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Voltammetric And Flow Injection Amperometric Determination Of Cysteine At A Glassy Carbon Electrode In The Presence Of Copper(Ii) Ions, Zekerya Dursun, İlyas Şahbaz, F. Ni̇l Ertaş, Gürel Ni̇şli̇

Turkish Journal of Chemistry

The voltammetric behaviour of cysteine was investigated in the presence of Cu(II) ions at a rotating glassy carbon electrode (RGCE). Two reduction peaks related to the successive reduction of the cysteine complexes of Cu(II) and Cu(I) ions were observed at --0.30 and --0.60 V vs. SCE respectively. These peaks were increased upon the addition of cysteine into a pH 9.20 borate buffer solution containing 0.1 M KNO_{3} and 1.0 x 10^{-5} M Cu(II) ions. The calibration curve was linear in the concentration range of 5.0 x 10^{-10}- 2.0 x 10^{-8} M for cysteine by utilising the peak current at --0.6 …

Comparison Between The Ultraviolet Emission From Pulsed Microhollow Cathode Discharges In Xenon And Argon, Isfried Petzenhauser, Leopold D. Biborosch, Uwe Ernst, Klaus Frank, Karl H. Schoenbach

Bioelectrics Publications

We measured the dynamic I–V characteristics and vacuum ultraviolet (VUV) emission lines of the second continuum in xenon (170 nm) and argon (130.5 nm) from pulsed microhollow cathode discharges (MHCD). For pulse lengths between 1 and 100 μs the dynamic I–V characteristics are similar in both inert gases. Only the time variation of the VUV emission line at 170 nm for xenon can be related to the dimer excited states. In argon the energy transfer between the Ar*₂ dimers and the oxygen impurity atoms is responsible for a qualitatively different time behavior of the resonance line at 130.5 nm. …

Design And Synthesis Of Constrained Dipeptide Units For Use As Β-Sheet Promoters, Umut Oguz

LSU Doctoral Dissertations

The study of factors promoting beta-sheet formation has recently gained interest due to the suspected involvement of beta-sheets in brain degenerative diseases such as Alzheimer's disease (AD), Creutzfeldt-Jacob disease (CJD) and bovine spongiform encephalopathy. Understanding beta-sheet formation and the factors that stabilize beta-sheet structure may serve as a basis for future drug design. The extended structure of a beta-sheet can be stabilized by constrained amino acid analogs that are pre-organized to adopt the extended conformation. In this dissertation using innovative synthetic organic chemistry methods, two dipeptide units are designed and synthesized that are constrained to form the extended conformation and …

Synchrotron Radiation As A Probe Of Chemical Information Using Novel Experimental Configurations, George Farquar

LSU Doctoral Dissertations

Determination of chemical information with synchrotron radiation is an area of great scientific interest, and expanding the range of available techniques is the topic of this dissertation. The experimental methods described herein allows for a significant advancement of the availability of subtle chemical information. This dissertation uses ionizing radiation to study three chemical systems. First, the l=3 shape resonance in CO is investigated using a cryogenically cooled gas jet. Shape resonant effects have been studied for many years. Previously, this was accomplished on the vibrational structure of molecules with a limited ability to determine the rotational substructure effects. A dramatic …

Resonance Two Photon Ionization Study Of Binary Clusters Of Styrene With Polar Molecules, Hatem Ahmed Mahmoud

Theses and Dissertations

One-color resonance two-photo ionization (R2PI) spectra of mixed clusters of styrene molecule (S) with polar molecules [water (W), methanol (M), ethanol (E), and trifuoroethanol (T)] were measured through the S1←S0 transition of the styrene molecule. The spectra reveal a rapid increase in complexity with the number of polar molecules in the cluster, associated with van der Waal modes and isomeric forms. The spectral shifts of the cluster origins from the S1-S0 transition of the bare styrene molecule reflect the nature of the intermolecular interactions within the binary clusters. The obtained R2PI spectra xv were compared with the spectra of the …

