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2003

Chemistry

Chemistry Faculty Research and Publications

Articles 1 - 17 of 17

Full-Text Articles in Physical Sciences and Mathematics

Investigation Of Nanodispersion In Polystyrene-Montmorillonite Nanocomposites By Solid State Nmr, Serge Bourbigot, David L. Vanderhart, Jeffery W. Gilman Sr., Walid Awad, Rick D. Davis, Alexander B. Morgan, Charles A. Wilkie Dec 2003

Investigation Of Nanodispersion In Polystyrene-Montmorillonite Nanocomposites By Solid State Nmr, Serge Bourbigot, David L. Vanderhart, Jeffery W. Gilman Sr., Walid Awad, Rick D. Davis, Alexander B. Morgan, Charles A. Wilkie

Chemistry Faculty Research and Publications

Nanocomposites result from combinations of materials with vastly different properties in the nanometer scale. These materials exhibit many unique properties such as improved thermal stability, reduced flammability, and improved mechanical properties. Many of the properties associated with polymer–clay nanocomposites are a function of the extent of exfoliation of the individual clay sheets or the quality of the nanodispersion. This work demonstrates that solid-state NMR can be used to characterize, quantitatively, the nanodispersion of variously modified montmorillonite (MMT) clays in polystyrene (PS) matrices. The direct influence of the paramagnetic Fe3, embedded in the aluminosilicate layers of MMT, on polymer protons within …

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The Role Of The Dielectric Barrier In Narrow Biological Channels: A Novel Composite Approach To Modeling Single-Channel Currents, Artem B. Mamonov, Rob D. Coalson, Abraham Nitzan, Maria G. Kurnikova Jun 2003

The Role Of The Dielectric Barrier In Narrow Biological Channels: A Novel Composite Approach To Modeling Single-Channel Currents, Artem B. Mamonov, Rob D. Coalson, Abraham Nitzan, Maria G. Kurnikova

Chemistry Faculty Research and Publications

A composite continuum theory for calculating ion current through a protein channel of known structure is proposed, which incorporates information about the channel dynamics. The approach is utilized to predict current through the Gramicidin A ion channel, a narrow pore in which the applicability of conventional continuum theories is questionable. The proposed approach utilizes a modified version of Poisson-Nernst-Planck (PNP) theory, termed Potential-of-Mean-Force-Poisson-Nernst-Planck theory (PMFPNP), to compute ion currents. As in standard PNP, ion permeation is modeled as a continuum drift-diffusion process in a self-consistent electrostatic potential. In PMFPNP, however, information about the dynamic relaxation of the protein and the …

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Synthesis Of Tin Oxide Nanocrystalline Phases Via Use Of Tin (Ii) Halide Precursors, Hongmei Deng, Frank K. Lamelas, Jeanne Hossenlopp May 2003

Synthesis Of Tin Oxide Nanocrystalline Phases Via Use Of Tin (Ii) Halide Precursors, Hongmei Deng, Frank K. Lamelas, Jeanne Hossenlopp

Chemistry Faculty Research and Publications

Nanocrystalline tin oxides are synthesized via precipitation from heated solutions as well as from a novel above-solution vapor deposition route that occurs at low temperatures and atmospheric pressure. Crystalline phases are characterized via powder X-ray diffraction. Samples precipitated from reactions of SnCl2 are found to exist primarily as mixtures of tetragonal SnO and tetragonal SnO2 or tetragonal SnO2 and tin(II) oxyhydroxide (Sn6O4- (OH)4), depending on reaction conditions. A mixed tin(II)/tin(IV) sample is shown to produce a rarely observed form of the intermediate oxide Sn3O4 upon annealing in air at 600 °C. SnBr2 exclusively forms tetragonal SnO2 via precipitation. Variation in …

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Kinetic And Spectroscopic Characterization Of The H178a Methionyl Aminopeptidase From Escherichia Coli, Alicja J. Copik, Sabina I. Swierczek, W. Todd Lowther, Ventris M. D'Souza, Brian W. Matthews, Richard C. Holz May 2003

Kinetic And Spectroscopic Characterization Of The H178a Methionyl Aminopeptidase From Escherichia Coli, Alicja J. Copik, Sabina I. Swierczek, W. Todd Lowther, Ventris M. D'Souza, Brian W. Matthews, Richard C. Holz

