Chemistry Commons^™

Regional Scale Evidence For Improvements In Surface Water Chemistry 1990-2001, B. L. Skjelkvåle, J. L. Stoddard, D. S. Jeffries, K. Tørseth, T. Høgåsen, J. Bowman, J. Mannio, D. T. Monteith, R. Mosello, M. Rogora, D. Rzychon, J. Vesely, J. Wieting, A. Wilander, A. Worsztynowicz

United States Environmental Protection Agency: Publications

The main aim of the international UNECE monitoring program ICP Waters under the Convention of Long-range Transboundary Air Pollution (CLRTAP) is to assess, on a regional basis, the degree and geographical extent of the impact of atmospheric pollution, in particular acidification, on surface waters. Regional trends are calculated for 12 geographical regions in Europe and North America, comprising 189 surface waters sites. From 1990-2001 sulphate concentrations decreased in all but one of the investigated regions. Nitrate increased in only one region, and decreased in three North American regions. Improvements in alkalinity and pH are widely observed. Results from the ICP …

The Composition Of Coexisting Jarosite-Group Minerals And Water From The Richmond Mine, Iron Mountain, California, Heather E. Jamieson, Clare Robinson, Charles N. Alpers, D. Kirk Nordstrom, Alexei Poustovetov, Heather A. Lowers

United States Geological Survey: Staff Publications

Jarosite-group minerals accumulate in the form of stalactites and fine-grained mud on massive pyrite in the D drift of the Richmond mine, Iron Mountain, California. Water samples were collected by placing beakers under the dripping stalactites and by extracting pore water from the mud using a centrifuge. The water is rich in Fe³⁺ and SO₄^2–, with a pH of approximately 2.1, which is significantly higher than the extremely acidic waters found elsewhere in the mine. Electron-microprobe analysis and X-ray mapping indicate that the small crystals (<10 > μm in diameter) are compositionally zoned with respect to Na …

Recurrent Structural Rna Motifs, Isostericity Matrices And Sequence Alignments, Neocles B. Leontis, Aurélie Lescoute, Christian Massire, Eric Westhof

Chemistry Faculty Publications

The occurrences of two recurrent motifs in ribosomal RNA sequences, the Kink-turn and the C-loop, are examined in crystal structures and systematically compared with sequence alignments of rRNAs from the three kingdoms of life in order to identify the range of the structural and sequence variations. Isostericity Matrices are used to analyze structurally the sequence variations of the characteristic non-Watson-Crick base pairs for each motif. We show that Isostericity Matrices for non-Watson-Crick base pairs provide important tools for deriving the sequence signatures of recurrent motifs, for scoring and refining sequence alignments, and for determining whether motifs are conserved throughout evolution. …

Stability Of Single Particle Tracers For Differentiating Between Heavy- And Light-Duty Vehicle Emissions, Deborah S. Gross, Alexander R. Barron, Ellen M. Sukovich, Benjamin S. Warren, Julia C. Jarvis, David T. Suess, Kimberly A. Prather

Chemistry Faculty Work

To determine the size and chemical composition of particles derived from on-road vehicle emissions, individual particles were sampledcontinuously with an aerosol time-of-flight mass spectrometer (ATOFMS) at the Caldecott Tunnel in Northern California. In this tunnel, traffic is segregated, such that in theory only light duty vehicle emissions or a mix of heavy- (HDV) and light-duty vehicle (LDV) emissions can be sampled separately. Two studies were carried out, one in November 1997 anda secondin July 2000, time periods with average ambient temperatures of 10–15 and 26–32 1C, respectively, with the instrument operating at ambient outdoor temperatures. Analysis of the chemical composition …

The Edam Project: Mining Atmospheric Aerosol Datasets, Raghu Ramakrishnan, James J. Schauer, Lei Chen, Zheng Huang, Martin M. Shafer, Deborah S. Gross, David R. Musicant

Chemistry Faculty Work

Data mining has been a very active area of research in the database, machine learning, and mathematical programming communities in recent years. EDAM (Exploratory Data Analysis and Management) is a joint project between researchers in Atmospheric Chemistry and Computer Science at Carleton College and the University of Wisconsin-Madison that aims to develop data mining techniques for advancing the state of the art in analyzing atmospheric aerosol datasets. There is a great need to better understand the sources, dynamics, and compositions of atmospheric aerosols. The traditional approach for particle measurement, which is the collection of bulk samples of particulates on filters, …

Fluorescence Prediction Through Computational Chemistry, Daniel Craig Lathey

Theses, Dissertations and Capstones

With the growing demand for diverse fluorescent dyes, it is imperative to find a more efficient methodology by which to synthesize dyes. Our research group has found a computational method that can efficiently predict the optical properties of a molecule before it is synthesized. By evaluating different semi-empirical methods, we have found a way to predict the fluorescence maxima. With the new ability of Hyperchem 7.5 to geometrically optimize a molecule in an excited state, we can predict not only the absorption maxima, but we can also predict the fluorescence maxima within 25 nm of the actual fluorescence.

