Chemistry Commons^™

^1h Nmr, Infrared And Mass Spectrometry Of Di- And Tri-Organotin Derivatives Of 1-Nitroso-2-Naphthol, Saqib Ali, Muhammad Mazhar, Moazzam Hussain Bhatti, Sohail Mahmood, Abida Kalsoom

Turkish Journal of Chemistry

The di- and tri-organotin derivatives R\2SnL\2 and R\3SnL where R = CH\3, n--C\4H\9, C\6H\5, C\6H_{11} and C\6H\5CH\2 and L = 1-nitroso-2-naphthoxy were synthesized. These derivatives were characterized by elemental analysis, infrared, ^1H NMR and mass spectrometry.

Catalytically Active Intermediates In Photochemical Metathesis, Çetin Bozkurt, Yavuz İmamoğlu

Turkish Journal of Chemistry

The nature of the active species in photocatalytic metathesis reaction was investigated. The formation of Wittig-type addition products with benzaldehyde indicates that catalytically active carbene is the product of olefin and tungsten hexacarbonyl under reaction conditions.

Application Of Environmental Organic Petrology And Geochemistry To Fingerprint Organic Pollutants In The Recent Sediments Of Lake Ontario, Prasanta K. Mukhopadhyay, Michael A. Kruge, C.F. Michael Lewis

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

Selected surface sediment samples (sediment depth 0-10 cm) collected in the Niagara basin (western Lake Ontario) were chosen for organic matter characterization using organic petrological and geochemical techniques normally reserved for the study of coal, petroleum source rock and crude oil. The study was performed to assess the effectiveness of these techniques in discriminating between natural and anthropogenic organic matter and to determine the extent of organic pollution of the lake sediments. The organic carbon contents of the samples vary from 1.5 to 3.5%, with upper layer (0-5 cm) samples have higher TOC values than those from the lower layer …

The Computational Study Of "Model" Pollutants In Clay Montmorillonite, Sung-Ho Park

Dissertations

No abstract provided.

Separation And Artificial Maturation Of Macerals From Type Ii Kerogen, Michael A. Kruge, Patrick Landais, David F. Bensley, B Artur Stankiewicz, Marcel Elie, Olivier Ruau

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

Immature Type II kerogen (HI= 660 mg/g) from the Lower Toarcian of the Paris Basin was separated into an alginite concentrate (HI = 952 mg/g) and an amorphous organic matter (AOM) concentrate (HI = 573 mg/g) by density centrifugation. The flash pyrolyzate of the alginite is characterized by high relative concentrations of several series of n-alkanones and n-alkenones (including mid-chain alkyl ketones), in addition to n-alkanes, n-alk-1-enes and n-alkadienes. To our knowledge, this Toarcian alginite is the oldest example of marine organic matter whose pyrolyzate contains mid-chain alkanones in such high relative concentrations. In sharp …

Induced Acceleration Of Phosphine Exchange In Metal Carbonyls By Pendant Groups Of Coordinated Polyphosphines, Ping Ye

Masters Theses

The kinetics and thermodynamics of isomerization of (OC)₅CrPPh₂CH₂CH(PPh₂)₂ to its linkage isomer, (OC)₅CrPPh₂CH(PPh₂)CH₂PPh₂, in chloroform-d have been studied with ³¹P{¹H} NMR.

(OC)₅Cr[η¹-PPh₂CH₂CH(PPh₂)₂] ⇄ (OC)5Cr[η¹-PPh₂CH(PPh₂)CH₂PPh₂]

The equilibrium constants for the reaction are 3.60, 2.61, 2.04, and 1.67 at 10 °C, 25 °C, 40 °C, and 53 °C, respectively. The forward reaction becomes more favorable as the temperature …

An Expeditious Synthesis Of Β,Γ-Unsaturated Δ-Lactones: Useful Pharmacological Synthetic Intermediates, Li Xiong

Masters Theses

Two-carbon ring expansions of vinyl β-lactones, were carried out by Lewis acids (BF₃-Et₂O or Et₂AlCl) via an ionization/cation rearrangement. β,γ-unsaturated δ-lactones were produced as efficient protocols for the synthesis of bioactive substances.

Vinyl β-lactones were prepared via ring closure of corresponding unsaturated β-hydroxy acids. Differently structured substrates were examined to study the influence of the substituents on the rearrangement. Other factors, such as temperature, solvent and catalyst were also studied in search of suitable reaction conditions.

This method is moderately successful in providing fused-ring δ-lactones, but higher yields (so far total yield of 24.8%) …

Identification Of Organosulfur Compounds In Illinois Coal, Mandy N. Amin

Masters Theses

The goal of this research was to identify representative organosulfur compounds in Illinois coal which are removed by a mild, chemical desulfurization procedure. Pyridine was used to extract three raw Illinois coals. Coal with a significant amount of elemental sulfur was treated with 1:1 HCl/HF followed by lithium aluminum hydride before pyridine extraction. Pyridine soluble extracts were extracted with tetrahydrofuran. Nickel boride desulfurization was performed on the soluble extracts of the three coals. The before and after desulfurized THF soluble extracts were fractionated and purified by liquid chromatography and the eluents were anlyzed by gas chromatography/mass spectrometry to characterize the …

Constancy Of Bond Dissociation Energy Ratios For Ab₂/Ab Systems, Danyu Xu

Masters Theses

G2 and G2(MP2) theories have been used to study the bond dissociation energies D⁰_m of a series of AB₂, AB₂⁺, AB₂^-, AB, AB⁺ and AB^- systems. A total of fifty-four molecules and ions have been examined, for which B = O, S or Se and A = C, S, Ge, N⁺, P⁺, As⁺, B^-, Al^- or Ga^-. Each triatomic system has sixteen valence electrons and each diatomic system has ten valence electrons. Both triplet and singlet spin …

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.

