Chemistry Commons^™

Going Green: Experimental Adaptation Of Scenedesmus Dimorphus To Marine Conditions, Mohammed Khalil

Undergraduate Research Posters 2017

Algae has gained some interest as the need for alternative fuels becomes more pressing. Reliance on fossil fuels is causing our environment and economy harm, and is not sustainable moving forward. Lipid rich algae strains can be used in the production of biofuels, and provide an alternative fuel source. One challenge facing the prospect of algae as a fuel source is that lipid rich algae grows exclusively in freshwater. Considering the scarcity and cost to use freshwater for algae growth, interest has grown in the possibility of adapting lipid rich, freshwater algae to a seawater environment. Seawater can have up …

Evaluation Of Cetane Values Of Glycerolipids Extracted From Algae Scenedesmus Dimorphus Grown In Various Salinity Concentrations Using Gas Chromatography And Mass Spectrometry (Gc-Ms), Paul Lin, Chandana Mannem

Undergraduate Research Posters 2017

Algae's ability to store lipids, renewability, and potentially safer for the environment has made it a promising alternative fuel source. An industry rating for a biofuel's potential is the cetane value, which is a measure of a fuel's quality related to various glycerolipid concentrations. Growing conditions will affect lipid profile in algae, thereby affecting the cetane value. This project will attempt to identify changes in the centane value of the algae Scenedesmus dimorphus grown in various salinity concentrations. Scenedesmus dimorphus is the algae chosen for this experiment because of its ability to rapidly grow under harsh conditions. In this experiment …

P1: Salt Concentration And Ph Affect The Size Of Elastin-Like Polypeptide Nanoparticles, Bryce Noe, Ilona Tsuper, Daniel Terano, Richard Schmitt

Undergraduate Research Posters 2017

The transport of therapeutic drugs to specific tissues in the body can be accomplished using nanoparticles that encapsulate the drugs. Elastin-like polypeptides (ELP) is a class of materials that can reversibly form such nanoparticles in response to environmental cues. FLPs transition from soluble compounds to a phase separated system under particular solution conditions and have been used to produce temperature responsive surfactants. When these ELP surfactants are above their transition temperature, they spontaneously form energetically stable spherical micelles. When the temperature drops below the transition temperature, the micelles break apart and the ELP goes into solution. The size of these …

P2: Light Scattering Study Of The Size And Shape Of Mixed Elastin-Like Polypeptide Micelles, Ilona Tsuper, Daniel Terrano, Bryce Noe

Undergraduate Research Posters 2017

Elastin-Like Polypeptides (ELP) can be used to form thermoreversible vehicles for drug delivery systems. The ELP nanoparticles are composed of three-armed star polypeptides. Each of the three arms extending from the negatively charged foldon domain include 20 repeats of the (GVGVP) amino acid sequence. In addition, linear constructs composed of 40 repeats of the same (GVGVP) sequence are introduced into the system. The mixed ELP polymer system is soluble at room temperature and becomes insoluble at the transition temperature (~ 50°C) forming micelles with the foldons on the exterior and linear constructs at the core. Above the transition, the size …

Soft Robotic Actuators, Filip Ilievski, Xin Chen, Aaron D. Mazzeo, George M. Whitesides, Robert F. Shepherd, Ramses V. Martinez, Won Jae Choi, Sen Wai Kwok, Stephen A. Morin, Adam Stokes, Zhihong Nie

Department of Chemistry: Faculty Publications

A soft robotic device includes a flexible body having a width, a length and a thickness, wherein the thickness is at least 1 mm, the flexible body having at least one channel disposed within the flexible body, the channel defined by upper, lower and side walls, wherein at least one wall is strain limiting; and a pressurizing inlet in fluid communication with the at least one channel, the at least one channel positioned and arranged such that the wall opposite the strain limiting wall preferentially expands when the soft robotic device is pressurized through the inlet.

