Chemistry Commons^™

Gumbos And Nanogumbos: Applications As Photosensitizers In Dye-Sensitized Solar Cells, Atiya Nicole Jordan

LSU Doctoral Dissertations

Renewable energy is a major concern due to increased world energy consumption. In particular, solar energy is a type of renewable energy source that uses devices known as solar cells to convert sunlight to electricity. Specifically, devices referred to as dye-sensitized solar cells (DSSCs) employ dyes to absorb solar energy. Dyes derived from ruthenium complexes have been typically used in DSSCs. Unfortunately, several disadvantages are associated with current ruthenium complex photosensitizers, which can be attributed to limited supply and expense of metals, as well as reduced absorption in the near-infrared region of the electromagnetic spectrum. Accordingly, this dissertation is a …

No Longer A Complex, Not Yet A Molecule: A Challenging Case Of Nitrosyl O-Hydroxide, Hoon, Majher I. Sarker, Tasnuva Shahrin, Mark G. Steinmetz, Qadir K. Timerghazin

Chemistry Faculty Research and Publications

N-(9-Oxothioxanthenyl)benzothiophene carboxamides bearing leaving groups (LG⁻ = Cl⁻, PhS⁻, HS⁻, PhCH₂S⁻) at the C-3 position of the benzothiophene ring system photochemically cyclize with nearly quantitative release of the leaving group, LG⁻. The LG⁻ photoexpulsions can be conducted with 390 nm light or with a sunlamp. Solubility in 75% aqueous CH₃CN is achieved by introducing a carboxylate group at the C-6 position of the benzothiophene ring. The carboxylate and methyl ester derivatives regiospecifically cyclize at the more hindered C-1 position of the thioxanthone ring. …

Concerted And Sequential Pathways Of Proton-Coupled Electron Transfer In Hydrogen Halide Elimination, Aimable Kalume, Lisa George, Nicole Cunningham, Scott A. Reid

Chemistry Faculty Research and Publications

Proton-coupled electron transfer (PCET) is a key reaction in a diverse array of chemical and biochemical processes. Concerted PCET, a single step process where no intermediates are expected, is often difficult to distinguish from sequential electron transfer/proton transfer (or proton transfer/electron transfer) events that involve one or more reactive intermediates. Here we demonstrate that in an apparently simple and fundamental organic reaction, hydrogen halide elimination (dehydrohalogenation), both mechanisms occur, with concerted PCET kinetically favored over sequential ET/PT. The latter involves a well-defined reactive intermediate, the corresponding iso-halon.

Ro-Vibrational Quenching Of Co (V = 1) By He Impact In A Broad Range Of Temperatures: A Benchmark Study Using Mixed Quantum/Classical Inelastic Scattering Theory, Alexander Semenov, Mikhail V. Ivanov, Dmitri Babikov

Chemistry Faculty Research and Publications

The mixed quantum/classical approach is applied to the problem of ro-vibrational energy transfer in the inelastic collisions of CO(v = 1) with He atom, in order to predict the quenching rate coefficient in a broad range of temperatures 5 < T < 2500 K. Scattering calculations are done in two different ways: direct calculations of quenching cross sections and, alternatively, calculations of the excitation cross sections plus microscopic reversibility. In addition, a symmetrized average-velocity method of Billing is tried. Combination of these methods allows reproducing experiment in a broad range of temperatures. Excellent agreement with experiment is obtained at 400 < T < 2500 K (within 10%), good agreement in the range 100 < T < 400 K (within 25%), and semi-quantitative agreement at 40 < T < 100 K(within a factor of 2). This study provides a stringent test of the mixed quantum/classical theory, because the vibrational quantum in CO molecule is rather large and the quencher is very light (He atom). For heavier quenchers and closer to dissociation limit of the molecule, the mixed quantum/classical theory is expected to work even better.

Mixed Quantum/Classical Theory Of Rotationally And Vibrationally Inelastic Scattering In Space-Fixed And Body-Fixed Reference Frames, Alexander Semenov, Dmitri Babikov

Chemistry Faculty Research and Publications

We formulated the mixed quantum/classical theory for rotationally and vibrationally inelastic scattering process in the diatomic molecule + atom system. Two versions of theory are presented, first in the space-fixed and second in the body-fixed reference frame. First version is easy to derive and the resultant equations of motion are transparent, but the state-to-state transition matrix is complex-valued and dense. Such calculations may be computationally demanding for heavier molecules and/or higher temperatures, when the number of accessible channels becomes large. In contrast, the second version of theory requires some tedious derivations and the final equations of motion are rather complicated …

