Chemistry Commons^™

Computational Studies Of Constant Bond Dissociation Enthalpy Ratios And Novel Structures For [H3, B, C, F]+, Le Li

Masters Theses

This thesis describes two separate computational chemistry projects. The first project is a study of constant bond dissociation enthalpy ratios, and the second project is a study of the rearrangement and fragmentation processes on the singlet potential energy surface of the [H₃, B, C, F]⁺ system.

G2 and G2(MP2) enthalpies have been calculated for isoelectronic AB₂ systems with singlet-linear, singlet-nonlinear, triplet-linear, and triplet-nonlinear electronic states and geometries, and for isoelectronic AB systems with singlet and triplet electronic states. For these systems, A = B^-, Al^-, Ga^-, C, Si, Ge, N …

Pentacarbonyl Derivatives Of Polydentate Phosphines, Yi Zang

Masters Theses

Four phosphines (Ph₂P)₂C=CHPPh₂, (p-tol)₂PCH₂P(p-tol)₂, (o-tol)₂PCH₂P(o-tol)₂, Ph₂PCH₂P(p-tol)₂ and their pentacarbonyltungsten complexes have been prepared and studied as part of a continuous investigation of polydentate phosphines that are coordinated as monodentate ligands. The ligand, (Ph₂P)₂C=CHPPh₂, was prepared by base-catalyzed addition of Ph₂PH to Ph₂PC=CPPh₂. Reaction of this ligand with (OC)₅WNH₂Ph led to formation …

Computational Studies Of Regularities In Bond Dissociation Enthalpies And Interactions Of Acetylthiocholine With Solvent Molecules, Wencui Zheng

Masters Theses

This thesis reports the results of two different research projects. One project is an evaluation of the feasibility of applying constant bond dissociation enthalpy ratios to neutral molecules for which one atom is from group 13 or group 17 and the other atom is from group 16. The other project attempts to validate the proposal that the aromatic residues lining the acetylcholinesterase (AChE) gorge will induce entry of acetylthiocholine (ATCh) into the gorge in a manner similar to that of the neural transmitter acetylcholine.

A total of thirty AB₂ and AB molecules have been examined, where A = B, …

The Reactivity Of Boron And Aluminum Compounds With Silica Gel Surfaces, Jeannine M. Christensen

Masters Theses

The unmodified silica gel surface contains isolated silanols, vicinal silanols, and siloxane species. Silica gels can be thermally and/or chemically treated to obtain a desired surface. Hexamethyldisilazane (HMDS) was used to chemically modify the silica gel to obtain a surface that contains vicinal silanol groups and siloxane species. The silica gel was thermally treated at 600°C to create a surface that contains isolated silanols and siloxane species. Four types of silica gels (unmodified, 600°C, HMDS and 600°C/HMDS) were reacted with three boron compounds. The boron compounds used were boron trichloride (BCl₃), triethyl borane (B(CH₂CH₃) …

Electrorheological Properties Of Suspensions Prepared From Polystyrene- Block- Polyisoprene Copolymer, Hali̇l İbrahi̇m Ünal, Yilmaz Yildirir, Mustafa Yavuz

Turkish Journal of Chemistry

Considerable scientific and industrial interest is currently being focused on a class of materials known as electrorheological (ER) fluids, which display remarkable rheological behaviour, being able to convert rapidly and repeatedly from a liquid to solid when an electric field (E) is applied or removed. In this article, the synthesis, characterization, partial hydrolysis and ER properties of polystyrene- block}-polyisoprene copolymer (COP) were investigated. The block copolymer was characterized by GPC, viscosity measurements, ^1 H-NMR and FTIR spectroscopies, particle size measurements, and elemental analysis. The polystyrene block of the copolymer was partially hydrolyzed by a series of chemical reactions and then …

Determination Of Hydrochlorothiazide And Enalapril Maleate In Tablet Formulations By Reversed-Phase Hplc, Idrees F. Al-Momani̇

Turkish Journal of Chemistry

A high-performance liquid chromatographic procedure is presented for the determination of hydrochlorothiazide (HCT) and enalapril maleate (EM) in pharmaceutical tablets. An aliquot of the sample is dissolved in 15% acetonitrile (ACN) containing thiophylline as an internal standard and chromatographed on a Supelcosil LC-8 (5 \mu m), (150 mm x 4.6 mm i.d.) column. The mobile phase was 3.0 mM tetrabutylammoniumhydrogen sulfate (TBAHS) in ACN/water/triethylamine (TEA), (14, 85.6, 6.4 V/V) adjusted to pH 4.1 by glacial acetic acid. The detection was at 220 nm. The method was tested for linearity, accuracy, recovery, and specificity.