Sonogashira Coupling Routes To Ortho-Alkynl-And- Fused-Ring Sydnones, Andrew John Weisner

Browse all Theses and Dissertations

In the present work, suitably functionalized arylsydnones were used to synthesize a variety of ortho-alkynyl sydnones both as potential precursors to novel sydnoquinolines and to provide non-linear optical (NLO) species of interest to Wright-Patterson Air Force Base (WPAFB). The versatile intermediate, 3-(2-(trimethylsilylethynyl)phenyl)sydnone, was prepared in good yield by the coupling of 3-(2-iodophenyl)sydnone with trimethylsilyl acetylene under Sonogashira conditions. From this intermediate, several ortho-alkynyl sydnones were prepared via a one-pot desilylation with tetrabutylammonium fluoride and Sonogashira coupling with para-substituted aryl iodides. In addition, a three-reaction-in-one-pot procedure was developed to access some of these species directly from 3-(2- iodophenyl)-sydnone. Subsequent reaction of …

Application Of The Chan-Evans Diaryl Ether Synthesis To The Formation Of Bis(Bibenzyls), Eric Rosenthal

Honors Theses

Alkene (6) was produced in three steps from 3-hydroxybenzaldehyde (8), and 3-bromobenzyl bromide (10). A variety of strategies were employed to synthesize the desired boronic acid (13), but as of this time none have been successful. The synthesis of this boronic acid is necessary to study the feasibility of applying the Chan-Evans copper mediated formation of diaryl ethers to a bis(bibenzyl) synthesis. In seeking to exploit the advantages of the Chan-Evans ether synthesis over the Ullman ether synthesis, we have encountered some of the associated difficulties. The utilization of an arylboronic acid to produce a diaryl ether first requires the …

Approaches To The Synthesis Of Novel Triptycene Dendrimers And Hyperbranched Poly(Phenylene Sulfides) And Poly(Phenylene Sulfones), Alfredo Mellace

Seton Hall University Dissertations and Theses (ETDs)

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Solid-Phase Dna Sequencing Reactions Performed In Micro-Capillary Reactors And Solid-Phase Reversible Immobilization In Microfluidic Chips For Purification Of Dye-Labeled Dna Sequencing Fragments, Yichuan Xu

LSU Doctoral Dissertations

The research presented in this dissertation involves micro-capillary reactors for solid phase DNA sequencing, the identification of dye terminator sequencing fragments with time-resolved methods, and purification of dye-labeled DNA fragments using solid- phase reversible immobilization in microfluidic chips. Solid-phase micro-reactors have been prepared for DNA sequencing applications using slab gel electrophoresis. A PCR product was immobilized to the interior wall of a fused-silica capillary tube via a biotin-streptavidin linkage. Solid-phase sequencing was carried out in micro-capillary reactors using a four-lane, single color dye primer chemistry strategy. The read length was found to be 589 bases. The complementary DNA fragments generated …

Adsorption And Reaction Of Benzaldehyde On Porous Glass Studied By Ftir And Tpd, Steven Michael Badger Ii

Dissertations and Theses @ UNI

Benzaldehyde was dosed onto porous borosilicate glass in order to better understand the catalytic behavior of the surface of the porous glass. 18,000 L of benzaldehyde was dosed onto the porous glass at approximately 50 K and heated to a temperature of 470 K. The reactions that occurred were studied using FTIR spectroscopy and Temperature Programmed Desorption (TPD). The FTIR spectrum of the porous glass confirmed the presence of isolated surface hydroxyl groups (Si-OH), seen in the spectrum at 3750 cm1 , and the presence of isolated boron-OH groups, seen in the spectrum at 3700 cm1 . Neighboring surface hydroxyl …

Synthesis, Characterization And Biological Applications Of Organotin(Iv) Derivatives Of 2-(2-Fluoro-4-Biphenyl)Propanoic Acid, Sohail Mahmood, Saqib Ali, Moazzam Hussain Bhatti, Mohammad Mazhar, Rashid Iqbal, Khalid Mohammed Khan, Ghulam Mustafa Maharvi

Turkish Journal of Chemistry

A series of organotin(IV) derivatives with the general formula R_{4 - n}SnL_{n} (where n = 1 or 2, R = Me, Et, n-Bu, Ph and L = 2-(2-fluoro-4-biphenyl)propanoate) have been synthesized and characterized by infrared, multinuclear NMR (^{1}H, ^{13}C, ^{119}Sn), ^{119m}Sn Mössbauer spectroscopy and mass spectrometry. Screening tests of these compounds showed that they are highly active against various bacteria and fungi.

