Chemistry Commons^™

No(Y) Partitioning From Measurements Of Nitrogen And Hydrogen Radicals In The Upper Troposphere, E. R. Keim, S. A. Mckeen, R. S. Gao, Stephen G. Donnelly Ph.D., R. C. Wamsley, L. A. Del Negro, D. W. Fahey, T. F. Hanisco, E. J. Lanzendorf, M. H. Proffitt, J. J. Margitan, E. J. Hintsa, L. Jaeglé, C. R. Webster, R. D. May, D. C. Scott, R. J. Salawitch, J. C. Wilson, C. T. Mcelroy, E. L. Atlas, F. Flocke, T. P. Bui

Chemistry Faculty Publications

Recent studies using NO, NO(y), OH and HO2 (HO(X)) observations have postulated acetone and convection of peroxides as significant sources of HO(X) in the upper troposphere (UT). This work focuses on the effect these additional HO(X) sources have on the modeled NO(y) partitioning and comparisons of the modeled NO(x)/NO(y) ratio to observations. The measured NO(x)/NO(y) ratio is usually much higher than predicted regardless of the presence of acetone in the model. The exception occurs for air parcels having low NO(y) and O3 values. For these air parcels the measured NO(x)/NO(y) ratio is much lower than the calculated ratio unless acetone …

Observation And Application Of Optical Interference And Diffraction Effects In Reflection From Photochemically Fabricated Gaussian Interfaces, Lynne Koker, Kurt W. Kolasinski

Chemistry Faculty Publications

No abstract provided.

Dynamics Of Acrylic Coupling Agents At Interfaces Of Composites, Hyoryoon Jo, Frank D. Blum

Chemistry Faculty Research & Creative Works

Most applications of polymers involve composites, wherein a polymer is used in conjunction with another material, typically a solid fiber or filler. A coupling agent can enhance the adhesion between a polymer matrix and an inorganic filler. Organofunctional silanes, RSiX are often used as coupling agents. The methoxy or ethoxy group, X, can typically be hydrolyzed with water and an acid or a base catalyst in a protic solvent. The silanol groups of a hydrolyzed coupling agent can condense with other silanol groups from a glass surface, while the alkyl group, R, blends physically or bonds chemically to the polymer …

Soft X-Ray Photochemistry At The L₂,₃-Edges In K₃[Fe(Cn)₆], [Co(Acac)₃] And [Cp₂Fe][Bf₄], David Collison, Catherine David Garner, Catherine M. Mcgrath, J. Fred Willem Mosselmans, Mark D. Roper, Jon M. W Seddon, Ekkehard Sinn, Nigel A. Young

Chemistry Faculty Research & Creative Works

Soft X-ray photoreduction has been observed in K3[Fe(CN)6], [Co(acac)3] and [Cp2Fe][BF4].

Separation Of Enantiomers By Capillary Electrophoresis Using Pentosan Polysulfate, Xiande Wang, Jauh Tzuoh Lee, Daniel W. Armstrong

Chemistry Faculty Research & Creative Works

Pentosan polysulfate, a semisynthetic polysaccharide, was employed as a chiral un buffer additive in capillary electrophoresis. Twenty-eight racemic analytes were resolved. The separations were successful only at low pH when the analytes were significantly protonated. This suggests that ionic interactions were the dominant associative interactions between the anionic pentosan polysulfate and the positively charged analytes. Compared to other linear, carbohydrate-based chiral selectors (i.e., chondroitin sulfates, heparin and dextran sulfate) pentosan polysulfate has some characteristics common of anionic polysaccharides; yet it has several differences in its structure and properties which account for its unusual enantioselectivity. The effects of pH, concentration of …

Magnetic And Crystallographic Properties Of Lani₅₋ₓfex, C. Tan, Oran Allan Pringle, Mingxing Chen, William B. Yelon, J. Gebhardt, Naushad Ali, C. Y. Tai, G. K. Marasinghe, George Daniel Waddill, William Joseph James

Physics Faculty Research & Creative Works

No abstract provided.

Optimisation Studies In A Batch Pharmaceutical Company, Sarah Fitzgerald

Theses

This thesis outlines a collaborative project between industry and academia based on a short term research contract.

In the past in Eli Lilly, process optimisation in a multi-purpose, modular building had been mainly confined to equipment commissioning and new product development. It was necessary to embark upon an exercise to develop an optimisation programme m order to meet the increased requirements and demands of the building. Increased market demands, through the introduction of over-the-counter (OTC) drugs, and the demand for cycle time reduction through the expiry of existing patents, made the need for optimisation inevitable.

