Chemistry Commons^™

Analysis Of Localized Diabatic States Beyond The Condon Approximation For Excitation Energy Transfer Processes, Ethan Alguire, Shervin Fatehi, Yihan Shao, Joseph E. Subotnik

School of Integrative Biological & Chemical Sciences (Formerly Dept. of Chemistry)

In a previous paper [Fatehi, S.; et al. J. Chem. Phys. 2013, 139, 124112], we demonstrated a practical method by which analytic derivative couplings of Boys-localized CIS states can be obtained. In this paper, we now apply that same method to the analysis of triplet–triplet energy transfer systems studied by Closs and collaborators [Closs, G. L.; et al. J. Am. Chem. Soc.1988, 110, 2652]. For the systems examined, we are able to conclude that (i) the derivative coupling in the BoysOV basis is negligible, and (ii) the diabatic coupling will likely change little over the configuration space explored …

Fabrication Of Cds Nanoparticle Coated Jasmonate Conjugates And Their Interactions With Mammalian Cells, Nazmul Sarker Fcrh '13, Stacey Barnaby Fcrh '11, Ipsita Bannerjee

The Fordham Undergraduate Research Journal

In this work, we have grown CdS nanoparticles on jasmonate nanoassemblies biomimetically and examined their interactions with mammalian cells. In general, plants naturally secrete the phytohormone jasmonic acid during development and in response to biotic and abiotic stress as a defense mechanism (Traw and Bergelson 2003; Sembdner and Parthier 1993). We have developed a new class of nanomaterials by utilizing nanoassemblies of the plant phytohormone jasmonic acid (JA) as templates for the growth of quantum dots, which may have potential applications as sensors and may potentially be utilized for bioimaging applications.

Br[O/]Nsted Acid Catalyzed Asymmetric Allylation And Propargylation Of Aldehydes, Pankaj Jain

USF Tampa Graduate Theses and Dissertations

Carbonyl allylation and propargylation reactions have been an important tool for the stereocontrolled formation of carbon-carbon bonds for synthetic chemists. The chiral homoallylic and homopropargylic alcohols obtained from these reactions serve as versatile intermediates for the synthesis of natural and pharmaceutical products. Over the past three decades and continuing on, various synthetic groups around the globe have directed their research towards the efficient synthesis of these chiral moieties. In spite extensive research, asymmetric allylation and propargylation reactions remain an enduring challenge in organic chemistry.

Chapter 1 of this thesis describes the first phosphoric acid catalyzed asymmetric allylboration of aldehydes. We …

Synthesis And Characterization Of Mono- And Di-O-Alkylated Derivatives Of Methyl 3,5-Dihydroxy Benzoate, Michele Paccagnini Fcrh '12, Matthew Tracey Fcrh '11, J. Ryan Combs Fcrh '10, Amy M. Balija

The Fordham Undergraduate Research Journal

In the course of searching for monomers for larger macromolecular structures, we attempted the bis-O-alkylation of methyl 3,5-dihydroxy benzoate (1) with (bromomethyl)cyclohexane (2). To our knowledge, no literature procedures have been published on the preparation of ethers by alkylation of a phenol substrate with (bromomethyl)cyclohexane. We were surprised to find that the mono-O-alkylated product was predominantly obtained in this reaction. This finding is in contrast with those reported for alkylations, utilizing benzyl bromide where bis-O-alkylation is the predominant reaction (Yan et al. 2011). Herein we report a convenient synthesis of the bis-alkylated product 3 in good yield.

Synthesis And Characterization Of New Gd3+-Containing Complexes As Potential Targeted Contrast Agents For Magnetic Resonance Imaging, Sashiprabha Manjari Vithanarachchi

Wayne State University Dissertations

The focus of the research described in this thesis is the study of chemistry relevant to target-specific contrast agents for magnetic resonance imaging (MRI). MRI is a widely used technique in diagnostic medicine and biomedical research to obtain anatomical and physiological details of soft tissues. Contrast agents are used to enhance the contrast of MR images by causing changes to the chemical environment of water molecules. Clinically approved GdIII-containing contrast agents for MRI are non-specific, and consequently, have limited utility. Target-specific contrast agents represent one way to circumvent this limitation. In the research described in this thesis, myelin and Β-amyloid …

