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2020

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Articles 1441 - 1470 of 1562

Full-Text Articles in Chemistry

Developing And Testing Redox Active Organic Molecules For Nonaqueous Redox Flow Battery Applications, Nuwan Harsha Attanayake Jan 2020

Developing And Testing Redox Active Organic Molecules For Nonaqueous Redox Flow Battery Applications, Nuwan Harsha Attanayake

Theses and Dissertations--Chemistry

Non-emissive, sustainable energy sources such as solar, wind, and geothermal power have continued to provide an increasing amount of electricity to support electrical grids. Due to the intermittent nature of renewable energy sources like wind and solar, grid energy storage systems must adjust for variations in and mismatches between electricity production and consumption. Among the available energy storage technologies, redox flow batteries (RFBs) are expected to play a critical role in the grid energy storage due to their decoupled energy and power, long service life, and simple manufacturing. However, the worldwide market penetration of RFB systems is still limited due …

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Identification Of Adsorbate Ft-Ir Bands Using In-Situ Techniques: Pd Speciation And Adsorption Chemistry Of Pd-Zeolites For Passive Nox Adsorption, Robert Bruce Pace Iii Jan 2020

Identification Of Adsorbate Ft-Ir Bands Using In-Situ Techniques: Pd Speciation And Adsorption Chemistry Of Pd-Zeolites For Passive Nox Adsorption, Robert Bruce Pace Iii

Theses and Dissertations--Chemistry

To meet increasingly stringent automotive emissions standards, further improvements in catalytic converter design are necessary. Current automotive catalyst systems are effective at eliminating emission of nitrogen oxides (NOx) once the catalyst reaches operational temperature (~200 °C). NOx emitted at lower catalyst temperatures now comprises most of the NOx released during a typical test cycle. Referred to as “the cold start problem” this issue has come to the forefront of automotive catalyst development, as mitigating these emissions is necessary to further reduce automotive emissions. Passive NOx adsorbers present an appealing solution to the cold start problem, …

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Sorption Of U(Vi) Onto Manganese Oxides In The Presence Of Siderophore Desferrioxamine-B, Morgan Snyder Jan 2020

Sorption Of U(Vi) Onto Manganese Oxides In The Presence Of Siderophore Desferrioxamine-B, Morgan Snyder

Electronic Theses and Dissertations, 2020-2023

Anthropogenic activities, such as uranium mining and the production of nuclear energy and nuclear weapons, have led to significant uranium contamination of the environment, leaving populations vulnerable to negative health effects. In order to effectively remediate uranium contamination, the mobility of uranium in the environment and its natural attenuation through sorption with active mineral phases, needs to be studied in depth first. This study aims to determine how U(VI) mobility is affected by manganese oxides in the presence and absence of siderophore Desferrioxamine-B (DFOB). Experiments focused on two common manganese minerals, pyrolusite (ß-MnO2) and manganite (γ-MnOOH). Adsorption experiments with U(VI)-DFOB …

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Spectroscopic Techniques To Characterize And Develop Sensing Methods For Titanium Dioxide Nanoparticles In Water, Reagan Scott Turley Jan 2020

Spectroscopic Techniques To Characterize And Develop Sensing Methods For Titanium Dioxide Nanoparticles In Water, Reagan Scott Turley

Open Access Theses & Dissertations

Titanium dioxide nanoparticles are being used in ever increasing amounts and applications in many consumer products and industrial processes including water treatment. These nanoparticles have not been shown to be toxic to humans via ingestion, but it is worthwhile to develop a portable and rapid detection method to quantify the concentration of nanoparticles in treated drinking water. Current detection methods include single particle inductively coupled plasma mass spectrometry, inductively coupled plasma optical emission spectrometry, tunneling electron microscopy and scanning electron microscopy. While extremely sensitive, these techniques are expensive and sometimes require extensive sample preparation before analysis. A preliminary study on …

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Synthesis Of Nanotemplated, Glucose-Derived Adsorbents For The Removal Of Organic And Inorganic Pollutants From Water, Luis Alfonso Barrera Jan 2020

Synthesis Of Nanotemplated, Glucose-Derived Adsorbents For The Removal Of Organic And Inorganic Pollutants From Water, Luis Alfonso Barrera

