Chemistry Commons^™

An Alternative Use For Bagasse: Stabilizing Agent For Lead Waste, Michael A. Janusa

Faculty Publications

Bagasse amounts to one- third of the cane ground and supplies fuel for the generation of steam in raw factories; however, most factories have an excess of bagasse during regular grinding season. Another method for the utilization of bagasse was investigated using bagasse as a stabilizing agent for heavy metal waste solidified /stabilized in cement. Lead nitrate was used as the model heavy me ta l waste with a 10 or 15 per cent lead by weight to cement loading. Samples were cured for 7, 14, and 28 days at 24°C. Samples containing bagasse typically resulted in TCLP extract lead …

Preliminary X-Ray Diffraction Studies Of The Transcriptional Inhibitory Antibody Fab41.4, Johanna Mazlo, Robyn L. Stanfield, Ian A. Wilson, Steven H. Hinrichs, John J. Stezowski

Department of Chemistry: Faculty Publications

The binding of transcription factor ATF-1 to DNA contributes to gene expression and regulation of cell growth. Antibody Mab41.4, raised against ATF-1, and its derivatives Fab41.4 and scFv41.4 inhibit specific DNA binding in vitro and induce apoptotic death of tumor cells in vivo. Structural studies of Fab41.4 were performed to gain insight into the mechanism of action of this potentially therapeutic antibody. The optimal conditions for crystallization of Fab41.4 were determined. Crystals were needle-like in appearance, displayed C2 space-group symmetry and diffracted to a resolution of 1.6 Å. The unit-cell parameters were determined to be a = 186.64, b = …

Multiple Separations Facilitate Identification Of Protein Variants By Mass Spectrometry, Zhongli Zhang, David L. Smith, Jean B. Smith

Department of Chemistry: Faculty Publications

Identification of variant proteins from complex biological samples promises to contribute much to our understanding of the etiology of pathological states. Characterization of variants, due either to genetic mutations in protein sequences or to post-translational modifications, is considerably more difficult than the simple protein identifications typical of most current proteomic investigations. Identification of a few peptides by database retrieval is not adequate when the goal is to have a complete understanding of the modifications of the protein. Although one advantage of mass spectrometry is its ability to obtain specific responses to several components, the complexity of biological samples is often …

Halogen Oxidation Reactions Of (C5ph5)Cr(Co)3 And Lewis Base Addition To [(C5ph5)Cr(Μ-X)X]2: Electrochemical, Magnetic, And Raman Spectroscopic Characterization Of [(C5ph5)Crx2]2 And (C5ph5)Crx2(Thf) (X = Cl, Br, I). X-Ray Crystal Structure Of [(C5ph5)Cr(Μ-Cl)Cl]2, Marc A. Hutton, James C. Durham, Robert W. Grady, Brett E. Harris, Carter S. Jarrell, J. Matthew Mooney, Michael Castellani, Arnold L. Rheingold, Ulrich Kölle, Brenda J. Korte, Roger D. Sommer, Gordon T. Yee, J. Matthew Boggess, Roman S. Czernuszewicz

Chemistry Faculty Research

The 17-electron complex (C5Ph5)Cr(CO)3 reacts with halogens (C6H5I•Cl2, Br2, and I2) in C6H6 to yield the dimeric oxidation products [(C5Ph5)Cr(m-X)X]2 as thermally stable solids. Reactions with other chlorinating agents similarly yield [(C5Ph5)CrCl2]2. An X-ray crystal structure of [(C5Ph5)Cr(m-Cl)Cl]2 was obtained. The magnetic properties of the Cl₂ bridged dimer have been determined and modeled using the usual isotropic hamiltonian which yields J/k = –30 K. Low-temperature (77 K) Raman spectra of solid [(C5Ph5)CrX2]2 (X = Cl, I) allow assignments to be made for the metal-ring and metal halogen stretching modes in the low frequency region (< 600 cm-1). Tetrahydrofuran (THF) cleaves these dimers to yield complexes of the form (C5Ph5)CrX2(THF).

