Chemistry Commons^™

Thermal Stabilities Of Hydroxyalkyl Terminated Polydimethylsiloxane Oligomers, İskender Yi̇lgor, Emel Yi̇lgor

Turkish Journal of Chemistry

The thermal stabilities of \alpha,\omega-hydroxypropyl, \alpha,\omega-hydroxybutyl \alpha,\omega-2-hydroxypentyl and \alpha,\omega-hydroxyhexyl terminated polydimethylsiloxane oligomers were investigated. Hydroxypropyl and hydroxybutyl terminated polydimethylsiloxane oligomers showed degradation upon heating through the loss of functional end groups, as determined by FTIR spectroscopy and gel permeation chromatography. \alpha,\omega-Hydroxyhexyl and \alpha,\omega-2-hydroxypentyl terminated polydimethylsiloxane oligomers were stable under similar conditions. The instability of the end groups is due to the backbiting of the terminal silicon in the PDMS by the primary hydroxyl oxygen, leading to the formation of 5-and 6-membered stable, heterocylic compounds. Loss of end groups also resulted in a dramatic increase in the molecular weights of the …

New Synthetic Approach For The Synthesis Of Liquid Crystalline Block And Graft Copolymers, Yeşim Hepuzer, İ. Ersin Serhatli, Yusuf Yağci

Turkish Journal of Chemistry

Liquid crystalline block and graft copolymers were synthesized according to the macroinitiator and macroinimer concept. For this purpose, side chain block copolymers (polytetrahydrofuran-b-polymethylmethacrylate) having liquid crystalline 4,4'- cyanobiphenyl blocks were prepared and characterized. Unlike the liquid-crystalline homopolymer with mesogenic units in the side chain, all block and graft copolymers showed a smectic A mesophase. The transition temperatures are hardly affected by the composition and molecular weight of the blolck copolymers.

Conducting Polymer Grafts Of Polypyrrole, Levent Toppare

Turkish Journal of Chemistry

Conducting polymer grafts of pyrrole with poly[(methyl methacrylate)-co-(2-(N-pyrollyl) ethyl methacrylate)] wwere synthesized via elctrochemical polymerization of pyrrole in different media. Samples were characterized by SEM, thermal analysis and conductivity measurements.

Electrical Conductivities Of Poly (Alkyl Vinyl Ketones) Reacted With Dopant Solutions, Jun Hui Ma, J. David Tauber, Ülkü S. Ramelow

Turkish Journal of Chemistry

Poly ethyl vinyl ketone (PEVK) and poly methyl vinyl ketone (PMVK) were prepared using photochemical processes. The irradiation of monomers with UV light provides a new method, different from the methods previously used for the polymerization of these monomers. FTIR and UV spectroscopies were used for the structure and reaction mechanism of the polymers. NMR was used to calculate the conversion percentage of MVK and EVK polymers. The conductivity change at various temperatures was traced during reactions of PMVK and PEVK with various dopant concentrations and the activation energy of these reactions were calculated by adding dopants and by adjusting …

A Two-Dimensional Monte Carlo Polymerization Of 5-Membered Rings, Okan Esentürk, H. Önder Pamuk, E. Yurtsever

Turkish Journal of Chemistry

A modification of the kinetic growth model in two dimensions for the polymerization of 5-membered rings is presented. The preliminary results reveal the validity of the modified model.

Calculation Of Spreading Pressure Of Water On Cellulosic Films From Contact Angle Data, H. Yıldırım Erbi̇l

Turkish Journal of Chemistry

The correlations between the surface properties of the modified cellulose papers with their toner compatibility were investigated. The surface tension components of the cellulosic films, their interfacial tension with the liquid drops and the work of adhesion components were calculated using van Oss-Good's One-Liquid contact angle approach. The electron donor (or Lewis base) \gamma^- components of the cellulosic films were found to represent the main interactions with the the electron acceptor (acidic) \gamma^+ components of the contacting liquids. Allyl ketene dimer (AKD) grafting of the cellulose affected the surface properties; the higher the substitution of the hydroxyl group, the smaller …

A Quantum-Chemical Investigation On 5,5'-Bi(1h-1.2,4-Triazole)), A. A. İki̇zler, R. Abbasoğlu, N. Saltek, M. Şeri̇fova