With this …

Flavonol Glycosides From Asperula Arvensis L., Zühal Güvenalp, L. Ömür Demi̇rezer

Turkish Journal of Chemistry

From the aerial parts of Asperula arvensis L. 9 known flavonol glycosides, namely quercetin (1), isoquercitrin [= quercetin 3-O-\beta-glucopyranoside] (2), hyperin [= quercetin 3-O-\beta -galactopyranoside] (3), quercetin 7-O-\beta-galactopyranoside (4), quercetin 4'-O-\beta-galactopyranoside (5), isorhamnetin 3-O-\beta -galactopyranoside (6), isorhamnetin 5-O-\beta-galactopyranoside (7), dihydrokaempferol 7-4'-dimethylether 3-O-\beta -glucopyranoside (8) and isorhamnetin 3-O-\alpha -rhamnopyranosyl (1''' \to 6'')-\beta -glucopyranosid (9), were isolated. The structures of the compounds were elucidated by high field 1D and 2D NMR and ESI-MS spectroscopies.

Terpenoids And Steroids From The Roots Of Salvia Blepharochlaena, Ufuk Kolak, Gülaçti Topçu, Seher Bi̇rteksöz, Gülten Ötük, Ayhan Ulubelen

Turkish Journal of Chemistry

From the roots of Salvia blepharochlaena Hedge and Hub. Mor. 4 triterpenoids, 4 steroids, 6 diterpenoids, and an aromatic ester were isolated. The structures of these compounds were established by spectroscopic methods. Formosanolide was isolated for the first time from the genus Salvia.

Synthesis And Structural Characterization Of The 2-[(O-Pyridyl)-Sulfanylmethyl]-Pyrimidine-Silver(I) Complex [Ag_2(Opsp)_2](No_3)_2, Li-Rong Wen, Ming Li, Gui-Long Zhao, Xue-Mei Li, Ou-Yang Pingkai, Shu-Sheng Zhang

Turkish Journal of Chemistry

The new silver(I) complexe [Ag_2(opsp)_2](NO_3)_2 (1) was synthesized by the self-assembly of AgX (X = NO_3^-) with the versatile multidentate ligand opsp (opsp = 2-[(o-pyridyl)-sulfanylmethyl]- pyrimidine). X-ray single-crystal diffraction analyses show that 1 is dinuclear molecule. In 1, 1 opsp ligand acts in a bidentate mode with 2 nitrogen atoms from a pyridine ring and a pyrimidine ring coordinating to 2 Ag(I) atoms, and the Ag(I) center is 2-coordinated by 2 nitrogen atoms showing linear coordination geometry.

Manganese(Iii) Acetate Mediated Free Radical Cyclization Of 1,3-Dicarbonyl Compounds With Sterically Hindered Olefins, Mehmet Yilmaz, Emre Bi̇çer, A. Tarik Pekel

Turkish Journal of Chemistry

The manganese(III) acetate mediated radical cyclization of dimedone 1a, 2,4-pentanedione 1b, ethyl acetoacetate 1c, 1,3-cyclohexanedione 1d and 5-phenyl-1,3-cyclohexanedione 1e with 1,1-diphenyl-1-butene 2a afforded 4,5-dihydrofurans (3c, 3e) and tetrahydrobenzofurans (3a, 3g, 3h) in good yields (55% - 77%). Additionally, the reactions of trifluoromethyl-group containing 1,3-dicarbonyls, 4,4,4-trifluoro-1-phenylbutane-1,3-dione 1f and 4,4,4-trifluoro-1-thien-2ylbutane-1,3-dione 1g with 2a 3-trifluoroacetyl-4,5-dihydrofurans gave in 74% and 78% yields, respectively. Treatment of 1a, 1b and 1c with 1,2-diphenyl-1-pentene 2a resulted in the formation of tetrahydrobenzofuran 3b and 4,5-dihydrofurans 3d and 3f in lower yields.