The purpose of this thesis …

A Comparison Of Observations And Model Simulations Of NoX/NoY In The Lower Stratosphere, R. S. Gao, D. W. Fahey, L. A. Del Negro, Stephen G. Donnelly Ph.D., E. R. Keim, J. A. Neuman, E. Teverovskaia, P. O. Wennberg, T. F. Hanisco, E. J. Lanzendorf, M. H. Proffitt, J. J. Margitan, J. C. Wilson, J. W. Elkins, R. M. Stimpfle, R. C. Cohen, C. T. Mcelroy, T. P. Bui, R. J. Salawitch, S. S. Brown, A. R. Ravishankara, R. W. Portmann, M. K.W. Ko, D. K. Weisenstein, P. A. Newman

Chemistry Faculty Publications

Extensive airborne measurements of the reactive nitrogen reservoir (NOy) and its component nitric oxide (NO) have been made in the lower stratosphere. Box model simulations that are constrained by observations of radical and long-lived species and which include heterogeneous chemistry systematically underpredict the NOx (= NO + NO2) to NOy ratio. The model agreement is substantially improved if newly measured rate coefficients for the OH + NO2 and OH + HNO3 reactions are used. When included in 2-D models, the new rate coefficients significantly increase the calculated ozone loss due to NOx and modestly change the calculated ozone abundances in …

Note On The Voltammetry Of Ferrocene Carboxylate In Aqueous Solution, John Cassidy, John O'Gorman, M. Ronane, Enda Howard

Articles

Cyclic voltammetry of ferrocene dicarboxylate in aqueous solutions at high pH, in the presence of oxygen, showed evidence of an EC' mechanism where the oxidised form of ferrocene dicarboxylate reacts with H02- , which had been produced at a lower potential. However, an analogous experiment with ferrocene carboxylate yielded a cyclic voltammogram with a post peak: following the anodic peak: for ferrocene carboxylate. The reason for the post peak: is not clear but may be due to a delay in the reaction between the oxidised form of ferrocene carboxylate and H02-.

Chemical Constituents Of Centaurea Cuneifolia, Ümi̇t Aslan, Sevi̇l Öksüz

Turkish Journal of Chemistry

The whole plant material fo Centaurea cuneifolia Sm. afforded three sesquiterpene lactones; cnicin (1), dehydromelitensin (2) and dehydromelitensin-8-[(2^{'}-\alpha-hydroxy-\beta- hydroxyethyl)-acryloyl)] (3), the lignan; (-)-arctigenin (4), flavonoids; salvigenin (5), eupatilin (6), jaceosidin (7), acacetin (8), kaemferol (9), 5,7,4^{'}-trihydroxy-3-methylether (10), 5-hydroxy-3^{'},^{'},6,7-tetramethoxyflavone (11) and 5-hydroxy-3^{'},4^{'},7,8-tetramet hoxyflavone (12), a triterpene; \alpha-amyrin and a sterol; \beta-sitosterol. The structures of the isolates were determined by IR, UV, ^1H and ^{13}C NMR and MS spectroscopy.

Analysis Of Phytoestrogens By High Performance Liquid Chromatography, Anne A. Grippo, Yan Xie, Benjamin L. Rougeau, William V. Wyatt

Journal of the Arkansas Academy of Science

Phytoestrogens are biochemicals synthesized in plants which mimic steroidal estrogen activity in mammals. Analysis of these compounds in the legumes which produce them and in body fluids is important to the study of their physiological effects. High pressure liquid chromatography (HPLC) has been found to be an efficient and sensitive method of identification and quantitation of isoflavonoids, one class of phytoestrogen. Here we report the separation of three isoflavonoids, biochanin A, genistein and daidzein using an HPLC system with a Cg reverse phase column and a linear gradient mobile phase containing acetonitrile and acetic acid/water (10/90, v/v) over 60 minutes. …

Synthesis And Molecular Structure Of [Cpru(Pph3)(Pms)2]Otf1.3/4 C2>H4C12, Paul M. Nave, Mark Draganjac, A. W. Cordes, Tosha M. Barclay

Journal of the Arkansas Academy of Science

No abstract provided.

