Chemistry Commons^™

Understanding The Antioxidant Mechanism Of Inorganic Selenium, Oxo- Sulfur, And Polyphenol Compounds, And The Biological Implications Of Functionalized Nanoparticles, Ria Ramoutar

All Dissertations

Inorganic selenium, oxo-sulfur, and polyphenol compounds are found in foods and dietary supplements, and are recognized for their nutritional benefits and their potential to treat or prevent diseases caused by oxidative stress. In our experiments to determine the effects of inorganic selenium compounds on iron-mediated DNA damage, Na₂SeO₃3 and SeO₂ exhibit antioxidant and pro-oxidant activities depending on concentrations of both the compound and hydrogen peroxide. Additional experiments demonstrate that iron coordination is a novel mechanism responsible for the observed activities. In similar experiments, oxo-sulfur compounds prevent Cu+/ H₂O₂-mediated DNA damage significantly …

Development Of Improved Torsional Potentials In Classical Force Field Models Of Poly (Lactic Acid), James Mcaliley

All Dissertations

In this work, existing force field descriptions of poly (lactic acid), or PLA, were improved by modifying the torsional potential energy terms to more accurately model the bond rotational behavior of PLA. Extensive calculations were carried out using density functional theory (DFT), for small PLA molecules in vacuo, and also using DFT with a continuum model to approximate the electronic structure of PLA in its condensed phase. From these results, improved force field parameters were developed using a combination of the OPLS and CHARMM force fields. The new force field, PLAFF2, is an update to the previously developed PLAFF model …

Structure - Property Relationships Of New Polystyrene Nanocomposites Prepared From Initiator-Containing Layered Double Hydroxides Of Zinc Aluminum And Magnesium Aluminum, Charles Manzi-Nshuti, Dan Chen, Shengpei Shu, Charles A. Wilkie

Chemistry Faculty Research and Publications

Polystyrene/layered double hydroxides (PS/LDHs) nanocomposites were prepared by free radical polymerization of styrene monomer in the presence of LDHs intercalated with 4,4′-azobis(4-cyanopentanoate) anions (LDH–ACPA). XRD and ATR-IR are used to confirm that the materials produced are layered and the presence of the azo-initiator anions in these LDHs. These LDHs were used successfully to polymerize styrene and both XRD and TEM images of the composites support the formation of a mixed exfoliated-intercalated nanocomposite for ZnAl–ACPA but a microcomposite for MgAl–ACPA. The magnesium-containing LDHs decreased the glass transition temperature (T_g) of the composites while ZnAl–ACPA did not affect T …

Regioselective Intermolecular Coupling Reaction Of Arylketones And Alkenes Involving C-H Bond Activation Catalyzed By An In Situ Formed Cationic Ruthenium-Hydride Complex, Chae S. Yi, Do W. Lee

Chemistry Faculty Research and Publications

The cationic ruthenium hydride complex, formed in situ from the treatment of the tetranuclear ruthenium hydride complex {[(PCy₃)(CO)RuH]₄(μ₄-O)(μ₃-OH)(μ₂-OH)} with HBF₄·OEt₂, was found to be a highly effective catalyst for the intermolecular coupling reaction of arylketones and 1-alkenes to give the substituted indene and ortho-C−H insertion products. The formation of the indene products resulted from the initial alkene isomerization followed by regioselective ortho-C−H insertion of 2-alkene and dehydrative cyclization. The preliminary mechanistic studies revealed a rapid and reversible ortho-C−H bond activation followed by the …

Recent Applications Of Acyclic (Diene)Iron Complexes And (Dienyl)Iron Cations In Organic Synthesis, William A. Donaldson, Subhabrata Chaudhury

Chemistry Faculty Research and Publications

Complexation of (tricarbonyl)iron to an acyclic diene serves to protect the ligand against oxidation, reduction, and cycloaddition reactions, whereas the steric bulk of this adjunct serves to direct the approaches of reagents to unsaturated groups attached to the diene onto the face opposite to iron. Furthermore, the Fe(CO)₃ moiety can serve to stabilize carbocation centers adjacent to the diene (i.e. pentadienyl-iron cations). Recent applications of these reactivities to the synthesis of polyene-, cyclopropane-, cycloheptadiene-, and cyclohexenone-containing natural products or analogues are presented.