Some Notable Discoveries In Organosilicon Chemistry: Proceedings Of The History And Retrospective Session Of The 34th Organosilicon Symposium (2001), Adrian G. Brook, Robert West, Kim M. Baines, William B. Herdle, Larry H. Wood, Kenrick M. Lewis, George H. Wagner, Bernard Kanner

Proceedings

The 34th Organosilicon Symposium at White Plains, NY, in 2001 featured a History and Retrospective Session, during which invited speakers from academic and industrial laboratories recounted the path to some significant 20th century discoveries in organosilicon chemistry.

• The Si=C Story: The Way it Happened, Adrian G. Brook (University of Toronto)

• The Discovery of Stable Disilenes and Silylenes, Robert West (University of Wisconsin)

• Yellow Fever: The Story Behind the Synthesis of Germasilenes, Kim M. Baines (University of Western Ontario)

• Direct Synthesis of Tris(dimethylamino)silane, William B. Herdle (OSi Specialties, formerly of Union Carbide Corporation)

• Discovery of Tin and Phosphorus Effects on …

Investigation Of The Microporous And Mesoporous Structures Of The Reşadiye (Tokat/Turkey) Bentonite And Its Fractions, Müşerref Önal, Yüksel Sarikaya, Tülay Alemdaroğlu

Turkish Journal of Chemistry

It was determined by X-ray diffraction that, besides containing clay minerals such as montmorillonite and illite, the original bentonite contained also clinoptilolite, opal-C, quartz, calcite and dolomite. The original bentonite was separated into four fractions by decantation and precipitation from its aqueous suspension. The adsorption and desorption of nitrogen on the original bentonite and its fractions at 77 K were investigated. The specific surface areas of the samples were determined according to the methods of Brunauer-Emmett-Teller, de Boer-Lippens, and Harkins-Jura by using the adsorption data. The mesopore size distribution curves were plotted by using the desorption data. The specific micropore …

Investigations On The Electrochemical Surface Treatment Of Carbon Fibers, Erdal Bayramli, Levent Toppare, Naci̇ Kutay Eri̇nç

Turkish Journal of Chemistry

Desized polyacrylonitrile (PAN) based carbon fibers (CF) were chemically and electrochemically oxidized and reduced. CF surfaces were activated via cyclic voltammetry studies with anodic and cathodic scans. The changes in CF surfaces were studied by contact angle measurements. Lifshitz-van der Waals and acid-base components of single fibers were determined. In general, oxidation resulted in the formation of an acidic surface energy component and reduction gave rise to no change in the number of basic functionalities at the CF surface.

Oxidation Of Ethylenediaminetetraacetic Acid By N-Bromosuccinimide In Aqueous Alkaline Medium -- A Kinetic Study, S. K. Mavalangi, M. R. Kembhavi, S. T. Nandibewoor

Turkish Journal of Chemistry

The kinetics of oxidation of ethylenediaminetetraacetic acid (EDTA) by N-bromosuccinimide (NBS) in aqueous alkaline media was investigated at 25°C. Analysis of the results showed the reaction is first -- order with respect to [NBS] and apparently less than unit order each with respect to [EDTA] and [alkali]. The influence of the reaction products, ionic strength, temperature effect and dielectric constant of the medium on the rate of reaction was studied. The proposed mechanism is consistent with the observed kinetics. The reaction constants involved in the mechanism were derived. There is a good agreement between the observed and calculated rate constants …

Separation Process Of Citric Acid With Tertiary Amines/Diluents In Supercritical Co_{2}, Arzu Koparan, Afi̇fe Güvenç, Nurcan Kapucu, Ülkü Mehmetoğlu, Ayla Çalimli

