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Mechanistic Studies And Optimization Of Microwave-Assisted Palladium-Catalyzed Carbon-Carbon Bond Forming Reactions And An Academic Prospective On “Quality By Design”, Neha K. Grewal

Honors Scholar Theses

This compilation of work includes four aspects: (1) an academic review on the significance and implementation of Quality by Design (QbD), (2) mechanistic studies on the palladium-catalyzed synthesis of diarylmethanes, (3) the optimization of microwave-assisted click reactions and Suzuki couplings for use in an undergraduate organic chemistry laboratory manual, and (4) monitoring the progress of organic transformations using Raman spectroscopy.

Nuclear Translocation Of Foxo3a Transcription Factor During Prelamin A Induced Cell Cycle Arrest In 3t3 Cells., Jessica B. Keasler

Undergraduate Honors Theses

As the so-called “Mothership of the Human Genome,” the cell nucleus must keep all vital genetic information safe, but accessible, inside a strong protective envelope. The inner membrane of the nuclear envelope is lined by tough but adaptable proteins called lamins. While lamins polymerize into fibrous structures that hold up the “walls” of the nucleus, they also serve as an internal scaffold for the complex machinery involved in DNA replication and gene expression. It is in this later role that we have been looking for clues to premature and possibly to normal aging. One type of lamins, Lamin A is …

Studies On The Preparation, Immobilization, And Luminescence Properties Of Zinc Oxide (Zno)Quantum Dots, Yasemin Hakat

Electronic Theses and Dissertations

Quantum dots are a part of very important our technological future because of their intriguing and useful properties. These properties are different in character from those of the corresponding bulk material. Quantum dots are inorganic artificial semiconductor nanocrystal whose electrons influence their physical and chemical properties. Zinc oxide quantum dots were synthesized through an ethanol based precipitation via colloidal synthesis method at various pH values. Various emission colors were obtained because the excited quantum dots of various sizes emitted specific wavelengths of light. The emission spectra indicated that the pH dependent quantum dots were successfully synthesized. Zinc oxide quantum dots …

The Analysis Of Protein-Bound Thiocyanate In Plasma Of Smokers And Non-Smokers As A Marker Of Cyanide Exposure, Stephanie L. Youso, Gary A. Rockwood, Brian A. Logue

Chemistry and Biochemistry Faculty Publications

When cyanide is introduced into the body, it quickly transforms through a variety of chemical reactions, normally involving sulfur donors, to form more stable chemical species. Depending on the nature of the sulfur donor, cyanide may be transformed into free thiocyanate, the major metabolite of cyanide transformation, 2-amino-2-thiazoline-4-carboxylic acid or protein-bound thiocyanate (PB-SCN) adducts. Because protein adducts are generally stable in biological systems, it has been suggested that PB-SCN may have distinct advantages as a marker of cyanide exposure. In this study, plasma was analyzed from 25 smokers (chronic low-level cyanide exposure group) and 25 non-smokers for PB-SCN. The amount …

Synthesis And Structural Studies Of Calcium And Magnesium Phosphinate And Phosphonate Compounds, Victoria Naa Kwale Bampoh

Chemistry - Dissertations

The work presented herein describes synthetic methodologies leading to the design of a wide array of magnesium and calcium based phosphinate and phosphonates with possible applications as bone scaffolding materials or additives to bone cements. The challenge to the chemistry of the alkaline earth phosphonate target compounds includes poor solubility of compounds, and poorly understood details on the control of the metal's coordination environment. Hence, less is known on phosphonate based alkaline earth metal organic frameworks as compared to transition metal phosphonates. Factors governing the challenges in obtaining crystalline, well-defined magnesium and calcium solids lie in the large metal diameters, …

Blind Prediction Of Host-Guest Binding Affinities: A New Sampl3 Challenge, H. S. Muddana, C. D. Varnado, C. W. Bielawski, Adam R. Urbach, L. Isaacs, M. T. Geballe, M. K. Gilson