Two-Photon Excitation Of Rhenium Metal-Ligand Complexes, Joseph R. Lakowicz, Felix N. Castellano, Ignacy Gryczynski, Zygmunt Gryczynski, Jonathan D. Dattelbaum

Chemistry Faculty Publications

We describe the emission spectral properties of two rhenium metal-ligand complexes with one and two-photon excitation, Re(bpy)₂(CO)₃Cl and [Re(bpy)(CO)₃CH₃CN]⁺, where bpy is 2,2’-bipyridyl and CH₃CN is acetonitrile. Similar emission spectra and intensity decay times characteristic of the metal-to-ligand charge transfer state were observed for one- and two-photon excitation. The lifetime and quantum yield of the acetonitrile complex are approximately 14-fold higher than that of the chloride complex. Both complexes display high anisotropies near 0.33 in frozen solution with one-photon excitation. Two-photon excitation results in anisotropies about 40% larger, …

Reply To Comment On ‘Nondipole Resonant X-Ray-Raman Spectroscopy: Polarized Inelastic Scattering At The K Edge Of Cl2,’, J. D. Mills, J. A. Sheehy, T. A. Ferrett, S. H. Southworth, R. Mayer, Dennis W. Lindle, P. W. Langhoff

Chemistry and Biochemistry Faculty Research

Mills et al. Reply: In their Comment on our Letter [1], Gel’mukhanov and Ågren [2] reiterate recent assertions [3] based on their earlier theoretical studies [4]. The primary purpose of their Comment is apparently to refute our stated conclusion that core-excited-state localization/ delocalization mechanisms are irrelevant to interpretations of reported Raman scattering experiments on homonuclear diatomic molecules.

Thermodynamics Of The Dissociation Of Chromium Soap Solutions In Benzene-Dimethyl Formamide, Hüseyi̇n Topallar, Yüksel Bayrak

Turkish Journal of Chemistry

Critical micelle concentrations and dissociation constants for chromium soaps (myristate, palmitate and stearate) in a mixture of benzene and dimethyl formamide (7:3, vol/vol) were determined by means of conductivity measurements. These soaps behave as simple moderate electrolytes in dilute solutions. Critical micelle concentrations and dissociation constants decreased with increasing numbers of carbon atoms in the soap molecules. Thermodynamic parameters such as heat of dissociation, \DeltaH_d, change in free energy, \DeltaG_d, and entropy, \DeltaS_d, per mole for the dissociation process were also evaluated.

Synthesis And Spectral Characterisation Of Novel Azo-Azomethine Dyes, Hati̇ce Karaer, İsmai̇l E. Gümrükçüoğlu

Turkish Journal of Chemistry

The synthesis of novel azo-azomethine dye derivatives of substituted Schiff bases were carried out by the reaction of substituted 1-naphtylamine with 4-nitro and 2-chloro benzenediazonium tetraflouroborate salts as a coupling component. These compounds were identified by IR, UV-Vis and ^1H-NMR spectroscopic techniques, and elemental analysis.

Nonyl-And Dodecylamines Intercalated Bentonite And Illite From Turkey, Gülten Akçay, M. Kadi̇r Yurdakoç

Turkish Journal of Chemistry

Bentonite and illite were interacted with nonyl- and dodecylammonium salt solutions to see how the alkylammonium ions became attached and oriented within the interlamellar space of the clays. X-ray diffraction analyses were carried out to obtain information on the interlamellar organization and orientation of the adsorbed alkylammonium compounds. Thermogravimetric analysis (TG, DTG) and Fourier Transform Infrared Analyses (FTIR) were performed to characterize the samples and to determine the amounts adsorbed by the clay samples. The modification process was effective in nonyl- and dodecylammonium bentonites. Alkylammonium ions were adsorbed in the interlamellar space of the clays. Regarding the orientation of the …

Determination Of Patent Blue V And Carmoisine In Gelatine Desserts By Derivative Spectrophotometry, Yüksel Özdemi̇r, Ayşe Arzu Akkan

Turkish Journal of Chemistry

A first-derivative spectrophotometric method was developed for quantitative determination of two synthetic organic dyes, Carmoisine and Patent Blue V, which are under governmental regulations all over the world because of their toxicity and carcinogenity. In this study, Carmoisine and Patent Blue V were simultaneously determined in their binary mixtures by first-derivative spectrophotometry. The method was applied to different gelatine desserts. The first-derivative derivative method did not eliminate turbid background in the samples. A simple background correction procedure involving a C_{18}-cartridge sample preparation step was developed for determination of dyes in gelatine dessert by first-derivative spectrophotometry. The C_{18}-cartridge sample preparation step …

Hydrogen Evolution At Platinum (Pt) And At Platinized Platinum (Ptz) Cathodes, Bi̇rgül Yazici