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 …

Development Of A Tire Pyrolysis Process And Apparatus Using Steam Displacement Of The Combustible Atmosphere, Timothy Whitney Burrell

Dissertations and Theses @ UNI

It is the purpose of this research to convert a batch vacuum pyrolysis process into a pyrolytic process that operates at ambient air pressure with the capabilities of a continuous material flow operation. Further, it is important to optimize the conditions of the pyrolysis process so as to reduce costs of operation and to reasonably maximize products that have value. Steam will be used to displace the combustible atmosphere which enables ambient air pressure operation and elimination of need for inert carrier gasses or evacuation of the apparatus. The use of steam also allows water traps to be used as …

Some Remarks On Solid State Polymerization, George Adler

Turkish Journal of Chemistry

No abstract provided.

Dielectric Studies Of Various Olefin/So2 Copolmers, B. Baysal, Candan Erbi̇l, Paul L. Morganelli, W. H. Stockmayer

Turkish Journal of Chemistry

Dielectric constant and loss have been measured at low and high frequencies for several poly(1-olefin sulfones) as well as for the polysulfones of allybenzene and allyl cyclopentane. The low-frequency dispersion in allylbenzene due to helical sequences is weaker in benzene than in dioxane, and in both solvents is much lower than for the 1-olefin polymers. Solvent effects on the high frequency process are also reported, but yield no simple uniform picture.

Synthesis Characterization And Miscibility Of Polyvinyl Butyrals Of Varying Vinyl Alcohol Contents, Z. M. Zhou, D. J. David, W. J. Macknight, F. E. Karasz

Turkish Journal of Chemistry

Polyvinyl butyrals (PVB) of systematically varying vinyl alcohol content have been synthesized and characterized using wet chemistry, IR, DSC, and TGA. The miscibility of PVB-PVB blends was studied by DSC as a function of vinyl alcohol content and vinyl alcohol content differences between the respective blend components. These data were use to construct an isothermal miscibility map of PVB and to calculate the intramolecular interaction parameter \chi_{VA,VB}. The \chi_{VA,VB} was a function of the absolute level of the vinyl alcohol (VA) and vinyl butyral (VB) contents of the polymers. In addition, the thermal stability of polyvinyl butyral was found to …

Network Characterization Of Energetic Poly(Glycidyl-Azide), Mehmet S. Eroğlu, Olgun Güven

Turkish Journal of Chemistry

Energetic poly(glycidyl azide) (PGA) elastomers with different crosslink densities were prepared by varying the NCO/OH reactive-groups ratio from 0.8 to 1.0. In the preparation of the elastomers, PGA chains were end-liked with a mixture of hexamethylene diisocyanate (HMDI) and trimethylol propane (TMP) at a fixed TMP/PGA mole ratio. The number average molar mass between junction points of the network chains \overline{{\rm M}}_c was calculated using data obtained from swelling and uniaxial tensile tests and the results were compared. For the mechanical characterization of the networks, Mooney-Rivlin plots were prepared and the values of the constants 2C_1 and 2C_2 of PGA …

Synthesis Of The New Cation Exchange Resins Having Poly (Styrene-Caprolactone) Units, S. Savaşkan Yilmaz, Hulisi Özbayrak, Baki Hazer

Turkish Journal of Chemistry

The crosslinked polystyrene-polycaprolactone , PS-PCL-, block copolymers were prepared by the copolymerization of styrene and poly(caprolacton dimethylmethacrylate) (PCL-DM). The molecular weights of polycaprolactone, PCL, PCL-DM were 1250 and 2000. The swelling in H_2O or CHCl_3 of the sulfonated and unsulfonated block copolymers were determined under comparable conditions and investigated. The capacities of the obtained ion exchange resins were 1.31 and 1.10 meq/g.

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.

Electrical Conductivity Of Sodium Doped Poly(4-Vinylpyridine), Murat Özyalçin, Zuhal Küçükyavuz, Aref Jarvaherian, Savaş Küçükyavuz

Turkish Journal of Chemistry

Poly(4-Vinylpyridine) was synthesized by free radicalic polymerization. Solution doping process with metallic sodium was carried out. A conductivity value around 10^{-6} S/cm was obtained. Relative change in the coductivity with dopant concentration, temperature dependence of conductivity, conductivity behavior in atmospheric conditions for the samples were analyzed. SEM and EDX techniques were also used for the characterization of the polymer.

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.

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 …

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 …

Phase Transition Of Hydrolyzed Polyacrylamide Gels In Aqueous Solutions Of Poly(Ethylene Glycol), Nilhan Kayaman, Oğuz Okay, B. M. Baysal

Turkish Journal of Chemistry

Hydrolyzed polyacrylamide gels immersed in aqueous solutions of poly(ethylene glycol) (PEG) of molecular weight 300 exhibit a discontinuous volume change upon continuous increase of the PEG concentration in the external solution. As the duration of hydrolysis increases, that is, as the proportion of the ionic groups on the network chains increases, the critical concentration of PEG required for a discontinuous volume change rises and, also, the magnitude of the volume collapse becomes larger. Experimental results indicate that the gel collapse in PEG solution is due to the osmotic deswelling of the ionic gel rather than due to a complex formation …

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