Determination Of H_{2}O_{2} Content Of Various Water Samples Using A Chemiluminescence Technique, Tuğba Tüğsüz, Elmas Gök, Serdar Ateş

Turkish Journal of Chemistry

Hydrogen peroxide (H_{2}O_{2}) plays an important role in natural water samples. In this study H_{2}O_{2} concentrations were quantified in different water samples by chemiluminescence detection. This method was chosen because of its high sensitivity and suitability for determining low concentrations of H_{2}O_{2}. H_{2}O_{2} is introduced to the oxidation reaction of alkaline luminol solutions in the presence of Co^{2 + } ion catalyst. When these components are mixed, blue light (\lambda = 440 nm) is emitted. Maximum chemiluminescence intensity occurs within 2 s after mixing and is continuous for up to a few minutes, permitting accurate measurements at selected delay times. …

Characterization Of Native And Bypass Human Coronary Artery Plaque Deposits From The Same Heart: Investigation Of The Chemical Form Of Calcium In Human Coronary Artery Plaque Deposits, Serigne Thiam

LSU Doctoral Dissertations

Gradual deposits of lipids, proteins, and calcium on the coronary arterial walls cause atherosclerosis, leading to blockage of the blood flow and possible heart attack. Despite many studies, the mechanism underlying these processes remains unclear. In this research, differences between native and bypass plaque deposits from the same heart were examined. In addition, the crystalline and the amorphous plaques within these native and bypass vessels were characterized. The techniques used to characterize the deposits included inductively coupled plasma mass spectrometry (ICPMS), solid-state nuclear magnetic resonance (NMR), high performance liquid chromatography (HPLC), etc. The results from the ICPMS technique showed that …

Genome Analysis: Mutation Analysis Using Near Infrared Laser-Induced Fluorescence (Nir-Lif) And Single Molecule Detection In Microfluidic Devices, Musundi Ben Wabuyele

LSU Doctoral Dissertations

A number of genotyping methods have been developed for mutation analysis, each of which has its own unique advantage. DNA amplification via polymerase chain reaction (PCR) provides an unlimited supply of material for subsequent genetic analysis even in case where only a single copy of the DNA molecule is present in the sample. Research presented in this dissertation first examines the efficiency of in vitro amplification of single copy DNA with subsequent sequencing analysis of PCR product. The PCR products (amplicons) were investigated for possible alteration, distortions or mutations due to the amplification process. The sequencing data for single copy …

Mechanistic Studies Of Carbon Steel Corrosion Inhibition By Cashew Nut Shell Liquid, J Y N Philip, J Buchweishaija, L L Mkayula

Tanzania Journal of Science

The inhibition mechanism of the Cashew Nut Shell Liquid (CNSL) on SAE 1008 carbon steel corrosion in CO 2  saturated 3% NaCl solutions has been studied by weight loss, UV/VIS and electrochemical techniques. The phenoxide, R-Ar-O- ions from the CNSL inhibitor were found to be responsible for the reduction of the corrosion rate of the carbon steel. Also, it was observed that the surface charge of the carbon steel electrodes was positive with respect to the solutions containing CNSL inhibitor. It is likely that the mechanism of the CNSL inhibitor adsorption involved the electrostatic attraction between the positively charged metal …

Preparation And Characterization Of Activated Carbons From Rice Husks And Shells Of Palm Fruits, Jeg Mdoe, Ll Mkayula

