Chemistry Commons^™

Probing The Mechanisms Of Enantioselective Hydrogenation Of Simple Olefins With Chiral Rhodium Catalysts In The Presence Of Anions, Jillian M. Buriak, Jason C. Klein, Deborah Herrington, John A. Osborn

Peer Reviewed Articles

The strong influence of various anions upon the hydrogenation of 2-phenyl-1-butene, catalyzed by chiral rhodium catalysts was investigated. Both sulfonates and halides exert large increases in the enantioselectivity when [Rh{(−)-bdpp}(NBD)]ClO4 (bdpp=2,4-bis(diphenylphosphino)pentane, NBD=2,5-norbornadiene) is used as the catalyst precursor at high pressures (70 atm) of dihydrogen in nonpolar solvents. A dihydride mechanism similar to that for Wilkinson's catalyst [RhCl(PPh3)3] was shown to be operating at both high- and low-pressure conditions through a combination of catalytic studies, 31P, 1H and parahydrogen-induced polarization (PHIP) NMR experiments. With sulfonate and in neat methanol, however, a mechanistic switch takes place from a dihydride route (dihydrogen …

Emissions Of Formaldehyde, Acetic Acid, Methanol, And Other Trace Gases From Biomass Fires In North Carolina Measured By Airborne Fourier Transform Infrared Spectroscopy, Robert J. Yokelson, Jon G. Goode, Darold E. Ward, Ronald A. Susott, Ronald E. Babbitt, D. D. Wade, Issac T. Bertschi, David W. T. Griffith, Wei Min Hao

Chemistry and Biochemistry Faculty Publications

Biomass burning is an important source of many trace gases in the global troposphere. We have constructed an airborne trace gas measurement system consisting of a Fourier transform infrared spectrometer (FTIR) coupled to a “flow-through” multipass cell (AFTIR) and installed it on a U.S. Department of Agriculture Forest Service King Air B-90. The first measurements with the new system were conducted in North Carolina during April 1997 on large, isolated biomass fire plumes. Simultaneous measurements included Global Positioning System (GPS); airborne sonde; particle light scattering, CO, and CO₂; and integrated filter and canister samples. AFTIR spectra acquired within …

A Patching Model For Surface Tension Of Spherical Droplet And Tolman Length. Ii, T.V. Bykov, Xiao Cheng Zeng

Xiao Cheng Zeng Publications

In the framework of density functional theory (DFT), two patching models for the density profile of spherical liquid droplet are developed. The patching is based on analytical expressions of the asymptote of the density profiles. The first model leads to analytic expressions of the Tolman length and the effective rigidity constant, from which the temperature dependence of the Tolman length and effective rigidity constant can be determined. The second model is developed particularly for small spherical droplets, from which the dependence of chemical potential and the surface tension of the droplet on the radius are obtained. The results are compared …

Synthesis And Reactivity Of Acyclic (Pentadienyl)Iron(1+) Cations: Model Studies For The Preparation Of The 8E,10Z,16E,18E-Tetraene Segment Of Macrolactin A, Abdel-Aziz S. El-Ahl, Young Yun, William Donaldson

Chemistry Faculty Research and Publications

The dicarbonyl(1,2-dimethylpentadienyl)triphenylphosphineiron(1+) cation (11) has been prepared from methyl 4-methyl-2E,4E-hexadienoate in four steps. The cation (11) reacts with hydride and carbon nucleophiles in a regiospecific fashion to afford (3-methyl-2E,4Z-diene)iron complexes. Dicarbonyl(3-methyl-7-nitro-2E,4Z-heptadiene)triphenylphosphineiron (15), the product from the reaction of 11 with nitromethane anion, has been utilized as a precursor for nitrile oxide–olefin cyclocondensations.

