Chemistry Commons^™

1,1,2,2,2,3,3,3-Octa­Carbonyl-1,1,2,3-Tetra­Kis­(1,3,5-Tri­Aza-7-Phosphatri­Cyclo­[3.3.1.13,7]Decane-Κp)-Triangulo-Triosmium(0), David M. Marolf, Kristen L. Brehm, Vincent M. Lynch, Gregory Powell

Chemistry and Biochemistry

The title compound, [Os3(C6H12N3P)4(CO)8], crystallizes in the orthorhombic space group Pbca with Z = 8. The molecule consists of a triangular triosmium(0) core surrounded by eight carbonyl ligands and four 1,3,5-triaza-7-phosphatri- cyclo[3.3.1.13,7]decane (or PTA) ligands. One Os atom is coordinated by two PTA ligands and two CO ligands, while the other two Os atoms are each bonded to a single PTA ligand and three CO ligands. There is a small disorder associated with the Os3 unit so that a minor orientation has an occupancy of 2.17 (4)%. The title compound represents the first structurally characterized triangular Os3 carbonyl cluster with …

Chemical Manipulation Of Macrophages: Nanomaterial And Molecular Approaches, Joseph Hardie

Doctoral Dissertations

Macrophages, phagocytic cells of the innate immune system, are the body’s first line of defense against pathogens and are responsible for tissue maintenance. Macrophages are capable of sensing and internalizing external stimuli, and in response change their morphology and phenotype accordingly. Because macrophages are integral to immune function and tissue maintenance, dysregulation of macrophage behavior is associated with a range of diseases including infections, cancer, autoimmune disorders, atherosclerosis, and more. Because of the implications of macrophage failure, there is interest in creating new materials to manipulate macrophage behavior for a therapeutic effect. In this thesis, I describe the application of …

Structural Analysis Of Protein Therapeutics Using Covalent Labeling – Mass Spectrometry, Patanachai Limpikirati

Doctoral Dissertations

Using mass spectrometry (MS) to obtain information about a higher order structure of protein requires that a protein’s structural properties are encoded into the mass of that protein. Covalent labeling (CL) with reagents that can irreversibly modify solvent accessible amino acid side chains is an effective way to encode structural information into the mass of a protein, as this information can be read-out in a straightforward manner using standard MS-based proteomics techniques. The differential reactivity of proteins under two or more conditions can be used to distinguish protein topologies, conformations, and/or binding sites. CL-MS methods have been effectively used for …

Chemical Investigation Of Floridian Mangrove Endophytes And Antarctic Marine Organisms, Bingjie Yang

USF Tampa Graduate Theses and Dissertations

Nature creates diseases and illnesses for mankind, however, nature also provides therapeutics by making biological systems produce secondary metabolites. Although the secondary metabolites originally play roles in chemical defense or evolution, researchers have been working on them for drug discovery. Plants, fungi and marine organisms have been mostly explored by natural products chemists over the century and contributed most drugs to the market. With the increasing need of new drugs resulting from drug resistance and pathogen evolution, the natural products area has been focused on developing innovative methodologies to achieve higher efficiency of isolating new bioactive compounds.

This dissertation herein …

Comparison Of Accelerated Solvent Extraction (Ase) And Energized Dispersive Guided Extraction (Edge) For The Analysis Of Pesticides In Leaves, Ashlie D. Kinross, Kimberly J. Hageman, William J. Doucette, Alexandria L. Foster

Chemistry and Biochemistry Faculty Publications

Various techniques have been evaluated for the extraction and cleanup of pesticides from environmental samples. In this work, a Selective Pressurized Liquid Extraction (SPLE) method for pesticides was developed using a Thermo Fisher Scientific Accelerated Solvent Extraction (ASE) system. This instrument was compared to the newly introduced (2017) extraction instrument, the Energized Dispersive Guided Extraction (EDGE) system, which combines Pressurized Liquid Extraction (PLE) and dispersive Solid Phase Extraction (dSPE). We first optimized the SPLE method using the ASE instrument for pesticide extraction from alfalfa leaves using layers of Florisil and graphitized carbon black (GCB) downstream of the leaf homogenate in …