Turkish Journal of Chemistry

The conformational analysis of flexible 5,5'-bi(1H-1,2,4-triazole) molecule containing various reaction centers has been performed by the semiempirical methods MNDO,AM1 and PM3, and the internal rotation barrier calculated. The most stable conformation of the molecule has been determined to be the planar trans conformation. According to the three methods, 5,5'-bi(1H-1,2,4-triazole) molecule (C) has been found to be relatively more stable than its tautomer 3,3'-bi(1H-1,2,4-triazole)(B) and to be less stable than its other tautomer 3,3'-bi(4H-1,2,4-triazole)(A). Moreover, the electronic properties of 5,5'-bi(1H-1,2,4-triazole) molecule and the effect of conformational changing on electronic and geometric properties have also been investigated. To determine the protonation sites …

High Rates Of Fluorescence Quenching Between Perylene Dodecyldiimide And Certain \Pi-Electron Donors, S. İçli̇, H. İci̇l, İ. Gürol

Turkish Journal of Chemistry

Perylene bis-n-dodecyl diimide is found to quench fluorescenc emissions of naphthalene, phenanthrene and dihydrocarbazolocarbazole molecules at rates of 4.4\times10^{11}, 2.8\times10^{12} and 2.5\times10^4 M^{-1} sec^{-1}, in respective order of aromaticity. These unusulally high rates of fluorecence quenchings are attributed to Perrin model static quenching and presence of electron transfer through singlet excited state of perylene diimide. Calculated free energy of electron transfer, \Delta G_{ET}=-120.5 kJ/mol, between perylene diimide and dihydrocarbazolocarbazole is taken as evidence for observation of high fluorescence quenching rate for carbazolocarbazole molecule. Keywords: Fluorescence quenching, Photoenergy transfer, Perylene diimide and Carbazolocarbazole

Constituents Of Salvia Verticillata, Ufuk Sönmez, Gülaçtı Topçu, Ayhan Ulubelen

Turkish Journal of Chemistry

Three new and fourteen known compounds were isolated from the roots of {\it Salvia verticillata L.} Spectral methods were used for the structure determination besides TLC comparisons with authentic samples for the known compounds.

The Reliability Of Jung-Biggs-Moorhead Method For Cholesterol Determination In The Presence Of Ergosterol, Lemi Türker, Şahinde Demi̇rci̇, Marjan Akdağ

Turkish Journal of Chemistry

In the present study, the reliability of Jung-Biggs-Moorhead method for cholesterol determination has been tested in the presence of another steroid, ergosterol. It was observed that presence of ergosterol interferes with the absorbance measurement of cholesterol. When both steroids are present in the sample maximum absorption wavelength are not shifted by the mutual interaction but absorbance values are changed considerably. Therefore this method may be used only for qualitative bu not quantitative analysis for cholesterol in the presence of ergosterol.

Synthesis And Characterisation Of Anhydrous Magnesium Phosphate Mg$_3$(Po$_4$)$_2$, A. Baykal, M. Kizilyalli, R. Kniep

Turkish Journal of Chemistry

The synthesis and characterization of anhydorus Mg_3(PO$_4)_2 was investigated. Mg_3(PO$_4)_2 is reported to have similar structural arrangements with Co_3(PO_4)_2 and \gamma-Zn_3(PO_4)_2 compounds. The sample was prepared by a new technique which is the reaction of MgCl_2.6H_2O and Na_3PO_4.12H_2O solutions at pH=5.1, which was adjusted by adding concentrated H_3PO_4 to the reaction mixture and heating the precipitated product at 600^{\circ}C untill constant weight. The purity of the product was checked by X-ray powder diffraction, IR, density measurement, SEM and DTA analysis. The monoclinic unit cell dimensions of product are a=7.605 (2), b=8.233 (3), c=5.080 (1)A^{\circ} and \beta= 94.19^{\circ} (3), which was …

A Topological Approach To The Stabilities Of Isomeric Hückel And Mobius Type Cyclacenes, Lemi Türker

Turkish Journal of Chemistry

Within the constraints of Hückel molecular orbital theory, Hückel and Mobius type cyclacenes were investigated in terms of their angle of total \pi-electron energy, O_{\pi}, and cos O_{\pi} to find out how structural changes affect the stabilities. It has been theoretically deduced that as the number of benzenoid rings (R) increases the isomeric Hückel and Mšbius type cyclacenes should have comparable stabilities, although for low values of R odd-Hückel type and even-Mobius type are predicted to be more stable.