Turkish Journal of Chemistry

Reactive extraction of citric acid was investigated at atmospheric and supercritical conditions. The most suitable diluent and amine from among the tertiary amines and eight different diluents were determined at atmospheric conditions. The distribution coefficient values obtained with Hostarex A 327 were higher than those of Alamine 336. The selected amine (Hostarex A327) and the diluent (Oleyl alcohol) were used for reactive extraction of citric acid at supercritical conditions. Separation yields of citric acid were obtained in the temperature ranges of 308 to 328 K and in the pressure ranges of 80 to 180 bars in a supercritical extraction system …

Electronic Structure And Bonding In Metal Phthalocyanines, Metal=Fe, Co, Ni, Cu, Zn, Mg, M.-S. Liao, Steve Scheiner

Chemistry and Biochemistry Faculty Publications

Electronic structure and bonding in metal phthalocyanines (Metal=Fe, Co, Ni, Cu, Zn, Mg) is investigated in detail using a density functional method. The metal atoms are strongly bound to the phthalocyanine ring in each case, by as much as 10 eV. The calculated orbital energy levels and relative total energies of these D_4h structures indicate that Fe and Co phthalocyanines have ³A_2g and ²E_g ground states, respectively, but that these states are changed upon interaction with strong-field axial ligands. The valence electronic structures of Fe and Co phthalocyanines differ significantly from those of …

Intrinsically Bent Dna In The Promoter Regions Of The Yeast Gal1–10 And Gal80 Genes, Ralph C. Bash, Jeff Vargason, P. Shing Ho, D. Lohr

Faculty Publications - Department of Biological & Molecular Science

Circular permutation analysis has detected fairly strong sites of intrinsic DNA bending on the promoter regions of the yeast GAL1–10 and GAL80 genes. These bends lie in functionally suggestive locations. On the promoter of the GAL1–10 structural genes, strong bends bracket nucleosome B, which lies between the UASG and the GAL1 TATA. These intrinsic bends could help position nucleosome B. Nucleosome B plus two other promoter nucleosomes protect the TATA and start site elements in the inactive state of expression but are completely disrupted (removed) when GAL1–10 expression is induced. The strongest intrinsic bend (;70°) lies at the downstream edge …

Cerumen Composition By Flash Pyrolysis-Gas Chromatography/Mass Spectrometry, Craig N. Burkhart, Michael A. Kruge, Craig G. Burkhart, Curtis Black

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

Objective: To assess the chemical composition of cerumen by flash pyrolysis-gas chromatography/mass spectrometry.

Study Design: Collected earwax specimens were fractionated into residue and supernatant by means of deoxycholate. This natural bile acid produces significantly better disintegration of earwax in vitro than do presently available ceruminolytic preparations, and also has demonstrated excellent clinical results in vivo to date.

Patients: The sample for analysis was obtained from a patient with clinical earwax impaction.

Results: The supernatant is composed of simple aromatic hydrocarbons, C₅-C_{l 7} straight-chain hydrocarbons, a complex mixture of compounds tentatively identified as diterpenoids, …

Production Of A Novel Copper-Binding Ligand By Marine Synechococcus (Cyanobacteria) In Response To Toxic Concentrations Of Copper, Arunsi C. Brown, Andrew S. Gordon

Virginia Journal of Science

Marine Synechococcus spp. are extremely sensitive to copper toxicity. Some strains have been shown to produce high-affinity, extracellular ligands of unknown structure which form complexes with free cupric ion. They are also known to produce metallothioneins (MT) in response to cadmium and zinc stress. In the present study, marine Synechococcus PCC 73109 (Agmenellum quadruplicatum BG-1) (Van Baalen) was exposed to three concentrations of CuSO₄ for various times. Size exclusion chromatography, atomic absorption spectrophotometry, and reverse phase HPLC were used to isolate an intracellular copper binding ligand of low molecular weight (< 6,500 Da). The ligand was detected after exposure to ≥ 8 μM CuSO₄ for 2 hr in BG-11 medium. …

Use Of Py-Gc/Ms Analysis Techniques In Animal Waste Management: A Preliminary Survey Of Dairy Manures, Daniel L. Vaughn, Michael A. Kruge

