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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.

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 …

Impedance Feedback Control For Scanning Electrochemical Microscopy, David O. Wipf, Mario A. Apuche-Avlles

CAS Publications

A new constant-distance imaging method based on the relationship between tip impedance and tip-substrate separation has been developed for the scanning electrochemical microscope (SECM). The tip impedance is monitored by application of a high frequency ac voltage bias between the tip and auxiliary electrode. The high frequency ac current is easily separated from the dc level faradaic electrochemistry with a simple RC filter, which allows impedance measurements during feedback or generation/collection experiments. By employing a piezo-based feedback controller we are able to maintain the impedance at a constant value and, thus, maintain a constant tip-substrate separation. Application of the method …

Isolation And Characterization Of Chromium- And Cobalt-Binding Peptides, Michael J. Jose

Honors Theses

Metal substitution has been proposed as an aid in the characterization of the structure of Low-Molecular-Weight Chromium-binding substance (LMWCr), which appears to be the biologically active chromium species. Preparations of bovine liver were diced and suspended in an isolation solution containing either a cobalt or a chromium salt. Peptide samples from these preparations were isolated by precipitation and centrifugation and purified by liquid chromatography. Several methods were used to analyze these samples, which may contain LMWCr or the cobalt-substituted form (LMWCo), in order to determine their purity, molecular weight (MW), and metal-to-peptide ratio. Methods used to determine MW included sodium …

Increased Severity Of Hsv-1 Keratitis And Mortality In Mice Lacking The 2–5a-Dependent Rnase L Gene, Xiaodong Zheng, Robert H. Silverman, Aimin Zhou, Tomoko Goto, Byoung Se Kwon, Herbert E. Kaufman, James M. Hill

Chemistry Faculty Publications

Purpose: The2′,5′-oligoadenylate-dependent RNase L gene functions in the interferon-inducible RNA decay pathway known as the 2–5A system. The purpose of this study was to determine whether the absence of this gene affects the pathogenesis of herpes simplex virus type 1 (HSV-1) ocular infection in the mouse. Methods: HSV-1 (strain McKrae) was applied bilaterally to unscarified corneas of RNase L–null mice and congenic controls. To evaluate the severity of herpetic keratitis, slit lamp examinations (SLE) were performed every other day for 14 days. To study corneal histology and apoptosis, HSV-1–inoculated RNase-L-null and congenic control mice, as well as mock-inoculated mice (apoptosis …

Observations Of Apan During Texaqs 2000, James M. Roberts, Frank Flocke, Andrew Weinheimer, Hiroshi Tanimoto, Bertram T. Jobson, Daniel Riemer, Eric Apel, Elliot Atlas, Stephen G. Donnelly Ph.D., Verity Stroud, Kristen Johnson, Rachel Weaver, Fredrick C. Fehsenfeld

Chemistry Faculty Publications

Measurements of peroxycarboxylic nitric anhydrides (PANs) made in Houston, Texas during TexAQS (Texas Air Quality Study) 2000 showed a relatively abundant PAN compound that had not been identified in previous studies in North America [cf. Williams et al., 2000]. This compound was hypothesized to be peroxyacrylic nitric anhydride { CH2=CHC(O)OONO2, APAN} based on the work of Tanimoto and Akimoto, [2001]. APAN was synthesized and characterized on one of the two GC systems used to make those measurements, subsequent to the TexAQS 2000 field study, confirming that APAN was observed during TexAQS 2000, both on the ground and in airborne measurements. …

Synthesis And Spectrophotometric Investigation Of A New Vic-Dioxime Ligand And Its Transition Metal Complexes, Mustafa Dolaz, Mehmet Tümer, Ayşegül Gölcü, Selahatti̇n Seri̇n

Turkish Journal of Chemistry

A new vic-dioxime ligand and its Cu(II), Co(II), Ni(II), Pd(II), VO(IV) and Zn(II) complexes have been prepared and characterized by elemental analyses, infrared, electronic spectra, magnetic moment and molar conductance data. The Ni(II), Pd(II) and Zn(II) complexes have a diamagnetic character. The ^{1}H- and ^{13}C-nmr and GC/MS spectra of the vic-dioxime ligand and its Ni(II), Pd(II) and Zn(II) complexes were recorded. In addition, all compounds are non-electrolyte.