Chemistry Faculty Research and Publications

To gain insight into the role of the strictly conserved histidine residue, H178, in the reaction mechanism of the methionyl aminopeptidase from Escherichia coli (EcMetAP-I), the H178A mutant enzyme was prepared. Metal-reconstituted H178A binds only one equivalent of Co(II) or Fe(II) tightly with affinities that are identical to the WT enzyme based on kinetic and isothermal titration calorimetry (ITC) data. Electronic absorption spectra of Co(II)-loaded H178A EcMetAP-I indicate that the active site divalent metal ion is pentacoordinate, identical to the WT enzyme. These data indicate that the metal binding site has not been affected by altering H178. …

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Co-Catalytic Metallopeptidases As Pharmaceutical Targets, Richard C. Holz, Krzysztof P. Bzymek, Sabina I. Swierczek Apr 2003

Co-Catalytic Metallopeptidases As Pharmaceutical Targets, Richard C. Holz, Krzysztof P. Bzymek, Sabina I. Swierczek

Chemistry Faculty Research and Publications

Understanding the reaction mechanism of co-catalytic metallopeptidases provides a starting point for the design and synthesis of new molecules that can be screened as potential pharmaceuticals. Many of the enzymes that contain co-catalytic metallo-active sites play important roles in cellular processes such as tissue repair, protein maturation, hormone level regulation, cell-cycle control and protein degradation. Therefore, these enzymes play central roles in several disease states including cancer, HIV, stroke, diabetes, bacterial infections, neurological processes, schizophrenia, seizure disorders, and amyotrophic lateral sclerosis. The mechanism of AAP, an aminopeptidase from Aeromonas proteolytica, is one of the best-characterized examples of a metallopeptidase …

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Regio- And Stereoselective Ruthenium Catalyzed Hydrovinylation Of 1,3-Dienes: Application To The Generation Of A 20s-Steroidal Sidechain, Zhengjie He, Chae S. Yi, William A. Donaldson Apr 2003

Regio- And Stereoselective Ruthenium Catalyzed Hydrovinylation Of 1,3-Dienes: Application To The Generation Of A 20s-Steroidal Sidechain, Zhengjie He, Chae S. Yi, William A. Donaldson

Chemistry Faculty Research and Publications

The addition of ethylene to 1,3-dienes and 1-vinylcycloalkenes, catalyzed by two ruthenium complexes, proceeds in a regioselective fashion to afford 3-methyl-1,4-dienes as products. For a steroidal-based 1-vinylcycloalkene, the addition is stereospecific, giving a product with a 20(S) configuration.

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Synthesis Of (+)-Decarestrictine L, Julie Lukesh, William Donaldson Mar 2003

Synthesis Of (+)-Decarestrictine L, Julie Lukesh, William Donaldson

Chemistry Faculty Research and Publications

A synthesis of (+)-decarestrictine L 1, a cholesterol biosynthesis inhibitory metabolite isolated from Penicillium simplicissimum, is described. Beginning from tri-O-acetyl- -glucal, alkylation with trimethylaluminum introduced the axial methyl group at C-2 in a stereoselective fashion. Chain extension at the C-6 carbon was accomplished by generation of the primary tosylate, followed by displacement with cyanide anion. The synthesis of (+)-1 was completed in 13 steps and 6.3% overall yield.

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A Stibonium-Modified Clay And Its Polystyrene Nanocomposite, Dongyan Wang, Charles A. Wilkie Jan 2003

A Stibonium-Modified Clay And Its Polystyrene Nanocomposite, Dongyan Wang, Charles A. Wilkie

Chemistry Faculty Research and Publications

Triphenylhexadecylstibonium trifluoromethylsulfonate has been prepared and ion-exchanged with sodium montmorillonite to obtain a new organically-modified clay. The clay has higher thermal stability than an ammonium clay; only a portion of the alkyl chain is lost during degradation and all of the antimony is retained. This clay has been used to prepare a polystyrene nanocomposite in which the clay is not uniformly distributed throughout the polymer. Nonetheless the polymer does insert into the clay layers and the d-spacing of the clay expands from 2.0 to 3.0 nm. The enhanced thermal stability of this system may mean that it could be …

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Iron-Mediated Preparation Of Vinylcyclopropanes. Scope, Mechanism, And Applications, Young K. Yun, Kamil Godula, Yeyu Cao, William A. Donaldson Jan 2003

Iron-Mediated Preparation Of Vinylcyclopropanes. Scope, Mechanism, And Applications, Young K. Yun, Kamil Godula, Yeyu Cao, William A. Donaldson