Chemistry Faculty Research

The computational prediction of protein–ligand binding affinities is of central interest in early-stage drug-discovery, and there is a widely recognized need for improved methods. Low molecular weight receptors and their ligands—i.e., host–guest systems—represent valuable test-beds for such affinity prediction methods, because their small size makes for fast calculations and relatively facile numerical convergence. The SAMPL3 community exercise included the first ever blind prediction challenge for host–guest binding affinities, through the incorporation of 11 new host–guest complexes. Ten participating research groups addressed this challenge with a variety of approaches. Statistical assessment indicates that, although most methods performed well at predicting some …

Synthesis, Structure, And Characterization Of Hybrid Solids Containing Polyoxometalates And Ruthenium Polypyridyl Complexes, Yanfen Ll

Masters Theses & Specialist Projects

Polyoxometalates (POMs), which are inorganic metal oxide cluster anions with discrete structures, have been extensively studied in recent years due to their large variety of applications such as medicine, biology, catalysis, material sciences and chemical analysis. Ruthenium polypyridyl complexes have been extensively studied for their applications as photosensitizers in solar energy conversion and photoelectronic materials. Recently, ruthenium heterocyclic ligand complex-based building blocks have been used for the synthesis of hybrid organic-inorganic solids through the self-assembly. We are interested in the synthesis of ruthenium polypyridyl complexes and polyoxometalate anions through different ways such as coordination bonds, hydrogen bonds and ionic bonds …

The Reaction Of Methionine With A Non-C2-Symmetrical Platinum (Ii) Diamine Compound, Nilesh Sahi

Mahurin Honors College Capstone Experience/Thesis Projects

The research that we have conducted has allowed us to discover that the amino acids, methionine (Met) and N-acetyl methionine (N-AcMet), will react in a 1:1 and 1:2 molar ratio with platinum complexes containing bulky diamine ligands. Previous research has allowed us to gain a plethora of information on the experimentation and results of specific bulky diamine ligands such as N,N,N',N'-tetramethylethylenediamine and N,N-diethylethylenediamine. In the current study, we have investigated the bulky diamine ligand of N,N-dimethylethylenediamine, or Me₂en. With our focus on the bulk of the Me₂en ligand, we have been able to synthesize a platinum …

Time-Dependent Density-Functional-Theory Calculation Of High-Order-Harmonic Generation Of H-2, Xi Chu, Gerrit C. Groenenboom

Chemistry and Biochemistry Faculty Publications

The observation of the isotope effect in the high-order-harmonic generation (HHG) of H-2 presents a challenge for time-dependent density-functional-theory (TDDFT) methods, since this effect is related to the dynamics of the ion created in the tunneling ionization step of HHG and it depends on the harmonic order. As an initial step toward describing this effect within current computational capacity, we benchmark a method in which the nuclear and electronic degrees of freedom are separated and both treated quantum mechanically. For the electrons two TDDFT formalisms are adopted. Although the ion-dynamics effect is not described in our method, it reproduces the …

Oxaliplatin And Oxaliplatin Derivatives: Synthesis, Characterization, And Reactivity With Biologically Relevant Ligands, Amy Poynter

Mahurin Honors College Capstone Experience/Thesis Projects

Oxaliplatin is a third generation anticancer drug that has proven to be successful in fighting ovarian and testicular cancer. We are interested in determining how oxaliplatin and oxaliplatin derivatives interact with proteins, as well as how that interaction is affected by the size and shape of these platinum compounds. We have synthesized oxaliplatin as it is used in cancer treatment, as well as similar platinum compounds with the same diaminocyclohexane ligand as oxaliplatin but with additional bulk added to the nitrogen atoms. We are reacting oxaliplatin with key amino acids, including methionine, and will be comparing the kinetics of this …

Hydrodynamic Evaluation And Characterization Of Capillary Channeled Polymer (C-Cp) Fibers As A Stationary Phase In Hplc Of Macromolecules, Kelum Randunu Pathirannahalage