A Chemical Investigation Of Three Antarctic Tunicates Of The Genus Synoicum, Sofia Kokkaliari

USF Tampa Graduate Theses and Dissertations

Marine invertebrates, mainly sponges, tunicates and corals, have in the past few decades attracted the interest of the scientific community in regard to their secondary metabolites and their potential as leads in drug discovery. The genus Synoicum is comprised of multiple organisms found in both deep and shallow waters, tropical and cold environments around the world. The majority of the members of this genus that have been investigated can be found in shallow tropical waters due to the ease of accessing and collecting them. Of the cold environments, Antarctica is a representative of the environments where members of the Synoicum …

Small Molecule Analog Studies Of Paramagnetic Dmso Reductase Enzyme Family Intermediates, Khadanand Kc

Chemistry and Chemical Biology ETDs

Pyranopterin molybdenum and tungsten enzymes are expressed in numerous organisms from all domains of life. These enzymes catalyze a variety of atom, hydride, and electron transfer reactions. The enzymes are of great importance in the biogeochemical cycles of nitrogen, carbon, and sulfur. In recent years, chemists have investigated applications for some of these enzymes as industrial biocatalysts. The dimethylsulfoxide reductase (DMSOr) enzyme family is the broadest family of pyranopterin Mo enzymes. The first coordination sphere of the Mo or W-containing active site for each member of this family is made up of 4 sulfur donors from the two pyranopterin dithiolenes …

Global Atmospheric Budget Of Acetone: Air-Sea Exchange And The Contribution To Hydroxyl Radicals, Siyuan Wang, Eric C. Apel, Rebecca H. Schwantes, Kelvin H. Bates, Daniel J. Jacob, Emily V. Fischer, Rebecca S. Hornbrook, Alan J. Hills, Louisa K. Emmons, Laura L. Pan, Shawn Honomichl, Simone Tilmes, Jean‐François Lamarque, Mingxi Yang, Christa A. Marandino, E. S. Saltzman, Warren J. De Bruyn, Sohiko Kameyama, Hiroshi Tanimoto, Yuko Omori, Samuel R. Hall, Kirk Ullmann, Thomas B. Ryerson, Chelsea R. Thompson, Jeff Peischl, Bruce C. Daube, Róisín Commane, Kathryn Mckain, Colm Sweeney, Alexander B. Thames, David O. Miller, William H. Brune, Glenn S. Diskin, Joshua P. Digangi, Steven C. Wofsy

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Acetone is one of the most abundant oxygenated volatile organic compounds (VOCs) in the atmosphere. The oceans impose a strong control on atmospheric acetone, yet the oceanic fluxes of acetone remain poorly constrained. In this work, the global budget of acetone is evaluated using two global models: CAM‐chem and GEOS‐Chem. CAM‐chem uses an online air‐sea exchange framework to calculate the bidirectional oceanic acetone fluxes, which is coupled to a data‐oriented machine‐learning approach. The machine‐learning algorithm is trained using a global suite of seawater acetone measurements. GEOS‐Chem uses a fixed surface seawater concentration of acetone to calculate the oceanic fluxes. Both …

Solvation Structures And Dynamics Of Small Molecules: Experimental And Computational Studies Using Carbonyl Vibrational Modes As Probe, Xiaoliu Zhang

LSU Doctoral Dissertations

Solutions are ubiquitous in both the global environment and the human body, and play a significant role in scientific research and industrial production. The structures and dynamics of solutions have been studied for centuries. However, conventional experimental methods, whose intrinsic measuring time is on the order of nanoseconds to microseconds, could not detect the fast dynamics taking place in the solution on the timescale of femto- and pico-second. In this dissertation, the ultrafast two-dimensional infrared (2DIR) spectroscopy was applied to characterize the structure and dynamics in three different types of solutions on the sub-picosecond timescale. Linear Fourier transform infrared spectroscopy …

(S)-2-[(4-Fluoro­Phen­Yl)Formamido]-3-Phenyl­Propanoic Acid, Kathleen Lee, Luke Turner, Cynthia Powell, Eric W. Reinheimer

Chemistry and Biochemistry

No abstract provided.