Chemistry Faculty Research and Publications

The addition of stabilized carbon nucleophiles to tricarbonyl(1-methoxycarbonylpentadienyl)iron(1+) cation (1a) proceeds via attack at C2 on the face of the ligand opposite the Fe(CO)3 group to generate tricarbonyl(pentenediyl)iron complexes 2. Oxidation of complexes 2 affords vinylcyclopropanecarboxylates in good yield. In general, the relative stereochemistry about the cyclopropane ring reflects reductive elimination with retention of configuration. In cases where the C2 substituent is bulky (i.e., 2b) the major cyclopropane product 9b represents ring closure with inversion at C3. A mechanism involving π−σ−π rearrangement of the initially oxidized (pentenediyl)iron species is proposed to account for these results. …

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An Xps Investigation Of Thermal Degradation And Charring On Poly(Vinyl Chloride)–Clay Nanocomposites, Jianxin Du, Dongyan Wang, Charles A. Wilkie, Jiangqi Wang Jan 2003

An Xps Investigation Of Thermal Degradation And Charring On Poly(Vinyl Chloride)–Clay Nanocomposites, Jianxin Du, Dongyan Wang, Charles A. Wilkie, Jiangqi Wang

Chemistry Faculty Research and Publications

More information concerning the thermal degradation and charring of nanocomposites of poly(vinyl chloride), dioctyl phthalate and clay has been obtained by the use of X-ray photoelectron spectroscopy and the acquisition of the carbon (C1s), chlorine (Cl2p), and oxygen (O1s) spectra. In the cases of polystyrene–clay and poly(methyl methacrylate)–clay nanocomposites, it has been shown that the clay migrates to the surface as the temperature is raised and the polymer degrades, thereby confirming the barrier properties as a mechanism by which these materials function. For PVC–clay nanocomposites the surface at high temperatures is dominated by carbon, and not the oxygen of the …

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Flame Retardancy Of Polystyrene Nanocomposites Based On An Oligomeric Organically-Modified Clay Containing Phosphate, Xiaoxia Zheng, Charles A. Wilkie Jan 2003

Flame Retardancy Of Polystyrene Nanocomposites Based On An Oligomeric Organically-Modified Clay Containing Phosphate, Xiaoxia Zheng, Charles A. Wilkie

Chemistry Faculty Research and Publications

Novel modified clays, which may enable the formation of flame retarded polystyrene nanocomposites by melt or solution blending, have been prepared using an ammonium salt which contains an oligomeric material consisting of vinylbenzyl chloride, styrene and vinyl phosphate reacting with dimethylhexadecylamine. These nanocomposites have been characterized by X-ray diffraction, transmission electron microscopy, thermogravimetric analysis, cone calorimetry and the evaluation of mechanical properties. Melt blending is an effective, economical way to produce intercalated nanocomposites with greatly reduced peak heat release rate and a decreased total heat release; the polymer does not all undergo thermal degradation.

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Nanocomposites Based On Poly (Ε-Caprolactone) (Pcl)/Clay Hybrid: Polystyrene, High Impact Polystyrene, Abs, Polypropylene And Polyethylene, Xiaoxia Zheng, Charles A. Wilkie Jan 2003

Nanocomposites Based On Poly (Ε-Caprolactone) (Pcl)/Clay Hybrid: Polystyrene, High Impact Polystyrene, Abs, Polypropylene And Polyethylene, Xiaoxia Zheng, Charles A. Wilkie

Chemistry Faculty Research and Publications

Nanocomposites of polystyrene, high impact polystyrene, acrylonitrile–butadiene–styrene terploymer, polypropylene and polyethylene have been prepared using an organically-modified clay that contains polycaprolactone—PCL-modified clay. Depending upon the mode of preparation of the PCL-modified clay, all three types of nanocomposites, immiscible, intercalated and exfoliated, may be produced. The materials have been characterized by X-ray diffraction, transmission electron microscopy, cone calorimetry, thermogravimetric analysis, and the evaluation of mechanical properties.

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Preparation And Flammability Properties Of Polyethylene-Clay Nanocomposites, Jinguo Zhang, Charles A. Wilkie Jan 2003

Preparation And Flammability Properties Of Polyethylene-Clay Nanocomposites, Jinguo Zhang, Charles A. Wilkie

Chemistry Faculty Research and Publications

Polyethylene (PE)–clay nanocomposites have been prepared using melt blending in a Brabrender mixer. X-ray diffraction and transmission electron microscopy were used to characterize the nano-structure of these composites while the thermal stability was evaluated from thermogravimetric analysis and the flammability parameters using cone calorimetry. It is found that the PE–clay nanocomposites have a mixed immiscible-intercalated structure and there is better intercalation when maleic anhydride is combined with the polymer and clay to be melt blended. The reduction in peak heat release rate is 30–40%.

