Chemistry Commons^™

Nickel-Catalyzed Oxidative Decarboxylative (Hetero)Arylation Reactions, Aaron P. Honeycutt

Graduate Theses, Dissertations, and Problem Reports (ETD)

Transition-metal-catalyzed decarboxylative coupling reactions have gained considerable attention over the past decade as an efficient route to form heterobiaryls. However, current methods for oxidative decarboxylative (hetero)arylation with unactivated C-H bonds have been limited by poor substrate scope, control of regioselectivity, and chemospecificity. This thesis describes the development of a new nickel-catalyzed oxidative decarboxylative coupling (ODC) with unactivated C-H bonds. The first chapter discusses the development of the new nickel-catalyzed ODC reaction to enable the coupling of a N,N'-bidentate directing group with a broad scope of heteroaromatic carboxylates and ortho-substituted benzoates, a scope that has not been achieved in previous …

Electroplating Pennies Lab, Jacob W. Doehring

A with Honors Projects

This write up for a chemistry lab at Parkland College details the process of attempting to electroplate a copper penny with zinc using a current and creating a cell system and to experiment with varying voltages and currents and analyzing how these fluctuations affect the system.

Semi-Conductors Lab, Gino Cangialosi

A with Honors Projects

This write-up for a chemistry lab at Parkland College details the student's experiences in a semi-conductor lab, in which the student learned what positive and negative biases are, how semiconductors work, how to treat them in a lab setting, how to make a functioning circuit, how to take accurate readings at different points in a circuit.

Quantitation Without Calibration: Response Profile As An Indicator Of Target Amount, Mrittika Debnath

Graduate Research Theses & Dissertations

Quantitative assessment of biomarkers is essential in numerous contexts from decision-making in clinical situations to food quality monitoring to the interpretation of life-science research findings. However, appropriate quantitation techniques are not as widely addressed as detection methods. One of the major challenges in biomarker’s quantitation is the need to have a calibration for correlating a measured signal to a target amount. The step complicates the methodologies and makes them less sustainable. In this work, we addressed the issue via a new strategy: relying on the position of response profile rather than absolute signal for assessment of a target nucleic acid’s …

The Role Of The Hydrolysis And Zirconium Concentration On The Structure And Anticorrosion Performances Of A Hybrid Silicate Sol-Gel Coating, Maikki Cullen, Mary O’Sullivan, Aditya Madhan Kumar, Ahmad A. Sorour, Brendan Duffy, Mohamed Oubaha

Articles

In sol-gel chemistry, hydrolysis is the key step in the formation of the reactive hydroxide groups that are responsible for the formation of inorganic networks via the occurrence of condensation reactions. Though previous studies have investigated the effect of the hydrolysis conditions on the structure of organically modified silicates (ormosils), no study, to our knowledge, has investigated this variable on the structure of hybrid materials prepared by combinations of an ormosil and a transition metal (TM). Here, we propose to investigate this effect in a hybrid material composed of 3-trimethoxysilylpropylmethacrylate and a zirconium complex. To also highlight the effects of …

A Novel Quantitative Electrochemical Method To Monitor Dna Double-Strand Breaks Caused By A Dna Cleavage Agent At A Dna Sensor, Anna Banasiak, John Cassidy, John Colleran

Articles

Biosensors and Bioelectronics, Vol. 117

Comparison Of Fungal Spores Concentrations Measured With Wideband Integrated Bioaerosol Sensor And Hirst Methodology, S. Fernández-Rodríguez, R. Tormo-Molina, N. Lemonis, B. Clot, David O'Connor, John R. Sodeau

Articles

The aim of this work was to provide both a comparison of traditional and novel methodologies for airborne spores detection (i.e. the Hirst Burkard trap and WIBS-4) and the first quantitative study of airborne fungal concentrations in Payerne (Western Switzerland) as well as their relation to meteorological parameters. From the traditional method -Hirst trap and microscope analysis-, sixty-three propagule types (spores, sporangia and hyphae) were identified and the average spore concentrations measured over the full period amounted to 4145 ± 263.0 spores/m3. Maximum values were reached on July 19th and on August 6th. Twenty-six spore types reached average levels above …

The Janus-Faced Chromophore: A Donor-Acceptor Dyad With Dual Performance In Photon Up-Conversion, Natalia Kiseleva, Mikhail Filatov, Michael Oldenburg, Dimitry Busko, Marius Jakoby, Ian Howard, Bryce Richards, Mathias Senge, Sergey Borisov, Andrey Turshatov

Articles

An electron donor-acceptor dyad based on BODIPY (acceptor) and anthracene (donor) plays either the role of sensitizer or emitter in triplet-triplet annihilation photon up-conversion (TTA-UC). This Janus-like behavior was achieved via altering the relative ordering of charge-transfer and local excited state energies in the dyad through the polarity of TTA-UC media.