Airborne Measurements Of Western U.S. Wildfire Emissions: Comparison With Prescribed Burning And Air Quality Implications, Xiaoxi Liu, L. Gregory Huey, Robert J. Yokelson, Vanessa Selimovic, Isobel J. Simpson, Markus Müller, Jose L. Jimenez, Pedro Campuzano-Jost, Andreas J. Beyersdorf, Donald R. Blake, Zachary Butterfield, Yonghoon Choi, John D. Crounse, Douglas A. Day, Glenn S. Diskin, Manvendra K. Dubey, Edward Fortner, Thomas F. Hanisco, Weiwei Hu, Laura E. King, Lawrence Kleinman, Simone Meinardi, Tomas Mikoviny, Timothy B. Onasch, Brett B. Palm, Jeff Peischl, Ilana B. Pollack, Thomas B. Ryerson, Glen W. Sachse, Arthur J. Sedlacek, John E. Shilling, Stephen Springston, Jason M. St. Clair

Chemistry and Biochemistry Faculty Publications

Wildfires emit significant amounts of pollutants that degrade air quality. Plumes from three wildfires in the western U.S. were measured from aircraft during the Studies of Emissions and Atmospheric Composition, Clouds and Climate Coupling by Regional Surveys (SEAC4RS) and the Biomass Burning Observation Project (BBOP), both in summer 2013. This study reports an extensive set of emission factors (EFs) for over 80 gases and 5 components of submicron particulate matter (PM1) from these temperate wildfires. These include rarely, or never before, measured oxygenated volatile organic compounds and multifunctional organic nitrates. The observed EFs are compared with previous measurements of temperate …

A Dual-Chamber Method For Quantifying The Effects Of Atmospheric Perturbations On Secondary Organic Aerosol Formation From Biomass Burning Emissions, Daniel S. Tkacik, Ellis S. Robinson, Adam Ahern, Rawad Saleh, Chelsea Stockwell, Patrick Veres, Isobel J. Simpson, Simone Meinardi, Donald R. Blake, Robert J. Yokelson, Albert A. Presto, Ryan C. Sullivan, Neil M. Donahue, Allen L. Robinson

Chemistry and Biochemistry Faculty Publications

Biomass burning (BB) is a major source of atmospheric pollutants. Field and laboratory studies indicate that secondary organic aerosol (SOA) formation from BB emissions is highly variable. We investigated sources of this variability using a novel dual-smog-chamber method that directly compares the SOA formation from the same BB emissions under two different atmospheric conditions. During each experiment, we filled two identical Teflon smog chambers simultaneously with BB emissions from the same fire. We then perturbed the smoke with UV lights, UV lights plus nitrous acid (HONO), or dark ozone in one or both chambers. These perturbations caused SOA formation in …

In Situ Measurements Of Water Uptake By Black Carbon-Containing Aerosol In Wildfire Plumes, Anne E. Perring, Joshua P. Schwarz, Milos Z. Markovic, David W. Fahey, Jose L. Jimenez, Pedro Campuzano-Jost, Brett D. Palm, Armin Wisthaler, Tomas Mikoviny, Glenn Diskin, Glen Sachse, Luke Ziemba, Bruce Anderson, Taylor Shingler, Ewan Crosbie, Armin Sorooshian, Robert Yokelson, Ru Shan Gao

Chemistry and Biochemistry Faculty Publications

Water uptake by black carbon (BC)-containing aerosol was quantified in North American wildfire plumes of varying age (1 to ~40 h old) sampled during the SEAC4RS mission (2013). A Humidified Dual SP2 (HD-SP2) is used to optically size BC-containing particles under dry and humid conditions from which we extract the hygroscopicity parameter, κ, of materials internally mixed with BC. Instrumental variability and the uncertainty of the technique are briefly discussed. An ensemble average κ of 0.04 is found for the set of plumes sampled, consistent with previous estimates of bulk aerosol hygroscopicity from biomass burning sources. The temporal evolution of …

Sequential Growth Of Molecular Complexity Via Alternating Ground State And Photochemical Reactions, Haibo Li

Electronic Theses and Dissertations

A new strategy of increasing molecular complexity by post photochemical oxidation followed by secondary intramolecular photochemical reaction is developed. It is based on the mild oxidation of photochemical generated alcohol by primary intramolecular cycloaddition of aromatic o-aminoaldehydes and a secondary intramolecular cycloaddition of aromatic o-aminoketone. Both cycloadditions are triggered via excited-state intramolecular proton transfer (ESIPT). Additionally, an efficient continuous reaction of photocatalyzed 2-nitrobenzyl alcohol intramolecular reduction and aryl nitroso Diels-Alder (NDA) reaction was discovered.