Phosphorylation Of Adp-Glucose Pyrophosphorylase During Wheat Seeds Development, Danisa M. L. Ferrero, Claudia V. Piattoni, Matías D. Asencion Diez, Bruno E. Rojas, Matías D. Hartman, Miguel A. Ballicora, Alberto A. Iglesias

Chemistry: Faculty Publications and Other Works

Starch is the dominant reserve polysaccharide accumulated in the seed of grasses (like wheat). It is the most common carbohydrate in the human diet and a material applied to the bioplastics and biofuels industry. Hence, the complete understanding of starch metabolism is critical to design rational strategies to improve its allocation in plant reserve tissues. ADP-glucose pyrophosphorylase (ADP-Glc PPase) catalyzes the key (regulated) step in the synthetic starch pathway. The enzyme comprises a small (S) and a large (L) subunit forming an S2L2 heterotetramer, which is allosterically regulated by orthophosphate, fructose-6P, and 3P-glycerate. ADP-Glc PPase was found in a phosphorylated …

Phosphorus Variability In The Area Of Influence Of The Mid-Barataria Sediment Diversion, Peter Mates

LSU Master's Theses

Man-made levees along the lower Mississippi River prevent delivery of sediment from building and maintaining Louisiana’s coastal wetlands. The Mid-Barataria sediment diversions is designed to reintroduce Mississippi River water, sediment, and nutrients into the sediment-starved Barataria Basin. Phosphorus (P) is an important macronutrient for regulating primary production in coastal marine ecosystems. Wetlands can serve as a sink or source for phosphorus to the overlying water column through various retention and release processes, dependent on concentration. Louisiana coastal systems can be phosphorus limited due to much higher concentrations of bioavailable Nitrogen in river water. The high soluble molar N:P ( >50:1) …

Allosteric Regulation At The Crossroads Of New Technologies: Multiscale Modeling, Networks, And Machine Learning, Gennady M. Verkhivker, Steve Agajanian, Guang Hu, Peng Tao

Mathematics, Physics, and Computer Science Faculty Articles and Research

Allosteric regulation is a common mechanism employed by complex biomolecular systems for regulation of activity and adaptability in the cellular environment, serving as an effective molecular tool for cellular communication. As an intrinsic but elusive property, allostery is a ubiquitous phenomenon where binding or disturbing of a distal site in a protein can functionally control its activity and is considered as the “second secret of life.” The fundamental biological importance and complexity of these processes require a multi-faceted platform of synergistically integrated approaches for prediction and characterization of allosteric functional states, atomistic reconstruction of allosteric regulatory mechanisms and discovery of …

Mapping Gadolinium Contrast In A Complex Ionic And Photosynthesis Environment Of Pineapple By Near-Infrared And X-Ray Imaging, Subhendra Sarkar, Zoya Vinokur, Chen Xu, Tetiana Soloviova, Amina Shahbaz, Aldona Gjoni

Publications and Research

This work explores the diffusivity of a lanthanide complex, Eovist (Gadolinium-Ethoxy Benzyl Diethylenetriamine pentaacetate) that is stable in neutral media but is not in acidic environment. In the current work an acidic fruit model like pineapple that is rich in transition metals was used and a possible transmetallation reaction among Eovist and transition metal complexes was tested using X-ray imaging. Another goal of this work was to perturb the usual and the unusual photosynthesis systems that pineapple has maintained for millions of years during the evolution of circadian genes for efficient water conservation by dark photosynthesis. To detect such photosynthesis …

Chemist Table: A Tool For Designing Or Modifying Instruction For A Systems Thinking Approach In Chemistry Education, Sarah York, Marykay Orgill

Chemistry and Biochemistry Faculty Research

Recently, there have been calls to integrate systems thinking approaches into chemistry education in order to strengthen students’ conceptual understanding, build their problem-solving capabilities, and prepare them to make informed, ethical decisions about globally relevant issues, such as sustainability. Unfortunately, implementation of systems thinking approaches in chemistry classrooms currently poses challenges. Exemplar systems thinking materials with a STEM focus are limited, particularly at the tertiary level. Moreover, the science education community has yet to agree upon a systems thinking definition or develop a comprehensive list of systems thinking skills that students should develop. Thus, a current priority for the advancement …