Does Organic Modification Of Layered Double Hydroxides Improve The Fire Performance Of Pmma?, Calistor Nyambo, Dan Chen, Shengpei Shu, Charles A. Wilkie

Chemistry Faculty Research and Publications

The effect of modified layered double hydroxides (LDHs) on fire properties of poly(methyl methacrylate) is investigated. Organically-modified LDHs were prepared via rehydration of calcined hydrotalcite in a palmitate solution. Composites consisting of the organo-LDHs, unmodified hydrotalcite and calcined oxides were prepared with poly(methyl methacrylate) using melt blending. Thermal and fire properties of the (nano)composites were studied. The thermogravimetric analyses of the composites show an increase in thermal stability. Fire performance, evaluated using cone calorimetry, show that organically-modified LDHs composites give the best reductions in peak heat release rate, PHRR, i.e., 51% at 10% weight loading. Dispersion of the LDHs was …

Investigations Of 2-Thiazoline-2-Thiol As A Ligand: Synthesis And X-Ray Structures Of [Mn2(Co)7(Μ-Ns2C3H4)2] And [Mn(Co)3(Pph3)(Κ2-Ns2C3H4)], Shishir Ghosh, Faruque Ahmed, Rafique Al-Mamun, Daniel T. Haworth, Sergey V. Lindeman, Tasneem Siddiquee, Dennis W. Bennett, Shariff E. Kabir

Chemistry Faculty Research and Publications

Treatment of Mn₂(CO)₁₀ with 2-thiazoline-2-thiol in the presence of Me₃NO at room temperature afforded the dimanganese complexes [Mn₂(CO)₇(μ-NS₂C₃H₄)₂] (1) and [Mn₂(CO)₆(μ-NS₂C₃H₄)₂] (2) in 51 and 34% yields, respectively. Compound 1 was quantitatively converted into 2 when reacted with one equiv of Me₃NO. Reaction of 1 with triphenylphosphine at room temperature furnished the mononuclear complex [Mn(CO)₃(PPh₃)(κ ^{2 …}

Physico-Chemical Characteristics Of Storage-Ripened Mango (Mangifera Indica L.) Fruits Varieties Of Eastern Tanzania, O C Othman, G P Mbogo

Tanzania Journal of Science

Two mango (Mangifera indica L.) fruit varieties, Dodo and Viringe, from two localities of Eastern Tanzania, (Muheza in Tanga and Ifakara in Morogoro), were harvested as mature green fruits during early, mid and late season and allowed to ripen while stored at room temperature. The fruits were analyzed for their proximate composition (ash, titratable acidity, crude fat, crude fibre, moisture), reducing and total sugars content, ascorbic acid and total soluble solids content, concentration of four macro elements (Ca, Mg, K, Na) and seven heavy metals (Al, Cd, Cu, Fe, Mn, Pb, Zn). The results showed that the mango fruits had …

Plants As A Source Of Green Corrosion Inhibitors: The Case Of Gum Exudates From Acacia Species (A. Drepanolobium And A. Senegal), J Buchweishaija

Tanzania Journal of Science

The inhibitive performance of gum exudates from Acacia drepanolobium and Acacia senegal from Tanzania, towards the corrosion of mild steel in fresh water has been investigated. The experimental methods include potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) studies. The results indicate that gum exudates (Acacia drepanolobium and Acacia senegal) exhibit good inhibition characteristics to corrosion on mild steel under fresh water medium and the inhibition efficiency of up to 90.7% and 99.7% respectively was attained at 30 oC. Furthermore, the studies have shown that the inhibition performance remained above 90% on both Acacia exudates independent of the raise in temperature. …