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

The increasing practice of industrial-scale agriculture tends to concentrate large masses of animal waste in relatively compact areas, potentially leading to excessive release of polluting nutrients into waterways during major storms. Anaerobic treatment conditions are generally favored to conserve nitrate N as an agricultural commodity. However, overall N contents in waste are often in excess of crop fertilization needs: storing excess N in soluble nitrate form increases pollution potential. Thus the perceived needs of agriculture and society-at-large become at odds. Organic nitrogen forms (e.g., proteins) are more environmentally stable and are less subject to unintentional release. Although U.S. farmers tend …

Uranium-Uranium Collisions At Relativistic Energies, Bao-An Li, Matt Tilley

Journal of the Arkansas Academy of Science

No abstract provided.

Non-Commercial Software For The Analysis And Interpretation Of High Resolution Molecular Spectra, A. R. Ford, Scott W. Reeve

Journal of the Arkansas Academy of Science

No abstract provided.

The Effect Of Aluminium Oxide And Cerium Oxide As Dispersoids In Chitosan-Lithium Acetate Complexes, Hoi Mien Leow

Student Works (2000-2009)

In this study, chitosan with 85% deacetylation was used with Ni(OAc)₂·2H₂O as doping salt and Al₂O₃, or CeO₂ as dispersoid. They were mixed in certain weight percentages and dissolved in 100ml of 0.5% acetic acid solution. These solutions were poured into petri dishes and left at room temperature for film formation. Infrared Spectroscopy has shown that there is interaction between chitosan and LiOAc with and without dispersoid. The peaks are shifted. broadened. split and differs in intensity. The electrical conductivity of all samples was calculated using the bulk resistance value obtained from the complex admittance plot. The highest electrical conductivity …

Preparation And Characterization Of Lithiated Cathode Materials For Lithium Batteries, Shanti Navaratnam

Student Works (2000-2009)

Four different cathode materials, LiNiO₂, LiCoO₂, LiCo₀.₂ Ni₀.₈O₂ and LiCo₀.₄, Ni₀.₆O₂ were synthesized by sol - gel technique. The prepared materials were characterized X-ray diffraction pattern, FT-IR and cyclic voltammetry. X-ray diffraction pattern shows crystallinity of materials, increases with higher calcination temperature. From FT- IR studies, it was shown, that the purity of sample also increased with prolong heating at higher temperatures. It was possible to obtain pure and highly crystalline LiNiO₂ after heating for fourteen hours at 800°c. Cyclic voltammetry shows the four prepared materials are suitable for fabrication of cathode, as lithium ions can intercalate and de-intercalate. LiNiO₂ …

Infared Spectroscopy And Electrical Conductivity Of Copper(Ii) Cinnamate And Iodine-Doped Copper(Ii) Cinnamate, Kumar Krishnan

Student Works (2000-2009)

Copper(II) cinnamate (CC) was prepared from copper(II) acetate monohydrate and cinnamic acid. It was a light-blue powder. The Fourier Transform Infrared (FTIR) spectrum of CC, recorded as potasium bromide (K.Br) disc, indicated the presence of all bonds and functional groups expected of it and showed that it exist as an equal mixture of cis- and trans- isomers. The conductivity of CC at room temperature was 5.22 x 10⁻¹¹Scm⁻¹. It showed metallic behaviour in the temperature range 78-300 K, and its conduction mechanism obeyed Mott's variable range hopping (VRH) model in the same temperature range. The density of states at Fermi …

Analysis Of Loratadine By Potentiometry And Reverse-Phase High Performance Liquid Chromatography, Kian Yong Puen

Student Works (2000-2009)