Equivalence Of The Ehrenfest Theorem And The Fluid-Rotor Model For Mixed Quantum/Classical Theory Of Collisional Energy Transfer, Alexander Semenov, Dmitri Babikov

Chemistry Faculty Research and Publications

The theory of two seemingly different quantum/classical approaches to collisional energy transfer and ro-vibrational energy flow is reviewed: a heuristic fluid-rotor method, introduced earlier to treat recombination reactions[M. Ivanov and D. Babikov, J. Chem. Phys.134, 144107 (Year: 2011)10.1063/1.3576103], and a more rigorous method based on the Ehrenfest theorem. It is shown analytically that for the case of a diatomic molecule + quencher these two methods are entirely equivalent. Notably, they both make use of the average moment of inertia computed as inverse of average of inverse of the distributed moment of inertia. Despite this equivalence, each of the two formulations …

Turning Stealth Liposomes Into Cationic Liposomes For Anticancer Drug Delivery, Vijay Gyanani

University of the Pacific Theses and Dissertations

Targeting the anticancer agents selectively to cancer cells is desirable to improve the efficacy and to reduce the side effects of anticancer therapy. Previously reported passive tumor targeting by PEGylated liposomes (stealth liposomes) have resulted in their higher tumor accumulation. However their interaction with cancer cells has been minimal due to the steric hindrance of the PEG coating. This dissertation reports two approaches to enhance the interaction of stealth liposomes with cancer cells. First, we designed a lipid-hydrazone-PEG conjugate that removes the PEG coating at acidic pH as in the tumor interstitium. However, such a conjugate was highly unstable on …

Plant Virus Based Materials For Cell Alignment And Differentiation, Elizabeth Balizan

Theses and Dissertations

This research focused on developing and using plant virus based scaffolds to understand substrate control over cell alignment and differentiation. The first part of this work centered on development of virus based patterns that were then used to align and elongate aortic smooth muscle cells (SMCs). Virus patterns were generated in capillary tubes via a simple drying method. Three experimental parameters were used to control pattern formation: (1) protein concentration, (2) salt concentration, and (3) hydrophobicity of the pre-deposition surface. By controlling these parameters several aspects of the final virus patterns were controlled. First, virus orientation was controlled. Patterns were …

Development And Figures Of Merit Of Microextraction And Ultra-Performance Liquid Chromatography For Forensic Characterization Of Dye Profiles On Trace Acrylic, Nylon, Polyester, And Cotton Textile Fibers, Scott James Hoy

Theses and Dissertations

Methodology for the microextraction of basic dyes on acrylic, acid dyes on nylon, disperse dyes on polyester, and reactive dyes, direct dyes, and indigo on cotton textile fibers is reported. Although these processes are destructive to the fiber evidence, the ability to analyze dye extracts from sub-millimeter fiber lengths of single fibers, coupled with detection limits in the hundred picogram range by ultra-performance liquid chromatography (UPLC) with both diode array detection (DAD) and tandem mass spectrometry (MS-MS) makes routine forensic characterization feasible.

Microextraction, followed by UPLC, can often distinguish similar fibers containing different, but similar, dyes with the combination of …

Instrument And Method Development For Single-Cell Classification Using Fluorescence Imaging Multivariate Optical Computing, Joseph Swanstrom

Theses and Dissertations

Multivariate optical computing (MOC) is an all-optical approach of predictive spectroscopy that utilizes multivariate calibration and spectral pattern recognition techniques while operating in a simple filter photometer instrument, removing the need for expensive instrumentation and post-processing of spectral data. This is accomplished with specially designed interference filters called multivariate optical elements (MOEs). MOC can provide analytical solutions for applications requiring low cost, rugged, and simple to operate instrumentation for use in remote and hazardous environments such as open ocean waters. These instrument specifications are central for developing a method for classifying phytoplankton in their natural environment. Phytoplankton are photosynthetic single …

Study Of Porous, Crystalline Supramolecular Boronates, Vincenzo Michael Disantis

Theses and Dissertations

Porous materials with the ability to selectively absorb volatile organic compounds are of high interest for applications in sensing, sequestration and separations. Utilizing the covalent yet reversible boronate ester bonds between boronic acids and diols in conjunction with dative boron-nitrogen coordination bonds has allowed for the discovery of a new class of porous materials. Preliminary results show the ability to obtain porous, crystalline supramolecular boronate networks from the coordination of diamine linkers with boronate diester backbones. Further exploration of porous, crystalline supramolecular boronates has revealed the discovery of a porous crystalline coordination polymer that exhibits reversible, selective guest adsorption properties …