Turkish Journal of Chemistry

In this study, the cathodic behaviours of bright platinum (Pt) and at platinized platinum (Ptz) on the platinum anode were investigated in a 1M Na_2SO_4 electrolyte (pH, from 2 to 8) by means of electrolysis. The theoretical (\Delta Erev) and experimental (\Delta E_{exp}) discharge potentials and the cathodic overpotentials (\etac) of the systems were determined. The amounts of hydrogen gas produced at different times on the cathodes at a constant potential (5V) were measured and the hydrogen yield was calculated. The resulting scheme has been very helpful to obtain wodified electrocatalytic coating and electrode structures at Ptz cathode, able to …

Effect Of Temperature On The Electrooxidation Of Some Organic Molecules On Pt Doped Conducting Polymer Coated Electrodes, İpek Beceri̇k, Fehmi̇ Fiçicioğlu, Fi̇gen Kadirgan

Turkish Journal of Chemistry

Polymer modified electrodes are of importance as possible electrocatalysts for various electrode reactions, i.e., platinum incorporated into polypyrrole or polyaniline films are known to be good systems for the electrooxidation of various organic molecules. In this study, the effect of temperature on the electrooxidation of D. glucose and methanol on Pt doped films was investigated, apparent activation energies were calculated and the results were evaluated.

Monitoring The Effects Of Indoor Pollution Using Fourier Transform Infrared Spectroscopy, Rachel Farrell

Presidential Scholars Theses (1990 – 2006)

Fourier Transform Infrared Spectroscopy {FTIR) was used to develop an effective way to monitor indoor pollution and to observe the effects of such indoor pollution under various conditions of the ventilation system of McCollum Science Hall of the University of Northern Iowa, Cedar Falls, Iowa. This was done by monitoring the absorbance of acetone as it evaporated over time, and the data were used to create concentration vs. time plots. Several parameters from these plots were used to judge the ventilation system, with some general conclusions including that having the system on reduces peak time and end time. Also, the …

1-Hydroxyethyl-2,2′-Biimidazole, Geng Lin, Harvest L. Collier, Russell G. Baughman

Chemistry Faculty Research & Creative Works

The two imidazole rings in the title compound, C₈H₁₀N₄O, are almost coplanar, having an angle of 2.3 (2)° about the C-C bond connecting the rings. the conformation adopted is such that the nitrogen substituents (-H and -CH₂CH₂OH) are in a trans orientation. the molecules are connected by intermolecular O-H. . .O and N-H. . .N hydrogen bonds to yield an arrangement of pairs of molecules reminiscent of side-by-side stacks of crinkled ribbon.

The Role Of Electrolytically Co-Deposited Platinum-Palladium Electrodes On The Electrooxidation Of D. Glucose In Alkaline Medium: A Synergistic Effect, İpek Beceri̇k

Turkish Journal of Chemistry

The electrooxidation of D. glucose was investigated on platinum-palladium alloy electrodes of different compositions in alkaline aqueous solutions. The surface characteristics of the alloys in contact with electrolytic solution were studied using cyclic voltammetry. In particular, a surface enrichment in platinum due to a preferential dissolution of palladium was shown. Enhanced electrocatalytic activity at about 37 at. % in Pd was obtained when compared to pure metals, thus leading to a synergistic effect. The electrocatalytic activity of different alloys for D. glucose oxidation has been chacterized by exchange current densities obtained from extrapolation of Tafel lines to calculated equilibrium potential. …

Electrooxidation Of Linear Alkyl Benzene Sulfonate (Las) On Pt Electrodes, Bi̇rgül Yazici, Si̇bel Zor

Turkish Journal of Chemistry

The electrochemical behaviour of linear alklybenzene sulfonate (LAS) on Pt electrodes was investigated in 0.05M Na_2SO_4 and in 0.1M NaCl at pH=8 by the potentiokinetic method and by electrolysis. The anodic and cathodic semilogarithmic current-potential curves were obtained between -1.6V - +1.6V. The experimental discharge potentials were determined by means of current-potential-curves obtained by electrolysis between 0-3V. The percentages of surface active material remaining in the solution after specified periods (0-6hrs) were determined for different initial concentrations of LAS (30, 150, 300 ppm) by using a potentiostat at +1.6V and by applying a potential of 20V via a direct current …

Nepetalactones And Other Constituents Of Nepeta Nuda Ssp. Albiflora, Gamze Kökdi̇l, Sabi̇ha M. Yalçin, Gülaçti Topçu