Hydrolysis And Condensation Reactions Of Methacrylate-Modified Aluminum Alkoxides, Ertuğrul Arpaç, Efraim Avşar

Turkish Journal of Chemistry

The hydrolysis of aluminum tri-sec-butoxide and compounds obtained by substituting the larger functional groups for the present alkly groups in Al(O-sec-Bu)_3, and the reaction of these products with a polymerizable organic ligand, i.e. methacrylic acid, were studied together with the hydrolysis reactions of the final products. A good method of preparing high-tech materials and new composites uses organo-substituted silicon esters and/or alkoxides of various elements in a polycondensation process. Introducing a suitable organic network into the inorganic backbone gives desirable properties in new coating materials. The preparation of such materials is possible via the hydrolysis of metal alkoxides. Usually, different …

Semiclassical Approach To The Hydrogen-Exchange Reaction- Reactive And Transition-State Dynamics, Sophya V. Garashchuk, Grossmann Frank, David Tannor

Faculty Publications

Scattering matrix elements and symmetric transition-state resonances for the collinear H ₂ + H → H + H ₂ reaction are obtained using a time-dependent approach. The correlation function between reactant channel wavepackets and product channel wavepackets is used to determine the S-matrix elements. In a similar fashion, autocorrelation functions are used to extract the positions and widths of transition-state resonances. The time propagation of the wavepackets is performed by the improved semiclassical frozen Gaussian method of Herman and Kluk, which is an initial value, uniformly converged method. The agreement between the quantum and semiclassical results is far better …

Properties And Macromolecular Structure Of Unacetylated And Acetylated Nata De Coco, Ma. Assunta C. Cuyegkeng, Ma. Amy L. Dimalanta

Chemistry Faculty Publications

This study aims to gain more insight into the supramolecular structure of the cellulose in nata de coco, and to compare its ability to be modified with the known types of cellulose. The investigations were done using IR spectroscopy and thennal analysis. The IR spectra of microcrystalline cellulose were identical to cellulose spectra. However, those of dried nata de coco cellulose showed additional peaks that indicated a loss of inter- and intra-sheet hydrogen bonding, usually extensive in other cellulose forms where sheets are the prevalent secondary structures. This kind of structure would be consistent with the necessary framework for gel …

Construction Of Gold Micro-Bead Ultramicroelectrodes, Deon T. Miles, Andrew Knedlik, David O. Wipf

CAS Publications

A new way to construct small electrodes by the use of metal micro-beads is described. Gold beads of 1.5 to 3.0 mm diameter were used to construct inexpensive and disposable microelectrodes with overall structural diameters of £ 6 mm and electrode diameters of £ 5 mm. The voltammetric response of these electrodes is consistent with existing theory and the electrodes exhibited the sigmoidal waves expected at ultramicroelectrodes.

Observation Of Upper Tropospheric Sulfur Dioxide- And Acetone-Pollution: Potential Implications For Hydroxyl Radical And Aerosol Formation, F. Arnold, J. Schneider, K. Gollinger, H. Schlager, P. Schulte, Donald E. Hagen, Philip D. Whitefield, Peter F. J. Van Velthoven

Physics Faculty Research & Creative Works

Aircraft-based measurements of sulfur dioxide, acetone, carbon dioxide, and condensation nuclei (CN) were made over the north-eastern Atlantic at upper tropospheric altitudes, around 9000 m. On October 14, 1993, strong SO ₂- and acetone-pollution (both up to 3 ppbv) were observed, which were accompanied by a CO ₂-enhancement of up to 6 ppmv, and large CN-concentrations of up to about 1500 cm ^-3 (for radii ≥ 6 nm). CN, excess CO ₂, and to a lesser degree also acetone, were positively correlated with SO ₂. Air mass trajectory analyses indicate, that most of the air masses …

Crystal Structure Effect In Radiation-Induced Solid-State Polymerization Of Acrylamide, Ali Usanmaz

Turkish Journal of Chemistry

Crystal structure of arcylamide at -150^{\circ}C was studied to understand the role of the crystal structure on the reaction mechanism of radiation-induced polymerization in the solid-state. Acrylamide crystallizes in the monoclinic unit cell with the unit cell parameters as ; a=828.0(2) pm, b=578.0(4) pm, c=974.9(2) pm, \beta=119.62(4)^0, space group =P 2_1/c, Z=4 molecules/unit cell, d_x = 1.165 g/cm^3. From the results of the structural data a polymerization mechanism in the solid-state is suggested. The radiation damage in single crystal of acrylamide was also investigated in detail. The result showed the formation of the amorphous polymer, that phase separated from the …

A Study Of The Thermodynamical Interactions Of Bisphenol-A Polycarbonate With Some Solvents By Gas Chromatography, Özlem Cankurtaran, Ferdane Yilmaz