Programmable Polymers Preparation Optimization And Applications On Solute Templates, Yinyan He

Theses and Dissertations

Programmable polymer is a type of stimuli-responsive polymer which can keep their induced properties after removal of the stimulu, as well as programmable polymers maintain the general properties as stimuli-responsive polymers, such as recognize and respond to the stimulus. The previous reported solvent Caryl-Nimide bonds based programmable polymers (SPP-1) can freely rotate and change the carboxylic acid recognition group orientation in response to templates. Solvent templates were used in the SPP-1. One potential application for SPPs is using their recognition and memory properties for the identification and separation of mixture solutions of various analytes. In my first project, I wanted …

Functional Block Copolymers For Applications In Advanced Materials, Energy Storage, And Lithography, Christopher George Hardy

Theses and Dissertations

Block copolymers spontaneously self-assembly into a wide variety of ordered nanostructures on the length scale of 5 - 100 nm due to the thermodynamic immiscibility between the covalently linked, chemically distinct polymer chains. Incorporating desirable functional groups into block copolymer systems can lead to confinement of the functional group to a specific domain upon microphase separation of the block copolymer. The resulting materials display desirable characteristics of the functional group in a well-ordered nanostructure. Such systems have been utilized in a wide variety of applications including catalysis, ceramic materials, and membranes. This dissertation is focused on the synthesis, characterization, self-assembly …

Argumentation As A Lens To Examine Student Discourse In Peer-Led Guided Inquiry For College General Chemistry, Ushiri Kumarihamy Kulatunga

USF Tampa Graduate Theses and Dissertations

This dissertation work entails three related studies on the investigation of Peer-Led Guided Inquiry student discourse in a General Chemistry I course through argumentation. The first study, Argumentation and participation patterns in general chemistry peer-led sessions, is focused on examining arguments and participation patterns in small student groups without peer leader intervention. The findings of this study revealed that students were mostly engaged in co-constructed arguments, that a discrepancy in the participation of the group members existed, and students were able to correct most of the incorrect claims on their own via argumentation.

The second study, Exploration of peer leader …

A Polarizable And Transferable Carbon Dioxide Potential For Materials Simulation, Ashley Lynn Mullen

USF Tampa Graduate Theses and Dissertations

Intermolecular potential energy functions for CO₂ have been developed from first principles for use in heterogeneous systems, including one with explicit polarization. The intermolecular potentials have been expressed in a transferable form and parameterized from nearly exact electronic structure calculations. Models with and without explicit many-body polarization effects, known to be important in simulation of interfacial processes, are constructed. The models have been validated on pressure-density isotherms of bulk CO₂ and adsorption in three metal-organic framework (MOF) materials. The present models appear to offer advantages over high quality fluid/liquid state potentials in describing CO₂ interactions in interfacial …

Asymmetric Nitrene Transfer Reactions With Azides Via Co(Ii)-Based Metalloradical Catalysis (Mrc), Jingran Tao

USF Tampa Graduate Theses and Dissertations

Asymmetric nitrene transfer reactions via metalloradical catalysis (MRC) with

azides has attracted research interest because of its fundamental and practical importance.

The resulting nitrogen-containing units are recurrent motifs in biologically important

molecules and can serve as versatile precursors in organic synthesis.

The [Co(D2-Por*)] have emerged as a new class of catalysts for asymmetric

aziridination and C-H amination. These metalloradical catalysts have been shown to be

highly effective for the asymmetric intermolecular aziridination of a broad scope of

substrates with different classes of azides with excellent to good enantioselectivity. The

intramolecular C-H amination utilizing various azides can allow for the construction …

The Spectrophotometric Analysis Of Lead Carbonate Complexation And Carbonate Saturation States In Seawater, Regina Anita Easley

USF Tampa Graduate Theses and Dissertations

The carbon dioxide (CO₂) system is the primary buffer in seawater which controls oceanic pH. Changes in the marine CO₂ system affect a number of processes such as metal speciation, mineral saturation states, auditory responses in fish, and primary productivity rates. Increased atmospheric concentrations of CO₂ from human activities (e.g. burning of fossil fuels, deforestation, and cement production) has led to a global decrease in surface ocean pH termed anthropogenic ocean acidification. One particular concern in response to increased oceanic CO₂ is a substantial decrease in the calcium carbonate (CaCO₃) saturation states, Ω …

Refinement, Application, And Evaluation Of Cognitive And Affective Chemistry Measures For College Students, Keily Heredia

USF Tampa Graduate Theses and Dissertations

This work describes three case studies conducted to address two major problems in the area of chemistry education research, the lack of reported psychometrics regarding instrument scores, and the need for well-characterized assessments to evaluate college chemistry curricula.