Physical And Chemical Composition Of Storage-Ripened Papaya (Carica Papaya L.) Fruits Of Eastern Tanzania, O C Othman

Tanzania Journal of Science

The proximate composition (ash, titratable acidity, crude fat, crude fibre, moisture and sugars), soluble solids, ascorbic acid, polyphenol oxidase activity, macro-nutrients and heavy metal contents of storage-ripened papaya (Carica papaya L.) fruits from Mbezi, Dar es Salaam, Tanzania were determined. The determinations were repeated for early, middle and late-season papaya fruits. The fruits were always harvested at the mature green stage and allowed to ripen during room temperature storage. The results showed that papaya fruits had high moisture content (>85.5%), low acidity (<0.18% c.a.), low crude fat (0.10 g/100 g-edible portion), moderate crude fibre (1.45 g/100 g-edible portion), high ascorbic acid content (>84.5 mg/100 g- fw), moderate total sugars (>13.0%) and soluble solids (>12.9%) content. Early-season …

A Top-Down Proteomic Approach For The Discovery Of Novel Serum Biomarkers Of Pregnancy-Related Disease, Karen Merrell

Theses and Dissertations

The serum fraction of blood is an ideal material in which to search for novel biomarkers for disease. It is easily obtained through relatively non-invasive means, routinely collected, and a rich treasure-trove of information about the health of an individual. Cells react to signal molecules, take up nutrients, and release waste products, fragments that are the result of proteolysis, and other molecules out into the bloodstream. If these components are unique to the cells in question, that part of the complex mixture that is the blood stream can potentially characterize the health of the tissue or organ those cells are …

51st Rocky Mountain Conference On Analytical Chemistry

Rocky Mountain Conference on Magnetic Resonance

Final program, abstracts, and information about the 51st annual meeting of the Rocky Mountain Conference on Analytical Chemistry, co-endorsed by the Colorado Section of the American Chemical Society and the Society for Applied Spectroscopy. Held in Snowmass, Colorado, July 19-23, 2009.

Simultaneous, Noninvasive Observation Of Elastic Scattering, Fluorescence And Inelastic Scattering As A Monitor Of Blood Flow And Hematocrit In Human Fingertip Capillary Beds, Joseph Chaiken, Jerry Goodisman, Bin Deng, Rebecca J. Bussjager, George Shaheen

Chemistry - All Scholarship

We report simultaneous observation of elastic scattering, fluorescence, and inelastic scattering from in vivo near-infrared probing of human skin. Careful control of the mechanical force needed to obtain reliable registration of in vivo tissue with an appropriate optical system allows reproducible observation of blood flow in capillary beds of human volar side fingertips. The time dependence of the elastically scattered light is highly correlated with that of the combined fluorescence and Raman scattered light. We interpret this in terms of turbidity (the impeding effect of red blood cells on optical propagation to and from the scattering centers) and the changes …

Polymer Nanocomposites Using Zinc Aluminum And Magnesium Aluminum Oleate Layered Double Hydroxides: Effects Of Ldh Divalent Metals On Dispersion, Thermal, Mechanical And Fire Performance In Various Polymers, Charles Manzi-Nshuti, Ponusa Songtipya, Evangelos Manias, Maria Del Mar Jimenez-Gasco, Jeanne Hossenlopp, Charles Wilkie

Chemistry Faculty Research and Publications

Oleate-containing layered double hydroxides of zinc aluminum (ZnAl) and magnesium aluminum (MgAl) were used to prepare nanocomposites of polyethylene, poly(ethylene-co-butyl acrylate) and poly(methyl methacrylate). The additives and/or their polymer composites were characterized by X-ray diffraction, FTIR, elemental analysis, thermogravimetric analysis, mechanical testing, and cone calorimetry. The unusual packing of the monounsaturated oleate anions in the gallery of these LDHs facilitates the dispersion of these nanomaterials. The inorganic LDH protects the polymer from thermal oxidation, shown by enhancement of the thermal and fire properties of the corresponding polymer nanocomposites. There is a qualitative difference in the morphology of the …