Open Access Theses & Dissertations

With an ever-present rise in population, along with an increase in industrial and manufacturing plants, contamination of potable water has become a global concern. While water treatment facilities exist which can help with the purification of water from bacterial and organic contaminants, these facilities are expensive to set in place and maintain. Therefore, in impoverished areas, point of use (POU) purification systems are often preferred, such as filters made from activated carbon. These filters are inexpensive and relatively easy to install and use. However, while activated carbons generally display excellent adsorption capabilities towards organic contaminants, their adsorption towards inorganic pollutants …

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Some Fermi-Lowdin Orbital Self-Interaction Correction Studies On Atomic Systems, Christopher Alexis Ibarra Jan 2020

Some Fermi-Lowdin Orbital Self-Interaction Correction Studies On Atomic Systems, Christopher Alexis Ibarra

Open Access Theses & Dissertations

Density Function Theory (DFT) is a popular quantum chemistry calculation method with many appeals but also deficiencies. Many modification and additions to the method have been made over the years, such as self-interaction corrections and new density functional approximations. We review here the theoretical background needed for a basic understanding of quantum chemistry calculations. In addition, we present the quantum chemistry calculation method used in this paper called Fermi-Lowdin Self-Interaction Correction (FLOSIC), including the base code it was implemented on, the Naval Research Laboratory Molecular Orbital Library (NRLMOL) Code, and the resulting modified code simply called FLOSIC. Furthermore, we explore …

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Life Cycle Studies To Evaluate The Physiological And Biochemical Effects Of Copper Oxide And Surface-Coated Titanium Dioxide Nanoparticles On Green Onion (Allium Fistulosum) And Carrot (Daucus Carota L.) Plants: Insights Utilizing Two-Photon Microscopy And Spectroscopy, Yi Wang Jan 2020

Life Cycle Studies To Evaluate The Physiological And Biochemical Effects Of Copper Oxide And Surface-Coated Titanium Dioxide Nanoparticles On Green Onion (Allium Fistulosum) And Carrot (Daucus Carota L.) Plants: Insights Utilizing Two-Photon Microscopy And Spectroscopy, Yi Wang

Open Access Theses & Dissertations

With the recent increase of nanomaterial production, nano copper oxide (nCuO) and surface-modified titanium dioxide nanoparticles (nTiO2) are among the most widely applied nanoparticles in industry and daily lives. Their use has resulted in accumulation in soils as a consequence of their direct or indirect release. Hence, these NPs may raise a potential risk to crops cultivated in soils. Moreover, the physiological effects of nCuO on green onion (Allium fistulosum) and surface-coated nTiO2 on full-grown carrot (Daucus carota L.) are still unknown. Green onion is characterized by its high content of the antioxidant allicin, and carrot is a worldwide economic …

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Multimodal Vibrational Studies Of Drug Uptake In Vitro: Is The Whole Greater Than The Sum Of Their Parts?, David Perezguaita, Karolina Chrabaszcz, Kamilla Malek, Hugh Byrne Jan 2020

Multimodal Vibrational Studies Of Drug Uptake In Vitro: Is The Whole Greater Than The Sum Of Their Parts?, David Perezguaita, Karolina Chrabaszcz, Kamilla Malek, Hugh Byrne

Articles

Herein, we investigated the use of multimodal Raman and infrared (IR) spectroscopic microscopy for the elucidation of drug uptake and subsequent cellular responses. Firstly, we compared different methods for the analysis of the combined data. Secondly, we evaluated whether the combined analysis provided enough benefits to justify the fusion of the data. A459 cells inoculated with doxorubicin (DOX) at different times were fixed and analysed using each technique. Raman spectroscopy provided high sensitivity to DOX and enabled an accurate estimation of the drug uptake at each time point, whereas IR provided a better insight into the resultant changes in the …

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Raman Mapping Coupled To Self Modelling Mcr-Als Analysis To Estimate Active Cosmetic Ingredient Penetration Profile In Skin, Aline Stella, Franck Bonnier, Ali Tfayli, Florent Yvergnaux, Hugh Byrne, Igor Chourpa, Emilie Munnier, Clovis Tauber Jan 2020

