Chemistry Commons^™

Prediction Of Acidity Constants Of Thiazolidine-4-Carboxylic Acid Derivatives Using Ab Initio And Genetic Algorithm-Partial Least Squares, Ali Niazi, Saeed Jameh Bozorghi, Davood Nori Shargh

Turkish Journal of Chemistry

A quantitative structure-property relationship study is suggested for the prediction of the acidity constants of some thiazolidine-4-carboxylic acid derivatives in aqueous solution. Ab initio theory was used to calculate some quantum chemical descriptors, including electrostatic potentials and local charges at each atom, highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energies, etc. Modeling of the acidity constant of thiazolidine-4-carboxylic acid derivatives as a function of molecular structures was established by means of the partial least squares algorithm. The subset of descriptors, which resulted in a low prediction error, was selected by genetic algorithm. This model was applied …

Electrochemical Copolymerization Of Thiophene Containing Pseudo-Polyether Cages With Pyrrole, Ati̇lla Ci̇haner, Ahmet M. Önal

Turkish Journal of Chemistry

Conducting copolymers were synthesized via the electrochemical oxidation of pyrrole (Py) in the presence of the monomer 1,12-bis(2-thienyl)-2,5,8,11-tetraoxadodecane (I). The presence of monomer I in the electrolytic solution greatly changed the CV behavior of Py during its potensiodynamic polymerization. The electroactivity of poly(I-co-Py) increased with the increasing amount of I in the comonomer mixture. Copolymer films were prepared via constant potential electrolysis in an electrolytic solution containing 0.1 M tetrabutylammonium hexafluorophosphate (TBAPF_6) dissolved in acetonitrile. The spectroelectrochemical properties of the films were investigated using UV-VIS spectroscopy.

Attempted Synthesis Of 1-Cyclohepta-1,2-Dien-1-Ylbenzene And Wurtz-Like Condensation Products In The Reaction Of 1-(2,3-Dibromocyclohept-1-En-1-Yl)Benzene With Zinc, Mustafa Ceylan, Yakup Budak, M. Burcu Gürdere

Turkish Journal of Chemistry

7,7-Dibromo-1-phenylbicyclo[4.1.0]heptane 4 was synthesized and its thermal and silver ion-catalyzed rearrangements were studied. Alcohol 8 was converted to 1-(2,3-dibromocyclohept-1-en-1-yl)benzene 6. The zinc-mediated elimination of 1-(2,3-dibromocyclohept-1-en-1-yl)benzene 6 resulted in the formation of 2 isomeric Wurtz-like condensation products 15 and 16 (whose structural assignments were based on ^1H-and ^{13}C-NMR spectral data) instead of the expected 1-cyclohepta-1,2-dien-1-ylbenzene 14.

A New Flame-Retardant Polyamide Containing Phosphine Oxide And N,N-(4,4-Diphenylether) Moieties In The Main Chain: Synthesis And Characterization, Khalil Faghihi

Turkish Journal of Chemistry

A new flame-retardant polyamide containing phosphine oxide moieties in the main chain was synthesized from the solution polycondensation reaction of bis(3-aminophenyl) phenyl phosphine oxide with N,N-(4,4-diphenylether) bis trimellitimide, using thionyl chloride, N-methyl-2-pyrolidone, and pyridine as condensing agents. This new polymer was obtained in high yield (92%), has high inherent viscosity (0.73 dL/g), and was characterized by elemental analysis, FT-IR spectroscopy, thermal gravimetric analysis (TGA and DTG), and solubility testing. Furthermore, another polyamide was prepared by the solution polycondensation reaction of N,N-(4,4-diphenylether) bis trimellitimide with 1,4-phenylene diamine, and its flame-retardant behavior was compared to that of the previous one.