Synthesis, Characterisation And Dna Intercalation Studies Of Regioisomers Of Ruthenium (Ii) Polypyridyl Complexes, Laura Perdisatt, Samar Moqadasi, Luke O'Neill, Gary Hessman, Alessandra Ghion, Muhammad Qasim Mushtaq Warraich, Alan Casey, Christine O'Connor

Articles

Regioisomers of the functional group of the main ligand (L) on a series of [Ru(phen)2L]2+and [Ru(bpy)2L]2+ complexes, where phen is 1,10 phenanthroline and bpy is 2,2′-bipyridine, were synthesised to investigate the interaction with deoxyribonucleic acid (DNA) as potential therapeutics. UV–Vis binding titrations, thermal denaturation and circular dichroism were used to evaluate their interaction with DNA. The conclusions indicated the significance of the auxiliary ligand; especially 1,10-phenanthroline has on the binding constants (Kb). The systematic variation of auxiliary ligand(phen or bpy), and polypyridyl ligand (4-(1H-Imidazo[4,5-f][1,10]phenanthrolin-2-yl)benzonitrile (CPIP), 2-(4-formylphenyl)imidazo[4,5-f] [1,10] phenanthroline (FPIP), 2-(4-bromophenyl)imidazo[4,5-f][1,10]phenanthroline (BPIP) and 2-(4-nitrophenyl)imidazo[4,5-f] [1,10] phenanthroline (NPIP), split in terms of …

Development Of Novel Phenanthroline And Thiazole Orange Derived G-Quadruplex Ligands And Telomerase Inhibitors, Siwen Wang

University of the Pacific Theses and Dissertations

The end of the human chromosome is protected by telomeres which contain a special tandem guanine-rich DNA sequence, 5’-TTAGGG. The length of telomeres is shortened during cell replications, and its length limits the replication capacity of cells. Telomerase is over-expressed in 85–90% of cancer cells, responsible for extending the telomere length in cancer cells. Guanine-rich DNA sequence can self-assemble into unique G-quadruplex structures that interfere with the extension of telomeres by telomerase. Therefore, DNA G-quadruplex has recently received much attention because of its important regulatory functions in telomerase-mediated cancerization. The formation of G-quadruplex requires monovalent cations (Na+ and K+) or …

Characterization Of Tetraethyl Orthosilicate-Based Dynamic Hydrogels For Use As Reversible 3-D Cell Culture Matrices, Krisitan Stipe

Graduate Student Theses, Dissertations, & Professional Papers

No abstract provided.

The Development Of A Simplified Alkalinity Titration Analyzer, Reba Van Beusekom

Graduate Student Theses, Dissertations, & Professional Papers

Alkalinity is the acid neutralizing capacity for water, meaning alkalinity measures how sensitive an aquatic system is to acidic inputs. Currently, there are various measuring systems for alkalinity available including chemical test kits, potentiometric techniques, and colorimetric methods. Commercially available products lack the ease of use combined with precision and accuracy desired for on-line process and environmental monitoring. The goal of this project is to develop a simplified alkalinity titration analyzer, called the easyTMT, to measure alkalinity with precision and accuracy comparable to the best conventional methods. The system, under development, uses the Tracer Monitored Titration (TMT) technique. TMT …

Structure-Property Relationships In Paes Prepared From 2-(2,4-Difluorophenyl)Benzoxazole Derivatives, Amy Slaybaugh

Browse all Theses and Dissertations

The synthesis of N-heterocycle functionalized poly(arylene ether)s, derived from 2-(2,4-difluorophenyl)benzoxazole, was explored. The platform monomer, 2-(2,4-difluorophenyl)benzoxazole (3), was prepared in one-step and characterized using NMR spectroscopy and elemental analysis. The “pre” approach involved introducing a carbazole moiety, using a copper catalyzed C-N coupling reaction, while the “post” approach required conversion of monomer 3 to the corresponding poly(arylene ether)s (PAE)s first, then performing the C-N coupling reaction. Both “pre” and “post” approaches utilized bisphenol-A (BPA) and 4,4’-difluorophenylsulfone (DPS) as comonomers as well as 4,4’-dihydroxydiphenyl ether (DPE) and 4,4’difluorotriphenylphosphine oxide (dfTPPO). All of the materials had sufficient molecular weights (Mn) to allow …