The Periodical Winter 2017, Southern Adventist University

the Periodical – Chemistry Department Newsletter

Volume 4, issue 2 of the Periodical includes articles about the Chemistry Club's service activities, a student missions feature, student research at N.C. State, a pictorial directory of May 2017 graduates, and an alumni spotlight.

Do Fractionally Incremented Nuclear Charges Improve Time-Dependent Density Functional Theory Excitation Energies As Reliably As Fractional Orbital Populations?, Darya N. Komsa, Viktor N. Staroverov

Chemistry Publications

Gaiduk et al. (Phys Rev Lett 108:253005, 2012) showed that one can improve local, semilocal, and hybrid approximations to the Kohn–Sham effective potentials of atoms and molecules by removing a system-independent fraction of electron charge from the highest occupied molecular orbital (HOMO); if the corrected Kohn–Sham potential is used for adiabatic linear-response time-dependent density functional theory (TDDFT) calculations, accurate Rydberg excitation energies are obtained. One may ask whether the same effect could also be achieved by fractionally increasing the positive charges of the nuclei. We investigate this question and find that a small increase in nuclear charges can indeed …

Exact Exchange-Correlation Potentials Of Singlet Two-Electron Systems, Ilya G. Ryabinkin, Egor Ospadov, Viktor N. Staroverov

Chemistry Publications

We suggest a non-iterative analytic method for constructing the exchange-correlation potential, vXC(r), of any singlet ground-state two-electron system. The method is based on a convenient formula for vXC(r) in terms of quantities determined only by the system’s electronic wave function, exact or approximate, and is essentially different from the Kohn–Sham inversion technique. When applied to Gaussian-basis-set wave functions, the method yields finite-basis-set approximations to the corresponding basis-set-limit vXC(r), whereas the Kohn–Sham inversion produces physically inappropriate (oscillatory and divergent) potentials. The effectiveness of the procedure is demonstrated by computing accurate exchange-correlation potentials of several two-electron systems (helium isoelectronic series, H2, H3+) …

Synthesis, Properties, And Degradation Of Polyisobutylene-Polyester Graft Copolymers, Bethany A. Turowec, Elizabeth R. Gillies

Chemistry Publications

The development of copolymers is a promising approach for combining the favorable properties of two polymers and obtaining new properties of the combination. In this work, graft copolymers of polyisobutylene (PIB) and polycaprolactone (PCL) or poly(D,L-lactide) (PDLLA) were synthesized and studied. Amine terminated polyesters were synthesized and were grafted onto an activated PIB backbone synthesized from butyl rubber, a copolymer of isobutylene and 2 mol % isoprene. The polyester content was tuned from 15 to 44 wt % by varying the molar mass of the polyester blocks and the number of molar equivalents used in the grafting reaction. The graft …

Phosphine-Imine And-Enamido Ligands For Acceptorless Dehydrogenation Catalysis, J. M. Stubbs, K. F. Firth, B. J. Bridge, K. J. Berger, R. J. Hazlehurst, P. D. Boyle, J. M. Blacquiere

Chemistry Publications

A highly tunable phosphine-imine ligand family is introduced. Following metallation with ruthenium, deprotonation of the ligand affords a phosphine-enamido species. Complexes with the ligand in both the imine and enamido forms are active toward acceptorless dehydrogenation reactions.

Using Nucleotide Analogs As Biochemical Probes To Evaluate The Mechanisms Involved In Translesion Replication By A High Fidelity Dna Polymerase, Anvesh Dasari

ETD Archive

Translesion DNA synthesis (TLS) allows DNA polymerases to incorporate nucleotides opposite and beyond damaged DNA. This activity is an important risk factor for the initiation and progression of genetic diseases including cancer. My study evaluates the ability of a high-fidelity DNA polymerase to perform TLS with 8-oxo-guanine, a pro-mutagenic DNA lesion formed by reactive oxygen species. Using modified purine and non-natural indole analogs as biochemical probes, I have evaluated the influence of desolvation, hydrogen bonding interactions, and shape complementarity towards nucleotide binding and incorporation opposite the miscoding lesion 8-oxo-guanine by the high fidelity gp43exo- DNA polymerase. In Chapter II, I …