Langmuir Monolayers As Disordered Solids: Disorder And Elastic Fluctuations In Mesophases , Tadeusz Luty, Craig J. Eckhardt, Jacques Lefebvre

Craig J. Eckhardt Publications

Ordering in Langmuir monolayer mesophases is examined using an approach based on the elastic theory of crystals. Molecular tails are modeled as ‘‘defects’’ grafted onto a two-dimensional elastic medium and are characterized by elastic dipoles. It is assumed that disorder in the parent, LS, phase is due to competition between local (within a domain) and global (hexagonal arrangement of domains) structure. By treating the LS phase as a mixture of rectangular and/or oblique domains (rectangular and/or oblique defects within the two-dimensional elastic medium), density fluctuations due to elastic interactions between domains are analyzed. The correlation function for the elastic dipoles …

17th International Herman F. Mark Symposium: Polypropylene - A Material Of The Future, Otto Vogl, Helga Roder

Emeritus Faculty Author Gallery

No abstract provided.

12. Pierre Sigwalt, Otto Vogl

Emeritus Faculty Author Gallery

No abstract provided.

Thermal Degradation Of Blends Of Polystyrene And Poly(Sodium 4-Styrenesulfonate) And The Copolymer, Poly(Styrene-Co-Sodium 4-Styrenesulfonate), Qiang Yao, Charles Wilkie

Chemistry Faculty Research and Publications

The thermal degradation of blends and copolymers of styrene with styrenesulfonic acid has been studied using thermogravimetric analysis, TGA/FTIR, and cone calorimetry. The blends have enhanced thermal stability relative to virgin polystyrene but there is no enhancement in thermal stability for the copolymers. Apparently, it is necessary to have adjacent sulfonic acid groups in order to permit the formation of a graphite-like char which can provide thermal protection to the polymer. It is necessary to have a good match in degradation temperatures of the two components if one is to have significantly enhanced thermal stability.

Tga/Ftir: An Extremely Useful Technique For Studying Polymer Degradation, Charles A. Wilkie

Chemistry Faculty Research and Publications

Thermogravimetric analysis coupled to Fourier transform infrared spectroscopy, TGA/FTIR, has been used to probe the degradation of several polymeric systems. These include poly(methyl methacrylate) in the presence of various additives, graft copolymers of acrylonitrile-butadiene-styrene and styrene-butadiene with sodium methacrylate and styrene with acrylonitrile, blends of styrene-butadiene block copolymers with poly(vinylphosphonic acid) and poly(vinylsulfonic acid), and cross-linked polystyrenes. Additives may interact with poly(methyl methacrylate) by coordination to the carbonyl oxygen to a Lewis acid and the subsequent transfer of an electron from the polymer chain to the metal atom or by the formation of a radical which can trap the degrading …

A Study Of The Thermal Properties Of Peti-5/Im7, Yan Tang

Masters Theses & Specialist Projects

PETI-5 (Phenylethynyl-terminated polyimide) is a substance that shows a great deal of potential in the high-speed aircraft and the aerospace industry. PETI-5 has been used for the High Speed Civil Transport (HSCT), a supersonic passenger aircraft in development at NASA. In this project, four staging samples, one fresh sample, one fully cured sample and one partially cured sample were analyzed and compared using thermal analytical techniques. The sample staged at 450°F with full vacuum showed the highest thermal properties among four staging samples. The results indicated that vacuum is helpful in improving the thermal stability of PETI-5. The mechanism of …

Further Studies On Fire Retardant Polystyrene By Friedel–Crafts Chemistry, Zhitao Wang, David D. Jiang, Charles Wilkie, Jeffery W. Gilman

Chemistry Faculty Research and Publications

The combination of a copolymer of 4-vinylbenzyl alcohol and styrene with 2-ethylhexyldiphenylphosphate (DPP) and with metal chlorides has been studied by TGA, radiative gasification, Cone Calorimetry, and oxygen index measurements. Evidence is presented in support of a cross-linking reaction with the additives and the copolymer, which proceeds through a Friedel–Crafts mechanism. This approach reduces the peak heat release rate (HRR) by 60% as measured in the Cone Calorimeter. There is a significant reduction in the mass loss rate during the thermal degradation, and evidence of char formation is observed in the radiative gasification experiments.