Turkish Journal of Chemistry

Retentin diagrams of polycarbonate for n-nonane, ethyl acetate and n-butyl acetate were obtained using inverse gas chromatography in the temperature range 80-240^{\circ}C. The specific retention volumes, V^{\circ}_{g} the Flory-Huggins interaction parmeters, \chi^{\infty}_{12}, interaction parameters, \chi^{\ast}_{12}, and effective exchange-energy parameters \bar{X}_{12} of the equation-of-state theory of polycarbonate for n-octane, n-nonane, n-decane, ethyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, tert-butyl acetate and isoamyl acetate were obtained in the temperature range 200-240^{\circ}C. The parameter \delta_2 was estimated to be 10.7 (cal/cm^3)^{1/2} at room temperature using the \chi^{\infty}_{12} extrapolated to room temperature. Keywords: Bisphenol-A polycarbonate, polymer-solvent interactions, inverse gas chromatography, solubility parameter.

Synthesis Of An Organophosphorus Analog Of Acetylcholine, Darshan Mehta '97

Honors Projects

Acetylcholinesterase (AChE) is an important enzyme in our nervous system In normal nerve function, AChE catalyzes the hydrolysis of acetylcholine (ACh) into its respective components, choline and acetate. Recent interest has been focused on AChE because of its potential role in the pathology of neurodegenerative diseases such as Alzheimer's disease. Studies have revealed that the active site of AChE contains an esteratic and several hydrophobic/anionic subsites. AChE is inhibited by organophosphorus (OP) compounds like sarin and soman. As a result, OP compounds have been used to study the structure of AChE and the mechanism by which it catalyzes the hydrolysis …

Immunologic And Hematopoietic Effects Of Cd40 Stimulation After Syngeneic Bone Marrow Transplantation In Mice, Satoshi Funakoshi, Dennis D. Taub, Miriam R. Anver, Arati Raziuddin, Osamu Asai, Prakash Reddy, Helen C. Rager, William C. Fanslow, Dan L. Longo, William J. Murphy

Chemistry Faculty Research & Creative Works

CD40 is a molecule present on multiple cell types including B lymphocyte lineage cells. CD40 has been shown to play an important role in B cell differentiation and activation in vitro, although little is known concerning the effects of CD40 stimulation in vivo. We therefore examined the effects of CD40 stimulation in mice using a syngeneic bone marrow transplantation (BMT) model in an effort to augment B cell recovery after high dose therapy with hematopoietic reconstitution. After the BMT, mice were treated with or without 2-6 μg of a soluble recombinant murine CD40 ligand (srmCD40L) given intraperitoneally twice a week. …

Calcium Metabolismn In Volvox Carteri, Bridget Anne Neville

Honors Theses

Calcium metabolism is involved in many ways in the cellular activities of the colonial green alga, Volvox carteri. Various drugs that are known in other systems to cause specific changes in calcium metabolism, gave rise to various visible metabolic effects in this study. These effects provide evidence for calcium's role in Volvox growth and development and in its cytoskeleton. Another way that calcium exerts its effect on Volvox is by acting as a second messenger in a G-protein/inositol phosphate signal transduction pathway.

This study also supports the fact that cytoskeletal components are important for development in Volvox. Both microtubules and …

The Role Of HoX In Super- And Subsonic Aircraft Exhaust Plumes, T. F. Hanisco, P. O. Wennberg, R. C. Cohen, J. G. Anderson, D. W. Fahey, E. R. Keim, R. S. Gao, R. C. Wamsley, Stephen G. Donnelly Ph.D., L. A. Del Negro, R. J. Salawitch, K. K. Kelly, M. H. Proffitt

Chemistry Faculty Publications

The generation of sulfuric acid aerosols in aircraft exhaust has emerged as a critical issue in determining the impact of supersonic aircraft on stratospheric ozone. It has long been held that the first step in the mechanism of aerosol formation is the oxidation of SO2 emitted from the engine by OH in the exhaust plume. We report in situ measurements of OH and HO2 in the exhaust plumes of a supersonic (Air France Concorde) and a subsonic (NASA ER-2) aircraft in the lower stratosphere. These measurements imply that reactions with OH are responsible for oxidizing only a small fraction of …

The Effects Of Exercise Training On Resting Prostacyclin And Thromboxane A(2) In Older Adults, R D. Kauffman, G S. Sforzo, Blaise Frost, M K. Todd

Chemistry Faculty Publications

Ten adult volunteers participated in 16 weeks of cardiovascular exercise training (EG) to determine the effects of training on resting prostacyclin (PGI(2)) and thromboxane A(2) (TXA(2)). Six volunteers of similar age served as sedentary controls (CG). Blood was collected in tubes after training and eicosanoids were measured by standard I-125 RIA methods. Over the 16 weeks of the study, PGI(2) decreased 48% for EG and 33% for CG. There were no between-group differences for PGI(2) values. No significant within-group changes in TXA(2) were found, whereas between-group pretraining TXA(2) values were significantly different. A time main effect for PGI(2) may indicate …