The Great Potential Of Redox Active Ligands: Applications In Cancer Research And Redox Active Catalysis, Meredith Miles

Browse all Theses and Dissertations

Metal N-heterocyclic carbene (NHC) complexes have recently gained much popularity due to their tunable, steric, and electronic properties. Applications for such versatile molecules include organocatalysis, olefin metathesis, sundry cyclization reactions, and materials chemistry. Redox active NHCs are of special interest due to their ability to alter the electronic properties of the metal centers they are ligated to. In the first chapter, Au(I)-NHC complexes were synthesized and tested for biological activity in human cancer cell lines. Increasing reactive oxygen species (ROS) in cellular systems has proven to be a successful pathway for treating cancer. The redox active group in this case …

Plasmon-Enhanced Optical Sensing By Engineering Metallic Nanostructures, Peng Zheng

Graduate Theses, Dissertations, and Problem Reports (ETD)

The world’s booming population projected to reach 10 billion by 2050 causes enormous stresses on environmental safety, food supply, and healthcare, which in return threatens human civilizations. One of the most promising solutions lies at innovating point-of-care (POC) sensing technologies to conduct detection of environmental hazards, monitoring of food safety, and early diagnosis of diseases in a timely and accurate manner. The discovery of surface-enhanced spectroscopy in the 1970s has significantly stimulated research on light-matter interaction which gives rise to enhanced optical phenomena such as surface-enhanced Raman scattering (SERS), plasmon-enhanced fluorescence (PEF), and particularly, they have found enormous applications in …

Chalcone And Cinnamate Synthesis Via One-Pot Enol Silane Formation-Mukaiyama Aldol Reactions Of Ketones And Acetate Esters, C. Wade Downey, Hadleigh M. Glist, Anna Takashima, Samuel R. Bottum, Grant J. Dixon

Chemistry Faculty Publications

Aryl alkyl ketones, acetate esters, and acetamides undergo facile one-pot enol silane formation, Mukaiyama aldol addition, and dehydrosilyloxylation in the presence of an amine base and excess trimethylsilyl trifluoromethanesulfonate. The chalcone and cinnamate products are generally recovered in high yield. The relative stoichiometry of the trimethylsilyl trifluoromethanesulfonate and amine base reagents determines whether the reaction yields the β- silyloxy carbonyl product or the α, β -unsaturated carbonyl.

Optical Properties Of Single Nanoparticles And Two-Dimensional Arrays Of Plasmonic Nanostructures, Yadong Zhou

Electronic Theses and Dissertations

The tunability of plasmonic properties of nanomaterials makes them promising in many applications such as molecular detection, spectroscopy techniques, solar energy materials, etc. In the thesis, we mainly focus on the interaction between light with single nanoparticles and two-dimensional plasmonic nanostructures using electrodynamic methods. The fundamental equations of electromagnetic theory: Maxwell's equations are revisited to solve the problems of light-matter interaction, particularly the interaction of light and noble nanomaterials, such as gold and silver. In Chapter 1, Stokes parameters that describe the polarization states of electromagnetic wave are presented. The scattering and absorption of a particle with an arbitrary shape …

Development And Characterization Of Solid-Contact Paper-Based And Micro Ion-Selective Electrodes For Environmental Analysis, Stephanie Armas

Electronic Theses and Dissertations

Ion-selective electrodes (ISEs) have extensively been used for food analysis, as medical diagnostic tools, and for some environmental applications. However, ISEs are hindered by the need of a bulky reference electrode and the pre-conditioning step of the sensor, which can often be lengthy. This work will discuss how the direct addition of target analyte into the cocktail sensing membrane can circumvent the pre-conditioning step. Furthermore, the work is presented in an optimized ready-to-use single strip design, where the bulky glass reference electrode (RE) is no longer needed. The bulky RE was replaced by drop casting a simple two-component mixture consisting …

Advancements In Liquid Chromatography For The Determination Of Polycyclic Aromatic Compounds In Environmental Samples, Hugh Hayes