A Comparative Study On The Recovery Of Ecori Endonuclease From Two Different Genetically Modified Strains Of Escherichia Coli, Candan Tamerler, Zeynep İlsen Önsan, Betül Kirdar

Turkish Journal of Chemistry

A laboratory scale procedure developed for the purification of EcoRI restriction endonuclease was applied to two different Escherichia coli} strains, E. coli 294 and E. coli M5248, which are genetically modified to overproduce the enzyme. The purification method consisted of three successive chromatographic steps including phosphocellulose and hydroxyapatite columns and further fractionation in a second phosphocellulose column. It was shown that the second phosphocellulose separation can be omitted in the case of E. coli 294. Quality control tests indicated enzyme preparations free of contaminants and endo- or exo-nucleases. The yields obtained at the final stage of the purification were 1.3x10^{5} …

Fluorimetric Detection Of Insulin In The Presence Of Eu(Iii) - {Pyridine - 2,6 - Dicarboxylate} Tris Complex, Elmas Gök, Serdar Ateş

Turkish Journal of Chemistry

Bovine insulin solutions (pH=9.3) have maximum absorption at 278 \pm 2 nm and an intrinsic emission at 305 nm when excited at 282 nm. The relative fluorescence intensities show linear dependence on its concentration: 10 \mug/mL< [Ins] < 200 \mug/mL. When Eu(PDA)_{3}^{3-} tris complex is added to these solutions, it has a hyperchromic effect at 278 nm absorption band of insulin, sensitizing the emission intensities of central Eu^{3+} metal ion of the complex at 590 and 615 nm, and simultaneously quenching the emission intensity of hormone at 305 nm. Stern-Volmer plots show that a mechanism of bimolecular quenching at 305 nm and sensitization at 615 nm are valid up to a mole ratio, R = [Eu(PDA)_{3}^{3-}]/[Ins] < 2.0. An intramolecular rather than an intermolecular energy transfer is proposed. An apparent binding constant, log K_{app}=4.70 \pm 0.13, is calculated for Ins-[Eu(PDA)_{3}^{3-}]_{2} type product, the presence of which may offer a new luminescence technique as a diagnostic tool and an alternative to radio-iodinated (^{131}I -) insulin. A simple, rapid and accurate quantitation of insulin is proposed by using a fixed concentration of Eu(PDA)_{3}^{3-}, and measuring its initial F_{0} at \lambda_{exc}/ \lambda_{em}=282/615 nm and the difference, \DeltaF after sensitization when \sim 100 microliters of insulin sample is added. The coefficient of variation (CV), the relative error and minimum detectable amount of bovine insulin hormone are found to be 3.0%, 1.2% and 7.3 \pm 0.2 \mug /mL respectively.

The Isolation Of Carboxylic Acids From The Flowers Of Delphinium Formosum, Nedi̇me Dürüst, Seçki̇n Özden, Esra Umur, Yaşar Dürüst, Mustafa Küçüki̇slamoğlu

Turkish Journal of Chemistry

From the flowers of Delphinium formosum Boiss. et Huet. (Ranunculaceae) trans-aconitic, p-hydroxybenzoic, p-coumaric, caffeic and chlorogenic acids were isolated and identified. In addition, protocatechuic, vanillic and gentisic acids were identified.