A non-aqueous titration method was developed to assay Loratadine bulk active and a High Performance Liquid Chromatography (HPLC) method was developed to determine Loratadine's manufacturing impurity. The HPLC method was also suitable for simultaneously assay and related substance determination of Loratadine pharmaceutical preparations. In the tritation method, glacial acetic acid was chosen as an amphiprotic solvent. Loratadine ionised in glacial acetic acid; the conjugated base of acetic acid (Ac·), was then titrated with standardised perchloric acid. The method was validated found to be precise, linear and robust. Reverse-phase HPLC method using a Novapak Cl8 column with a CH3CN: I0mM K2HPO4 …

Electronic Structures And Magnetism Of Lani₅₋ₓfeₓ Compounds, Jinbo Yang, Chiu-Ying Tai, G. K. Marasinghe, George Daniel Waddill, Oran Allan Pringle, William Joseph James

Physics Faculty Research & Creative Works

A systematic study of the magnetic moments and hyperfine interactions of the LaNi_5-xFe_x compounds was performed using the spin-polarized tight-binding-linear-muffin-tin-orbital methods (TBLMTO). The calculated results were compared with neutron diffraction and Mössbauer experimental data and found to be in good agreement. Fe atoms exhibit more localized magnetic moments in LaNi_5-xFe_x when the Fe content x is lower than 1.0. The calculated magnetic moments of the Fe atoms approach values as large as 2.5μ_B due to the dilution effect. The strong s-d hybridization between the Ni and La atoms and the neighboring Fe in …

Structural, Electronic, And Magnetic Properties Of Lani₅₋ₓtₓ (T = Fe, Mn) Compounds, Jinbo Yang, Chiu-Ying Tai, G. K. Marasinghe, George Daniel Waddill, Oran Allan Pringle, William Joseph James, Y. Kong

Physics Faculty Research & Creative Works

Structures and magnetic properties of the LaNi_5-xFe_x and LaNi_5-xMn_x compounds have been investigated using neutron diffraction and first-principles tight-binding-linear-muffin-tin-orbital methods. Both neutron diffraction refinement data and total energy calculations show that the Fe and Mn atoms preferentially occupy the 3g sites in the hexagonal CaCu₅-type structure. The calculated magnetic moments of Fe and Ni atoms are of 2.4-2.5μ_B and 0.2-0.5μ_B in LaNi_5-xFe_x, respectively. The magnetic structure exhibits more localized moments at Fe atoms in LaNi_5-xFe_x when x ≤ 1.0. Electronic structure calculations indicate …

Dynamics Of Polyacrylates In Concentrated Chloroform Solutions, Frank D. Blum, Raj B. Durairaj

Chemistry Faculty Research & Creative Works

The dynamics of polymers in polymer solutions have not been probed in great enough detail to provide a coherent picture of the behavior of these polymers, especially in more concentrated solutions. To help understand this behavior further, we have prepared a series of backbone-labeled polymers including poly(n-butyl acrylate)-d1 (PNBA). These provide a basis for comparison of the behavior among a group of related polymers. The dynamics have been probed by using deuterium relaxation times. Since the relaxation times are relatively fast and the quadrupolar relaxation mechanism is well understood, data from this technique provide a convenient means for comparison of …

Glass Transition Behavior Of Pmma Thin Films, Moses T. Kabomo, Frank D. Blum

Chemistry Faculty Research & Creative Works

In the last decade there has been an increased interest in the study of the properties of supported thin polymer films. This has been prompted by the incorporation of thin films into device applications and many other technologies. Although not without controversy, a large body of experimental work indicates departures from bulk behavior by thin films. Strong evidence from both theoretical and experimental work shows that the interaction of polymer with a substrate alters the polymer conformation and mobility. A variety of techniques has been employed to probe the mobility of thin supported polymer films. Some of these techniques indirectly …

Graduated Segmental Mobility In Polymer Layers On Silica, Frank D. Blum, Crystal E. Porter, Wuu-Yung Lin