Tanzania Journal of Science

Activated carbons from palm fruit shells (PFS) and rice husks (RH) were prepared using physical and chemical activation processes, respectively. The influence of activation time and temperature (in the case of PFS) and impregnation ratio and carbonization temperature (in the case of RH) on the properties of the resultant carbons were studied. In the case of PFS carbons, there were an increase in adsorption capacity and surface areas with increase in activation time and temperature. The surface area ranged between 292 and 642 m2g-1 at temperature range of between 1000 and 1200 K. In the case of RH carbons, surface …

Loading Microcolumns For The Separation Of Analytes From A Sample In The Millisecond Time Scale, David S. Hage, William A. Clarke

David Hage Publications

The present invention generally relates to a microcolumn capable of separating an analyte from a sample in the millisecond time domain. The microcolumn is capable of such rapid separation by employing small column volumes that can tolerate medium to high flow rates. The invention also relates to a method of loading a microcolumn capable of separating an analyte from a sample in the millisecond time domain using plural injections of the packing material.

Calcium Binding To Calmodulin Mutants Monitored By Domain-Specific Intrinsic Phenylalanine And Tyrosine Fluorescence, W. S. Vanscyoc, B. R. Sorensen, E. Rusinova, William Laws, J. B. A. Ross, M. A. Shea

Chemistry and Biochemistry Faculty Publications

Cooperative calcium binding to the two homologous domains of calmodulin (CaM) induces conformational changes that regulate its association with and activation of numerous cellular target proteins. Calcium binding to the pair of high-affinity sites (III and IV in the C-domain) can be monitored by observing calcium-dependent changes in intrinsic tyrosine fluorescence intensity (lambda(ex)/lambda(em) of 277/320 nm). However, calcium binding to the low-affinity sites (I and II in the N-domain) is more difficult to measure with optical spectroscopy because that domain of CaM does not contain tryptophan or tyrosine. We recently demonstrated that calcium-dependent changes in intrinsic phenylalanine fluorescence (lambdaex/lambdaem of …

Fragmentation Processes Following Core Excitation In Acetylene And Ethylene By Partial Ion Yield Spectroscopy, Maria Novella Piancastelli, Wayne C. Stolte, Gunnar Ohrwall, S-W Yu, D. Bull, K. Lantz, Alfred S. Schlachter, Dennis W. Lindle

Chemistry and Biochemistry Faculty Research

Partial ion yield spectroscopy provides a very detailed picture of fragmentation processes following core excitation in isolated molecules. We exploit this potential in the analysis of decay processes following C1s→π and C1s→Rydberg excitations in ethylene and acetylene. We show that the relative intensity of spectral features related to the excitation to empty molecular orbitals or to Rydberg states is a function of the time variation of the fragmentation process. Namely, we see an intensity increase in the Rydberg states compared to the molecular orbitals as the fragmentation process becomes more extensive, a result attributable to the diffuse nature of the …

Rapid Determination Of Serum Melatonin By Esi–Ms–Ms With Direct Sample Injection, Shuming Yang, Xiaohui Zheng, Yan Xu, Xiang Zhou

Chemistry Faculty Publications

This paper describes a rapid, simple and sensitive analytical method for the quantitative determination of melatonin in human serum by ESI–MS–MS with direct serum sample injection and on-line extraction. The method uses N-acetyltryptamine as the internal standard. It has high specificity and sensitivity for serum melatonin analysis. The internal calibration curve shows a wide linear range from 0.500 to 200 ng/ml with a correlation coefficient, R2>0.999. The limit of quantitation is 0.500 ng/ml and the limit of detection is 0.100 ng/ml with 10-μl sample injection. The recoveries of serum melatonin at three levels are approximately 70%. The intra-assay precision …

Deliquescence Behavior Of Organic/Ammonium Sulfate Aerosol, Sarah D. Brooks, Matthew E. Wise, Melinda Cushing, Margaret A. Tolbert