Crystal Structure Of (Μ-Tranis-4,4'-Dinitro-2,2'-Biimidazolato-N,N: N'',N''') Bis[Bis(Triphenylphosphine Copper(I))] N,N-Dimethylformamide, [C42h37cun4o3p2]2, R. G. Baughman, C. A. Hester, Harvest L. Collier

Chemistry Faculty Research & Creative Works

No abstract provided.

Varietal Differences In The Total And Enantiomeric Composition Of Theanine In Tea, K. Helen Ekborg-Ott, Andre Taylor, Daniel W. Armstrong

Chemistry Faculty Research & Creative Works

Theanine is the main amino acid component in tea. It usually constitutes between 1 and 2% of the dry weight of the tea leaves. It is as prevalent in tea as all other free amino acids combined. Both enantiomers of theanine were found to have a similar sweet taste, with little or no aftertaste. It was found that black and half-green teas (except for Formosa Oolong) contained as much, or more, theanine as green teas. No correlation was found between the absolute concentration of theanine in tea and its enantiomeric composition. An inverse correlation was found between certain grades of …

Surface Morphology Of Gan Films Determined From Quantitative X-Ray Reflectivity, D Lederman, Zhonghai Yu, T H. Myers, Michelle Richards-Babb

Faculty & Staff Scholarship

The surface of two GaN films grown under Ga-rich conditions by molecular beam epitaxywas characterized using x-ray reflectivity, assuming a self-affine/fractal surface morphology. The surface height fluctuations were similar for both samples at the largest lateral length scales at which the fractal description is valid, although this lateral length was significantly greater and the “jaggedness” significantly smaller for the sample grown under higher Ga flux. Previous atomic force microscopy images revealed a higher density of large features on the surface for the sample grown under lower Ga flux. The lateral size of the features are dominated by a convolution of …

Photoelectron Spectroscopy: A Tool In Sorption Studies, Şefik Süzer, Hasan N. Erten

Turkish Journal of Chemistry

Photoelectron spectroscopy using AlK\alpha (h\nu=1486.3 eV) has been applied to study the sorption of Cs^+, Sr^{2+}, Ba^{2+}, Zn^{2+} and Co^{2+} on magnesite kaolinite, smectite and chlorite. From the observed intensities of photoelectron peaks it was determined that in magnesite the sorption affinity of the above ions follow the order: Ba^{2+}>Co^{2+}\congSr^{2+}\congZn^{2+}>Cs^+. The order for the sorption of Ba^{2+} and Cs^+ are also determined as chlorite>magnesite>smectite>kaolinite and smectite>chlorite\congkaolinite>magnesite, respectively.

Dichlorobis[1-Methyl-3-(Prop-2-Enyl)Imidazole-2(3h)-Thione-S]Zinc(Ii), Daniel J. Williams, Tuan A. Ly, Jeffrey W. Mudge, William T. Pennington, George L. Schimek

Faculty Articles

The title compd. is monoclinic, space group P21/n, with a 14.0082(8), b 10.803(1), c 14.581(1) Å, and β 116.625(8)°; Z = 4, dc = 1.50; R = 0.043,Rw = 0.044 for 1935 reflections. The crystal structure shows a discrete mol. structure with tetrahedral geometry around the Zn ion. The mean Zn-Cl and Zn-S distances are 2.259(7) and 2.372(4) Å, resp. Bond angles around the Zn ion range from 102.8(1) to 113.7(1)°. Ring distances and angles in the ligand compare favorably with literature values of analogous compds., and the mean C-S bond distance of 1.71(1) Å is close to the av. …

Kinetics Of Autoxidative Polymerization Of Sunflowerseed Oil, Hüseyin Topallar, Yüksel Bayrak, Mehmet İşcan

Turkish Journal of Chemistry

The rates of polymerization of unhydrogenated and hydrogenated sunflowerseed oils were measured under atmospheric conditions in the various containers (glass, PET and metal). Polymerization rates showed a strong dependence on the degree of unsaturation and the light transmittance of the containers. The average molecular weights of polymerized oils were determined by viscosity measurements.The relationship between viscosity and average molecular weight was determined. It is seen that unhydrogenated sunflowerseed oil has a higher polymerization rate than hydrogenated oil samples in a glass container and they has higher viscosity values.