Reactions Of Alkenes With Sodium Perborate And Sodium Chloride, Erdal Şenocak, Yavuz Taşkesengi̇l, Ferhan Tümer, Cavi̇t Kazaz

Turkish Journal of Chemistry

Sodium perborate oxidatively chlorinates a variety of alkenes with sodium chloride to form the corresponding chloro derivatives under mild conditions.

Coupled Electrical And Magnetic Properties In (La,Sr)Feo3-Δ, X.-D. Zhou, Qingsheng Cai, Jinbo Yang, M. S. Kim, William B. Yelon, William Joseph James, Y.-W. Shin, B. J. Scarfino, Harlan U. Anderson

Materials Science and Engineering Faculty Research & Creative Works

This article is aimed at studying the temperature dependence oxygen nonstoichiometry, magnetic moments, Fe³⁺ fraction, Néel temperature and conductivity of (La,Sr)FeO_3-δ. It is found that the magnetic properties in La_0.60 Sr_0.40 Fe_3-δ is determined by Fe³⁺ and its concentration, and the conductance is resulted from Fe⁴⁺ ions, which act as electron holes. Both of magnetic and electrical properties were directly governed by oxygen nonstoichiometry (δ). when δ=0.2, the compound has maximum Fe³⁺, the saturation magnetic moments and Néel temperature are 3.8 µB and 410 °C, both at the highest level, …

Effect Of Phosphoric Acid Anion Structure On The Corrosion Inhibition Of Steel By Polyaniline, Yasir Idlibi, Thomas P. Schuman, James O. Stoffer

Chemistry Faculty Research & Creative Works

Conductive polymers such as polyaniline (PAni) have been examined as candidates for replacing the existing chromate systems. Protonation of emeraldine base creates polarons and bipolarons, single and paired radical cations, respectively, of higher bond energy levels within the molecular orbital band gap.' For a conductive coating, considerable delocalization of corrosion charge and potential may be obtained along or between the polymer chains, because of high electron mobility. Current corrosion systems based on polyaniline typically rely on sulfuric or sulfonic acids as a dopant material, since synthetic techniques utilize persulfates as the oxidant of choice. In our experience, sulfonic/sulfuric acid systems …

Magnetic Properties Of (Γ-Fe₂O₃)₈₀Ag₂₀ Nanocomposites Prepared In Reverse Micelles, Joan A. Wiemann, Jianbiao Dai, Jinke Tang, Gary J. Long, Leonard Spinu

Chemistry Faculty Research & Creative Works

The magnetic properties of nanoparticles of gamma-Fe2O3 prepared by reverse micelles have been studied by dc magnetization, transverse ac susceptibility, and Mössbauer spectroscopy. The nanoparticles of gamma-Fe2O3 in the nanocomposite (gamma-Fe2O3)80Ag20 exhibit superparamagnetic behavior. The blocking temperatures determined by the three methods indicate the superparamagnetic nature of (gamma-Fe2O3)80Ag20 above 70-80 K and show correlation with measuring time. The average particle diameter obtained by transmission electron microscopy of the gamma-Fe2O3 particles is ~10 nm and that of the Ag particles is ~20 nm. The average particle size determined from the magnetic analyses for the gamma-Fe2O3 particles is ~12 nm. Mössbauer spectra …

Electrochemical Detection Of Nanoscale Phase Separation In Binary Self-Assembled Monolayers, R. Carlisle Chambers, Christina E. Inman, James E. Hutchison

Faculty Publications - Department of Biological & Molecular Science

Developing methods to probe the nature and structure of nanoscale environments continues to be a challenge in nanoscience. We report a cyclic voltammetry investigation of internal, hydrogen-bond driven phase separation of amide-containing thiols and alkane thiols. Amide-containing thiols with a terminal ferrocene carboxylate functional group were investigated in two binary monolayers, one homogeneously mixed and the other phase separated. The electrochemical response of the ferrocene probe was used to monitor adsorbate coverage, environment and phase separation within each of these monolayers. The results demonstrate that the behavior of ferrocene containing monolayers can be used to probe nanoscale organization.

Preservation Of Eumelanin Hair Pigmentation In Proopiomelanocortin-Deficient Mice On A Nonagouti (A/A) Genetic Background, Andrzej Slominski, Przemyslaw M. Plonka, Alexander Pisarchik, James L. Smart, Virgine Tolle, Jacobo Wortsman, Malcolm J. Low

Faculty Publications - Department of Biological & Molecular Science

No abstract provided.