CUP Faculty Research

Recent studies have shown that tropospheric aerosols composed of internal mixtures of organics with sulfates are quite common with the organic composing up to 50% of the particle mass. The influences of the organics on the chemical and physical properties of the aerosol are not known. In this paper, we report the solubility of a series of dicarboxylic acids in saturated ammonium sulfate solution as a function of temperature. We also report the deliquescence relative humidity (DRH) of the pure dicarboxylic acids and of mixtures of dicarboxylic acids with ammonium sulfate. For the systems studied, we find that the presence …

Kinetic And Structural Characterization Of Manganese(Ii)-Loaded Methionyl Aminopeptidases, Ventris M. D'Souza, Sabina I. Swierczek, Nathaniel J. Cosper, Lu Meng, Shane Ruebush, Alicja J. Copik, Robert A. Scott, Richard C. Holz

Chemistry Faculty Research and Publications

Manganese(II) activation of the methionyl aminopeptidases from Escherichia coli (EcMetAP-I) and the hyperthermophilic archaeon Pyrococcus furiosus (PfMetAP-II) was investigated. Maximum catalytic activity for both enzymes was obtained with 1 equiv of Mn(II), and the dissociation constants (K_d) for the first metal binding site were found to be 6 ± 0.5 and 1 ± 0.5 μM for EcMetAP-I and PfMetAP-II, respectively. These K_d values were verified by isothermal titration calorimetry (ITC) and found to be 3.0 ± 0.2 and 1.4 ± 0.2 μM for EcMetAP-I and PfMetAP-II, respectively. The …

Chemistry & Biochemistry Newsletter, Department Of Chemistry & Biochemistry, South Dakota State University

Chemistry & Biochemistry Newsletter: 2002-2015

Inside:

Page 2 Utecht Enhances Freshman Labs with New Software

Page 3 Alumni News; Foundation donors

Page 4 2002 Graduates and Awards; Chinese Seminar Results in Research Project

Page 5 Faculty and Staff News

Page 6 Antarctic Ice Holds History of Earth’s Atmosphere; Renovations of Shepard Hall Complete

Page 7 ASL Staff Records Hectic Summer; Budner Attends Greek Conference ; Carlson Awarded National Scholarship

Page 8 Recent Faculty Publications

Structural Biology Of Bacterial Multidrug Resistance Gene Regulators, Michael H. Godsey, Ekaterina E. Zheleznova Heldwein, Richard G. Brennan

CUP Faculty Research

Multidrug resistance (mdr)¹ can be defined broadly as the ability of a cell to survive ordinarily lethal doses of more than one drug. Clearly, such resistance is a critical problem in the treatment of fungal and bacterial infections and cancer. Four general, but nonexclusive, mechanisms give rise to multidrug resistance: 1) detoxification by enzymatic modification or cleavage of drug; 2) genetic alteration of the intra- or extracellular targets; 3) decreased permeability of the cell membrane; and 4) active drug extrusion by multidrug transporters.

Paramount to our understanding of mdr is the issue of recognition of structurally dissimilar substrates and …

Guanine And 7,8-Dihydro-8-Oxo-Guanine-Specific Oxidation In Dna By Chromium(V), Kent D. Sugden, Brooke Martin

Chemistry and Biochemistry Faculty Publications

The hexavalent oxidation state of chromium [Cr(VI)] is a well-established human carcinogen, although the mechanism of cancer induction is currently unknown. Intracellular reduction of Cr(VI) forms Cr(V), which is thought to play a fundamental role in the mechanism of DNA damage by this carcinogen. Two separate pathways of DNA damage, an oxidative pathway and a metal-binding pathway, have been proposed to account for the lesions observed in cell systems. We have used a model Cr(V) complex, N,N´-ethylenebis(salicylidene-animato)oxochromium(V) [Cr(V)-Salen], to investigate the oxidative pathway of DNA damage and to elucidate the lesions generated from this oxidation process. Reaction of Cr(V)-Salen with …

Chromium Tolerant Microbial Communities From The Chesapeake Bay Watershed, Kristine L. Lowe, Ruth E. Fliflet, Tony Ly, Brenda J. Little, Joanne Jones-Meehan