Kinetics Of Proteolyic Enzymes Monitored Online With Mass Spectrometry, Jennifer L. Rutherford

Theses, Dissertations and Capstones

On-line reaction monitoring using electrospray ionization mass spectrometry was investigated with the goal of kinetically distinguishing the isomeric amino acids leucine and isoleucine. Leucine and isoleucine are isomers of identical mass (113.0946 Da) which are impossible to distinguish by their mass-to-charge ratios. These isomers are a source of ambiguity when sequencing peptides with exoproteases and mass spectrometry. Here we investigated the kinetics of on-line enzymatic reactions involving exoproteases for differentiating between leucine and isoleucine.

The kinetics of the stepwise exopeptidase degradation of 12 leucine/isoleucine isomeric peptides was monitored in real-time with a Finnigan Mat LCQ with an electrospray ionization source. …

Synthesis And Analysis Of Three-Dimensional Molecular Architectures, Patricia Beck

LSU Master's Theses

The use of resorcinarenes in the study of biologically significant phenomena has been the focus of much attention, due to the versatility of these macrocyclic compounds. In this thesis, two applications of resorcinarenes are explored. First, the search for the mechanism by which tetraarylboronic acid resorcinarenes lead to colorimetric detection and quantization of saccharide analyte concentration in solution is described. Second, the extension of the lower rim conjugation of the resorcinarene macrocycle by the fourfold addition of various length oligo(p-phenylene) rods is discussed. The synthesis of these tubular materials, with potential uses as artificial ion channels and for binding and …

Synthesis And Characterization Of Copper(Ii), Nickel(Ii), Cadmium(Ii), Cobalt(Ii) And Zinc(Ii) Complexes With 2-Benzoyl-3-Hydroxy-1-Naphthylamino-3-Phenyl-2-Propen-1-On, Mehmet Sönmez

Turkish Journal of Chemistry

Cu(II), Ni(II), Co(II), Zn(II) and Cd(II) complexes of 2-Benzoyl-3-hydroxy-1-naphthylamino-3-phenyl-2-propen-1-on, which is a derivative of carboxamide, were prepared and characterized by elemental, spectral and magnetic methods. Based on the analytical results, electronic and infrared spectral data and magnetic susceptibility measurements, suitable structures have been proposed. The formation of the complexes in solution was investigated conductometrically. 2-Benzoyl-3-hydroxy-1-naphthylamino-3-phenyl-2-propen-1-on was found to be a bidentate ligand coordinating through enolic oxygen and amide nitrogen. The complexes of Co(II) and Ni(II) are proposed to have an octahedral structure, while Cd(II), Cu(II) and Zn(II) are suggested to possess a square-planar environment in the complexes.

Evaluation Of Sample Pre-Treatment Procedures For The Determination Of Cr, Ni And V In Biological Matrices By Etaas, Jan Medved, Jana Kubova, Eva Chmielewska, Vladimir Stresko

Turkish Journal of Chemistry

Electrothermal atomic absorption spectrometry (ETAAS) was applied for the determination of chromium, nickel and vanadium in biological materials (earthworms, feather, lucerne). Three different decomposition procedures of biological matrices are presented. The utilization of NH_4H_2PO_4, Mg(NO_3)_2 and Pd(NO_3)_2+ Mg(NO_3)_2 as chemical modifiers are investigated and compared. Optimal temperature conditions for the electrothermal determination of Cr, Ni and V are selected. Precision of the determination expressed as relative standard deviations for Cr, Ni and V varied from 6 to 22% . The detection limits are for Cr 8 \\mu g kg^{ - 1}, Ni 12 \\mu g kg^{ - 1}, and V …

Development Of Amperometric Enzyme Electrodes For Glucose And Hypoxanthine., Eilish Broderick

Theses

This thesis is concerned with the immobilisation of enzymes on electrosynthesised poly (o- phenylenediamine) membranes for use on amperometric electrodes. The thesis opens with a discussion of the basic principles of enzymology and a review of a diverse range of biosensors, followed by a consideration of amperometry as governed by the Cottrell equation.