A Solvent-Free Baeyer–Villiger Lactonization For The Undergraduate Organic Laboratory: Synthesis Of Γ-T-Butyl-Ε-Caprolactone, John J. Esteb, James N. Hohman, Diana E. Schladaminger, Anne M. Wilson

Scholarship and Professional Work - LAS

We present an experiment involving the Baeyer–Villiger oxidation reactionfor a first-year organic chemistry class. The Baeyer–Villiger reactionprovides an efficient method to convert ketones to esters or lactones. Most organictextbooks cover the Baeyer–Villiger reaction but owing to a lack of suitableexperiments, students seldom get to explore the reaction in the undergraduateteaching laboratory. In this experiment, m-chloroperoxybenzoic acid(m-CPBA) and4-tert-butylcyclohexanone are mixed together for 30 minutes under solvent-freeconditions to produce γ-t-butyl-ε-caprolactone in 95%yield. The solvent-free nature of this procedure greatly limits the quantityof waste generated by students and keeps costs low by removing the need for solvent.

Development Of An Upper Level Undergraduate Research Based Laboratory: The Purification, Analysis, And Dinetic Study Of Cytochrome B5, Mary Mcphail

Senior Honors Theses and Projects

The purpose of this project was to develop an upper level undergraduate biochemistry laboratory (CHEM 453) based upon a novel research project, designed to replace an existing instructional laboratory that employs ‘cookbook’ exercises. Methods for the expression, purification, spectral analysis of structural integrity, and electron transfer capability of rabbit cyt b₅ were adapted from published work done by Dr. Lucy Waskell of the University of Michigan and Dr. Mansuy of the University of Paris. In our hands, rabbit liver cyt b₅ expressed in E. coli was purified to 45% specific content of the theoretical content. Additionally, 37 nmol …

Exploring Marine Biotoxins Using Analytical Techniques Based On Mass Spectrometry, Mónica Fernández Amandi

Theses

The impact of phycotoxins on human and animal health is of important concern for worldwide authorities and the scientific community. Domoic acid (DA) is a neurotoxin produced by phytoplankton {Pseudonitzchia spp.). It enters the food chain through the consumption of shellfish that feed on toxic diatoms. DA has been responsible for several outbreaks affecting humans and animals all around the world. Yessotoxin (YTX) is produced by dinoflagellate species {Protoceratiuni reticulatum) which are globally distributed. Its toxicity is low when ingested orally. However, the co-extraction of YTX with diarrhetic shellfish poisoning (DSP) toxins, derives false positives when the mouse bioassay is …

Photocontrol Of Upper And Lower Rim Complexation Of Neutral And Cationic Species By P-Tert-Butylcalix[4]Arene Tetraethyl Ester, Mary Deasy, Bernadette Creaven, Brian A. Murray, Catherine Mckenna, Darren Tobin

Articles

A number of sodium salt complexes of p-tert-butylcalix[4]arene tetraethyl ester, 1, were isolated both with and without upper-rim encapsulated solvent. Selective decomplexation of lower rim bound sodium cations and upper rim encapsulated solvent molecules could be successfully achieved using low pressure light sources. Oxidation of the counter anion at the lower rim of p-tert-butylcalix[4]arene tetraethyl ester triggered both the upper and lower rim decomplexation process. The extent of decomplexation at both rims is controlled both by the nature of the counter-anionic species at the lower rim and by the fate of the photoproducts generated. The calixarene host …

On-Road Remote Sensing Of Automobile Emissions In The Omaha Area: Year 2, September 2004, Gary A. Bishop, Daniel A. Burgard, Donald H. Stedman

Fuel Efficiency Automobile Test Publications

No abstract provided.

On-Road Emissions In Asia Measured By Remote Sensing (Presentation), Donald H. Stedman, Gary A. Bishop

Fuel Efficiency Automobile Test Publications

No abstract provided.

Vehicle Remote Sensing For Nitrogen Dioxide (Presentation), Thomas R. Dalton, Gary A. Bishop, Donald H. Stedman

Fuel Efficiency Automobile Test Publications

No abstract provided.

Portable Emission Measurements Of Snowcoaches And Snowmobiles In Yellowstone National Park (Presentation), John D. Ray, Gary A. Bishop

Fuel Efficiency Automobile Test Publications

No abstract provided.