Turkish Journal of Chemistry

The hexane extract of Nepeta nuda ssp. albiflora led to the isolation of six known monoterpene nepetalactones, 4a\alpha,7\alpha,7a\alpha-nepetalactone (1), 4a\alpha,7\alpha,7a\beta-nepetalactone (2), 4a\beta,7\alpha,7a\beta-nepetalactone (3), 4a\beta,7\alpha,7a\alpha-nepetalactone (4), 4a\alpha,7\beta,7a\beta-nepetalactone (5), 3\alpha-hydroxy-4a\alpha,7\alpha,7a\alpha-dihydron\-epe\-tal\-actone (=nepetalic acid) (6) and a dimeric 5,9-dehydronepetalactone (7) along with two known steroids \beta-sitosterol and sitosterol 3-one and a triterpene betulinic acid. The acetone extract of the same plant afforded compound 7 in a higher yield in addition to compounds 2 and 6, and sesquiterpene caryophyllene oxide, the iridoid glucoside 1,5,9-epideoxyloganic acid, the triterpenoids oleanolic, ursolic and betulinic acids, and sitosterol 3\beta-glucoside.

An Investigation Of The Formation Mechanism Of Allene Or Alkyne In The 6,7-Benzobicyclo[3.2.1]Octane System By Deuterium Labeling Experiments, Yavuz Taşkesenligil, Ferhan Tümer, Cavi̇t Kazaz, Meti̇n Balci

Turkish Journal of Chemistry

In order to reveal the real intermediate in the base-promoted reaction of 1, 3-bromo-4,4-dideuterio-6,7-benzobicyclo[3.2.1]octa-2,6-diene 10 was synthesized and its HBr elimination reaction studied. Reaction of 10 with potassium tert-butoxide yielded butoxyl ether 18 in which proton-deuterium exchange has occured.

Reaction Of Tribromonitromethane With Aldehydes And Ketones In The Presence Of Zn Metal In Aqueous Medium, Ali̇ Shaker Mahasneh

Turkish Journal of Chemistry

Aldehydes and ketones react with tribromonitromethane in the presence of zinc metal dust, ammonium chloride and water to give dibromonitroalcohols in good yields.

A Study Of The Thermodynamic Properties Of Poly [2-(3-Mesityl-3-Methylcyclobutyl)-2-Hydroxyethyl Methacrylate] At Infinite Dilution Using Inverse Gas Chromatography-2-Hydroxyethyl, İsmet Kaya, Kadi̇r Demi̇relli̇

Turkish Journal of Chemistry

Some thermodynamic quantities were obtained for the interactions of poly [2-(3-mesityl-3-methylcyclobutyl)-2-hydroxyethyl methacrylate] with alcohols, ketones, acetates, aromatics and alkanes by inverse gas chromatography in the temperature range 160-200°C. The specific retention volumes, V°_g, weight fraction activity coefficients of solute probes at infinite dilution, \Omega^{\infty}_1, Flory-Huggins thermodynamic interaction parameters, \chi^{\infty}_{12} between polymer and solvents were determined. The partial molar free energy, \Delta \bar{G}^{\infty}_{1}, the partial molar heat of mixing, \Delta\bar{H}^{\infty}_1 at infinite dilution and the solubility parameters of the polymer, \delta_2 were calculated.

Electrochemical Reduction Of Methyl Cinnamate In The Presence Of 1,3-Bis(4-Methyl Phenylsulphonyloxy)Propane, Mustafa Güllü

Turkish Journal of Chemistry

Electrochemical reduction of methyl cinnamate in the presence of a dielectrophile, such as 1,3-bis(4-methyl phenylsulphonyloxy)propane gives two major products: trans- (\pm) methyl 2-phenylcyclopentanecarboxylate and trans- (\pm) methyl 2,3-diphenyl-5-oxo-cyclopentanecarboxylate. The ratio of products basically depends on the electrolysis conditions.

Electrochemical Characterization Of Al_2 O_3 -Ni Thin Film Selective Surface On Aluminium, Fi̇gen Kadirgan, Ewa Wackelgard, Mete Söhmen

Turkish Journal of Chemistry

Solar thermal collectors represent a widely used type of system for the conversion of solar energy. In order to produce selective coatings on aluminium substrates to be used as absorber plates in high efficiency solar collectors, nickel pigmentation was applied to anodically oxidised surfaces. Electrochemical dc methods are used to study the oxidation of aluminium as functions of the following electrolysis conditions: applied current, pH, temperature and concentration of electrolyte. The properties of the oxidised aluminium surfaces are investigated by cyclic voltammetry. Nickel pigmentation of porous aluminium surfaces was also performed as a function of electrochemical pigmentation conditions by ac …