Glucose oxidase and horseradish peroxidase were co-immobilised in poly (o-phenylenediamine) on platinum electrodes at + 0.6 V versus Ag/AgCl. Using this approach the enzymes are entrapped in a strongly adherent, highly reproducible thin membrane, of thickness approximately 10 nm. This one-step procedure produces a glucose sensor with …

Analysis Of Wine For Penicillin, Gary Morris, James Yuan, Roy Williams

Chemistry & Biochemistry Faculty Publications

This study addresses the question of whether the antibiotic Penicillin, which is produced by the common mold Penicillium notatum, could possibly become a contaminate of wine during the fermentation process. The significance of this study is related to the potential health effects this agent might produce in those consumers who have an allergic response to Penicillin. It has been estimated that between 6% and 8% of the American population is subject to this type of allergic response. A method is developed for the detection of penicillin in wines using high-pressure liquid chromatography. We demonstrate that penicillin G hydrolyzes rapidly …

Meso-1, 2-Bis (Methylazo)-1, 2-Diphenylethane, Craig A. Bayse, Barry K. Carpenter, Rudy L. Luck

Chemistry & Biochemistry Faculty Publications

The title compound, meso-1,2-bis(methyldiazenyl)-1,2-diphenylethane, C16H18N4, is arranged in a disordered manner around an inversion point. The N—N atom distances in the azo group of 1.192 (8) and 1.195 (8) Å, and the C—C atom distances in the ethylene moiety at 1.512 (8) and 1.503 (8) Å in the two models [refined to 51.7 (6) and 48.3 (6)% occupancies] were not significantly different.

Chemically Accurate Conformational Energies For Aziridine-2-Carbonitrile, Gregory S. Tschumper

Chemistry Faculty Research & Creative Works

The energy of trans-aziridine-2-carbonitrile relative to cis-aziridine-2-carbonitrile was determined by carrying out extensive ab initio computations. The coupled cluster technique was used to determine the higher order computations, that includes perturbative estimate of the triple excitations. The electronic energy of the transition structure connecting the two conformers was determined to be 77.15 kJ/mol higher than the cis-isomer.

Probing The Capabilities Of Copper Complexes With Nitrogen And Sulfur Containing Macrocyclic Ligands As Aziridination Catalysts, Jonathan Natkin

Honors Theses

Aziridines are three-membered rings containing one nitrogen atom. They are useful as synthetic intermediates in many organic reactions. Much work has been devoted to synthesizing their analogs, cyclopropanes and epoxides, but little work has been done on the aziridination reaction. This study endeavored to probe the efficiencies of novel copper aziridination catalysts with N3 and S3 macrocyclic ligands compared to an NS2 analog for the reaction with the nitrene precursor (N-(paratosylsulfonyl) imino)phenyliodinane, PhINTs, and the olefin styrene. The nitrogen containing catalyst complex gave higher yields than the sulfur containing catalyst complex. Both ligands were found to decrease the yield of …

Identification Of The Domains Of Urer, An Arac-Like Transcriptional Regulator Of The Urease Gene Cluster In Proteus Mirabilis, Carrie A. Poore, Christopher Coker, Jonathan D. Dattelbaum, Harry L.T. Mobley

Chemistry Faculty Publications

Proteus mirabilis urease catalyzes the hydrolysis of urea to CO₂ and NH₃, resulting in urinary stone formation in individuals with complicated urinary tract infections. UreR, a member of the AraC family, activates transcription of the genes encoding urease enzyme subunits and accessory proteins, ureDABCEFG, as well as its own transcription in the presence of urea. Based on sequence homology with AraC, we hypothesized that UreR contains both a dimerization domain and a DNA-binding domain. A translational fusion of the leucine zipper dimerization domain (amino acids 302 to 350) of C/EBP and the C-terminal half of UreR …

A Ring-Closing Strategy For The Synthesis Of Β,Γ-Unsaturated Δ-Lactones, Erbing Hua

Masters Theses

Spiro β,γ-unsaturated δ-lactones and fused β,γ-unsaturated δ-lactones are integral to a large number of naturally occurring compounds exhibiting a diverse range of biological activity. A new synthetic route to β,γ-unsaturated δ-lactones, consisting of a three-step sequence, has been investigated for the synthesis of these kinds of pharmacological intermediates. Ring closure of a β-hydroxy acid by dehydration, providing a 4-vinyl substituted β-lactone, and its ring expansion/rearrangement are the two key steps in this protocol. The results have proved that this new method is efficient and quite expeditious. One spiro and four fused β,γ-unsaturated δ-lactones were synthesized through this protocol albeit in …