Chemistry Faculty Research & Creative Works

The behavior of thin polymer layers on oxide substrates has gotten a great deal of attention as the size of materials, and hence polymer films, has gotten smaller. Indeed, the properties of adsorbed polymers are such that they can be different from those of bulk polymers, especially when the films are very thin. A wide variety of studies have been made on adsorbed polymers and sometimes the results seem contradictory. One of the properties often measured in thin films is the apparent glasstransition temperature, Tg. In principle, many techniques are sensitive to phenomenological changes occurring around Tg and, therefore, can …

Thermal Analysis Of Ultrathin Ps-R-Pmma Copolymer Films On Silica, Bing Zhang, Frank D. Blum

Chemistry Faculty Research & Creative Works

Composite materials represent a major part of man-made materials that are used in many applications. The interaction of polymers with surfaces plays a crucial role in the final properties of these materials and, by understanding the surface processes and adsorption mechanisms, better systems can be designed. Therefore, the behavior of polymer molecules at interfaces has been the topic of many studies in recent years and a rough picture has been obtained. Keddie et al. Obtained experimental results showing the dependence of the glass transition temperature (Tg) on the thickness of supported polystyrene films using ellipsometry. Later, they also investigated supported …

Resonant Energy Transfer From Argon Dimers To Atomic Oxygen In Microhollow Cathode Discharges, M. Moselhy, R. H. Stark, K. H. Schoenbach, U. Kogelschatz

Bioelectrics Publications

The emission of atomic oxygen lines at 130.2 and 130.5 nm from a microhollow cathode discharge in argon with oxygen added indicates resonant energy transfer from argon dimers to oxygen atoms. The internal efficiency of the vacuum-ultraviolet (VUV) radiation was measured as 0.7% for a discharge in 1100 Torr argon with 0.1% oxygen added. The direct current VUV point source operates at voltages below 300 V and at current levels of milliamperes.

Photochemical Degradation Of 2,4-D And Atrazine In Well-Defined Media, Asher D. Ghertner

Honors Theses

Atrazine and 2,4-D are common herbicides used for crop, lawn, and rangeland management. Photochemical degradation has been proposed as one safe and efficient remediation strategy for both 2,4-D and Atrazine. In the presence of iron(llI) and hydrogen peroxide these herbicides decay by both thermal and light induced oxidation. Past studies have focused primarily on sun light as an energy source. This work provides a mechanistic description of herbicide degradation incorporating intermediate degradation products produced in the dark and under well-defined light conditions.

Study Of The Effects Of Co2(G) On The Fe(Ii)-Luminol Chemiluminescence System: Application To Ultra-Trace Analysis Of Fe(Ii), Sara Beth Lovitz

Honors Theses

The Fe(II)-catalyzed oxidation of luminol has been a well-accepted chemiluminescence method for the trace and ultra-trace analysis of Fe(II) and Fe(III) in natural waters. Investigation into this chemiluminescence system has shown that COlg) is essential to Fe-catalyzed luminol chemiluminescence. In absence of CO2(g) there is no chemiluminescent signal. These reactions worked well in the past because CO2 is present in most laboratory H20 supplies. Intentional saturation of CO2 results in a 5-fold increase for this conventional system. We propose a mechanism for CO 2(g) enhancement that includes formation of a CO2-superoxide intermediate, which serves as the oxidant of luminol to …

Exploratory Chemistry In Route To Aromatic Natural Products, Nicholas P. Bizier

Honors Theses

The focus of this research was the synthesis of two natural products, 1-methyl-s-(1,2,2-trimethy1cyclopentyl)-benzene (formally cuparene), and 3-(1,2dimethylcyclopenty1)-5-methylbenzene-l,2-diol (formally herbertene diol). Cuparene possesses anti-fungal and anti-arthritic properties. This molecule has been the target of a number of syntheses. Herbertene diol, a natural product itself, represents one retrosynthetic step back from mastigophorane; a compound isolated form the liverwort Mastigophora diaclolades. Mastigophorane has been shown to have neural network forming capabilities and has warranted complete synthetic efforts. Through the same chemistry involve in the formation of cuparene, we sought a route to herbertene diol in two steps. We report a successful route to …