Virginia Journal of Science

Chromium tolerant bacteria were enumerated from portions of the Chesapeake Bay watershed and examined for their potential to reduce Cr(VI). Water and sediment samples were collected from various locations in Baltimore Harbor and Bear Creek, as well as Sandy Point State Park in Maryland and the Anacostia River in Washington, DC. Samples were spread onto agar plates with CrO₄^2- (5 ppm) as the sole terminal electron acceptor. Plates were incubated anaerobically and colony forming units (CFU) enumerated. CFU arising on minimal-CrO₄^2- medium ranged from 10³-10⁴ mL^-1 or g^-1 and community estimates …

A Comparison Of The Low Mode And Monte Carlo Conformational Search Methods, Carol A. Parish, Rosina Lombardi, Kent Sinclair, Emelyn Smith, Alla Goldberg, Melissa Rappleye, Myrianne Dure

Chemistry Faculty Publications

The Low Mode (LM) and Monte Carlo (MC) conformational search methods were compared on three diverse molecular systems; (4R, 5S, 6S, 7R)-hexahydro-5,6-dihydroxy-1,3,4,7-tetrakis(phenylmethyl)-2H-1,3-diazapin-2-one (1), 2-methoxy-2-phenyl-2-triflouromethyl-N-α-methyl benzyl propanamide (2) and a trimeric 39-membered polyazamacrolide (3). We find that either method, or a combination of the methods, is equally efficient at searching the conformational space of the smaller molecular systems while a 50:50 hybrid of Low Mode and Monte Carlo is most efficient at searching the space of the larger molecular system.

Doming Modes And Dynamics Of Model Heme Compounds, Dennis D. Klug, Marek Z. Zgierski, John S. Tse, Zhenxian Liu, James R. Kincaid, Kazimierz Czarnecki, Russell J. Hemley

Chemistry Faculty Research and Publications

Synchrotron far-IR spectroscopy and density-functional calculations are used to characterize the low-frequency dynamics of model heme FeCO compounds. The “doming” vibrational mode in which the iron atom moves out of the porphyrin plane while the periphery of this ring moves in the opposite direction determines the reactivity of oxygen with this type of molecule in biological systems. Calculations of frequencies and absorption intensities and the measured pressure dependence of vibrational modes in the model compounds are used to identify the doming and related normal modes.

The Aminopeptidase From Aeromonas Proteolytica: Structure And Mechanism Of Co-Catalytic Metal Centers Involved In Peptide Hydrolysis, Richard C. Holz

Chemistry Faculty Research and Publications

Enzymes containing multi-metal active sites are central to numerous biological processes and, consequently, characterization of their structure and function is a problem of outstanding importance. One of the least-explored groups of enzymes is the hydrolases that contain dinuclear metal centers. These enzymes play key roles in carcinogenesis, tissue repair, and protein degradation processes. In addition, some of these enzymes can catalyze the hydrolysis of phosphorus(V) compounds found in nerve gases and agricultural neurotoxins. The determination of detailed reaction mechanisms for these enzymes is required for the design of highly potent, specific inhibitors that can function as potential pharmaceuticals. Hydrolytic enzymes …

Enantioselective Synthesis Of The C11–C17 Segment Of Soraphen A1Α Via Organoiron Methodology, Yeyu Cao, Ahmad F Eweas, William A. Donaldson

Chemistry Faculty Research and Publications

The C11–C17 segment of the antifungal agent soraphen A_1α was prepared from glyceraldehyde acetonide in nine steps. The C12 stereocenter is derived from glyceraldehyde, while the C17 stereocenter as introduced by 1,6-asymmetric control via the coordinated Fe(CO)₃.

The C11–C17 segment of the antifungal agent soraphen A1α, with required inverted stereochemistry at C17, was prepared. The C12 stereocenter is derived from glyceraldehyde, while the C17 stereocenter is introduced by 1,6-asymmetric induction via a coordinated Fe(CO)₃.