An Investigation Into The Ring-Enlargement Reactions Of Boron Subphthalocyanine And Boron Subnaphthalocyanine, Andrew Jeremiah Jones

Master's Theses and Doctoral Dissertations

Ring enlargement syntheses of axially substituted boron subphthalocyanine and boron subnaphthalocyanine were investigated. The trihexylsiloxy derivatives of subphthalocyanine and subnaphthalocyanine were synthesized. These derivatives were then used in the ring-enlargement trials. Symmetrical and asymmetrical ring-enlargement reactions were carried out in a mixture of toluene and dimethylsulfoxide at room temperature. This study represents the first synthesis of boron subphthalocyanine with trihexylsiloxy group in the axial position and the first investigation into the ring enlargement of boron subnaphthalocyanine in which the axial ligand is a trihexylsiloxy group. Precipitates were formed, and it is believed that the precipitates are the metalfree ring-enlarged products. …

In Situ Screening To Optimize Variables In Organic Reactions, David Berkowitz, Mohua Bose, Sungjo Choi

Department of Chemistry: Faculty Publications

A biphasic process for rapid screening of organic reactions comprising monitoring relative rates of parallel organic reactions. The screening process is suitable to determine the efficacy of different reactants, process conditions, and process enhancers such as catalysts or promoters. The biphasic process also allows multiple samples to be analyzed/monitored simultaneously. In addition because enzymes are used to monitor the reaction product in this invention, when that product is chiral and an enantio-discriminating enzyme is used to monitor the product, in addition to the relative rates, enantioselectivities of a set of parallel organic reactions can also be determined. The monitoring is …

Potential Energy Surface Of The Reaction Of Imidazole With Peroxynitrite: Density Functional Theory Study, Valentin Gogonea

Chemistry Faculty Publications

This article presents a theoretical investigation of the reaction mechanism of imidazole nitration by peroxynitrite using density functional theory calculations. Understanding this reaction mechanism will help in elucidating the mechanism of guanine nitration by peroxynitrite, which is one of the assumed chemical pathways for damaging DNA in cells. This work focuses on the analysis of the potential energy surface (PES) for this reaction in the gas phase. Calculations were carried out using Hartree–Fock (HF) and density functional theory (DFT) Hamiltonians with double-zeta basis sets ranging from 6-31G(d) to 6-31++G(d,p), and the triple-zeta basis set 6-311G(d). The computational results reveal that …

Synthesis, Characterization And Application Of Polymeric Surfactants In Micellar Electrokinetic Chromatography: Use Of Ionic Liquids As Modifiers, Simon M. Mwongela

LSU Doctoral Dissertations

The goal of the research presented in this dissertation is to synthesize, characterize, and apply a novel chiral amino acid-based surfactant and achiral sulfate-based surfactants for the effective separations of chiral and achiral compounds in micellar electrokinetic chromatography (MEKC). The first part of this research involves novel synthesis, characterization, and application of polysodium oleyl-L-leucyl-valinate (poly-L-SOLV) for the separation of chiral compounds in MEKC. Surface tensiometry, proton nuclear magnetic resonance, infrared spectroscopy, densitometry and analytical ultracentrifugation were used as the characterization techniques. Optimal MEKC separating conditions were established by varying surfactant concentration, buffer concentration and pH, applied voltage, and capillary temperature. …

Predicted Properties Of Microhollow Cathode Discharges In Xenon, J. P. Boeuf, L. C. Pitchford, K. H. Schoenbach

Bioelectrics Publications

A fluid model has been developed and used to help clarify the physical mechanisms occurring in microhollow cathode discharges (MHCD). Calculated current-voltage (I-V) characteristics and gas temperatures in xenon at 100 Torr are presented. Consistent with previous experimental results in similar conditions, we find a voltage maximum in the I-V characteristic. We show that this structure reflects a transition between a low-current, abnormal discharge localized inside the cylindrical hollow cathode to a higher-current, normal glow discharge sustained by electron emission from the outer surface of the cathode. This transition, due to the geometry of …

Simulations Of Nanopore Formation And Phosphatidylserine Externalization In Lipid Membranes Subjected To A High-Intensity, Ultrashort Electric Pulse, Q. Hu, R. P. Joshi, K. H. Schoenbach

Bioelectrics Publications

A combined MD simulator and time dependent Laplace solver are used to analyze the electrically driven phosphatidylserine externalization process in cells. Time dependent details of nanopore formation at cell membranes in response to a high-intensity (100kV∕cm), ultrashort (10ns) electric pulse are also probed. Our results show that nanosized pores could typically be formed within about 5ns. These predictions are in very good agreement with recent experimental data. It is also demonstrated that defect formation and PS externalization in membranes should begin on the anode side. Finally, the simulations confirm that PS externalization is a nanopore facilitated event, rather than the …