Determination Of Fluoride And Some Metal Ion Levels In The Drinking Waters In Kayseri Province, Şeri̇fe Tokalioğlu, Uğur Şahi̇n, Şenol Kartal

Turkish Journal of Chemistry

Fluorine is one of the most common elements in the Earth's crust. Fluoride is recognized to be the most effective caries-preventive agent. The main sources of fluoride for people are generally food and drinking water. For this reason, the fluoride and also the metal ion (Ca, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb and Zn) concentrations in the drinking waters collected from the city center of Kayseri and its counties were investigated. In the determination of fluoride and of Na and K, an ion-meter with a combination-fluoride electrode and a flame photometer were used, respectively. The levels of …

Cross-Correlation Noise Studies In Atomic Magnet-Optic Rotation Spectroscopy, Ahmet T. İnce

Turkish Journal of Chemistry

Analytical signals in an Atomic Magneto-Optic Rotation spectrometer are buried in noise at the limit of detection. The noisy analytical signals were analysed by carrying out mathematical correlation of their time domain waveforms. The noise components of signals were removed by auto-correlation to simplify the study. If noise interferes in analytical signals whose source is unclear, a cross-correlation of the output waveform with noise source may identify the source, e.g., mains frequencies and background radio signals. A cross-correlation will reveal whether the two signals are derived from the same source. This can also lead to an improvement in the signal …

Simultaneous Determination Of Inorganic Anions And Organic Acids By Capillary Electrophoresis, Nevi̇n Özteki̇n, F. Bedi̇a Eri̇m Berker

Turkish Journal of Chemistry

A rapid, easy, and reproducible method for the simultaneous determination of inorganic anions and organic acids is reported. The method is based on the separation of anions in a capillary coated with a cationic polymer, polyethyleneimine (PEI). Four inorganic anions (chloride, sulfate, iodate and phosphate) and eight organic acids (oxalate, tartarate, malate, succinate, citrate, acetate, lactate, and propionate) were separated and quantified within 7 min by using 2,6-pyridinedicarboxylic acid (PDC) as the background electrolyte. The minimum detection limits are 0.67-2.87 \mu g/mL for inorganic ions and 0.38-2.84 \mu g/mL for organic acids. Reproducibilities in migration times (RSD%) for both inorganic …

Analysis Of Polychlorinated Dibenzofurans (Pcdfs) Isomers In Soil Samples, Mustafa Pehli̇van, Erol Pehli̇van

Turkish Journal of Chemistry

This study presents an analytical method for the separation of a series of polychlorinated dibenzofurans (PCDFs) emitted to the soil. PCDF contaminants were concentrated from soil samples and isolated from other materials by chromatographic methods and their quantitative determinations were performed by GC/MS (gas chromatography/mass spectroscopy).

Usefulness Of A Technique Based On Negative Corona Discharge For The Degradation Of Selected, Condensed Pahs: Application To The Oxidation Of Anthracene And Similar Structures, D. Tessi̇er, C. Oguic, J. Pinart, J. J. Aaron

Turkish Journal of Chemistry

The usefulness of negative corona discharge for oxidation of condensed polycyclic aromatic hydrocarbons (PAHs), including anthracene, naphthalene and 2,3-benzanthracene, adsorbed on a solid substrate is evaluated. In the case of anthracene, the application of corona discharge under high voltage (10-20 kV) for 10 to 180 min with a current intensity of 5-120 \mu A in a controlled, humid atmosphere leads to the progressive formation of anthraquinone. A kinetic study of the anthracene oxidation shows that the apparent half-lives range from 5 to 48 min, according to the initial anthracene amount (50-5000 nmol), indicating a reaction order between 0 and 1. …

Accumulation Of Heavy Metals In Freshwater Organisms: Assessment Of Toxic Interactions, Neylan Di̇ri̇lgen

Turkish Journal of Chemistry

Heavy metals are continuously released into the terrestrial environment by natural sources and human activities. The uptake and accumulation of heavy metals by plants promotes a mechanistic understanding of the biological significance of particular metal concentrations and distributions in biota. The toxicity of chromium, zinc, copper and cobalt ions and their binary mixtures are studied at varying test levels using duckweed as the test organism. The accumulation of metal ions are determined by atomic absorption spectroscopy. The type of toxic interactions in binary mixtures is assessed as `synergistic', `antagonistic' and `additive' by a statistical approach.