Synthesis And Coordination Chemistry Of New Oxazoline And Benzoxazole Based Ligands With Lanthanides, Edicome Cornel Shirima

Chemistry and Chemical Biology ETDs

In Chapter 1, a brief literature review on the chemistry of lanthanides (Ln) and actinides (An) is described. In addition, the coordination chemistry of lanthanides/actinides with various ligands comprised of organic backbones has also been described. In Chapters 2 and 3 the syntheses of oxazoline and benzoxazole ligands is described. Both ligands contain a hard donor group (P=O) and the nitrogen (N) atom from the heterocycle as a relatively softer donor atom. In Chapter 2 the oxazoline ligand was synthesized in two steps reaction that involves substitution with Ph₂P group and oxidation of the phosphine into P=O by …

Ion Transport Behaviors Upstream And Downstream From The Sampling Cone Of An Inductively Coupled Plasma Mass Spectrometer, Haibin Ma

Theses and Dissertations

Inductively coupled plasma - mass spectrometry (ICP-MS) is the technique of choice worldwide for trace elemental determinations because of its excellent ionization ability, low detection limits and fast analysis speeds. However, the ICP-MS still suffers from some disadvantages, such as spectral overlap and severe matrix effects. Matrix effects or interferences, partly arise from changes in the analyte transmission through the interfacial region between the ICP and mass spectrometer with changes in sample matrix. Better understanding of the transmission behaviors of analyte through the sampling and skimmer cones will provide the insights needed to alleviate matrix interferences and to improve the …

Relaxation Of Vibrationally Excited Trifluorobenzene And Tetrafluorobenzene By Collisions With Carbon Dioxide, Alan M. Johnson

Theses and Dissertations

An investigation into the relaxation of highly vibrationally excited trifluorobenzene and tetrafluorobenzene following collisions with carbon dioxide was performed using diode laser transient absorption spectroscopy. A 248 nm excimer laser prepared the vibrationally hot (E'~41,000 cm-1) fluorobenzene molecules. Large amounts of translational and rotational energy are transferred through collisions between the hot donor molecule and CO2. Rate constants and collisional probabilities were calculated by probing the high J states (J=58~80) of CO2 in the vibrational ground state, 0000, with measurements taken 1 µsec, ¼ the mean gas collision time, following each excimer laser pulse. The energy transfer probability distribution function, …

Single-Molecule Protein Unfolding In Solid State Nanopores, David Talaga, Jiali Li

Department of Chemistry and Biochemistry Faculty Scholarship and Creative Works

We use single silicon nitride nanopores to study folded, partially folded, and unfolded single proteins by measuring their excluded volumes. The DNA-calibrated translocation signals of β-lactoglobulin and histidine-containing phosphocarrier protein match quantitatively with that predicted by a simple sum of the partial volumes of the amino acids in the polypeptide segment inside the pore when translocation stalls due to the primary charge sequence. Our analysis suggests that the majority of the protein molecules were linear or looped during translocation and that the electrical forces present under physiologically relevant potentials can unfold proteins. Our results show that the nanopore translocation signals …

Reactivity-Dependent Pcr: Direct, Solution-Phase In Vitro Selection For Bond Formation, David J. Gorin, Adam S. Kamlet, David R. Liu

Chemistry: Faculty Publications

(Figure Presented) In vitro selection is a key component of efforts to discover functional nucleic acids and small molecules from libraries of DNA, RNA, and DNA-encoded small molecules. Such selections have been widely used to evolve RNA and DNA catalysts and, more recently, to discover new reactions from DNA-encoded libraries of potential substrates. While effective, current strategies for selections of bond-forming and bond-cleaving reactivity are generally indirect, require the synthesis of biotin-linked substrates, and involve multiple solution-phase and solid-phase manipulations. In this work we report the successful development and validation of reactivity-dependent PCR (RDPCR), a new method that more directly …

