to their conformations and chirality. In the first part of the study, two pairs of alanine (A)-based isomeric peptides consisting of a basic probe, lysine (Lys) or 2,3-diaminopropionic acid (Dap), were investigated to understand the nature of the enhanced basicity when the basic probe was moved from the N-terminus to the C-terminus. In the second part of the study, alanine-based peptides containing a cysteine (C) as the acidic probe were investigated to understand the chirality effects on the gas-phase acidity …

S-Type Stars: Lao Line List For The B²Σ⁺-X²Σ⁺ Band System, P. F. Bernath, Randika Dodangodage, J. Liévin

Chemistry & Biochemistry Faculty Publications

LaO bands are a characteristic feature in the spectrum of cool S-type stars. La is made primarily by the s-process during the asymptotic giant branch phase of stellar evolution. The B²Σ⁺–X²Σ⁺ and A²Π–X²Σ⁺ band systems can be used to determine the La abundances in cool S stars. The bands of the B²Σ+–X²Σ⁺ with v' and v" ⩽ 5 have been rotationally analyzed from an emission spectrum from a carbon furnace. Line strengths are calculated using an ab initio transition dipole …

Broadband Dielectric Spectroscopic Detection Of Aliphatic Alcohol Vapors With Surface-Mounted Hkust-1 Mofs As Sensing Media, Papa K. Amoah, Zeinab Mohammed Hassan, Rhonda R. Franklin, Helmut Baumgart, Engelbert Redel, Yaw S. Obeng

Electrical & Computer Engineering Faculty Publications

We leveraged chemical-induced changes to microwave signal propagation characteristics (i.e., S-parameters) to characterize the detection of aliphatic alcohol (methanol, ethanol, and 2-propanol) vapors using TCNQ-doped HKUST-1 metal-organic-framework films as the sensing material, at temperatures under 100 °C. We show that the sensitivity of aliphatic alcohol detection depends on the oxidation potential of the analyte, and the impedance of the detection setup depends on the analyte-loading of the sensing medium. The microwaves-based detection technique can also afford new mechanistic insights into VOC detection, with surface-anchored metal-organic frameworks (SURMOFs), which is inaccessible with the traditional coulometric (i.e., resistance-based) measurements.

From Evaluating The Performance Of Approximations In Density Functional Theory To A Machine Learning Design, Pedram Tavazohi

Graduate Theses, Dissertations, and Problem Reports (ETD)

Density-functional theory (DFT) has gained popularity because of its ability to predict the properties of a large group of materials a priori. Even though DFT is exact, there are inaccuracies introduced into the theory due to the approximations in the exchange-correlation (XC) functionals. Over the 50 years of its existence, scientists have tried to improve the design of the XC functionals. The errors introduced by these functionals are not consistent across all types of solid-state materials. In this project, a high throughput framework was utilized to compare the theoretical DFT predictions with the experimental results available in the Inorganic Crystal …

Heterogeneous Oxidation Of Multi-Component Aqueous Organic Aerosols: The Effect Of Transport Phenomena And Reaction Compartment On Reaction Kinetics., Tadini Wenyika Masaya

Graduate Theses, Dissertations, and Problem Reports (ETD)

The surface-bulk partitioning of small organic molecules in aqueous droplets was investigated using molecular dynamics. The air-particle interface was modeled using a 80-Å cubic water box containing series of organic molecules and surrounded by gaseous OH radicals. The properties of the organic solutes within the interface and the water-bulk were examined at a molecular-level using density profiles and radial pair distribution functions. Molecules containing only polar functional groups such as urea and glucose are found predominantly in the water bulk, forming an exclusion layer near the water surface. Substitution of a single polar group by an alkyl group in sugars …

Electronic Structure Of Early Transition Metal Complexes Supported By Pyridine Polypyrrolide Ligands, Dylan Connor Leary

Graduate Theses, Dissertations, and Problem Reports (ETD)