Electronic Theses and Dissertations

The purpose of this dissertation is to provide a new and improved analytical methodology for the analysis of polycyclic aromatic hydrocarbons (PAHs) and polycyclic aromatic sulfur heterocycles (PASHs) in environmental samples. Hundreds of PAHs and PASHs are present in the environment and have great toxicological importance and the chemical determination of these components is a priority. The complete normal-phase liquid chromatography (NPLC) retention behavior has been explored for these compounds. Retention indices were determined for 124 PAHs, 62 methyl-PAHs (MePAHs), 67 PASHs, and 80 alkyl-PASHs on an aminopropyl (NH2) stationary phase which represents the most comprehensive study of polycyclic aromatic …

Design, Synthesis, Stability, And Photocatalytic Studies Of Sustainable Metal-Organic Frameworks, Matthew Logan

Electronic Theses and Dissertations

The presented dissertation focuses on the design, synthesis, and characterization of metal-organic frameworks (MOFs) composed of earth-abundant elements the exhibit photoredox activity and studied their application as heterogeneous photocatalysts in organic synthesis and in solar-to-chemical energy conversion. In particular, the structure-property relationships of titanium-based MOFs relating the structure of the organic building unit and the photophysical and photochemical activity of the solid material is studied. The first novel family of seven MOFs isoreticular to MIL-125-NH2, includes functionalized with N-alkyl groups with increasing chain length (methyl to heptyl) and with varying connectivity (primary or secondary). The functionalized materials displayed reduced optical …

Qualitative And Quantitative Elemental Composition Analysis Of The Surrounding Pollen Coating Via Icp-Ms, Brandy Voyer

Electronic Theses and Dissertations

Pollen evidence has proven to be a powerful forensic tool to trace a suspect or item to a victim or a crime scene. This is possible because it is microscopic, abundant in nature, resistant to degradation and decay; it presents dispersal patterns that can be used to generate a 'fingerprint' within specific areas, and has illustrated a unique morphology that can be used to classify species. While the pollen grain morphology has been extensively used to characterize the specific species, not much has been investigated as pertains to the coating that surrounds the pollen grain aside from it being categorized …

Integration Of Fundamental Research And Cer: The Role Of Authenticity In Developing Views On The Nature Of Teaching, Learning, And Doing Science, Julie Donnelly

Electronic Theses and Dissertations

This dissertation is an integration of fundamental research and chemical education. It begins with two nonlinear spectroscopic studies of compounds important to the study of brain chemistry. In Chapter 2, we present a novel method using quantum mechanics for modelling ligand docking and the potential of nonlinear circular dichroism for elucidating the mechanism of cannabinoids docking to their receptor, a contribution to studies of varying psychological effects of cannabinoids. Considering existent challenges with measuring this phenomenon, in Chapter 3, we evaluate two-photon absorption properties of Thioflavin T (ThT) in varying glycerol/water content solutions and discuss the enhancement of nonlinear absorption …

Nanoscale Characterization And Mechanism Of Electroless Deposition Of Silver Metal, Christopher Grabill

Electronic Theses and Dissertations

This dissertation is an investigation of the nanoscale characteristics and mechanism of electrolessly deposited silver metal seeded by gold nanoparticles. The process of growing seed-nanoparticles on a polymer surface was studied. Several bifunctional amines and organic reducing agents were used to explore how these chemical factors affect the size and distribution of gold nanoparticles formed at the interface. The nanoparticles were characterized by transmission electron microscopy (TEM) and high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM). An electroless deposition (ED) bath developed by Danscher was selected to study electroless deposition of silver in detail. The chemical species in the bath …

Split Aptameric Turn-On Fluorescence Sensor For Detection Of Sequence Specific Nucleic Acid At Ambient Temperature, Nanami Kikuchi

Electronic Theses and Dissertations

Nucleic acid amplification tests (NAATs) enable sensitive detection of low density infections that microscopy and rapid diagnostic test are not capable of detecting. They enable quantitative and qualitative nucleic acid detection, genotype analysis, and single nucleotide polymorphism (SNP) detection. Current state of the art molecular probes used with NAATs includes molecular beacon (MB), Taqman and its variations. This work presents novel molecular probe designed from Spinach and Dapoxyl aptamers. The aptamers are split into two parts (split aptamer), allowing greater sensitivity and selectivity towards fully complementary nucleic acid analyte. The major advantage of split aptamer probe over state-of-the-art fluorescent probes …