The Cytotoxic Effect Of 2-Acylated-1,4-Naphthohydroquinones On Leukemia/Lymphoma Cells, Diego A. Pedroza, Fernando De Leon, Armando Varela-Ramirez, Carolina Lerma, Renato J. Aguilera, Shizue Mito

School of Integrative Biological & Chemical Sciences (Formerly Dept. of Chemistry)

Here, we tested seven 2-acylated-1,4-hydronaphthoquinones for their cytotoxic effects on a panel of cancer lymphoma/leukemia cells and compared to a non-cancer origin cell line. Several naphthohydroquinones exhibited selective cytotoxic effects on lymphoma/leukemia cells with lowest activity on non-cancer cells. The mode of cell death induced by an acylated naphthohydroquinone, which has a long alkyl chain, was found to be via apoptosis. Furthermore, the naphthohydroquinone provoked mitochondria depolarization and activation of its downstream effector, caspase-3, thus implicating the intrinsic apoptotic pathway as its mechanism to exert cell death.

Synergistic Adsorption Of Heavy Metal Ions And Organic Pollutants By Supramolecular Polysaccharide Composite Materials From Cellulose, Chitosan And Crown Ether, Tamutsiwa M. Mututuvari, Chieu D. Tran

Chemistry Faculty Research and Publications

We have developed a simple one-step method to synthesize novel supramolecular polysaccharide composites from cellulose (CEL), chitosan (CS) and benzo-15-crown 5 (B15C5). Butylmethylimidazolium chloride [BMIm⁺Cl⁻], an ionic liquid (IL), was used as a sole solvent for dissolution and preparation of the composites. Since majority of [BMIm⁺Cl⁻] used was recovered for reuse, the method is recyclable. The [CEL/CS + B15C5] composites obtained retain properties of their components, namely superior mechanical strength (from CEL), excellent adsorption capability for heavy metal ions and organic pollutants (from B15C5 and CS). More importantly, the [CEL/CS + B15C5] …

Resonance Raman Spectroscopy Reveals That Substrate Structure Selectively Impacts The Heme-Bound Diatomic Ligands Of Cyp17, Piotr J. Mak, Michael C. Gregory, Stephen G. Sligar, James R. Kincaid

Chemistry Faculty Research and Publications

An important function of steroidogenic cytochromes P450 is the transformation of cholesterol to produce androgens, estrogens, and the corticosteroids. The activities of cytochrome P450c17 (CYP17) are essential in sex hormone biosynthesis, with severe developmental defects being a consequence of deficiency or mutations. The first reaction catalyzed by this multifunctional P450 is the 17α-hydroxylation of pregnenolone (PREG) to 17α-hydroxypregnenolone (17-OH PREG) and progesterone (PROG) to 17α-hydroxyprogesterone (17-OH PROG). The hydroxylated products then either are used for production of corticoids or undergo a second CYP17 catalyzed transformation, representing the first committed step of androgen formation. While the hydroxylation reactions are catalyzed by …

Bsa–Boronic Acid Conjugate As Lectin Mimetics, Satya Nandana Narla, Poornima Pinnamaneni, Huan Nie, Yu Li, Xue-Long Sun

Chemistry Faculty Publications

We report bovine serum albumin (BSA)–boronic acid (BA) conjugates as lectin mimetics and their glyco-capturing capacity. The BSA–BA conjugates were synthesized by amidation of carboxylic acid groups in BSA with aminophenyl boronic acid in the presence of EDC, and were characterized by Alizarin Red S (ARS) assay and SDS–PAGE gel. The BSA–BA conjugates were immobilized onto maleimide-functionalized silica beads and their sugar capturing capacity and specificity were confirmed by ARS displacement assay. Further, surface plasmon resonance (SPR) analysis of the glyco-capturing activity of the BSA–BA conjugates was conducted by immobilizing BSA–BA onto SPR gold chip. Overall, we demonstrated a BSA–BA-based …

Henon-Heiles Model, Ronald Lovett

Topics in Quantum Mechanics

No abstract provided.