Raman Mapping Coupled To Self Modelling Mcr-Als Analysis To Estimate Active Cosmetic Ingredient Penetration Profile In Skin, Aline Stella, Franck Bonnier, Ali Tfayli, Florent Yvergnaux, Hugh Byrne, Igor Chourpa, Emilie Munnier, Clovis Tauber

Articles

Confocal Raman mapping (CRM) is a powerful, label free, non-destructive tool, enabling molecular characterization of human skin with applications in the dermo-cosmetic field. Coupling CRM to multivariate analysis can be used to monitor the penetration and permeation of active cosmetic ingredients (ACI) after topical application. It is presently illustrated how multivariate curve resolution alternating least squares (MCR-ALS) can be applied to detect and semi-quantitatively describe the diffusion profile of Delipidol, a commercially available slimming ACI, from Raman spectral maps. Although the analysis outcome can be critically dependent on the a priori selection of the number of regression components, it is …

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Metal Ions Impact On Shewanella Oneidensis Mr-1 Adhesion To Ito Electrode And The Enhancement Of Current Output, Aisha Awad Alshahrani Jan 2020

Metal Ions Impact On Shewanella Oneidensis Mr-1 Adhesion To Ito Electrode And The Enhancement Of Current Output, Aisha Awad Alshahrani

Dissertations

The goal of this study is to enhance the efficiency of bacterial extracellular electron transfer (EET) in Shewanella oneidensis MR-1 by enhancing adhesion to the electrode's surface. Our results clearly show a major difference in the attachment and behavior of Shewanella oneidensis MR-1 for Ca2+, Pb2+, Cd2+, and Mg2+, compared to the control. the final microbial coverage, as measured by confocal microscopy and cathodic peak charge in cyclic voltammetry (Qpc), increases with increasing metal ion concentrations. We found the cells attached to the electrode increased more with the addition of metal ion concentrations in the following order of metals: Ca2+ …

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Optimization Of Microbial Fuel Cells, Norberto M. Gonzalez Jan 2020

Optimization Of Microbial Fuel Cells, Norberto M. Gonzalez

Dissertations

Optimization of microbial fuel cells is investigated by utilizing Shewanella oneidensis as a model microorganism. the microbe's ability to grow and use glucose as a carbon source is explored under varying oxygen environments through an offline PMP derivatization method and HPLC analysis. Shewanella growth and glucose utilization is enhanced under aerobic environments; however, under microaerobic environments the addition of ferric iron results in a faster exponential growth initialization. a flavin mononucleotide modified indium tin oxide electrode is prepared and characterized for its usefulness in microbial fuel cells by controlled potential electrolysis, cyclic voltammetry, and electrochemical impedance spectroscopy studies. the electrode …

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Lewis Acid-Carbonyl Solution Interactions And Their Implications In Catalytic Systems, Carly Soren Hanson Jan 2020

Lewis Acid-Carbonyl Solution Interactions And Their Implications In Catalytic Systems, Carly Soren Hanson

Dissertations

The utilization of Lewis acids to activate substrates containing carbonyls is ubiquitous in organic synthetic methods. in order to facilitate the development of novel reaction pathways and understand existing methods, it is necessary to determine the solution interactions between Lewis acids and Lewis bases. Historically, the characterization of the interactions of Lewis pairs has relied on solid state infrared (IR) spectroscopy and X-ray crystallography, as well as in situ NMR. I have developed a method utilizing in situ IR spectroscopy and solution conductivity towards the identification of the solution structures formed when a range of carbonyl compounds are combined with …

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Development Of Methods For The Removal Of Selected Pollutants From Several Matrices And Identification Of Unknown Pollutants Adsorbed Onto Plastics Collected From Freshwater, Kathryn Marie Renyer Jan 2020

Development Of Methods For The Removal Of Selected Pollutants From Several Matrices And Identification Of Unknown Pollutants Adsorbed Onto Plastics Collected From Freshwater, Kathryn Marie Renyer

Dissertations

Plastic pollution represents one of greatest anthropogenic threats to the environment. Five to ten billion tons of plastic are manufactured every year. Currently, Earth's ecosystem is contaminated with billions of tons of plastic debris, much of which cannot be recycled. Over time, this plastic debris decomposes into small particles. Small plastic particles are known to adsorb toxic compounds in marine environments. My research is concerned with creating novel methods for the detection and quantification of selected persistent organic pollutants from several media. Specifically, I developed methods for the detection and quantification of endosulfan sulfate (ESS) from Lumbricus terrestris tissue and …