The Synthesis Of Deuterated Arylamine Dna Adducts For Use In The Development Of An Isotope Dilution Lc/Ms/Ms Method, Philip Dmitri Olsen

LSU Doctoral Dissertations

Polycyclic aromatic amines (arylamines) are a class of chemical carcinogens that are prevalent in environmental and industrial settings. In order to study the mechanism of their toxicity a quantitative and qualitative detection method was developed to measure the C8-adenine adducts of benzidine and 2-aminofluorene in DNA samples. To do this a novel synthetic method using a palladium catalyst was developed to prepare authentic and deuterated arylamine adducts to serve as standards. These standards were then used to develop a high performance liquid chromatography, electrospray, tandem mass spectrometry, isotope dilution, detection method. To demonstrate the validity of this method two spike …

Chemical Constituents Of Desmos Dumosus, Roxb., Mazdida Sulaiman

Student Works (2000-2009)

The chemical content of the 'leaves and bark of Des mos dumosus has been carried out in this study. The leaves yielded nine isoquinoline type of alkaloids and two flavones. The isoquinoline alkaloids isolated were pronuciferine 37, stepharine 39, nomuciferine 40, (-) - 3 - hydroxynomuciferine 41, norlirioferine 42, asimilobine 43, liriodenine 44, lysicamine 45 and O - methylmoschatoline 46. The flavones were 5 - hydroxy - 6,7 - dimethoxyflavone 47 and 5 - hydroxy - 7,8 - dimethoxyflavone 48. The same flavones, 47 and 48 and the alkaloids 45 and 46 were also present in the bark of this …

The Coupling Of Biotechnology With Electrochemistry: Electrodenitrification Of Water Using The Enzyme Nitrate Reductase, Cyril Geyer

Dissertations and Theses @ UNI

Nitrate is a worldwide contaminant that causes environmental (eutrophication) and human health (methemoglobinemia, cancers) concerns. Very few techniques are available to eliminate it from natural environment and they suffer from major drawbacks, such as production of unwanted byproducts (toxins or brine). The electrochemical reduction of nitrate on any electrode is relatively slow and catalysts or electron mediators are needed. The goal of this project was to develop a new process that could overcome these disadvantages. The project demonstrates the feasibility of using an enzyme, nitrate reductase, and a mediator, methyl viologen to transfer the electrons from the electrode to nitrate, …

Municipal Waste Characteristics And Management In Pantai Dalam, Kuala Lumpur, Ratanam Andythaven

Student Works (2000-2009)

The primary purpose of this research was to study comprehensively the municipal waste generation (rate, quantity), waste characterization including (physical, chemical and biological parameters), heavy metal content, waste recovery and recycling, and socio economic aspects of municipal solid waste (MSW) generation and management in Taman Bukit Angkasa, Pantai Dalam, Kuala Lumpur and the surrounding areas. The waste characterization and management was determined with actual field observations coupled with questionnaire survey from a random sample of 250 households (200 flats houses, 25 long houses and 25 squatter residences). The quantification and other parameters (heavy metals, water extractable nutrients, nitrogen, pH, acidity, …

Towards The Asymmetric Synthesis Of Ascochlorin, Özdemi̇r Doğan, Wolfgang Oppolzer

Turkish Journal of Chemistry

A synthetic approach is described to the asymmetric synthesis of ascochlorin (1), an antiviral antibiotic, based on the construction of a sesquiterpene unit via asymmetric Diels-Alder reaction of tigloyl sultam 4 & butadiene, and the introduction of the aromatic side chain (C9-C12 unit) by employing cuprate chemistry.