Investigation And Characterization Of Pt-Modified Au Catalysts And Polymer Composites By Electrochemistry, Raman And Surface Enhanced Raman Spectroscopy (Sers), Ranjani Muralidharan

USF Tampa Graduate Theses and Dissertations

This dissertation thesis consists of six chapters. The main focus of this study is the need for understanding the reaction mechanism and intermediates formed on Pt-modified Au surface as anode catalysts in the formic acid fuel cells. Chapter 1 gives an introduction to formic acid and methanol fuel cells, an overview of the current catalysts employed at the anode of the fuel cells, specifically the Pt-modified Au electrodes as potential catalysts and the different deposition methods for preparing this catalytic surface. Information about different electrochemical methods used like cyclic voltammetry and potential step method along with other characterization methods and …

Collisional Dynamic Elements Of The Pyrazine - N2o System:Middle And Low J States, La Moyne Tyler Mix

Theses and Dissertations

Unimolecular reactions based on the Lindemann - Hinchelwood mechanism are important to understanding combustion and atmospheric processes. The main feature of this mechanism is the energy transfer probability distribution function, P(E',E). We have chosen to study P(E',E) through gas phase collisional dynamics probed with IR transient absorption spectroscopy. Post-collision absorption line widths for the pyrazine-N2O system are used to calculate lab frame translational temperatures. The translational temperatures reveal that collisions with large rotational energy transfer also transfer large amounts of translational energy. For J states >47 the relationship is linear indicating a constant impact parameter. Line widths for J=47 through …

Synthesis, Crystal Structure Refinement, And Electrical Conductivity Of Pb(8−X)Na2smx(Vo4)6o(X/2), Tatiana M. Savankova, Lev G. Akselrud, Lyudmyla I. Ardanova, Alexey V. Ignatov, Eugeni I. Get’Man, Roman E. Gladyshevskii, Stanislav N. Loboda

Biochemistry, Chemistry and Geology Department Publications

Solid solutions of Pb(8−x)Na2Smx(VO4)6O(x/2) were studied using X-ray diffraction analysis including Rietveld refinement and scanning electron microscopy and by measuring their electrical conductivity. Crystal structure of the solid solutions was refined and the solubility region 0 ≤ x ≤ 0.2 was determined for samarium substitution for lead under the scheme 2Pb2+ + ◻ → 2Sm3+ + O2-. The influence of degree of substitution on the electrical conductivity of solid solutions was established.

Reduction Of Uranium By Bacterial Products, Adesanya A. Akinleye, Sharon Bone, John Bargar

STAR Program Research Presentations

The Old Rifle Mill Processing site at Rifle, CO, contains uranium contaminated groundwater. The presence of uranium is one of the major problems at Department of Energy legacy sites. There is an initiative for attenuation of uranium by the Department of Energy. Uranium undergoes oxidation/reduction reactions with the substances at the site. Uranium’s oxidation state determines its solubility and mobility in the aquifer. The oxidation reduction pathways at this site have mineralogical, microbial and geochemical components. Understanding the oxidation/reduction pathways of these components will allow for better predictions of the changes and movement of uranium.

Sulfide [S^2- ] and …

Enhanced Magnetic Anisotropy In Cobalt-Carbide Nanoparticles, Ahmed A. El-Gendy, Meichun Qian, Zachary J. Huba, Shiv N. Khanna, Everett E. Carpenter

Chemistry Publications

An outstanding problem in nano-magnetism is to stabilize the magnetic order in nanoparticles at room temperatures. For ordinary ferromagnetic materials, reduction in size leads to a decrease in the magnetic anisotropy resulting in superparamagnetic relaxations at nanoscopic sizes. In this work, we demonstrate that using wet chemical synthesis, it is possible to stabilize cobalt carbide nanoparticles which have blocking temperatures exceeding 570 K even for particles with magnetic domains of 8 nm. First principles theoretical investigations show that the observed behavior is rooted in the giant magnetocrystalline anisotropies due to controlled mixing between C p- and Co d-states.

Wetting Transparency Of Graphene In Water, J. Driskill, D. Vanzo, D. Bratko, A. Luzar

Chemistry Publications

Measurements of contact angle on graphene sheets show a notable dependence on the nature of the underlying substrate, a phenomenon termed wetting transparency. Our molecular modeling studies reveal analogous transparency in case of submerged graphene fragments in water. A combined effect of attractive dispersion forces, angle correlations between aqueous dipoles, and repulsion due to the hydrogen-bond-induced orientation bias in polarized hydration layers acting across graphene sheet, enhances apparent adhesion of water to graphene. We show wetting free energy of a fully wetted graphene platelet to be about 8 mNm−1 lower than for graphene wetted only on one side, which gives …

Expression And Characterization Of The Novel Oxidase Virh-Ox, John Dronzek

Chemistry Honors Papers

No abstract provided.