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Electron Transfer Of Shewanella Oneidensis Mr-1 At Clay-Modified Ito Electrode, Reem Faez Alshehri Jan 2020

Electron Transfer Of Shewanella Oneidensis Mr-1 At Clay-Modified Ito Electrode, Reem Faez Alshehri

Dissertations

Various strategies have been established to enhance the extracellular electron transfer and energy output capability of microbial fuel cells, with the majority being aimed at anode modification. The anode has a significant impact on the electricity generation performance of MFCs because it is in direct contact with the microorganisms. The materials of the anode should be favorable for the bacterial cell and capable to facilitate the electron transfer. Developing of an electrode using low-cost and effective materials assists to enhance the bacterial cell attachment and extracellular electron transfer. This provides a significant improvement in MFC performance. In this study, clay …

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Synthesis And Evaluation Of Nebraska Red Derivatives For Protein Labeling Studies, Lauren Lesiak Jan 2020

Synthesis And Evaluation Of Nebraska Red Derivatives For Protein Labeling Studies, Lauren Lesiak

Honors Program: Senior Projects (Public)

G protein-coupled receptors (GPCRs) play a vital role in cell signaling, and imaging the internalization of these proteins will allow for better understand of protein trafficking within the cell, as well as identification of potential drug targets. However, there is a need for further development of fluorescent protein labels that are able to effectively monitor GPCR internalization in the near-infrared (NIR) range. We recently described a series of NIR fluorophores in which a phosphinate functionality is inserted at the bridging position of the xanthene scaffold, called the Nebraska Red (NR) dye series. These dyes are attractive reagents for the imaging …

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Synthesis, Characterization, And Biological Activity Of Imidazolium Salts, David Weader Jan 2020

Synthesis, Characterization, And Biological Activity Of Imidazolium Salts, David Weader

Williams Honors College, Honors Research Projects

Nonmuscle invasive bladder cancer (NMIBC) inflicts thousands of Americans annually, and is typically treated with the immunotherapy BCG. However, due to a BCG shortage, there is a new need for novel treatments of NMIBC. Addressing this issue, several imidazolium salt derivatives were synthesized and characterized with the intent of treatment within the bladder. These imidazolium salts were tested against different human bladder cancer cell lines in vitro to determine their reactivity and cytotoxicity. Among these results are GI50 concentrations for each drug, which is the concentration of drug needed to see growth inhibition in 50% of treated cells. Previous published …

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Greener Synthesis Of Chlorophosphazenes, Andrew Mcgee Jan 2020

Greener Synthesis Of Chlorophosphazenes, Andrew Mcgee

Williams Honors College, Honors Research Projects

This project will attempt to synthesize chlorophosphazene molecules in the absence of solvents by using mechanochemical techniques in order to create a more environmentally friendly synthesis route. In this pursuit, various parameters will be changed including the milling ball to reagent ratios, the molar ratios of the reactants, and the addition of different catalysts. The products of each reaction will be characterized in order to determine success. This work builds upon existing efforts to utilize mechanochemical techniques in main group chemistry. The output of this project will be a report in ACS style and a poster to be presented for …

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Influence Of The Coriolis Effect On The Properties Of Scattering Resonances In Symmetric And Asymmetric Isotopomers Of Ozone, Igor Gayday, Elizaveta Grushnikova, Dmitri Babikov Jan 2020

Influence Of The Coriolis Effect On The Properties Of Scattering Resonances In Symmetric And Asymmetric Isotopomers Of Ozone, Igor Gayday, Elizaveta Grushnikova, Dmitri Babikov

Chemistry Faculty Research and Publications

Scattering resonances above dissociation threshold are computed for four isotopically substituted ozone species: 16O18O16O, 16O16O18O, 18O16O18O and 16O18O18O, using a variational method with accurate treatment of the rotation–vibration coupling terms (Coriolis effect) for all values of the total angular momentum J from 0 to 4. To make these calculations numerically affordable, a new approach was developed which employs one vibrational basis set optimized for a typical rotational excitation (J,Λ), to run coupled rotation–vibration calculations at several …