Dnp-Enhanced Ultrawideline 207pb Solid-State Nmr Spectroscopy: An Application To Cultural Heritage Science, Takeshi Kobayashi, Frédéric A. Perras, Anna Murphy, Yao Yao, Jaclyn Catalano, Silvia A. Centeno, Cecil Dybowski, Nicholas Zumbulyadis, Marek Pruski

Department of Chemistry and Biochemistry Faculty Scholarship and Creative Works

Dynamic nuclear polarization (DNP) is used to enhance the (ultra)wideline 207Pb solid-state NMR spectra of lead compounds of relevance in the preservation of cultural heritage objects. The DNP SSNMR experiments enabled, for the first time, the detection of the basic lead carbonate phase of the lead white pigment by 207Pb SSNMR spectroscopy. Variable-temperature experiments revealed that the short T′2 relaxation time of the basic lead carbonate phase hinders the acquisition of the NMR signal at room temperature. We additionally observe that the DNP enhancement is twice as large for lead palmitate (a lead soap, which is a degradation product implicated …

Interface Structure, Precursor Rheology And Dielectric Properties Of Batio3/Pvdf-Hfp Nanocomposite Films Prepared From Colloidal Perovskite Nanoparticles, Y.N. Hao, K. Bi, S. O'Brien, X.X. Wang, J. Lombardi, F. Pearsall, Wanlu Li, M. Lei, Y. Wu, L.T. Li

Department of Chemistry and Biochemistry Faculty Scholarship and Creative Works

Nanocomposite materials with uniform microstructure and high permittivity have attracted extensive interest in modern electronics. The compatibility between the filler phase and the polymer matrix is crucial in preparing high-performance composites. As an alternative to conventional surface modification treatment methodologies, hydroxylated colloidal BaTiO₃ (BT) nanoparticles synthesized via a green and scalable process were directly used to fabricate high-permittivity nanocomposites. Interfacial interaction analyses between the BT nanoparticles and polymer matrix reveals that due to strong hydrogen bonding at the interface, transparent composite sols with excellent flow behavior can be observed. The sols are ideal formulations for the preparation of BT/PVDF–hfp …

Selective Atomic Layer Deposition Of Transition Metal Thin Films, Marissa Marie Kerrigan

Wayne State University Dissertations

Atomic layer deposition (ALD) affords highly conformal thin films with precise thickness control due to its self-limited growth mechanism. ALD enables the increasing demands for smaller feature sizes in microelectronics devices to be met. Area-selective ALD growth is receiving attention in the fabrication of microelectronic devices, since it can eliminate complicated etching steps from the fabrication process and minimizes expensive and toxic reagent use. Selectivity can be achieved by tailoring the surface chemistry of the precursor and substrate. To date, few area-selective ALD processes have been reported for metallic films. Thin films of cobalt metal deposited selectively are of considerable …

Design, Synthesis And Biological Evaluation Of Histone Deacetylase (Hdac) Inhibitors: Saha (Vorinostat) Analogs And Biaryl Indolyl Benzamide Inhibitors Display Isoform Selectivity, Ahmed Negmeldin

Wayne State University Dissertations

HDAC proteins have emerged as interesting targets for anti-cancer drugs due to their involvement in cancers, as well as several other diseases. Several HDAC inhibitors have been approved by the FDA as anti-cancer drugs, including SAHA (suberoylanilide hydroxamic acid, Vorinostat). Unfortunately, SAHA inhibits most HDAC isoforms, which limit its use as a pharmacological tool and may lead to side effects in the clinic. In this work we were interested in developing isoform selective HDAC inhibitors, which may decrease or eliminate the side effects associated with non-selective inhibitors treatment. In addition, isoform selective HDAC inhibitors can be used as biological tools …

Development Of Chemical Tools To Investigate Protein S-Glutathionylation In Response To Metabolic Alteration, Kusal Theekshana Gayan Samarasinghe