Developing Transfer Skills In A Biochemistry Class, Jeong V. Choe

Faculty Publications & Research

Students seem to struggle with transferring prior knowledge if the new problem they are given is in a different form from the way they learned the material. The process of transfer can be identified by four components: 1) recognizing the similarity between the old and new contexts; 2) identifying the potential of a certain skill or concept that has worked in the past, to give solutions to new problematic situations; 3) mental testing of the application of the potential solution; and 4) an attempt to apply the skill or concept to a new context (Georghiades 2000). These four components are …

Transition-Metal-Doped Manganese Oxide Hollow Nanospheres: Synthesis And Catalytic Activityc, Jeffrey Carmichael

Chemistry Honors Papers

Manganese oxide hollow spheres with approximate MnO2 stoichiometry were synthesized by aqueous precipitation with a redox reaction between Mn(II) and MnO4–in the presence of butyric acid. The butyric acid acts as a structure-directing agent, reducing the average particle size of the materials, while also acting as a soft template for the spheres to form. This is possible because butyric acid forms a thermodynamically stable microemulsion in water, which is unable to be broken up in solution. Without incorporation of the carboxylic acids, the materials have a surface area of 133 m2/g, while with the addition of butyric acid, the surface …

Effects Of Oxidation On Protein-Nanoparticle Interactions, Valdez R. Rahming, Md. Abul Fazal

Chemistry Faculty Publications

Aims: Upon entrance into the blood stream most nanoparticles bind to an array of proteins forming a “protein corona”. Fibrinogen is the second most abundant blood protein and has been reported to bind to a variety of nanoparticles including metal oxides, polymeric nanoparticles and carbon nanotubes.
Study Design: Study the effects of oxidation on the binding interactions between human serum fibrinogen and magnetic iron (III) oxide nanoparticles.
Place and Duration of Study: Department of Chemistry, College of St. Benedict, 37 South College Avenue, St. Joseph, MN 56374, U.S.A., between June 2011 and May 2012.
Methodology: Spectroscopic techniques (UV-Vis, IR, fluorescence, …

Simultaneous High-Performance Liquid Chromatography-Tandem Mass Spectrometry (Hplc-Ms-Ms) Analysis Of Cyanide And Thiocyanate From Swine Plasma, Raj K. Bhandari, Erica Manandhar, Robert P. Oda, Gary A. Rockwood, Brian A. Logue

Chemistry and Biochemistry Faculty Publications

An analytical procedure for the simultaneous determination of cyanide and thiocyanate in swine plasma was developed and validated. Cyanide and thiocyanate were simultaneously analyzed by high-performance liquid chromatography tandem mass spectrometry in negative ionization mode after rapid and simple sample preparation. Isotopically labeled internal standards, Na¹³C¹⁵N and NaS¹³C¹⁵N, were mixed with swine plasma (spiked and nonspiked), proteins were precipitated with acetone, the samples were centrifuged, and the supernatant was removed and dried. The dried samples were reconstituted in 10 mM ammonium formate. Cyanide was reacted with naphthalene-2,3-dicarboxaldehyde and taurine to form N-substituted …

06. Computer Science, University Of Central Oklahoma

Oklahoma Research Day Abstracts

No abstract provided.

04. Botany, University Of Central Oklahoma

Oklahoma Research Day Abstracts

No abstract provided.

09. Environmental Science, University Of Central Oklahoma

Oklahoma Research Day Abstracts

No abstract provided.

12. Kinesiology, University Of Central Oklahoma

Oklahoma Research Day Abstracts

No abstract provided.

08. Engineering, University Of Central Oklahoma

Oklahoma Research Day Abstracts

No abstract provided.

10. Forensic Science, University Of Central Oklahoma

Oklahoma Research Day Abstracts

No abstract provided.

05. Chemistry, University Of Central Oklahoma

Oklahoma Research Day Abstracts

No abstract provided.

14. Optometry, University Of Central Oklahoma

Oklahoma Research Day Abstracts

No abstract provided.

15. Pharmacy, University Of Central Oklahoma

Oklahoma Research Day Abstracts

No abstract provided.