Synthesis Of 1-Cyclohept-1,2-Dien-1-Yl Benzene From 1-(2-Iodo-, Chlorocyclohept-1-En-1-Yl)Benzene And 1-(2-Iodo-, Chlorocyclohept-2-En-1-Yl)Benzene: Its Trapping With Diphenylisobenzofuran, Mustafa Ceylan, Yakup Budak, Murat Ulukaya, M. Burcu Gürdere, Esra Findik

Turkish Journal of Chemistry

The key compounds vinyl iodides 12a and 13a, for the generation of 1-cyclohept-1,2-dien-1-ylbezene (1), were synthesized from cycloheptanone (5). Bromobenzene was converted to the Grignard reagent, which was condensed with 5. Dehydration of alcohol 6 gave alkene 7. Hydroboration of 7 followed by oxidation with PCC afforded ketone 9, which was converted to hydrazone 10. Treatment of 10 with iodine resulted in the formation of 12a and 13a. The other precursors, 12b and 13b, were synthesized from the reaction of 9 with PCl_5. Reactions of 12a, b and 13a, b with KOtBu in a sealed tube at 185 °C gave …

Simple Synthesis Of \Alpha -Oxime Derivatives Of 2-Ketomethyl Quinolines Under Mild And Heterogeneous Conditions, Javad Safari, Mehdi Adib, Firouzeh Sheibani, Zahra Sadeghi

Turkish Journal of Chemistry

2-Ketomethyl quinolines are converted to their \alpha-oximinoketone derivatives in quantitative yields using sodium nitrite in the presence of silica sulfuric acid as nitrosating agent under mild and heterogeneous conditions.

Synthesis And Properties Of Triazol-5-One Substituted Phthalocyanines By Microwave Irradiation, Bahatti̇n Kahveci̇, Selami̇ Şaşmaz, Musa Özi̇l, Ci̇han Kantar, Başak Koşar, Orhan Büyükgüngör

Turkish Journal of Chemistry

Triazol-5-one substituted phthalocyanines were prepared quickly by the reaction of 4-nitrophthalonitrile with anhydrous metal salts in DBU (1,8-diazabicyclo[5,4,0]undec-7-ene) and DMAE (dimethylaminoethanol) by microwave irradiation. Microwave yields were higher than those of the conventional synthesis methods. All of these complexes are insoluble in polar solvents such as ethanol, ethyl acetate and chloroform. The characterization of the compounds was accomplished by elemental analysis, ^1H NMR (for I and II), ^{13}C NMR (for I and II), IR and UV-Vis spectral data. In addition, the structure of the starting material (I) was determined by single crystal diffraction.

A New Method For The Preparation Of Pyridazine Systems: Experimental Data And Semiempirical Pm3 Calculations, Di̇lek Ünal, Emi̇n Saripinar, Yunus Akçamur

Turkish Journal of Chemistry

The reactions of 4-benzoyl-5-phenyl-2,3-furandione (1a) and 4-(4-methoxybenzoyl)-5-(4-methoxyphenyl)-2,3-furandione (1b) with acyl hydrazines (2) (namely hydrazides) are reported. From these reactions, novel pyridazinone systems (3a-g) are obtained as well as the cyclization product of 3g at high temperature (4). The electronic properties and conformational parameters for these molecules, such as bond lengths, bond angles, torsion angles and atom charges, are calculated with a semiempirical PM3 method. In order to determine the mechanism of the reaction between the model furandion (R1) and formic hydrazide (R2), the electronic properties, conformational parameters and imaginary frequencies of the reactants, transition states and intermediates are calculated at …

The Mechanism And Crystal Structure Of 2-Methoxy-2-Methyl-4-Phenyl-3,4,4a, 10b-Tetrahydro-2h,5h-Pyrano[3,2-C]Chromen-5-One. Acetal Of Warfarin Acid, Saira Shahzadi, Saqib Ali, Irum Asif, Rizwana Ashraf, Guo-Xin Jin

Turkish Journal of Chemistry

Acetal of warfarin acid has been synthesized via a hemi acetal intermediate and structurally characterized by X-ray diffraction. The crystal structure shows that the title compound was formed by the hydrolysis of warfarin acid in methanol at pH 3, with space group P2_1/n and unit cell parameters a = 5.859 (17), b =16.745 (5), c = 16.402 (5) Å, \alpha = 90.00; \beta = 94.853 (4), and \gamma = 90.00°.