All Theses

High Performance Liquid Chromatography (HPLC) is the most used analytical technique for the separation of samples in solution. HPLC of has progressed with successive use of new supports such as silica, polysaccharides, monoliths, and organic polymers. Although porous silica phases are very effective in small molecule separations, they suffer from certain drawbacks including pH stability, chemical robustness, high backpressure, and slow mass transfer for macromolecule separations. Thus, the most protein separations are carried out using nonporous, partially porous, and superficially porous phases to overcome mass transfer limitations. As a competing methodology, fiber based polymer support/stationary phases are also developed for …

Exploration Of The Chemistry Of Alkynes And Selectfluor : Search For Cytotoxic Agents From The Amazonian Rainforest., Zhuang Jin

Electronic Theses and Dissertations

Vicinal dithioethers and alkenyl thioethers were synthesized under environmentally friendly conditions using alkyne and thiol in water. Alkynes were also used to develop a multibond-fonning reaction that fonned cyclic ketones or ketoesters through a goldcatalyzed intramolecular oxygen transfer isomerization of 2-alkynyl-l ,5-diketones or 2- alkyny 1-5 -ketoesters. The investigation of Selectfluor chemistry yielded a highly stereoselective synthesis of fluoroalky (E)-a,ß-unsaturated ketones from allenyl esters, through a gold-catalyzed rearrangement that produced an intennediate dienyl ester. When Selectfluor was combined with copper, it produced two oxidative systems, F-TEDA-BF4 and F-TEDAPF 6, both of which efficiently converted amides into imides at room temperature …

Racemization Of Amino Acids In Teeth For The Determination Of Age, Andrea Lee Toll

Masters Theses & Specialist Projects

Instrumental to forensic investigations is the ability to identify unknown human remains providing key evidence to criminal cases, resolution to missing persons, and assistance in mass or natural disasters. Identification of remains in an effort to determine age is an area of forensics that has received considerable attention. Traditional methods in age determination such as morphology are often biased, antiquated, and frequently result in a large margin of error. Conversely, the emergence of new forensic techniques provide promise to reduce the margin of error in determining age. One such technique has focused on relating the extent of amino acid racemization …

Hydro/Solvothermal Synthesis, Structures And Properties Of Metal-Organic Frameworks Based On S-Block Metals, Raj Kishore Vakiti

Masters Theses & Specialist Projects

Carbon dioxide removal from flue gases of power plants is critical for reduction of greenhouse gas emissions implicated in global warming. Metal Organic Frameworks (MOFs) promising potential applications in carbon dioxide capture due to their unique structural properties such as high porosity and high thermal stability. These MOFs have application in separation processes and gas storage. By the assembly of the organic ligands and metal oxide clusters, porous MOFs can be synthesized. The use of s-block metals such as calcium, magnesium and rubidium in porous materials is appealing because their ionic binding characters with organic ligands will general flexible MOFs. …

Removal Of Heavy Metals Using Modified Limestone Media: Zinc And Cadmium, Keerthy Mandadi

Masters Theses & Specialist Projects

Heavy metal contamination is a serious concern throughout the world. Increased concentrations in drinking water have many negative impacts on human health. Limestone is an inexpensive and simple media for removing high concentrations of heavy metals from drinking water supplies. Ferric based media is commonly used to remove zinc, cadmium, lead, arsenic and other heavy metals. The drinking water standards set by the US EPA for cadmium, zinc and arsenic are 0.005 mg/L, 5 mg/L and 0.010 mg/L respectively. Bangladesh, parts of India, China and the United States have high concentrations of arsenic in drinking water. Although many technologies exist …

Reducing Lead And Selenium From Drinking Water Using Limestone-Based Material, Sindhu Tumati