A thorough study of photoluminescent molecules involving the pyridine polypyrrole(ide) ligand platform has been conducted. A detailed analysis on speciation of the proligand H₂(^MesPDP^Ph) (H₂^MesPDP^Ph = 2,6-bis(5-mesityl-3-phenyl-1H-pyrrol-2-yl)-pyridine) and its dilithium salt Li₂(^MesPDP^Ph) revealed temperature- and solvent-dependent effects. These molecules, along with the hydrochloric acid adduct [H₃(^MesPDP^Ph)]Cl were found to exhibit short-lived photoluminescence in both tetrahydrofuran and benzene solution. These findings confirm the hypothesis that heavy-atom involvement is crucial for the favorable photophysical properties observed for the Zr(PDP)_{2 …}

Characterization Of The Ch Addition Product From Meta- And Ortho-Xylene + Ch Reaction And Direct Experimental Observation Of The Tetrabromine Cluster Br4 Using Synchrotron Photoionization Mass Spectrometry, Rory R. Mcclish

Master's Theses

This thesis is centered on the use of a unique gas-phase spectroscopy technique to characterize products and elucidate reaction mechanisms. Experiments were carried out at the Chemical Dynamics Beamline 9.0.2 of the Advanced Light Source located at the Lawrence Berkeley National Laboratory in Berkeley, CA. Computational work was performed on the scientific supercomputer at USF to supplement experimental findings. Chapter 1 contextualizes the work spurred in response to the deleterious interactions of anthropogenic emissions on Earth’s climate. Chapter 2 describes the theoretical manipulations foundational to the experimental design and interpretation. Chapter 3 delves into the physical details of the experimental …

The Inhibition Activity Of Tert-Butylhydroquinone Towards Corrosion Of Aluminum, Copper And Stainless Steel In Biodiesel Blend B20 Alternative Fuel, Chaza Joumaa, Ibtissam Saad, Ghassan Younes

BAU Journal - Science and Technology

Tert-butylhydroquinone (TBHQ) has been investigated as corrosion inhibitor for aluminum; copper and stainless steel in biodiesel blend B20 by using electrochemical impedance spectroscopy (EIS) method. The results showed that the inhibition efficiency increases with an increase in the concentration of TBHQ but decreases with increasing temperature from 30℃ to 60℃. A maximum inhibition efficiency of about 61.52% for aluminum was recorded for THBQ in biodiesel blend B20 at temperature 30℃ and at a concentration of 4x10^-6 M which is the lowest concentration used compared to the concentrations of TBHQ used for the other metals (copper and stainless steel). Theoretical …

Self-Assembly Of Black Cumin Oil-Based Nanoemulsion On Various Surfactants: A Molecular Dynamics Study, Aulia Fikri Hidayat, Taufik Muhammad Fakih

Makara Journal of Science

Black cumin is commonly used as traditional medicine due to its wide range of pharmacological potential. Black cumin oil (BCO) was often prepared as nanoemulsion to improve its solubility, stability, and bioavailability. This study was conducted to investigate the molecular behavior as well as structural evolution of BCO-surfactant systems during self-assembly micellization using molecular dynamics (MD) simulations. Several BCO constituents and variations of surfactants were employed to model BCO-surfactant systems. 50 ns of MD simulations were performed to elucidate their evolution of structures and physicochemical properties during formation. Results showed that BCO-tween20 and BCO-lecithin were able to form spherical-shaped micelles …

Study On The Uniformity Of Microgrooves In Through-Mask Electrochemical Micromachining With Moving Cathode, Li-Qun Du, Yi-Kui Wen, Fa-Long Guan, Ke Zhai, Zuo-Yan Ye, Chao Wang

Journal of Electrochemistry

As a typical surface texture, microgrooves have broad prospects in the fields of mechanical engineering, bio-medicine, new energy and efficient heat dissipation of electronic products. Through-mask electrochemical micromachining (TMEMM) is widely used in the fabrication of micro-structures because of high processing efficiency and no residual stress. However, due to the edge effect of current distribution, there is often a serious dimension discrepancy problem in electrochemical machining of micro-structures. In order to weaken the influence of edge effect on the uniformity of microgrooves, the method that TMEMM with a moving cathode is presented. The current distribution in the electrochemical machining is …