The first case study describes a psychometric evaluation of the Colorado Learning Attitudes about Science Survey (CLASS), an instrument designed to assess student beliefs about the learning of chemistry. Results from this work suggest that the CLASS instrument provides fertile ground for short instruments with reasonable psychometric properties. Responses to a single scale instrument, created from CLASS, showed that students in an …

Characterizing Interactions Between Chromophores In Synthetic And Natural Macromolecular Films Via Maldi-Tof, Ibf And Dielectric Analyzer, Parul Jain

USF Tampa Graduate Theses and Dissertations

With the emergence of Matrix Assisted Laser Desorption/Ionization-Time-of-flight as a tool for diagnosis of diseases via proteomics, there is an increasing need for greater sensitivity. Analysis of peptides by MALDI-TOF-MS is affected by sample formulation and spotting onto a MALDI target. This dissertation investigates a novel MALDI sample preparation technique, Induction Based Fluidics (IBF), for depositing precise volumes (pL to nL) of samples onto the target. We have seen that while using IBF, the induced electric field accompanying deposition enhances matrix crystallization yielding smaller crystals with more homogeneity, as compared to conventional manual micropipette (MP) depositions. An investigation of the …

Chiral Phosphoric Acid-Catalyzed Acetalization And Iso-Pictet-Spengler Reactions, Matthew Jon Kaplan

USF Tampa Graduate Theses and Dissertations

The development of novel asymmetric reaction methodologies has been invaluable in both the academic and industrial world. In just 15 years, organocatalysis has provided a new means of developing asymmetric reaction methodologies using catalysts that are environmentally benign, relatively inexpensive, bench stable, and non-toxic. One development in organocatalysis that is important to our group in particular is chiral phosphoric acid-catalysis. BINOL-derived and VAPOL-derived phosphoric acids have proven to be excellent catalysts for a number of reactions.

The two projects I will discuss my efforts on are acetalization and iso-Pictet-Spengler reactions. These were projects that I performed during my first two …

Development Of Improved Models For Gas Sorption Simulation, Keith Mclaughlin

USF Tampa Graduate Theses and Dissertations

Computational chemistry offers one the ability to develop a better understanding of the complex physical and chemical interactions that are fundamental to macro- and mesoscopic processes that are seen in laboratory experiments, industrial processes, and ordinary, everyday life. For many systems, the physics of interest occur at the molecular or atomistic levels, and in these cases, computational modeling and two well refined simulation techniques become invaluable: Monte Carlo (MC) and molecular dynamics (MD). In this work, two well established problems were tackled. First, models and potentials for various gas molecules were produced and refined from first principles. These models, although …

The Bench Synthesis Of Silver Nanostructures Of Variable Size And An Introductory Analysis Of Their Optical Properties, Aoife Power, Tony Betts, John Cassidy

Articles

A laboratory practical was designed for use by both undergraduate and second level students to demonstrate the synthesis and characterisation of tuneable silver colloids. It clearly illustrates the novel optical properties of silver nanoparticles compared to the bulk metal. The synthesis is both rapid and repeatable, and can be conducted on the laboratory bench at room temperature.

Broadband Fourier Transform Rotational Spectroscopy For Structure Determination: The Water Heptamer, Cristóbal Pérez, Simon Lobsiger, Nathan A. Seifert, Daniel P. Zaleski, Berhane Temelso, George C. Shields, Zbigniew Kisiel, Brooks H. Pate

Faculty Journal Articles

Over the recent years chirped-pulse, Fourier-transform microwave (CP-FTMW) spectrometers have chan- ged the scope of rotational spectroscopy. The broad frequency and large dynamic range make possible structural determinations in molecular systems of increasingly larger size from measurements of heavy atom (¹³C, ¹⁵N, ¹⁸O) isotopes recorded in natural abundance in the same spectrum as that of the parent isotopic species. The design of a broadband spectrometer operating in the 2–8 GHz frequency range with further improvements in sensitivity is presented. The current CP-FTMW spectrometer performance is benchmarked in the analyses of the rotational spectrum of the water …

Energy Of The Quasi-Free Electron In Repulsive Atomic And Molecular Fluids, Yevgeniy Lushtak