Masters Theses & Specialist Projects

Contamination of drinking water with metals is a major problem facing many areas of United States and the World. There is a need for an inexpensive remediation technology for the removal of metals in drinking water that can be applied to small rural water systems. This research will focus on the development of a process for removal of select metals from drinking water by limestone-based material. Metals in drinking water considered for this research include lead and selenium. Limestone-based material has demonstrated the potential to reduce select metals (lead, cadmium and arsenic) in drinking water, with the additional benefit of …

Synthesis, Characterization And Applications Of Different Nanostructures, Whitney Snyder

All Theses

There has been a growing interest in the field of nanoscience for the last several decades including the use in optical, electrical, biological and medicinal applications. This thesis focuses on the synthesis of different nanoparticles for their potential uses in drug delivery and antimicrobial agents as well as porous alumina membranes as surface enhanced Raman scattering or SERS substrates.
The synthesis of nanocomposites (NCs) composed of silica and poly(4-vinyl pyridine) (P4VP) in a basic ethanol solution is presented in chapter 2. The composition of the NCs appears to be homogenous after synthesis and is greatly affected by heat and pH …

Insufficient Radiofrequency Ablation Promotes Angiogenesis Of Residual Hepatocellular Carcinoma Via Hif-1Α/Vegfa, Jian Kong, Jinge Kong, Bing Pan, Shan Ke, Shuying Dong, Xiuli Li, Aimin Zhou, Lemin Zheng, Wen Bing Sun

Chemistry Faculty Publications

Background: The mechanism of rapid growth of the residual tumor after radiofrequency (RF) ablation is poorly understood. In this study, we investigated the effect of hyperthermia on HepG2 cells and generated a subline with enhanced viability and dys-regulated angiogenesis in vivo, which was used as a model to further determine the molecular mechanism of the rapid growth of residual HCC after RF ablation. Methodology/Principal Findings: Heat treatment was used to establish sublines of HepG2 cells. A subline (HepG2 k) with a relatively higher viability and significant heat tolerance was selected. The cellular protein levels of VEGFA, HIF-1α and p-Akt, VEGFA …

Accessible High-Throughput Virtual Screening Molecular Docking Software For Students And Educators, Reed B. Jacob, Tim Andersen, Owen M. Mcdougal

Chemistry and Biochemistry Faculty Publications and Presentations

We survey low cost high-throughput virtual screening (HTVS) computer programs for instructors who wish to demonstrate molecular docking in their courses. Since HTVS programs are a useful adjunct to the time consuming and expensive wet bench experiments necessary to discover new drug therapies, the topic of molecular docking is core to the instruction of biochemistry and molecular biology. The availability of HTVS programs coupled with decreasing costs and advances in computer hardware have made computational approaches to drug discovery possible at institutional and non-profit budgets. This paper focuses on HTVS programs with graphical user interfaces (GUIs) that use either DOCK …

Synthesis Of A 2,2'-Bipyridyl Functionalized Oligovinylene- Phenylene Using Heck And Horner-Wadsworth-Emmons Reactions And X-Ray Crystal Structure Of E-(4-(4-Bromostyryl)Phenyl)(Methyl)Sulfane, Orsolya Karácsony, Jeffrey R. Deschamps, Scott A. Trammell, Rafaela Nita, D. Andrew Knight

Chemistry and Chemical Engineering Faculty Publications

The synthesis of a new 2,2'-bipyridyl functionalized oligovinylenephenylene (OVP-5) containing a methyl protected thiol using Heck coupling and the Horner-Wadsworth- Emmons reaction and is described. A key step involving a diisopropylcarbodiimide promoted dehydration of a stable ?-hydroxyphosphonate intermediate was identified. The structure of precursor E-(4-(4-bromostyryl) phenyl)(methyl)sulfane (1) was determined using X-ray crystallography. © 2012 by the authors.