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Route Exploration And Synthesis Of The Reported Pyridone-Based Pdi Inhibitor Stk076545, Eric Greve, Sergey V. Lindeman, Christina Scartelli, Lin Lin, Robert Flaumenhaft, Chris Dockendorff Jan 2020

Route Exploration And Synthesis Of The Reported Pyridone-Based Pdi Inhibitor Stk076545, Eric Greve, Sergey V. Lindeman, Christina Scartelli, Lin Lin, Robert Flaumenhaft, Chris Dockendorff

Chemistry Faculty Research and Publications

The enzyme protein disulfide isomerase (PDI) is essential for the correct folding of proteins and the activation of certain cell surface receptors, and is a promising target for the treatment of cancer and thrombotic conditions. A previous high-throughput screen identified the commercial compound STK076545 as a promising PDI inhibitor. To confirm its activity and support further biological studies, a resynthesis was pursued of the reported β-keto-amide with an N-alkylated pyridone at the α-position. Numerous conventional approaches were complicated by undesired fragmentations or rearrangements. However, a successful 5-step synthetic route was achieved using an aldol reaction with an α-pyridone allyl …

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Nonheme Iron–Thiolate Complexes As Structural Models Of Sulfoxide Synthase Active Sites, Danushka M. Ekanayake, Anne A. Fischer, Maya E. Elwood, Alexandra M. Guzek, Sergey V. Lindeman, Cordina V. Popescu, Adam T. Fiedler Jan 2020

Nonheme Iron–Thiolate Complexes As Structural Models Of Sulfoxide Synthase Active Sites, Danushka M. Ekanayake, Anne A. Fischer, Maya E. Elwood, Alexandra M. Guzek, Sergey V. Lindeman, Cordina V. Popescu, Adam T. Fiedler

Chemistry Faculty Research and Publications

Two mononuclear iron(II)–thiolate complexes have been prepared that represent structural models of the nonheme iron enzymes EgtB and OvoA, which catalyze the O2-dependent formation of carbon–sulfur bonds in the biosynthesis of thiohistidine compounds. The series of Fe(II) complexes reported here feature tripodal N4 chelates (LA and LB) that contain both pyridyl and imidazolyl donors (LA = (1H-imidazol-4-yl)-N,N-bis((pyridin-2-yl)methyl)methanamine; LB = N,N-bis((1-methylimidazol-2-yl)methyl)-2-pyridylmethylamine). Further coordination with monodentate aromatic or aliphatic thiolate ligands yielded the five-coordinate, high-spin Fe(II) complexes [FeII(LA)(SMes)]BPh …

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Voltammetry And Spectroelectrochemistry Of Tcnq In Acetonitrile/Rtil Mixtures, Abderrahman Atifi, Michael D. Ryan Jan 2020

Voltammetry And Spectroelectrochemistry Of Tcnq In Acetonitrile/Rtil Mixtures, Abderrahman Atifi, Michael D. Ryan

Chemistry Faculty Research and Publications

Understanding the solvation and ion-pairing interactions of anionic substrates in room-temperature ionic liquids (RTIL) is key for the electrochemical applications of these new classes of solvents. In this work, cyclic voltammetry and visible and infrared spectroelectrochemistry of tetracyanoquinodimethane (TCNQ) was examined in molecular (acetonitrile) and RTIL solvents, as well as mixtures of these solvents. The overall results were consistent with the formation of RTIL/acetonitrile nanodomains. The voltammetry indicated that the first electrogenerated product, TCNQ−, was not incorporated into the RTIL nanodomain, while the second electrogenerated product, TCNQ2−, was strongly attracted to the RTIL nanodomain. The visible …

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Enhanced Light Harvesting Ability In Zeolitic Imidazolate Frameworks Through Energy Transfer From Cds Nanowires, Yixuan Zhou, Wenhui Hu, Sizhuo Yang, Jier Huang Jan 2020

Enhanced Light Harvesting Ability In Zeolitic Imidazolate Frameworks Through Energy Transfer From Cds Nanowires, Yixuan Zhou, Wenhui Hu, Sizhuo Yang, Jier Huang