The Composition Of Essential Oils From Two Varieties Of Sideritis Erythrantha Var. Erythrantha And Var. Cedretorum, Nurhayat Tabanca, Neş'E Kirimer, K. Hüsnü Can Başer

Turkish Journal of Chemistry

Water distilled essential oils from two varieties of Sideritis erythrantha: var. erythrantha} and var. cedretorum, both endemic in Turkey, were analysed by GC/MS. The main components were characterized as \alpha -pinene (16.3-19.5%) and sabinene (6.1- 10.4%) for var. erythrantha; myrcene (21.9-24.3%) and \alpha -pinene (11.4- 12.4%) for var. cedretorum.

Structural Studies Of Water-Soluble \Beta-Brominated Manganese Porphyrins: Stabilities Of Mntdcsppbr _{8} And Mntsppbr _{8} As Homogeneous And Supported Reagents Toward Hydrogen Peroxide And Sodium Hypochlorite, Hayretti̇n Türk, Hüseyi̇n Berber

Turkish Journal of Chemistry

This article describes the structural stabilities of [2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetrakis(2,6-dichloro-3-sulfonatophenyl)porphinato]manganese(III) X (where X = H_{2}O and/or OH^{-} , depending on pH) (MnTDCSPPBr_{8} ) and [2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetra(4-sulfonatophenyl)porphinato] manganese(III) X (where X = H_{2}O and/or OH^{-} , depending on pH) (MnTSPPBr_{8} ) toward H_{2}O_{2} and NaOCl at various pH's, I = 0.2 M and 30^oC. In addition, the structural stabilities of these manganese porphyrins were investigated when they were bound to quaternary ammonium containing supports, namely, hexadecyltrimethylammonium bromide (CTAB), 2,6-ionene, 2,10-ionene and a poly[(vinylbenzyl)trimethylammonium chloride] latex. In alkaline media, both manganese porphyrins degraded and precipitated even in the absence of both of the oxidants. In …

Optimization Of Process Parameters For Reactive Lactic Acid Extraction, Emi̇ne Kahya, Emi̇ne Bayraktar, Ülkü Mehmetoğlu

Turkish Journal of Chemistry

The reactive extraction method was used to separate lactic acid from its aqueous solutions. In this method, the amine in the solvent phase reacts with the lactic acid in the aqueous phase, resulting in the extraction of acid into the organic phase. In this study, Alamine 336 diluted with oleyl alcohol was used as the solvent. The effects of initial lactic acid concentration, pH, temperature, extraction time, stirring rate, the amount of Alamine 336 in oleyl alcohol and the ratio of organic phase volume to aqueous phase volume, V_{org}/V_{aq}, on the distribution coefficient of the lactic acid, K_D, were investigated. …

Incorporation Of Edta For The Elimination Of Metal Inhibitory Effects In An Amperometric Biosensor Based On Mushroom Tissue Polyphenol Oxidase, Arzum Erdem, Di̇lşat Özkan, Burcu Meri̇ç, Kağan Kerman, Mehmet Özsöz

Turkish Journal of Chemistry

Enzyme based biosensors are highly selective devices which rely on the specific binding of the target analyte (the substrate) to the active-site regions of the enzyme. The enzymatic reaction between mushroom tissue polyphenol oxidase and its substrate phenol is coupled with the use of potassium ferrocyanide (K_{4}Fe(CN)_{6}) as the mediator in ammonia buffer solution (pH 8.80). The response of devices is often affected by the presence of inhibitors, which combine with the free enzyme in a manner that prevents substrate binding. The objective of this study is to describe an efficient and yet simple strategy to eliminate the interference of …

Determination Of Some Of The Physicochemical Properties Of Fine Alumina Powders Prepared By Emulsion Evaporation, Yüksel Sarikaya, İsmet Sevi̇nç, Müşerref Önal, Tülay Alemdaroğlu