Conformational Motions Associated With Ligand Binding In Dihydrofolate Reductase From Bacillus Stearothermophilus, Mayam Tobilola Alapa

Theses, Dissertations and Culminating Projects

A fluorescently-labeled, conformationally-sensitive Bacillus stearothermophilus (Bs) dihydrofolate reductase (DHFR) (C73A/S131C_MDCC DHFR) was developed and used to investigate kinetics and protein conformational motions associated with methotrexate (MTX) binding. This construct bears a covalently attached fluorophore, N-[2-(lmaleimidyl) ethyl]-7-(diethylamino)coumarin-3-carboxamide (MDCC) attached at a distal cysteine, introduced by mutagenesis. The probe is sensitive to the local molecular environment, reporting on changes in the protein structure associated with ligand binding. Intrinsic tryptophan fluorescence of the unlabeled Bs DHFR construct (C73A/S131C DHFR) also showed changes upon MTX association. Stopped-flow analysis of all data can be understood by invoking the presence of two native state DHFR …

Characterization Of A C-Jun N-Terminal Kinase Pathway In The Parasitic Nematode, Brugia Malayi, Agnieszka N. Chojnowski

Theses, Dissertations and Culminating Projects

Lymphatic filariasis (elephantiasis) is a major neglected disease caused by filarial nematodes including; Wuchereria bancrofti, Brugia malayi {B. malayi) and Brugia timori. Over 120 million individuals are infected and more than 1.3 billion people are at risk of infection in 81 endemic countries. Current treatments are limited, toxic and fail to kill adult parasites. There is a need for new target and treatments. One potential novel drug target for this disease is stress-activated protein kinases. It has been previously demonstrated in our laboratory that a B. malayi stress-activated protein kinase, Bm- MPK1, an ortholog of the human p38/Caenorhabditis elegans (C. …

Investigation Of Autoregulation Of Icer And Electrochemical Properties Of Tryptophan, Mark Demilio

Theses, Dissertations and Culminating Projects

A relatively new development in the field of research-based chemistry is to study biomolecules, their interactions, and a biochemical mechanisms by examination of their physical properties and application of laboratory techniques rooted in concepts of physical chemistry. Both projects that are encompassed within this master's thesis indeed fall under the umbrella of biophysical chemistry, as they apply physical chemical techniques study particular biomolecular interactions.

The first of these two projects is the study of a leucine zipper protein, Inducible cAMP Early Repressor [ICER], which is a product of the cAMP Responsive Element Modulator [CREM] gene. ICER functions as a transcriptional …

A Leishmania Mitogen Activated Protein Kinase As A Potential Anti-Parasitic Drug Target : Purification, Characterization And Inhibitor Interactions, Aysenur Sayakci

Theses, Dissertations and Culminating Projects

The disease, Leishmaniasis, is caused by the protozoal parasite Leishmania, which is transmitted by the bite of an infected Phlebotomine female sandfly. It is a significant health problem in tropical regions of the world and new therapeutic approaches for treating this disease are urgently needed.

Protozoal MAPKs (Mitogen Activated Protein Kinases) play important roles in parasite viability and infectivity and as such, represent viable drug targets. It has been demonstrated that LmxMPKl is an essential MAPK required for the parasite to establish infection and for proliferation of the amastigote stage (the mammalian stage of the parasite) of the parasite. In …

Synthesis Of Novel Alkaline Earth Tosylate Complexes Through Donor Studies, Adam J. Brooks

Renée Crown University Honors Thesis Projects - All

Salt metathesis has become a critical reaction pathway in organometallic chemistry; however, for alkaline earth metals this process is hindered by the need of highly pure and expensive metal iodides as starting materials. This contribution highlights recent attempts to identify inexpensive reagents for salt metathesis. Alkaline earth-tosylates can be prepared cost effectively using p-toluenesulfonic acid in one-pot reactions in water. The coordinated water molecules can be removed by gentle heating under vacuum. The anhydrous tosylates, however, have major solubility limitations as the result of extensive aggregation networks. The goal of this study was to increase the solubility of the tosylates …

Biologically-Derived Dye-Sensitized Solar Cells: A Cleaner Alternative For Solar Energy, Erika S. Falsgraf