Chemistry Faculty Research and Publications

Zeolitic imidazolate frameworks (ZIFs) represent a novel class of porous crystalline materials that have demonstrated potential as light harvesting materials for solar energy conversion. In order to facilitate their application in solar energy conversion, it is necessary to expand their absorption further into the realm of the solar spectrum. In this work, we report the incorporation of semiconductor cadmium sulfide nanowires (CdS NWs) into ZIF-67 (CdS@ZIF-67), where a broader region of the solar spectrum can be absorbed by CdS NWs and relayed to ZIF-67 through an energy transfer (EnT) process. Using steady-state emission and time resolved emission and absorption spectroscopy, …

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Adiabatic Trajectory Approximation Within The Framework Of Mixed Quantum/Classical Theory, Bikramaditya Mandal, Alexander Semenov, Dmitri Babikov Jan 2020

Adiabatic Trajectory Approximation Within The Framework Of Mixed Quantum/Classical Theory, Bikramaditya Mandal, Alexander Semenov, Dmitri Babikov

Chemistry Faculty Research and Publications

A hierarchy of approximate methods is proposed for solving the equations of motion within a framework of the mixed quantum/classical theory (MQCT) of inelastic molecular collisions. Of particular interest is a limiting case: the method in which the classical-like equations of motion for the translational degrees of freedom (scattering) are decoupled from the quantum-like equations for time evolution of the internal molecular states (rotational and vibrational). In practice, trajectories are pre-computed during the first step of calculations with driving forces determined solely by the potential energy surface of the entrance channel, which is an adiabatic trajectory approximation. Quantum state-to-state transition …

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Dynamic Evolution And Reversibility Of Single-Atom Ni(Ii) Active Site In 1t-Mos2 Electrocatalysts For Hydrogen Evolution, Brian Pattengale, Yichao Huang, Xingxu Yan, Sizhou Yang, Sabrina Younan, Wenhui Hu, Zhida Li, Sungsik Lee, Xiaoping Pan, Jing Gu, Jier Huang Jan 2020

Dynamic Evolution And Reversibility Of Single-Atom Ni(Ii) Active Site In 1t-Mos2 Electrocatalysts For Hydrogen Evolution, Brian Pattengale, Yichao Huang, Xingxu Yan, Sizhou Yang, Sabrina Younan, Wenhui Hu, Zhida Li, Sungsik Lee, Xiaoping Pan, Jing Gu, Jier Huang

Chemistry Faculty Research and Publications

1T-MoS2 and single-atom modified analogues represent a highly promising class of low-cost catalysts for hydrogen evolution reaction (HER). However, the role of single atoms, either as active species or promoters, remains vague despite its essentiality toward more efficient HER. In this work, we report the unambiguous identification of Ni single atom as key active sites in the basal plane of 1T-MoS2 (Ni@1T-MoS2) that result in efficient HER performance. The intermediate structure of this Ni active site under catalytic conditions was captured by in situ X-ray absorption spectroscopy, where a reversible metallic Ni species (Ni0) …

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A Theoretical And Experimental Study Of Charge Transport In Organic Thermoelectric Materials And Charge Transfer States In Organic Photovoltaics, Ashkan Abtahi Jan 2020

A Theoretical And Experimental Study Of Charge Transport In Organic Thermoelectric Materials And Charge Transfer States In Organic Photovoltaics, Ashkan Abtahi

Theses and Dissertations--Physics and Astronomy

Applications of organic electronics have increased significantly over the past two decades. Organic semiconductors (OSC) can be used in mechanically flexible devices with potentially lower cost of fabrication than their inorganic counterparts, yet in many cases organic semiconductor-based devices suffer from lower performance and stability. Investigating the doping mechanism, charge transport, and charge transfer in such materials will allow us to address the parameters that limit performance and potentially resolve them. In this dissertation, organic materials are used in three different device structures to investigate charge transport and charge transfer. Chemically doped π-conjugated polymers are promising materials to be used …

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Investigations Of Graphene-Supported Single-Atom Catalyst Model Ions In The Gas Phase, Michael Borrome Jan 2020

Investigations Of Graphene-Supported Single-Atom Catalyst Model Ions In The Gas Phase, Michael Borrome