Cerium(Iii) Ion-Selective Electrodes Based On 1,4,7-Trithiacyclononane, Hamid Reza Pouretedal, Abolfazl Semnani, Mohammad Hossein Keshavarz

Turkish Journal of Chemistry

Novel plasticized polymeric membrane (PPME) and coated platinum wire (CPWE) electrodes based on 1,4,7-trithiacyclononane and oleic acid, as a good lipophilic additive for highly selective determination of Ce^{3+} ions, have been developed. The electrodes exhibit a Nernstian slope of 19.4 mV/decade (for both electrodes) over a wide Ce^{3+} ion concentration range, from 5.0 \times 10^{-6}-5.0 \times 10^{-2} M and 1.0 \times 10^{-7}-1.0 \times 10^{-2} M for PPME and CPWE, respectively. The limits of detection were 3.5 \times 10^{-6} and 8.0 \times 10^{-8} M for PPME and CPWE, respectively. The electrodes possess a fast response time of 15 s, can be …

Hydrothermal And Microwave-Assisted Synthesis Of Boroarsenate, Baso_4, Abdulhadi̇ Baykal, Ayten Evren

Turkish Journal of Chemistry

BAsO_4 was previously synthesized by solid-state reactions at 800 °C and was characterized by X-ray powder diffraction. Now, we succeeded in preparing BAsO_4 from H_3BO_3 and As_2O_5 using hydrothermal synthesis by heating at 160 °C for 3 days (a single-phase product) and using microwave-assisted synthesis, which takes only 5 min to transform a solid mixture of As_2O_5 and (NH_4)_2B_4O_7.4H_2O into the crystalline titled compound (a single-phase product). The crystallinity of the products is higher than that of the solid-state synthesized product given in the literature. Its X-ray powder diffraction patterns, and both Raman and IR spectra were in good agreement …

Synthesis, Spectroscopic (Ft-Ir, ^1h, ^{13}C, Mass Spectrometry), And Biological Investigation Of Five-Coordinated Germanium-Substituted Tricyclohexyl Antimony Dipropionates: Crystal Structure Of Tricyclohexylantimony Dibromide, Muhammad Kaleem Khosa, Muhammad Mazhar, Saqib Ali, Kieran C. Molloy, Sarim Dastgir, Farkhanda Shaheen

Turkish Journal of Chemistry

A series of five-coordinated germanium-substituted tricyclohexylantimony dipropionates have been synthesized and characterized by different instrumental techniques, such as elemental analyses, FT-IR, multinuclear NMR (^1H, ^{13}C) and mass spectrometry. These compounds have also been screened against different microbes and they showed good activity against different bacteria that was comparable to the reference drugs. The crystal structure of the precursor (C_6H_{11})_3SbBr_2 is reported here, which showed that the antimony atom in an asymmetric unit exists in trigonal bipyramidal geometry, having space group C2/c with the monoclinic crystal system.

The Effect Of Acid Digestion On The Recoveries Of Trace Elements: Recommended Policies For The Elimination Of Losses, Güler Somer, Arzu Nakişci Ünlü

Turkish Journal of Chemistry

Digestion of biological materials is very important for trace element determinations. Although the microwave technique is mostly used, there are cases where open wet digestion is needed. This study examined the optimum conditions for the minimum loss of trace elements during the wet digestion of a sample. The effect of acid composition and digestion time for about 21 ions was investigated. The trace element concentrations were determined by differential pulse polarography. For the digestion procedure, a HClO_4-HNO_3 mixture was used for the first step and, after its evaporation (60 min), HCl was added as the second step, since in some …

Template Synthesis And Structural Characterization Of Homo Binuclear Chromium(Iii), Manganese(Iii), Iron(Iii), Cobalt(Iii), And Ruthenium(Iii) Complexes With Octaazamacrocyclic Ligands, Vinod K. Sharma, Shipra Srivastava