Pomona Senior Theses

This project employs the biological compounds hemin, melanin, and retinoic acid as photoactive dyes in dye-sensitized solar cells (DSSCs). These dyes are environmentally and economically superior to the standard ruthenium-based dyes currently used in DSSCs because they are nontoxic and widely available. Characterization by linear sweep voltammetry yielded averaged maximum overall conversion efficiency values of 0.059% for retinoic acid, 0.023% for melanin, and 0.015% for hemin. Absorption spectra of hemin and retinoic acid suggest that they would complement each other well when used in tandem in one cell because hemin has a secondary maximum absorption peak at 613nm and retinoic …

Nmr Characterization Of Parathion: Properties, Transport, And Reaction Kinetics, Emma Catherine Baker

Boise State University Theses and Dissertations

The hydrolysis reaction of parathion (PTH) to produce para-nitrophenolate (pNP) and O,O-diethylthiophosphate (DETP) was examined in a minimally disturbed liquid-liquid biphasic reaction system by proton and phosphorous nuclear magnetic resonance spectroscopy. The effect of the micellar cationic surfactant, cetyltrimethylammonium chloride (CTAC), on PTH transport, hydrolysis, and system characteristics including reactant-product concentrations, pNP partition coefficients, pNP surface activity, ultraviolet degradation of pNP, oxidation of pNP, and impurities in PTH are reported. Surfactant reaction systems resulted in a 2.5 order of magnitude increase in the amount of PTH transported into the aqueous layer as compared to the control system at 2100 …

Biomass Assisted Synthesis Of Antibacterial Gold Nanoparticles And Commentary On Its Future Potential And Applications In Medicine, Chad Willis

Mahurin Honors College Capstone Experience/Thesis Projects

Xylose is a natural monosaccharide found in biomass such as straw, pecan shells, cottonseed hulls, and corncobs. Using this monosaccharide, we report the green synthesis and characterization of biocompatible, biodegradable xylose encapsulated gold nanoparticles (Xyl-GNPs) with potential antibacterial activity. GNPs were synthesized using the bioreduction property of xylose on the chloroaurate anions in an aqueous solution at room temperature and at atmospheric pressure. The characterization of synthesized GNPs was examined by UV-vis spectroscopy; transmission electron microscopy (TEM), energy-dispersive x-ray spectroscopy (EDS) and fourier transform infrared spectroscopy (FTIR). Results indicate that the particles were stable; near spherical in shape with an …

Surface Modifications Of Capillary-Channeled Polymer (C-Cp) Fibers For Applications In Highly Selective Separations, Jennifer Pittman

All Dissertations

High Performance Liquid Chromatography (HPLC) is a key component in the purification and separation of biological samples. Stationary phases in HPLC are generally silica based porous particles or monoliths designed with high surface area and high capacities in mind. However, in the field of macromolecule separations, specifically proteins, the porous based stationary phases have inherent issues that include slow mass transfer, high operating back pressures, and analyte carryover. Recent research has looked to non-porous polymeric materials as stationary phases in HPLC to overcome these challenges. Specifically, fibrous based polymer stationary phases exhibit significant benefits for macromolecules that include improved mass …

1. Improving The Yield Of Biodiesel From Microalgae And Other Lipids. 2. Studies Of The Wax Ester Biosynthetic Pathway And Potential Biotechnological Application, Bradley D. Wahlen

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

The production of biofuels and oleochemicals from renewable sources offers an opportunity to reduce our dependence on fossil fuels. The work contained in this dissertation has focused on developing and improving methods for the production of biodiesel from non-traditional feedstocks and understanding biosynthetic pathways that result in the production of oleochemicals and fuels.

Pure vegetable oil can account for 70-80% of the total cost of biodiesel production. Many low-cost oils contain high amounts of free fatty acids, which are unsuitable for base-catalyzed transesterification. Herein an approach is described that efficiently accomplishes the simultaneous esterification and transesterification of both free fatty …