Wayne State University Dissertations

Oxidative stress is a common characteristic of age-related diseases such as vascular diseases, diabetes and cancer. Many diseases are known to be regulated by glutathionylation. Glutathionylation is referred to as the formation of disulfide bond between a protein cysteine and a glutathione. To understand the molecular mechanisms behind the disease initiation and progression, identification of such glutathionylated proteins is important. Even though existing methods have been widely used, several limitations of these methods hinder the identification of such proteins in disease conditions. Therefore, we developed a versatile chemical method that generates clickable glutathione inside the cells. In this method, we …

Ligand Binding Studies Of A Peptide Targeting Helix 69 Of 23s Rrna In Bacterial Ribosomes, Hyosuk Seo

Wayne State University Dissertations

In the development of finding a peptide targeting H69 of 23S rRNA in bacterial ribosomes, phage display was employed at pH 5.5, a buffer condition previously reported of H69 preferring a closed conformation. After sequencing, several peptides were chosen through sequence alignment, followed by preparation using solid-phase peptide synthesis. The peptides were characterized using MALDI-TOF and purified with HPLC. A truncated peptide TARHIY was selected from FID assay. Through binding studies using ESI-MS, SPR, BLItz, and NMR, the binding properties of the peptide to H69 were determined, such as binding affinity, stoichiometry, and interaction site. The peptide exhibited moderate binding …

The Development Of Chemical Methods To Discover Kinase Substrates And Map Cell Signaling With Gamma-Modified Atp Analog-Dependent Kinase-Catalyzed Phosphorylation, Dissanayaka Mudiyanselage Maheeka Madhubashini Embogama

Wayne State University Dissertations

Kinase-catalyzed phosphorylation plays an important role in cell physiology by regulating a myriad of cellular functions. Thus aberrant kinase activity is implicated in various diseases. Methods are needed to discover kinase substrates and map signaling pathways to explore biology and to help drug discovery. A few techniques are currently available to discover kinase substrate and map cell signaling. However, to augment kinase substrate discovery approaches, it is essential to develop alternative techniques. Pflum has recently discovered cosubstrate promiscuity of protein kinases with gamma-modified ATP analogs. Here, kinase-catalyzed biotinylation with ATP-biotin was used to develop novel tools to discover kinase substrates …

A New Three-Dimensional (3d) Particle Coincidence Imaging System And Its Applications In Strong Field Studies Of Reaction Dynamics In Atoms And Molecules, Yunfei Lin

Wayne State University Dissertations

Electron‐electron interaction is an important and interesting research theme both in chemistry and physics. Experimental study of electron correlation is hindered by the long dead time (the time within which no more than two electrons can be detected) of electron detection system. We developed a new three‐dimensional (3D) particle coincidence imaging system to remove this restriction. The detection system employs a new strategy: It uses a fast‐frame camera to record positional information on 2D MCPs/phosphor detector (so the particle velocities in two dimensions can be measured); It utilizes a high‐speed digitizer to pick up the signal from MCP lead, off‐line …

Gas-Phase Ion Spectroscopy Of Nucleobases And Mononucleotides: Models For Higher Order Nucleic Acids, Yuan-Wei Nei

Wayne State University Dissertations

Experiments examining the structures and stabilities of protonated and sodium cationized nucleobases, and deprotonated DNA and RNA mononucleotides are presented and discussed in this dissertation. These studies were carried out using the infrared multiple photon dissociation (IRMPD) action spectroscopy technique that utilizes a Fourier transform ion cyclotron mass spectrometer (FT-ICR MS) coupled to a free electron laser (FEL) located at the Radboud University Nijmegen. Ionic species of these biologically important complexes were generated using an electrospray ionization source and then mass isolated to have their infrared (IR) spectra measured by the experimental apparatus. Detailed analysis of the IR spectra measured …

Synthesis Of Netilmicin And Apramycin Derivatives For The Treatment Of Multidrug-Resistant Infectious Diseases, Amr Sayed Motawi Sonousi

Wayne State University Dissertations

The ever-growing bacterial resistance to existing antibiotics is alarming to humanity. Many researchers decided to revisit aminoglycosides with renewed emphasis on chemical modification as they have long been used as highly potent antibiotics for treating severe bacterial infections. The bactericidal effect of aminoglycosides is mainly due to protein synthesis inhibition by binding to the A-site of the bacterial ribosomes. However, the high potency and the broad spectrum of aminoglycosides has been outweighed by their side effects, especially ototoxicity, and by the resistance of pathogens. The goal of this research was the modification of existing aminoglycosides to develop derivatives which are …

Exploring Potential Energy Surfaces Of Chemical Reactions Using Electronic Structure Methods, Bishnu Thapa

Wayne State University Dissertations

This dissertation includes three topics: molecular dynamics in strong laser fields, pKa’s and redox potential calculations of bio–organic molecules, and oxidative damage of the nucleobases. Electronic structure calculations are used to provide a deeper understanding of experimental observations as well as to predict new results.