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

New Photochemical And Electrochemical Methods For The Degradation Of Pesticides In Aqueous Media. Environmental Applications, J. J. Aaron, Mehmet A. Oturan

Turkish Journal of Chemistry

The development of new electrochemical and photochemical methods for the decontamination of natural water containing significant concentrations of aromatic pesticides is described. The electrochemical method is based on the electro-Fenton process, i.e. the simultaneous reduction of O_{2} and Fe^{3+} ions. Hydroxyl (OH^{.}) radicals are electrosynthesized in aqueous solutions, followed by complete mineralization of the initial pollutants. The photochemical methods involve either a direct photodegradation reaction of pesticides by UV light, or indirect photodegradation processes including H_{2}O_{2} photolysis or photo-Fenton reagents (H_{2}O_{2}/ Fe^{3+} ). Examples of the application of these methods to chlorophenoxy acid herbicides and four aromatic pesticides (bendiocarb, pirimiphos-methyl, …

Auditing And Biological Treatment Of Oleochemical Industry Waste, Fauziah Shahul Hamid

Student Works (2000-2009)

The utilization of renewable resources particularly from plant-based industries, such as, in the oleochemical sector makes it possible for further expansion of down-stream process products. However, to remain competitive the pollution generated from this industry should not be taken lightly. Implementation of cleaner technology into the oleochemical process will increase the efficiency of resource utilization of the industry, concurrently reducing quantity of waste generated. Waste audit conducted at Cognis Oleochemical (M) (COM) Sdn. Bhd. indicated that the major process-wastes generated by the facility were glycerol residue (GR) from Cognis Rika (M) Sdn. Bhd. (CRM) and wastewater sludge (WWS) from COM …

Heavy Metals And Organic Pollutants In Sediments Of Dar Es Salaam Harbour Prior To Dredging In 1999, J F Machiwa

Tanzania Journal of Science

Heavy metals and organic contaminants were analysed in the sediments of the inner area of the Dar es Salaam harbour. Complementary analytical parameters, such as, the organic carbon content and the silt/clay fraction of the sediments showed good positive correlation (r = 0.64). Stations that had high content of fine grain material in the sediment also indicated relatively high level of organic carbon and pollutants. The Florida criteria (MacDonald 1993) for assessment of pollution of tropical marine sediments was adopted in oredr to evaluate the extent of pollution in Dar es Salaam harbour sediments. The Florida criteria is one of …

Composition And Anaerobic Digestion Of Single And Combined Organic Fractions Of Municipal Solid Waste Of Dar Es Salaam, A K Kivaisi, J Mukisa

Tanzania Journal of Science

The composition of major categories of municipal solid waste (MSW) of Dar es salaam city was determined. Food remains and vegetable matter constituted 80-90% of the categories. Organic fractions of the individual categories contained 18-20 % total solid (TS), 30-50 % (dry weight) total fibre and 1-1.3 % nitrogen. The assorted organic fractions were tested for anaerobic conversion into biogas at 55°C in batch cultures for 14 days with a mixed population of microorganisms. At a substrate concentration of 6-8 g volatile solids per litre fermenter volume (g VS l-1 FV) individual fractions were degraded by 51-75% and gave methane …

High-Performance Liquid Chromatographic Separation Of Enantiomers Of Synthetic Amino Acids On A Ristocetin A Chiral Stationary Phase, Antal Péter, Gabriella Török, Daniel W. Armstrong, Géza Tóth, Dirk Tourwé

Chemistry Faculty Research & Creative Works

A macrocyclic glycopeptide, ristocetin A, was used as chiral stationary phase for the high-performance liquid chromatographic separation of enantiomers of 28 unnatural amino acids, such as analogues of phenylalanine, tyrosine and tryptophan, and analogues containing 1,2,3,4-tetrahydroisoquinoline, tetraline or 1,2,3,4-tetrahydro-2-carboline skeletons. Excellent resolutions were achieved for most of the investigated compounds by using reversed-phase or a new polar-organic mobile phase system. The conditions of separation were optimized by variation of the mobile phase composition, temperature and flowrate. Copyright (C) 2000 Elsevier Science B.V.

Allosteric Tuning Of Ruthenium 2,2’-Bipyridyl Luminescent Sensor Systems, Daqing Gan

Masters Theses

A series of new ruthenium bipyridyl crown supramolecular sensor systems containing two binding sites were synthesized. The crystal structure and photophysical properties of the developed sensor systems were thoroughly studied using x-ray, nuclear magnetic resonance and photoscopy methods. It turned out that the chelation of transition metal on the remote sites of the bipyridyl crown ligands greatly reduced the reactivity of the crown cavity. It is believed that the chelation of transition metal on the nitrogen atoms forces the bipyridyl function towards coplanarity and restricts the conformational freedom of the crown ring. The conformational rigidity in turn influences the binding …