Turkish Journal of Chemistry

In order to prepare fine alumina powders, an emulsion was prepared under optimum conditions. The emulsion was examined by optical microscopy and the prepared fine alumina powders were characterised by electron microscopy. The particles were formed of porous spheres and their sizes were between 1 and 10 \\mum. The powder samples were sintered by varying the temperature between 700 and 1600°C. The adsorption and desorption of nitrogen on these samples were investigated. By using the adsorption data, the specific surface areas were calculated according to different procedures and the correlation between them was discussed. The specific micropore and mesopore volumes …

Flow Injection Analysis For Boron Determination By Using Methyl Borate Generation And Flame Atomic Emission Spectrometry, Deni̇z Yurtsever Sarica, Nusret Ertaş

Turkish Journal of Chemistry

Boron is one of the least sensitive elements in atomic emission spectrometry. As various refractory substances interfere in the analysis and because of the low sensitivity, sample enrichment and the separation of the interfering matrix is needed. Methyl borate has many advantages because of its simple generation conditions and its stability in the absence of moisture. New procedures for the generation of methyl borate without using external heating have also been investigated to produce a more rapid determination of boron. The on-line combination of flow injection analysis using methyl borate generation with flame atomic emission spectrometry as the detector is …

Thermogravimetric Investigation Of The Dehydration Kinetics Of Ksf, K10 And Turkish Bentonite, Yalçin Tonbul, Kadi̇r Yurdakoç

Turkish Journal of Chemistry

The kinetic parameters for the dehydration of bentonite from Turkey, KSF and K10 were determined by using dynamic TG techniques. The Ozawa method is better for the dehydration of the clay samples than the first order equation of Coats and Redfern. The former function calculates consistently higher activation energies than the latter. The mean values of the activation energies in the \\alpha range 0.1-0.7, are 56-66 kJ mol^{-1} in the Ozawa method.

Selenium Speciation In Karakaya Dam Lake's Water (Malatya-Turkey), F. Zehra Küçükbay, Mustafa Demi̇r

Turkish Journal of Chemistry

Concentrations of total inorganic selenium, Se(IV), Se(VI) and organically bonded selenium from samples of Karakaya dam lake\\\'s water were determined using ammonium pyrollidine dithio carbamate (APDC) as a chelating agent and subsequent adsorption on amberlite type XAD-8 resins. Eluted analytes are taken up in a matrix free acidic solution suitable for graphite furnace atomic absorption spectroscopy (GFAAS). According to our results, levels of the total inorganic selenium, Se(IV), Se(VI) and organically bonded selenium were found to be between 0.11 \\pm 0.01 and 0.17 \\pm 0.01 \\mug/L, 0.07 \\pm 0.01 and 0.12 \\pm 0.01 \\mug/L, 0.02 \\pm 0.01 and 0.05 \\pm …

Lewis Acid Catalyzed 1,3-Dipolar Cycloadditon Reactions Of Stabilized Azomethine Ylides, Özdemi̇r Doğan, Hasan Koyuncu, Ümi̇t Kanişkan

Turkish Journal of Chemistry

Diethylzinc was tested for the first time as the Lewis acid in 1,3-dipolar cycloaddition reactions of azomethine ylides to synthesize pyrrolidine derivatives. A new, easily applicable and highly selective method was developed for the synthesis of highly substituted pyrrolidines. By the application of this method, the synthesis of three new pyrrolidine derivatives was achieved.

Characterization Of Lipids And Fatty Acid Methyl Ester Contents In Leaves And Roots Of Crocus Vallicola, Nuretti̇n Yayli, Zerri̇n Kiran, Hasan Seymen, Hasan Genç, Mustafa Küçüki̇slamoğlu

Turkish Journal of Chemistry

The chemical composition of the fatty acids methyl esters (FAMEs) and other lipids in leaves and roots of Crocusvallicola were analyzed by gas chromatography-mass spectrometry(GC-MS). In this work, twenty-eight compounds, including 22 FAMEs, 1 aldehyde, 3 hydrocarbons (substitute alkane and alkene), 2 alcohols in the leaves and twenty-one compounds (17 FAMEs, 1 anhydride, 1 substitute alcohol, 1 ketone, 1 substitute amide) in the roots were identified by GC-MS from C. vallicola. The FAMEs in leaves and roots were highly similar; only the amounts of the esters were different. Key Words: Crocus vallicola, leaves, roots, FAMEs