Analytic Gradients For State-Averaged Multiconfiguration Pair-Density Functional Theory, Thais R. Scott, Matthew R. Hermes, Andrew M. Sand, Meagan S. Oakley, Donald G. Truhlar, Laura Gagliardi

Scholarship and Professional Work - LAS

Analytic gradients are important for efficient calculations of stationary points on potential energy surfaces, for interpreting spectroscopic observations, and for efficient direct dynamics simulations. For excited electronic states, as are involved in UV–Vis spectroscopy and photochemistry, analytic gradients are readily available and often affordable for calculations using a state-averaged complete active space self-consistent-field (SA-CASSCF) wave function. However, in most cases, a post-SA-CASSCF step is necessary for quantitative accuracy, and such calculations are often too expensive if carried out by perturbation theory or configuration interaction. In this work, we present the analytic gradients for multiconfiguration pair-density functional theory based on SA-CASSCF …

Quantitative Structure-Activity Relationship Studies Of Series Of Chalcones Derivatives As Inhibitors Of Tumor Necrosis Factor-Alpha, Wisam A. Radhi, Sadiq M. H. Ismael, Jasim M. Al-Shawi

Al-Qadisiyah Journal of Pure Science

Quantitative structure-activity relationship (QSAR) teqnique was used to predict the biological activity of a series of chalcones compounds as anti-inflammatory. 26 physicochemical descriptors are tested in QSAR equations configuration to predict biological effectiveness of compounds under study. The values of R2 in Eqs (1–3) ranged from 0.794–0.873, the F values ranged from 14.161–26.206 and the S values ranged from 0.262–0.334. The results demonstrated excellent models based on Eq.3, along with high of R2, F and minimum S by employing three parameters r(C3-C5), (LUMO+1) and (LUMO+2). This signifies that these parameters play a significant role in determining anti-inflammatory characteristics.

Collaborative Research: Mechanism And Target Recognition Of Protein Arginine Methyltransferases (Prmts), Joan Hevel

Funded Research Records

No abstract provided.

Observation Of The Low-Frequency Spectrum Of The Water Trimer As A Sensitive Test Of The Water-Trimer Potential And The Dipole-Moment Surface, Raffael Schwan, Chen Qu, Devendra Mani, Nitish Pal, Gerhard Schwaab, Joel M. Bowman, Gregory S. Tschumper, Martina Havenith

Faculty and Student Publications

© 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. Intermolecular interactions in bulk water are dominated by pairwise and non-pairwise cooperative interactions. While accurate descriptions of the pairwise interactions are available and can be tested by precise low-frequency spectra of the water dimer up to 550 cm−1, the same does not hold for the three-body interactions. Here, we report the first comprehensive spectrum of the water trimer in the frequency region from 70 to 620 cm−1 using helium-nanodroplet isolation and free-electron lasers. By comparison to accompanying high-level quantum calculations, the experimentally observed intermolecular bands can be assigned. …

Nobiletin Affects Circadian Rhythms And Oncogenic Characteristics In A Cell-Dependent Manner, Sujeewa S. Lellupitiyage Don, Kelly L. Robertson, Hui-Hsien Lin, Caroline Labriola, Mary E. Harrington, Stephanie R. Taylor, Michelle E. Farkas

Psychology: Faculty Publications

The natural product nobiletin is a small molecule, widely studied with regard to its therapeutic effects, including in cancer cell lines and tumors. Recently, nobiletin has also been shown to affect circadian rhythms via their enhancement, resulting in protection against metabolic syndrome. We hypothesized that nobiletin’s anti-oncogenic effects, such as prevention of cell migration and formation of anchorage independent colonies, are correspondingly accompanied by modulation of circadian rhythms. Concurrently, we wished to determine whether the circadian and anti-oncogenic effects of nobiletin differed across cancer cell lines. In this study, we assessed nobiletin’s circadian and therapeutic characteristics to ascertain whether these …