The Role Of Smpb In The Early Stages Of Trans-Translation, Deanna June Cazier

Theses and Dissertations

Ribosomes stall on defective messenger RNA transcripts in eubacteria. Without a mechanism to release stalled ribosomes, these cells would die. Transfer-messenger RNA (tmRNA) and small protein B (SmpB) reactivate stalled ribosomes in a process known as trans-translation. Together, tmRNA and SmpB mimic alanyl-tRNA, entering the A site of stalled ribosomes and accepting transfer of the stalled polypeptide. A portion of tmRNA is then positioned as a template for the ribosome to resume translating. The tmRNA open reading frame encodes a proteolysis tag to mark the aberrant polypeptide for degradation and a stop codon to release the ribosome. How are tmRNA …

Constructed Response Answers In A Multiple-Choice Universe, Carl W. David

Chemistry Education Materials

A scheme is introduced which allows computer readable multiple choice forms used in traditional examinations to be employed for constructed response items.

Structural Evidence For Consecutive Hel308-Like Modules In The Spliceosomal Atpase Brr2, L. Zhang, T. Xu, Corina Maeder, L.-O. Bud, J. Shanks, J. Nix, C. Guthrie, J. A. Pleiss, R. Zhao

Chemistry Faculty Research

Brr2 is a DExD/H-box helicase responsible for U4/U6 unwinding during spliceosomal activation. Brr2 contains two helicase-like domains, each of which is followed by a Sec63 domain with unknown function. We determined the crystal structure of the second Sec63 domain, which unexpectedly resembles domains 4 and 5 of DNA helicase Hel308. This, together with sequence similarities between Brr2's helicase-like domains and domains 1-3 of Hel308, led us to hypothesize that Brr2 contains two consecutive Hel308-like modules (Hel308-I and Hel308-II). Our structural model and mutagenesis data suggest that Brr2 shares a similar helicase mechanism with Hel308. We demonstrate that Hel308-II interacts with …

The Role Of Adenine In Fast Excited-State Deactivation Of Fad: A Femtosecond Mid-Ir Transient Absorption Study, Guifeng Li, Ksenija D. Glusac

Chemistry Faculty Publications

We present a study of excited-state dynamics of two flavin cofactors: flavin-adenine dinucleotide (FAD) and flavin-mononucleotide (FMN). We used femtosecond mid-R transient absorption spectroscopy to study the effect of FAD conformation oil its excited-state behavior. The conformation of FAD was modulated by changing the solvent polarity: in D(2)O, FAD is present predominantly in the "stacked" conformation, in which flavin and adenine moieties are in close proximity to each other, whereas the increased amount of DMSO led to an increased amount of the "open" conformer. FMN served as a model system which lacks adenine. We found that the "stacked" conformer undergoes …

The Use Of Fourier Transform (Ft) Surface-Enhanced Raman Scattering For Biochemical Analysis, Robert Butler Jeffers

Chemistry & Biochemistry Theses & Dissertations

Surface-enhanced Raman scattering (SERS) is a powerful spectroscopic technique that has created exciting opportunities in the field of bioanalytical chemistry, where it combines ultrasensitive detection of biologically relevant molecules with vibrational spectroscopy. Due to the difficulties in preparing reproducible SERS active substrates, SERS has been mainly used as a qualitative tool. In order for SERS to be utilized as a viable tool for quantitative analysis, simple, facile SERS substrates which generate clean, highly reproducible signals must be developed. This dissertation deals with the evaluation of three different methods of SERS that led to the development of a novel substrate for …

Electrospinning Route For The Fabrication Of P-N Junction Using Nanofiber Yarns, A. F. Lotus, S. Bhargava, E. T. Bender, E. A. Evans, R. D. Ramsier, D. H. Reneker, George G. Chase

Chemical, Biomolecular, and Corrosion Engineering Faculty Research

Electrospinning is a simple, versatile, and cost effective method for generating nanoscale fibers, wires, and tubes. Nanowires and nanotubes could be important building blocks for nanoscale electronics, optoelectronics, and sensors as they can function as miniaturized devices as well as electrical interconnects. We report on a simple method to fabricate free standing ceramic nanofiber heterostructures, which exhibit rectifying behavior of a p-n junction.