Turkish Journal of Chemistry

The Schiff base octaazamacrocyclic ligands derived from primary diamines and 3,6-dimethyl/diphenyl-4,5-diazaocta-3,5-diene-2,7-dione, and their binuclear complexes [M_2LCl_4]Cl_2 [M = Cr(III), Fe(III), Co(III), or Ru(III)] and [Mn_2L(AcO)_4](AcO)_2 were synthesized by template condensation reactions. Attempts to synthesize the corresponding metal-free macrocyclic ligands did not prove successful. The overall geometry and stereochemistry of these complexes were elucidated by elemental analyses, magnetic susceptibilities, electronic spectra, infrared spectra, molar conductance measurements, ^1H NMR, and thermogravimetric analysis. All the trivalent metal ion complexes appear to be 1:2 electrolytes. An octahedral geometry is proposed for all the complexes.

Performance Efficacy Using A Comparison Of Commerical And In-House Y-Str Multiplex Systems For Operational Use, Kathleen Mayntz-Press

Electronic Theses and Dissertations

It is routine for the forensic scientist to obtain a genetic profile of an individual from DNA recovered from a biological stain deposited at a crime scene. In contrast, only a limited number of laboratories in the United States have the capability of performing Y-STR analysis in casework. In order to aid in facilitating the transfer of Y-STR technology to the crime laboratory community for operational use, a comparison between commercial products from three main vendors (Applied Biosystems AmpFLSTR Yfiler PCR Amplification Kit, Promega PowerPlex - Y System, Reliagene Y-PLEX 12) and two in-house Y-STR multiplexes (MPI and MPB) commenced. …

Properties Of New York/New Jersey Harbor Sediments, K. W. Jones, Huan Feng, E. A. Stren, U. Neuhäusler, J. Osán, N. Marinkovic, Z. Song

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

Sediments found in waterways around the world may contain toxic compounds of anthropogeilic origin that can harm the environment and human health. As a result, it is often necessary to remove them and find disposal methods that are environmentally and economically acceptable. Here, we report on results obtained in an experimental program to characterize the nature of the sediment contamination. The objective was to gain a better understanding of the properties of the sediments to develop better methods for understanding the fate and transport of the contaminants and for improving methods for their removal from the sediments. Our investigations made …

Projects That Assist With Content In A Traditional Organic Chemistry Course, John J. Esteb, John R. Magers, Luanne Mcnulty, Anne M. Wilson

Scholarship and Professional Work - LAS

Projects that engage undergraduate students in content-based courses, such as organic chemistry, must relate to the material and provide useful tools for the divergent needs of the students. There are few examples of these types of projects in the literature. Herein, we describe two projects, the reaction notebook and the end-of-semester synthesis activity. Each project is designed to stimulate student ownership of the material and leads to engagement with the content of the course.

Synthesis Of An Aza-Cope Rearrangement - Mannich Cyclization Precursor From L-Proline, Patricia T. Sinawe

Senior Honors Theses and Projects

No abstract provided.

Lipid Metabolism In A549 And 9hte Cells Quantitation Of Lipid Peroxidation, Elizabeth Quintus

Senior Honors Theses and Projects

No abstract provided.

Tunneling Through Weak Interactions:  Comparison Of Through-Space-, H-Bond-, And Through-Bond-Mediated Tunneling, Westin Kurlancheek '03, Robert J. Cave

All HMC Faculty Publications and Research

Results from ab initio electronic structure theory calculations on model systems allow for the detailed comparison of tunneling through covalently bonded contacts, hydrogen bonds, and van der Waals contacts. Considerable geometrical sensitivity as well as an exponential distance dependence of the tunneling is observed for tunneling through various nonbonded contacts. However, the fundamental result from the present study is that at most a modest difference is observed between tunneling mediated by H-bonds and tunneling mediated by van der Waals contacts at typical distances for each type of interaction. These results are considered in relation to the pathways model of Beratan …

Nanodot-Based Organic Memory Devices, Zhengchun Liu

Doctoral Dissertations

In this study, resistor-type, diode-type, and transistor-type organic memory devices were investigated, aiming at the low-cost plastic integrated circuit applications. A series of solution-processing techniques including spin-coating, inkjet printing, and self-assembly were employed to fabricate these devices.