Chapters 2, 3 and 4 investigate the fragmentation and isomerization reactions of small monocations in the presence of strong laser fields. In the presence of intense laser pulses with 800 nm wavelengths, Born-Oppenheimer classical trajectory simulations were performed to investigate the dynamics of methanol monocation on the ground state potential energy surface (Chapter 2). With …

Synthesis Of Low-Coordinate Transition Metal Bis(Alkoxide) Complexes And Their Reactivity Toward Small Molecules, Maryam Yousif

Wayne State University Dissertations

This dissertation focused on the synthesis of new transition metal complexes in bis(alkoxide) ligand environments and the investigation of their reactivity in nitrene-group transfer catalysis and small molecule activation. Treatment of Cr(N(SiMe3)2)2(THF)2 with two equivalents of HOR (OR = OCtBu2Ph) led to the formation of the chromium(II) alkoxide dimer, Cr2(OR)4. Upon the reaction with bulky aryl and alkyl azides, Cr2(OR)4 led to the stable Cr(IV) mono(imido) complexes, Cr(OR)2(NR), featuring trigonal planar metal centers. In contrast, less bulky aryl azides led to the formation of chromium (VI) bis(imido) complexes Cr(OR)2(NR)2, independent of the amount of azide used. Chromium(IV) mono(imido) species Cr(OR)2(NR) …

Classical And Quantum Mechanical Simulations Of Condensed Systems And Biomolecules, Hedieh Torabifard

Wayne State University Dissertations

This work describes the fundamental study of two enzymes of Fe(II)/-KG super family enzymes (TET2 and AlkB) by applying MD and QM/MM approaches, as well as the development of multipolar-polarizable force field (AMOEBA/GEM-DM) for condensed systems (ionic liquids and water).

TET2 catalytic activity has been studied extensively to identify the potential source of its substrate preference in three iterative oxidation steps. Our MD results along with some experimental data show that the wild type TET2 active site is shaped to enable higher order oxidation. We showed that the scaffold stablished by Y1902 and T1372 is required for iterative oxidation. The …

Exploration Of Nanomaterials-Based Electrochemical Sensors For Peroxynitrite Detection, Ousama Al-Mahmoud, Haitham Kalil

Undergraduate Research Posters 2017

Peroxynitrite (PON, ONOO-) plays an essential role in several cardiovascular dysfunctions and other diseases triggered by oxidative stress. The precise detection of this analyte in biological systems is of paramount importance not only to understand the genesis and development of diseases, but also to design and assess efficient therapies. We fabricated highly sensitive and selective electrochemical sensors based on transition metal-decorated graphene nanocomposites as catalytic interfaces for peroxynitrite quantification. The interfaces of metal-decorated graphene nanostructures were immobilized on carbon electrodes by electro-grafting, electro- depositing, and drop-casting techniques. The morphology and surface chemistry of the nanostructured materials were characterized using Scanning …

Fidelity Of Implementation: An Overlooked Yet Critical Construct To Establish Effectiveness Of Evidence-Based Instructional Practices, Marilyne Stains, Trisha Vickrey

Department of Chemistry: Faculty Publications

The discipline-based education research (DBER) community has been invested in the research and development of evidence-based instructional practices (EBIPs) for decades. Unfortunately, investigations of the impact of EBIPs on student outcomes typically do not characterize instructors’ adherence to an EBIP, often assuming that implementation was as intended by developers. The validity of such findings is compromised, since positive or negative outcomes can be incorrectly attributed to an EBIP when other factors impacting implementation are often present. This methodological flaw can be overcome by developing measures to determine the fidelity of implementation (FOI) of an intervention, a construct extensively studied in …