Nitrogen-Sulfur Co-Doped Porous Carbon Preparation And Its Application In Lithium-Sulfur Batteries, Gui-Xiang Zhao, Wail Hafiz Zaki Ahmed, Fu-Liang Zhu

Journal of Electrochemistry

In recent years, lithium-sulfur (Li-S) batteries have been considered as a promising candidate for the next generation of energy storage system due to their ultrahigh theoretical capacity (1675 mAh·g^-1) and energy density (2600 Wh·kg^-1). However, the practical application of Li-S batteries is seriously limited by their insulating nature of sulfur, the shuttle effect of polysulfides (LiPSs), and volume expansion during charging and discharging. To overcome those disadvantages, one of the commonly methods is to infiltrate sulfur into porous conductive carbon framework, such as porous carbon, hollow carbon spheres, graphene, carbon nanotubes and some composites of the …

Photoelectrochemical Sensing Based On Zr-Mofs For Homocysteine Detection, Wen-Xia Dong, Guang-Ming Wen, Bin Liu, Zhong-Ping Li

Journal of Electrochemistry

Due to the independent form of the light source and detection system, photoelectrochemical (PEC) sensor has the advantages of low background, high sensitivity and simple operation. So far, PEC systems have been widely used in the fields including the actual detection of metal ions, biological antibodies or antigens in environmental pollutants. When the photosensitive material is irradiated by a light source with an energy being equal to or greater than its band gap, electrons (e^-) transition occurs from the valence band to the conduction band, leaving a hole (h⁺), at the same time, the generated electron-hole …

Structure Analysis Of Pemfc Cathode Catalyst Layer, Rui-Qing Wang, Sheng Sui

Journal of Electrochemistry

The sluggish oxygen reduction reaction (ORR) on the cathode of the proton exchange membrane fuel cell (PEMFC) has always been one of the key factors limiting its commercialization. The optimization of the cathode catalytic layer structure plays an important role in improving fuel cell performance and reducing production costs. In this paper, two different catalysts (platinum nanoparticles (Pt-NPs) and platinum nanowires (Pt-NWs)) were prepared by using catalyst coated substrate (CCS) method. By constructing a double-layer catalytic layer structure, we analyzed the effect of different catalytic layer structures by performing a single cell test. The results showed that the dense platinum …

Cyclic Voltammetric Simulations On Batteries With Porous Electrodes, Xue-Fan Cai, Sheng Sun

Journal of Electrochemistry

Lithium-ion batteries (LIBs) are among the most widely used energy storage devices. Whole-cell modeling and simulations of LIBs can optimize the design of batteries with lower costs and higher speeds. The Pseudo-Two-Dimensional (P2D) electrochemical model is among the most famous whole-cell models and widely applied in LIB simulations. P2D model consists of a series of kinetic equations to model Li⁺/Li diffusion in working/counter electrodes and electrolytes, which are filled in the porous electrodes and separator, and reactions at the interface of electrolyte and active particles. The traditional applications of P2D model, however, are limited to the cases where …

Effect Of Aluminum Alloy Surface Modification On Adhesion Of The Modified Polyurethane Coating And Its Corrosion Protective Performance, Xian-Yin Kuang, Shao-Qiang Jin, Yan-Hui Cao, Yan-Mei Zhang, Shi-Gang Dong, Long-Hui Zhu, Li-Wen Lin, Chang-Jian Lin

Journal of Electrochemistry

The ordinary organic coatings on aluminum alloy usually encounter a problem of low adhesion to the substrate, which results in destruction and failure of the long-term protective performance of the anticorrosion systems. The surface modification of aluminum alloy is able to enhance the adhesion of organic coating on aluminum alloys, and to improve their protective performance. In this work, a combined surface modification of anodic oxidation and mussel adhesion protein/CeO₂/3-aminopropyltriethoxysilane composite film (MCA) was developed on the aluminum alloy. The adhesion of modified polyurethane coated on the treated aluminum alloy and its corrosion protective performance were evaluated comprehensively …