Molecular-Dynamics Study Of Phase Transitions In Alkali Azides, M. M. Ossowski, John R. Hardy, Robert W. Smith

Physics Faculty Publications

An account is presented of our studies of the order-disorder phase transitions in KN₃, RbN₃, and CsN₃. These are based on parameter-free interionic potentials based on the Gordon-Kim modified electron-gas formalism extended to molecular ions. We performed static structural relaxations and supercell molecular dynamics and predicted with reasonable accuracy the temperatures for the onset of the transitions. In particular, we address the question of how the N₃^- ions reorient to yield the transitions. We found the existence of NaCl-type high-temperature phases in disordered KN₃ and RbN₃ and argue that this …

Enantioseparation Of Alkylaryl Sulfoxides Using Capillary Zone Electrophoresis, Chad Snyder

Masters Theses & Specialist Projects

Alkylaryl sulfoxides possess a chiral sulfur atom easily identifiable by capillary zone electrophoresis (CZE). Separation of chiral alkylaryl sulfoxides has already been accomplished by modified method of CZE known as micellar electrokinetic chromatography (MEKC). However, no articles have been published on the enantioseparation of alkylaryl sulfoxides using capillary zone electrophoresis.

A series of sulfoxides were synthesized, purified and identified via NMR. Enantioseparation was performed using CZE employing a 10 mmol. Phosphate buffer (pH 4.0, 25% acetonitrile, 2% sulfated-β-cyclodextrin). Synthesis of these sulfoxides will be presented along with the results of the procedure’s optimization. Separation of the sulfoxide enanitomers relies on …

Subsidence, Mixing, And Denitrification Of Arctic Polar Vortex Air Measured During Polaris, M. Rex, R. J. Salawitch, G. C. Toon, B. Sen, J. J. Margitan, G. B. Osterman, J. F. Blavier, R. S. Gao, Stephen G. Donnelly Ph.D., E. Keim, J. Neuman, D. W. Fahey, C. R. Webster, D. C. Scott, R. L. Herman, R. D. May, E. J. Moyer, M. R. Gunson, F. W. Irion, A. Y. Chang, C. P. Rinsland, T. P. Bui

Chemistry Faculty Publications

We determine the degree of denitrification that occurred during the 1996-1997 Arctic winter using a technique that is based on balloon and aircraft borne measurements of NOy, N2O, and CH4. The NOy/N2O relation can undergo significant change due to isentropic mixing of subsided vortex air masses with extravortex air due to the high nonlinearity of the relation. These transport related reductions in NOy can be difficult to distinguish from the effects of denitrification caused by sedimentation of condensed HNO3. In this study, high-altitude balloon measurements are used to define the properties of air masses that later descend in the polar …

A Study Of Cartenoids Uptake In Human Subjects And Their Metabolites, Yin Chen

FIU Electronic Theses and Dissertations

In this study, a metabolite of lutein was tentatively shown to result from oxidation of lutein by performing a reduction reaction. The result is important evidence that supports the hypothesis that lutein functions as an antioxidant in the human body. In a long term of dietary supplementary study of zeaxanthin in a human subject, the expected increase in the serum concentration of the supplement was accompanied by an increase in serum concentration of several metabolites. A six-month low dose dietary supplementation with lutein in 2 2 human subjects was performed with an expected result in increase of the serum concentration …

Stereoselective Determination Oftrihexyphenidyl In Human Serum By Lc–Esi–Ms, Vladimı́R Čápka, Yan Xu, Yong Hong Chen

Chemistry Faculty Publications

The antiparkinsonian drug trihexyphenidyl (THP) is currently manufactured and administered as a racemate. However, stereochemistry can play significant role in the drug’s pharmacokinetics, biotransformation, metabolism, interaction with cellular and tissue components and overall effect on human body. It is necessary to consider such a drug as a mixture of two compounds (drug enantiomers), with their own effect on the human body. The present paper describes a simple and sensitive LC–MS method for the stereoselective determination of THP in human serum. In this study, the sample was prepared by a solid-phase extraction (SPE) procedure. The enantiomer separation was done using native …

13. Josef Schurz, Otto Vogl

Emeritus Faculty Author Gallery

No abstract provided.