Effect Of Acid Treatment On Volumetric Swelling Ratios Of Coals, Nejat Mesci̇, Aki̇f Şenelt, Taner Toğrul, Aral Olcay

Turkish Journal of Chemistry

To remove Ca^{2+} ions, six low rank coals and one coking coal were treated with 0.1 and l.0 N HC1 for 24 h. IR spectra and proximate analysis of the lignites indicated that only slight structural changes had occurred during acid treatment. The swelling ratios of parent and acid-treated coal samples showed that removal of Ca^{2+} resulted in an increase in the swelling ratios. Higher swelling ratios were obtained with acid-washed coal samples. While the highest swelling ratios of the parent lignites were obtained in ethylenediamine, those of acid-treated samples were obtained in pyridine and dimethylformamide.

Calculation Of Multi-Center Integrals For The Region Of Moderate And Weak Overlap, Abdulhali̇k Karabulut, Gökhan Budak, Lütfü Demi̇r, Nagi̇f Sefteroğlu Nabi̇yev, Yusuf Şahi̇n

Turkish Journal of Chemistry

In this study a general formula was established for multi-center integrals over Gaussian basis sets using the two-center expansion of nuclear attraction and electron repulsion potentials. The terms of the formula are the analytical functions of interatomic distances. Three kinds of integrals contained in these formulae can be evaluated analytically. In the presented method, unlike many other popular methods, the numerical integrations procedure is unnecessary since it does not contain the incomplete gamma function. A computer program was written and tested for various orbitals. The calculations show that the series converge very rapidly.

Propylene Dimerization Over Nickel-Ion Exchanged Zeolites In The Liquid Phase, Mina K. Munshieva

Turkish Journal of Chemistry

The possibility of the dimerization of propylene in the liquid phase over nickel-ion exchanged zeolites (Ni-zeolites) modified by treatment with AlEt_{2}Cl to provide enhanced activity is studied. In order to determine the influence of the crystalline structure of zeolites on their catalytic activity and the selection of the most active catalyst the zeolites of faujasite (NaX, NaY), eryonite and mordenite types with various structures and different cell sizes have been chosen. The samples of Ni-zeolites were prepared by ion exchange with nickel nitrate in a corresponding zeolite. The treatment of these zeolites with AlEt_{2}Cl leads to the formation of active …

Hydrothermal And Microwave Synthesis Of Boron Phosphate, Bpo_{4}, A. Baykal, Meral Kizilyalli, M. Toprak, R. Kniep

Turkish Journal of Chemistry

BPO_4 was previously synthesized by the solid state reactions of (NH_4)_2HPO_4 and B_2O_3 at 1000 ^oC and was characterized by X-ray powder diffraction and IR methods. We have now succeeded in preparing BPO_4 from H_3BO_3 and P_2O_5 using hydrothermal synthesis by heating at 160 ^oC for 2 days and obtained a single phase product. We observed that a microwave-assisted synthesis takes only 3 to 5 minutes to transform a solid mixture of (NH_4)_2B_4O_7.4H_2O, and solid H_3PO_4 or B_2O_3 + P_2O_5 into the crystalline title compound. Its X-ray powder diffraction data and IR spectra were in good agreement with the literature …

The Influence Of Transition Metal Ions On The Kinetics Of Ascorbic Acid Oxidation By Methylene Blue In Strongly Acidic Media, M. Nasiruddin Khan, Anila Sarwar

Turkish Journal of Chemistry

The kinetics of the oxidation of L-ascorbic acid (H_{2} A) by methylene blue was investigated in strongly acidic media over the temperature range 22-40 ^oC. The kinetic studies were carried out as a function of different variables like concentration, pH, ionic strength and temperature. The rate was found to be a linear relation with [H_{2} A], [M.B.] and [H^{+}]. Ionic strength dependence formation indicated complex formation by monocationic and anionic species in solution. The reaction rate was greatly catalyzed by the presence of trace amounts of copper (II) ion. Possible mechanisms for the catalyzed and uncatalyzed reactions are proposed. Kinetic …