Dissertations, Theses, and Capstone Projects

The ability to predict accurately the energy V₀(ρ) of the quasi-free electron along the entire density (ρ) range of a supercritical fluid has applications in determining the ideal thermodynamic conditions for chemical reactions involving charged species. The previously established field ionization method of extracting V₀(ρ) from the fluid density dependent shift Δ(ρ) in the ionization energy of a dopant molecule has led to the discovery of a novel effect on V₀(ρ) occurring near the critical isotherm of the fluid. Unfortunately this method has limitations in determining V₀(ρ) in fluids with low critical …

Synthesis, Characterization, And Swelling Behaviors Of A Ph-Responsive Cmc-G-Poly(Aa-Co-Amps) Superabsorbent Hydrogel, Yizhe Wang, Xiaoning Shi, Wenbo Wang, Aiqin Wang

Turkish Journal of Chemistry

New superabsorbent hydrogels were synthesized through free radical graft copolymerization of partially neutralized acrylic acid (AA) and 2-acrylamido-2-methylpropanesulfonic acid (AMPS) onto carboxymethyl cellulose (CMC) backbones. The structure and morphology of the synthesized superabsorbent hydrogels were characterized by Fourier transform infrared spectroscopy and scanning electron microscope. The effect of the molar ratio of AMPS to AA, the APS concentration, and the CMC content on swelling ratio was optimized. The swelling properties in various pH solutions and saline solutions as well as the swelling kinetics were also evaluated. Results showed that the introduction of AMPS enhanced the swelling capacity, swelling rate, and …

A One-Pot Strategy For Regioselective Synthesis Of 6-Aryl-3-Oxo-2,3-Dihydropyridazine-4-Carbohydrazides, Mehdi Rimaz, Hossein Mousavi

Turkish Journal of Chemistry

A simple and efficient method for the synthesis of 6-aryl-3-oxo-2,3-dihydropyridazine-4-carbohydrazide derivatives was developed. The synthesis was achieved via one-pot multicomponent reaction of arylglyoxals, dialkylmalonates, and hydrazine hydrate in pyridine at room temperature. This procedure features high regioselectivity, generally good to excellent yields, the use of easily available starting materials, and operational simplicity. This chemistry provides an efficient and promising synthetic strategy for diversity-oriented construction of the 6-arylpyridazinone skeleton.

Iron (Iii) Tosylate Catalyzed Synthesis Of 3,4-Dihydropyrimidin-2(1h)-Ones/Thiones, Ram Mohan, Jacob Starcevich, Thomas Laughlin

Scholarship

No abstract provided.

Yellowstone Over-Snow Vehicle Emission Tests – 2012, John D. Ray, Gary A. Bishop, Brent G. Schuchmann, Chris Frey, Gurdas Sandhu, Brandon Graver

Fuel Efficiency Automobile Test Publications

No abstract provided.

Novel Microwave Assisted Synthesis Of Zns Nanomaterials, Suresh Pillai, Michael Seery, Damian Synnott, John Colreavy, Stephen Hinder

Articles

A novel ambient pressure microwave-assisted technique is developed in which silver and indium modified ZnS is synthesised. The as prepared ZnS is characterised by X-ray diffraction, UV-Vis spectroscopy, X-ray photoelectron spectroscopy and luminescence spectroscopy. This procedure produced crystalline materials with particle sizes below 10 nm. The synthesis technique leads to defects in the crystal which induce mid energy levels in the band gap and lead to indoor light photocatalytic activity. Increasing the amount of silver causes a phase transition from cubic blende to hexagonal phase ZnS. In a comparative study, when the ZnS cubic blende is heated in a conventional …

Single-Stranded Dna Scanning And Deamination With Single-Molecule Resolution, Padhuk Gamarala Senavirathne

Wayne State University Dissertations

SINGLE-STRANDED DNA SCANNING AND DEAMINATION WITH SINGLE-MOLECULE RESOLUTION

by

GAYAN SENAVIRATHNE

December 2013

Advisor: Dr. David Rueda & Dr.Ashok Bhagwat

Major: Chemistry (Analytical)

Degree: Doctor of Philosophy

APOBEC3G (Apo3G) and Activation-Induced cytidine Deaminase (AID) are the most notable members of APOBEC enzymes, a family of cytidine (C) deaminases with crucial functions in the immune system. In T cells, Apo3G deaminates C in viral cDNA to halt the replication of HIV 1 strains lacking viral infectivity factor (vif). In B cells, AID is required for the diversification of antibodies through initiation of somatic hypermutation (SHM), and class switch recombination (CSR), by …