The organic resistive memory device is based on a novel molecular complex film composed of tetracyanoquinodimethane (TCNQ) and a soluble methanofullerene derivative [6,6]-phenyl C61-butyric acid methyl ester (PCBM). It has an Al/molecules/Al sandwich structure. The molecular layer was formed by spin-coating technique instead of expensive vacuum deposition method. The current-voltage characteristics show that the device switches from the initial 'low' conduction state to …

Fluorescent Analysis Of Translesion Dna Synthesis By Using A Novel, Non-Natural Nucleotide Analogue, Irene Lee, Anthony J. Berdis

Chemistry Faculty Publications

The replication of damaged DNA is a promutagenic process that can lead to disease development. This report evaluates the dynamics of nucleotide incorporation opposite an abasic site, a commonly formed DNA lesion, by using two fluorescent nucleotide analogues, 2-aminopurine deoxyribose triphosphate (2-APTP) and 5-phenylindole deoxyribose triphosphate (5-PhITP). In both cases, the kinetics of incorporation were compared by using a 32 P-radiolabel extension assay versus a fluorescence-quenching assay. Although 2-APTP is efficiently incorporated opposite a templating nucleobase (thymine), the kinetics for incorporation opposite an abasic site are significantly slower. The lower catalytic efficiency hinders its use as a probe to study …

Recent Developments Inthe Mechanistic Enzymology Of The Atp-Dependent Lon Protease From Escherichia Coli: Highlights From Kinetic Studies, Irene Lee, Anthony J. Berdis, Carolyn K. Suzuki

Chemistry Faculty Publications

Lon protease, also known as protease La, is one of the simplest ATP-dependent proteases that plays vital roles in maintaining cellular functions by selectively eliminating misfolded, damaged and certain short-lived regulatory proteins. Although Lon is a homo-oligomer, each subunit of Lon contains both an ATPase and a protease active site. This relatively simple architecture compared to other hetero-oligomeric ATP-dependent proteases such as the proteasome makes Lon a useful paradigm for studying the mechanism of ATP-dependent proteolysis. In this article, we survey some recent developments in the mechanistic characterization of Lon with an emphasis on the utilization of pre-steady-state enzyme kinetic …

Density Functional Studies Of The Structure And Bonding Of Nitrosyl Metalloporphyrin Complexes, John P. Graham, Robbie Davis

Journal of the Arkansas Academy of Science

Density functional calculations were used to determine optimized geometries fornitrosyl-metalloporphyrin complexes of Fe(II),Co(II)and Mn(II).The optimized structures were found to be consistent with experimental data and previous computational predictions using single point density functional calculations. Vibrational frequencies for the N-0stretching mode were also calculated and shown to be consistent with experimental data. The nature of the bonding between the metal center and nitrosyl ligand is discussed in relation to the structure of the M-N-0 linkage. The results were found to be consistent with previous descriptions derived from the Fenske-Hall approximate molecular orbital method. Other interesting structural features in the optimized geometries …

Electron Shock Waves, Mostafa Hemmati, Michael Weller, Taylor Duncan

Journal of the Arkansas Academy of Science

In this paper we describe numerical investigations of breakdown waves concentrating on antiforce waves. We employed one-dimensional electron fluid dynamical equations for a luminous pulse wave propagating into a neutral gas region and subjected to an applied electric field. We assumed that the electrons were the main element in the propagation of the wave and that the electron gas partial pressure provided the driving force. These waves are considered to be shock fronted and are composed of two regions: the thin sheath region behind the shock front and the thicker quasi-neutral region following the sheath region. Our set of equations, …

The Adaptation Of The Fibrinolytic Enzyme Apcfib On Human Blood Stains, Gabriela Sanchez