The Forensic Characterization Of Bacterial And Fungal Organisms In Traditional Chinese Medicine, Julia Grzymkowski, Christopher J. Ehrhardt, Justin L. Poklis, Michelle R. Peace

Undergraduate Research Posters

There has been an increase in use of Traditional Chinese Medicine (TCM) in the United States because they are less expensive and believed to be more effective with less adverse effects in comparison to traditional pharmaceutics. Therefore, sales have increased in the US, despite articles and case studies demonstrating the dangers, such as injury and death, related to TCM, stemming from improper labelling, toxic contaminants, and, in some cases, the presence of pathogenic bacteria. The aim of this study was to perform a survival experiment to demonstrate the importance of proper herbal brewing technique and to conduct a molecular and …

Varied Length Stokes Shift Bodipy-Based Fluorophores For Multicolor Microscopy, Amy M. Bittel, Ashley M. Davis, Lei Wang, Michel A. Nederlof, Jorge O. Escobedo, Robert Strongin, Summer L. Gibbs

Chemistry Faculty Publications and Presentations

Multicolor microscopy tools necessary to localize and visualize the complexity of subcellular systems are limited by current fluorophore technology. While commercial fluorophores cover spectral space from the ultraviolet to the near infrared region and are optimized for conventional bandpass based fluorescence microscopy, they are not ideal for highly multiplexed fluorescence microscopy as they tend to have short Stokes shifts, restricting the number of fluorophores that can be detected in a single sample to four to five. Herein, we synthesized a library of 95 novel boron-dipyrromethene (BODIPY)- based fluorophores and screened their photophysical, optical and spectral properties for their utility in …

Boiling Points Of The Propylene Glycol + Glycerol System At 1 Atmosphere Pressure: 188.6–292 °C Without And With Added Water Or Nicotine, Anna K. Duell, James F. Pankow, Samantha M. Gillette, David H. Peyton

Chemistry Faculty Publications and Presentations

No abstract provided.

Wildfire Emissions In The Context Of Global Change And The Implications For Mercury Pollution, Aditya Kumar

Dissertations, Master's Theses and Master's Reports

Wildfires are episodic disturbances that exert a significant influence on the Earth system. They emit substantial amounts of atmospheric pollutants, which can impact atmospheric chemistry/composition and the Earth’s climate at the global and regional scales. This work presents a collection of studies aimed at better estimating wildfire emissions of atmospheric pollutants, quantifying their impacts on remote ecosystems and determining the implications of 2000s-2050s global environmental change (land use/land cover, climate) for wildfire emissions following the Intergovernmental Panel on Climate Change (IPCC) A1B socioeconomic scenario.

A global fire emissions model is developed to compile global wildfire emission inventories for major atmospheric …

Synthesis, And Structural, Electrochemical, And Magnetic Property Characterization Of Promising Electrode Materials For Lithium-Ion Batteries And Sodium-Ion Batteries, Ruixin Han

Theses and Dissertations--Chemistry

Iron oxides, have been widely studied as promising anode materials in lithium-ion batteries (LIBs) for their high capacity (≈ 1000 mA h g^-1 for Fe₂O₃ and Fe₃O_4,), non-toxicity, and low cost. In this work, β-FeOOH has been evaluated within a LIB half-cell showing an excellent capacity of ≈ 1500 mA h g^-1 , superior to Fe₂O₃ or Fe₃O_4. Reaction mechanism has been proposed with the assistance of X-ray photoelectron spectroscopy (XPS). Various magnetic properties have been suggested for β-FeOOH such as superparamagnetism, antiferromagnetism and complex …

New Approaches To Cyclopentadienyl-Fused Thiophene Complexes Of Iron And Synthesis And Characterization Of Carbonic Anhydrase Active-Site Mimics For Co2 Hydration, Deepshikha Gupta

Theses and Dissertations--Chemistry

Polyheterocycles such as polythiophene and its derivatives comprise an important class of conducting polymers used for electronic applications. They have been of great interest for use in electronic materials due to their increased environmental stability as well as novel electronic properties in their polymer states. We have been interested in exploring the electronic properties of organometallic analogues of the low-band-gap polymer poly(benzo[3,4-c]thiophene) (polyisothianaphthene) that incorporates η⁵-cyclopenta[c]thienyl monomers such as ferroceno[c]thiophene. First chapter of this dissertation involved synthetic attempts to ferroceno[c]thiophene. Exploring a shorter synthetic route to starting material, 1,2-di(hydroxymethyl)ferrocene was …