Confined Water In Hydrophobic Nanopores: Dynamics Of Freezing Into Bilayer Ice, Jan Slovak, Kenichiro Koga, Hideki Tanaka, Xiao Cheng Zeng

Xiao Cheng Zeng Publications

Molecular dynamics simulations for a thin film of water confined to a slit nanopore are performed in order to investigate the dynamic process of crystallization of the system. The system upon freezing creates a bilayer ice crystal composed of two layers of hexagonal rings. We perform one simulation at T=257 K during which the system remains a supercooled liquid state, and another one at T=253 K during which the system freezes. Many patterns of molecular arrangement are found upon freezing, and an account is given of the origin of multiple peaks in the distributions of binding energy and …

Imaging Point Defects In A Liquid Environment: A Model Afm Study, Kenichiro Koga, Xiao Cheng Zeng

Xiao Cheng Zeng Publications

Effects of the liquid on atomic force microscopy (AFM) imaging are examined for a model system consisting of a hexagonal flake of seven Lennard-Jones (LJ) atoms as a multiatom tip, a monolayer of LJ crystal containing a single point defect as a substrate, and three-site model water as the liquid. A previous simulation [Koutsos et al., Europhys. Lett. 26, 103 (1994)] has shown that the true atomic resolution of a point defect cannot be achieved in vacuum by use of the multiatom tip. Here we examine the feasibility of such atomic resolution when both the tip and substrate are immersed …

First Example Of A Double Stranded Helicate With Square-Planar Coordination For The Metal, Marc Zimmer, Derek A. Tocher, Goutam K. Patra, Jnan P. Naskar, Dipankar Datta

Chemistry Faculty Publications

Reaction of dichlorobis(benzildihydrazone)Ni(II) with biacetylmonoxime in 1:4 molar proportion generates diamagnetic Ni₂L₂ where LH₂ (H = dissociable oximato proton) is HO-N=C(CH₃)-C(CH₃)=N-N=C(C₆H₅)-C(C₆H₅)=N-N=C(CH₃)-C(CH₃)=N-OH. Our molecular mechanics calculations show that Ni₂L₂ is an unprecedented double stranded homotopic helicate with the metal ion having a square-planar N₄ coordination.

Cationic 5,10,15,20-Tetrakis(N-Methylpyridinium-4-Yl)Porphyrin Fully Intercalates At 5 '-Cg-3 ' Steps Of Duplex Dna In Solution, Anton B. Guliaev, Neocles B. Leontis

Chemistry Faculty Publications

The interaction of 5,10,15,20-tetrakis(N-methylpyridinium-4-yl)p (T4MPyP(4+)) with the oligonucleotide DNA duplex [d(GCACGTGC)](2) was studied by two-dimensional (1)H NMR spectroscopy, optical absorbance, circular dichroism, and molecular dynamics simulation employing particle mesh Ewald methods. T4MPyP(4+) is one of the largest aromatic molecules for which intercalative binding to DNA has been proposed, although this has been called into question by recent X-ray crystallographic work [Lipscomb et al. (1996) Biochemistry 35, 2818-2823]. T4MPyP(4+) binding to [d(GCACGTGC)](2) produced a single set of (mostly) upfield-shifted DNA resonances in slow exchange with the resonances of the free DNA. Intra- and intermolecular NOEs observed in the complex showed that …

Stabilization Of Polystyrene By Friedel-Crafts Chemistry: Effect Of Position Of Alcohol And The Catalyst, Jin Zhu, Michael A. Mckinney, Charles Wilkie

Chemistry Faculty Research and Publications

Polystyrene has been copolymerized with 4-vinylbenzyl alcohol, 4-(2-hydroxyethyl)styrene, and 4-(3-hydroxypropyl)styrene and it has been shown that thermal cross-linking of these copolymers is dependent upon the alcohol content. When the alcohol content is low, no thermal cross-linking is observed. When various phosphate esters are present as catalysts with these low alcohol content copolymers, cross-linking is observed at temperatures of about 250°C but not at lower temperatures. Cross-linking enhances the thermal stability of the copolymers. Studies of the thermal stability of the copolymers and their blends with the catalysts have been performed using thermogravimetric analysis and thermogravimetric analysis coupled to Fourier transform …

Method Of Storing Active Zero Valent Zinc Metal, Reuben D. Rieke

Chemistry Department: Faculty Publications

A novel Zerovalent Zinc species and an organozinc reagent are disclosed. The Zerovalent Zinc species is directly pro duced by reaction of a reducing agent on a Zinc Salt, preferably Zn(CN). The organozinc regent results from the reaction of the Zerovalent Zinc species and an organic compound having one or more stable anionic leaving groups. These organozinc reagents include a wide spectrum of functional groups in the organic radical, and are useful in a variety of reactions Schemes.