Whittier Scholars Program

Current research is aimed at testing a purified solution of a fibrinolytic enzyme. Apcfib, which comes from the venom of Agkistrodon piscivorus conanti (Florida cottonmouth Snake) to dissolve blood stains on two different makes of fabric (80% cotton/ 20% polyester and 100% polyester) and test the enzyme’s ability to dissolve blood stains when combined with a protease, in this case thermolysin, Treatment of blood stains on 100% polyester was more effective overall than on the 80% cotton/100% polyester fabric. 2.0x10^ -4 ��mol/min of Apcfib activity added to a 200��L of blood stain was the minimum needed in order to significantly …

Synthesis Of 2-Oxo-16-(3', 4'-Methylenedioxyphenyl)-Trans-15-Hexadecene, Adelajda Zorba

Honors Theses

This work presents the progress made towards synthesizing 2-oxo-16-(3', 4'methylenedioxyphenyl)-trans-15-hexadecene, an antimycobacterial compound that was originally isolated from the leaves of Piper Sanctum. The hydrocarbon chain of the molecule was synthesized first by opening a 15-pentadecanolactone ring by means of HI, and performing an E2 elimination reaction on the molecule followed by an organolithium reaction with CH3Li. Hexadec-15-en-2-one that was afforded this way was later reacted with 5-bromobenzo[d][1,3]dioxole following the appropriate Heck reaction protocol that allows for the formation of a palladium catalyzed carbon-carbon bond.

The modes of action of 2-oxo-16-(3', 4'-methylenedioxyphenyl)-trans-15hexadecene are comparable to the ones of rifampicin, a …

Characterization Of The Wheat Grain Pkaba1-Interacting Protein Tawd40, Natalie Wayne

Honors Theses

Abscisic acid (ABA)-mediated gene expression is a critical component of plant responses to this important hormone, which affects plant growth, development, and responses to environmental stresses. Plant responses to ABA are mediated by a number of factors including PKABA 1> an ABA-induced protein kinase involved in ABA-suppressed gene expression in cereal grains, and TaWD40, which has previously been shown to physically interact with PKABA1. A full-length 1.9 kb TaWD40 cDNA, CK210682, was sequenced as part of this project. Based on the deduced protein sequence, it is thought that TaWD40 may belong to the family of E3 ubiquitin ligases, possibly targeting …

Investigating The Mechanisms Of A Novel Ribosomal Rna Degradation System, Daniel Fowler

Honors Theses

Nonfunctional ribosomal RNA decay (NRD) is a novel quality control system that eliminates defective ribosomal RNAs (rRNAs) from yeast cells. Plasmid-encoded rRNAs containing single nucleotide substitutions in the peptidyl transferase center of 25S rRNA or the decoding center of 18S rRNA are co-expressed with endogenous rRNAs in Saccharomyces cerevisiae. Quantitative northern blots reveal the steady-state levels of the resulting nonfunctional rRNAs are markedly decreased compared to wild-type rRNAs . Furthermore, the decreased expression is not the result ofdefects in rRNA transcription or processing, but instead is due to decreased stability ofthe mature, nonfunctional rRNAs. Mutations in other functionally important rRNA …

Spectroscopic Investigation Of Metal-Substitution Of Cytochrome C, Deepthi Kandi

Masters Theses

We study, by absorbance spectroscopy, the incorporation of various metal ions (Cu²+ and Zn2*) into metal-free porphyrin cytochrome c (H₂cyt) as well as the various conformational forms of metal-substituted cytochromes. The H2cyt and desired metalsubstituted cytochromes have significantly different absorption spectra, providing a simple means of monitoring the incorporation of Cu²* or Zn2* into the empty porphyrin prosthetic group. The rates of metal-ion incorporation were studied under protein denaturating conditions using chemical denaturants, like urea and guanidine hydrochloride (GuHCI), and temperature that partially and completely unfold H2cyt, facilitating the incorporation of a metal ion. Moreover, the structural stability of copper …