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In Situ Reactive Blending To Prepare Polystyrene-Clay And Polypropylene-Clay Nanocomposites, Dongyan Wang, Charles A. Wilkie Jan 2003

In Situ Reactive Blending To Prepare Polystyrene-Clay And Polypropylene-Clay Nanocomposites, Dongyan Wang, Charles A. Wilkie

Chemistry Faculty Research and Publications

Nanocomposites of polystyrene and polypropylene with organically-modified clay may be prepared by melt blending in a Brabender mixer the clay and the polymer. The presence of maleic anhydride increases the likelihood of nanocomposite formation for polystyrene but is less important for polypropylene. The materials that result are immiscible materials, in that the clay is not uniformly distributed throughout the polymer matrix, but there is polymer inserted between the clay layers. The results from cone calorimetry suggest that nanocomposite formation has occurred, since there is a significant reduction in the peak heat release rate.

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Synergy Between Conventional Phosphorus Fire Retardants And Organically-Modified Clays Can Lead To Fire Retardancy Of Styrenics, Grace Chigwada, Charles A. Wilkie Jan 2003

Synergy Between Conventional Phosphorus Fire Retardants And Organically-Modified Clays Can Lead To Fire Retardancy Of Styrenics, Grace Chigwada, Charles A. Wilkie

Chemistry Faculty Research and Publications

Polystyrene–clay nanocomposites combined with phosphorous-containing fire retardants have been prepared and used to explore the thermal stability and mechanical properties of the polymer formed. The amounts of fire retardants and clay used were varied to study the effect of each on thermal stability and mechanical properties of the polymer. The samples were prepared by bulk polymerization and analyzed by X-ray diffraction, thermogravimetric analysis, cone calorimetry, Fourier Transform infrared spectroscopy and the evaluation of mechanical properties. The thermal stability of the polymers is enhanced by the presence of the phosphorus-containing fire retardants.

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Exfoliated Poly(Methyl Methacrylate) And Polystyrene/ Nanocomposites Occur When The Clay Cation Contains A Vinyl Monomer, Shengpei Su, Charles A. Wilkie Jan 2003

Exfoliated Poly(Methyl Methacrylate) And Polystyrene/ Nanocomposites Occur When The Clay Cation Contains A Vinyl Monomer, Shengpei Su, Charles A. Wilkie

Chemistry Faculty Research and Publications

The bulk polymerization of methyl methacrylate and styrene in the presence of an organically modified clay containing a vinyl group that can be involved in the polymerization produces exfoliated nanocomposites. These nanocomposites have been characterized by X-ray diffraction, transmission electron microscopy, thermogravimetric analysis, mechanical properties, and cone calorimetry. The onset temperature of thermal degradation increases with the mechanical properties. The peak heat release rate is significantly reduced for nanocomposites containing 3 or 5% clay. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 1124–1135, 2003

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Molecular Recognition Of No/No+ Via Multicenter (Charge-Transfer) Binding To Bridged Diarene Donors. Effect Of Structure On The Optical Transitions And Complexation Thermodynamics, Sergiy V. Rosokha, Sergey V. Lindeman, Rajendra Rathore, Jay K. Kochi Jan 2003

Molecular Recognition Of No/No+ Via Multicenter (Charge-Transfer) Binding To Bridged Diarene Donors. Effect Of Structure On The Optical Transitions And Complexation Thermodynamics, Sergiy V. Rosokha, Sergey V. Lindeman, Rajendra Rathore, Jay K. Kochi

Chemistry Faculty Research and Publications

Bridged diarenes form very strong [1:1] complexes with nitrosonium/nitric oxide in which the NO moiety is optimally sandwiched in the cleft between a pair of cofacial aromatic rings which act as a molecular “Venus flytrap”. The spectral features of these associates are generally similar to those for [1:1] and [2:1] nitrosonium complexes with mononuclear alkyl-substituted benzenes, and they are appropriately described within the LCAO molecular-orbital methodology and the Mulliken (charge-transfer) formulation of donor/acceptor electronic transitions. The thermodynamics study indicates that the efficient binding is determined by (i) the close matching of the donor/acceptor redox potentials and (ii) the ability of …

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