Theses and Dissertations

Recent developments in heterogeneous catalysis has led to the conception of single-atom catalysts (SACs), a class of catalysts based on isolated metal atoms anchored to a support scaffold. SACs are often much more reactive and can offer better selectivity when compared to nano-scale catalysts. In order to realize the full potential of SACs, a sound understanding of the underlying catalytic mechanisms is required. However, surface analysis tools can become less effective in studying catalytic mechanisms at the atomic scale. Mass spectrometry has proven to be a robust technique for studying organometallic catalytic mechanisms at the single-molecule level. Using mass spectrometry, …

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Modeling Iron And Light Controls On The Summer Phaeocystis Antarctica Bloom In The Amundsen Sea Polynya, Hilde Oliver, Pierre St-Laurent, Robert M. Sherrell, Patricia L. Yaeger Jan 2020

Modeling Iron And Light Controls On The Summer Phaeocystis Antarctica Bloom In The Amundsen Sea Polynya, Hilde Oliver, Pierre St-Laurent, Robert M. Sherrell, Patricia L. Yaeger

CCPO Publications

Of all the Antarctic coastal polynyas, the Amundsen Sea Polynya is the most productive per unit area. Observations from the 2010-2011 Amundsen Sea Polynya International Research Expedition (ASPIRE) revealed that both light and iron can limit the growth of phytoplankton (Phaeocystis antarctica), but how these controls manifest over the bloom season is poorly understood, especially with respect to their climate sensitivity. Using a 1-D biogeochemical model, we examine the influence of light and iron limitation on the phytoplankton bloom and vertical carbon flux at 12 stations representing different bloom stages within the polynya. Model parameters are determined by …

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Aldol Condensations And Nitrile Aldol Reactions Mediated By Trimethylsilyl Trifluoromethanesulfonate, Samuel R. Bottum Jan 2020

Aldol Condensations And Nitrile Aldol Reactions Mediated By Trimethylsilyl Trifluoromethanesulfonate, Samuel R. Bottum

Honors Theses

In the presence of excess trimethylsilyl trifluoromethanesulfonate (TMSOTf), ketones and esters undergo aldol addition and dehydration to yield chalcones and cinnamates. This one-pot reaction proceeds through in situ enol silane formation, avoiding the need to pre-form and purify the nucleophile in the Mukaiyama aldol reaction. The stoichiometry of the TMSOTf controls whether the reaction proceeds with simple addition or addition-dehydration. When (trimethylsilyl) acetonitrile is stirred with an aldehyde and TMSOTf, nitrile aldol addition is observed.

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Synthesis, Characterization, And Reactivity Of Palladium Proazaphosphatrane Complexes, Adrian D. Matthews Jan 2020

Synthesis, Characterization, And Reactivity Of Palladium Proazaphosphatrane Complexes, Adrian D. Matthews

Honors Theses

Palladium-catalyzed cross-coupling reactions provide an efficient pathway to a wide variety of otherwise inaccessible compounds. In this study, the synthesis and reactivity of novel palladium proazaphosphatrane complexes that are believed to be intermediates in C–N cross-coupling reactions are described. Both the fundamental reactivity of these complexes and elementary steps involved in a catalytic process are demonstrated. The catalytic viability of palladium proazaphosphatrane complexes is shown through stoichiometric and catalytic cross-coupling reactions. Our findings support the long-standing hypothesis that proazaphosphatranes are conformationally flexible ligands that stabilize a number of catalytic intermediates.

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Design Of New Ruthenium Complexes For Photoactivated Chemotherapy, Lindsey Paul Jan 2020

Design Of New Ruthenium Complexes For Photoactivated Chemotherapy, Lindsey Paul

Honors Theses

Photoactivated chemotherapy (PACT) offers a targeted approach to cancer treatment through selective drug activation. Substitutionally labile ruthenium-based prodrugs undergo ligand-loss when irradiated, producing an unbound ligand and a Ru-aqua complex. We report the synthesis and cytotoxicity of several new ruthenium-centered complexes and their irradiation products for use in PACT. A series of complexes were synthesized in order to study the effects of structural differences on cell viability. Cell viability was tested on T47D human breast cancer cells in the presence of compound to determine cytotoxicity and dose-response. While neither the Rucomplexes nor their ligands demonstrated cytotoxicity, their Ru-aqua dissociation complexes …

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