A Thermodynamic And Kinetic Characterization Of The Solvent Dependence Of The Saddle-Crown Equilibrium Of Cyclotriveratrylene (Ctv) Oxime, David C. French, Marlon R. Lutz Jr., Chichi Lu, Matthias Zeller, Daniel Becker

Chemistry: Faculty Publications and Other Works

The equilibration of the saddle conformer of cyclotriveratrylene (CTV) oxime to the corresponding crown conformer was followed by (1)H NMR in five separate solvents, and kinetic and thermodynamic parameters were determined from the NMR data. The oxime saddle conformers of 3 are favored in CDCl(3) (K(eq) = [saddle]/[crown] = 1.4), whereas the CTV oxime crown conformer 3a is favored in three more polar solvents studied (DMSO-d(6), acetonitrile-d(3), acetone-d(6)). Surprisingly, the CTV oxime crown conformer is also slightly favored in the nonpolar solvent 1,4-dioxane-d(8). These behaviors are discussed in terms of hydrogen bonding, entropy, and possible host-guest considerations. An X-ray crystal …

Probing Single-Molecule Interfacial Geminate Electron−Cation Recombination Dynamics, Yuanmin Wang, Xuefei Wang, H. Peter Lu

Chemistry Faculty Publications

Interfacial electron-cation recombination in zinc-tetra (4-carboxyphenyl) porphyrin (ZnTCPP)/TiO(2) nanoparticle system has been probed at the single-molecule level by recording and analyzing photon-to-photon pair times of the ZnTCPP fluorescence. We have. developed a novel approach to reveal the hidden single-molecule interfacial electron-cation recombination dynamics by analyzing the autocorrelation function and a proposed convoluted single-molecule interfacial electron-cation recombination model. Our results suggest that the fluctuations of the interfacial electron transfer (ET) reactivity modulate the ET cycles as well as the interfacial electron-cation recombination dynamics. On the basis of this model, the single-molecule electron-cation recombination time of ZnTCPP/-TiO(2) system is deduced to be …

Fluorenylidene−Pyrroline Biomimetic Light-Driven Molecular Switches, Laura Rivado-Casas, Diego Sampedro, Pedro J. Campos, Stefania Fusi, Vinicio Zanirato, Massimo Olivucci

Chemistry Faculty Publications

A new family of biomimetic photoactivated molecular switches based in the retinal chromophore is described. Expedient synthesis allows a library of compounds with a different substitution pattern, including chiral substituents, to be obtained. The effect of substitution, solvent, and light source on the photoisomerization step has been assessed. The absorption maximum has been red-shifted ca. 50 nm with respect to related systems and rotation is now easily achieved by using visible light.

Section Abstracts: Chemistry

Virginia Journal of Science

Abstracts of the Chemistry Section for the 87th Annual Meeting of the Virginia Academy of Science, May 27-29, 2009, Virginia Commonwealth University, Richmond Virginia.

Excess Of Glucocorticoid Induces Cardiac Dysfunction Via Activating Angiotensin Ii Pathway, Sreerupa Ghose Roy, Priyanka De, Debasri Mukherjee, Vivek Chander, Aditya Konar, Debasish Bandyopadhyay, Arun Bandyopadhyay

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

Background: Glucocorticoid is widely used as an anti-inflammatory drug in various diseases however excess of it often causes cardiovascular complications. The present study was undertaken to understand the molecular mechanism of glucocorticoid-induced cardiac dysfunction.

Methods: Rats were treated daily with synthetic glucocorticoid, dexamethasone with or without mifepristone or losartan up to 15 days. Hemodynamic parameters were measured by PV-loop method using Millar's instrument. Cardiac remodelling, fibrosis and oxidative stress were monitored after 15 days.

Results: The systolic blood pressure was increased whereas the heart beat and cardiac output (n=6) were decreased by dexamethasone. Dexamethasone caused increase in the heart …