Macrocyclic Antibiotics As Separation Agents, Daniel W. Armstrong

Chemistry Faculty Research & Creative Works

Macrocyclic antibiotics having ring structures with at least 10 members act as separation agents in crystallization, precipitation, filtration, electrophoresis and chromatography. The macrocyclic antibiotics include ansamacrolides, macrolides, macrocyclic peptides, polyenes and derivatives thereof. The process has been found to be especially advantageous for separation of optical isomers by electrophoresis and chromatography.

14. Paolo Galli, Otto Vogl, Anna Maria Marcon-Galli

Emeritus Faculty Author Gallery

No abstract provided.

Validity Of The Independent-Particle Approximation In X-Ray Photoemission: The Exception, Not The Rule, D. Hansen, Oliver Hemmers, H. Wang, Dennis W. Lindle, P. Focke, I. A. Sellin, Clemens Heske, H. S. Chakraborty, P. C. Deshmukh, S. T. Manson

Environmental Studies Faculty Publications

A combined experimental and theoretical study of argon valence photoionization illustrates the discovery of the broad lack of validity of the independent-particle approximation (IPA) for x-ray photoemission. In addition to previously known breakdowns of the IPA, which are limited to high photon energies and regions very near threshold, the observed breakdown in photoionization at intermediate energies demonstrates generally that the IPA is valid only in very restricted domains. These restrictions are expected to be relevant throughout the periodic table, with consequences for a wide variety of applications.

Pretransitional Behavior Above The Nematic-Isotropic Phase Transition Of An Auxetic Trimer Liquid Crystal, Daeseung Kang, Milind P. Mahajan, Shiyong Zhang, Rolfe G. Petschek, Charles Rosenblatt, Chaobin He, Puwei Lu, A.C. Griffin

Faculty Publications

Static Light scattering and electric field-induced Kerr measurements were performed above the nematic-isotropic phase transition of a terminal-lateral-lateral-terminal negative Poisson ratio trimer. Far both measurements the inverse susceptibility was observed to be nearly linear with temperature, a result inconsistent with our previously reported Kerr data [Phys. Rev. E 58, 2041 (1998)]. [S1063-651X(99)11010-9].

Effect Of Interfacial Mobility On Flexural Strength And Fracture Toughness Of Glass/Epoxy Laminates, T. W. H. Wang, Frank D. Blum, Lokeswarappa R. Dharani

Chemistry Faculty Research & Creative Works

Mechanical testing and surface fractography were used to characterize the fracture of E-glass fiber reinforced epoxy composites as a function of the silane coupling agent used. gamma-Aminopropyltriethoxysilane (APS) and delta-aminobutyltriethoxysilane (ABS) were used because these have been shown to have different interfacial mobilities at multilayer coverage. The values of the properties studied generally increased from untreated c, as determined from a Mode I translaminar fracture toughness tests, for the untreated composites (10.5 ± 0.4 kJ/m2) was lower than that for the ABS-treated composites (14.3 ± 2.1 kJ/m2) which was lower than that for the APS-treated composites (17.1 ± 2.4 kJ/m2). …

Enantioselective Synthesis Of Dual Serotonergic Azanoradamantane Sc-52491, Daniel Becker, Robert K. Husa, Alan E. Moormann, Clara I. Villamil

Chemistry: Faculty Publications and Other Works

A racemic synthesis of azanoradamantane (±)-3 was accomplished via Yamamoto's MAD-catalyzed Diels-Alder protocol. Subsequently, a scalable asymmetric synthesis of azanoradamantane benzamide SC-52491 was carried out employing Helmchen's asymmetric Diels-Alder methodology to construct all four contiguous asymmetric centers with the correct relative stereochemistry and in 99.3% e.e.

An Xps Study Of The Radiation-Induced Effect On The Thermal Degradation And Charring Of Butadiene And Its Copolymers, Jianwei Hao, Shaoli Wu, Charles Wilkie, Jianqi Wang

Chemistry Faculty Research and Publications

A pseudo-in-situ XPS approach shows that cross-linking induced by irradiation may lead to char formation even though it shows only a small or no effect on the onset temperature of degradation.