Physical Sciences and Mathematics Commons^™

Experiments In Aerobic And Anaerobic Biodegradation Of Trichloroethylene, Qiong Liao

Theses

The removal of trichloroethylene (TCE) from industrial waste has been intensively studied in recent years, Biodegradation has been determined to be an effective treatment for TCE in the environment. Many researchers have studied the biodegradation of TOE and obtained successful results based on the use of specific isolated bacteria. At the NJIT Biotechnology Laboratory, a new method is being developed in which immobilized activated sludge is used to degrade several toxic chemicals in various reactor configurations. The objective of this research is to determine if these methods can be extended to treat TCE.

Activated sludge from a wastewater treatment plant …

Paint Stripper Composition Having Reduced Volatility Containing Decanolactone, N-Methylpyrrolidone And Butyrolactone And Method Of Use, Harvest L. Collier, Gary L. Bertrand, Raymond L. Venable

Chemistry Faculty Research & Creative Works

An improved composition of matter and method of use for removing cured coatings of paint or varnish or other similar coatings from substrates. The composition comrpises chlorinated solvent paint strippers (especially methylene chloride (CH₂CI₂)), waxes and an additive selected from the group consisting of decanolactone (C₁₀H₁₈O₂), N-methylpyrrolidone (CH₃NCH₂CH₂CH₂CH₂) and butyrolactone (OCH₂CH₂CH₂CO). The additive retards the evaporation of the solvent resulting in a composition that is environmentally less hazardous to a user and also resulting …

Resolution Of Enantiomeric Hydrocarbon Biomarkers Of Geochemical Importance, Daniel W. Armstrong, Yubing Tang, Janusz Zukowski

Chemistry Faculty Research & Creative Works

Chlral isoprenoid and hydroaromatic compounds occur in all crude oils, coals, shales, and most sediments. Many of these compounds are referred to as biological markers since they are thought to be derived from biological sources and their presence, relative concentrations, or stereochemistry can provide information as to a geological deposit's age, maturity, diagenetic history, and so forth. Because of the previous lack of effective and efficient analytical methodologies for resolving hydrocarbon enantiomers, the stereochemical information encoded in these molecules is largely untouched. A series of derivatized α-, β-, and γ-cyclodextrin chiral stationary phases (CSPs) were used for the gas chromatographic …

Polymer Research In Austria. I: Introduction And The Facilities, Otto Vogl, Josef Schurz, Bernd Thrattnigg, Klaus Hummel, Wolfgang Daimler, Klaus Lederer

Emeritus Faculty Author Gallery

No abstract provided.

Japan-U.S. Seminar On Polymer Synthesis, Otto Vogl, Hiroyuki Nishide

Emeritus Faculty Author Gallery

No abstract provided.

Consumption Rates, Evacuation Rates And Diets Of Pygmy Killifish, Leptolucania Ommata, And Mosquitofish, Gambusia Affinis In The Okefenokee Swamp, J. Douglas Oliver

Faculty Publications and Presentations

I studied feeding dynamics of Leptolucania ommata and Gambusia affinis in the Okefenokee Swamp. Both fishes mainly ate insect larvae (such as Chironomidae) and Cladocera. Evacuation rates ranged from 0.143 (L. ommala in winter) to 0.279/hour (L. ommala in summer). Daily food consumption (dry weight) ranged from 24.2 (L. ommata in winter) to 148.3 mg/g/day (G. affinis in summer). Maximum consumption by both species was estimated at 26.31 mg/t m2 / day, in summer. These values are consistent with other observations supporting a hypothesis that invertebrate prey production is substantial in these blackwater wetlands.

Polymer Research In Austria. I: Introduction And The Facilities, Otto Vogl, Josef Schurz, Bernd Thrattnigg, Klaus Hummel, Wolfgang Daimler, Klaus Lederer

Otto Vogl

No abstract provided.

Japan-U.S. Seminar On Polymer Synthesis, Otto Vogl, Hiroyuki Nishide

Otto Vogl

No abstract provided.

Electron-Energy And –Angular Distributions In The Double Photoionization Of Helium, R. Wehlitz, Franz Heiser, Oliver Hemmers, B. Langer, A. Menzel, U. Becker

Environmental Studies Faculty Publications

Photoelectron spectra of helium have been measured at different angles and at various energies above the double-ionization threshold up to 120 eV to investigate the behavior of the energy and angular distributions, of shake-off electrons. Both energy and angular distributions clearly show a U-shaped profile which turns to a flat curve near threshold pointing to a uniform intensity distribution over the kinetic energy for all angles in this excitation energy regime. Our results for the angular-distribution asymmetry parameter indicate qualitative agreement with theoretical predictions but fail to provide them quantitatively.

Surface Structure Of √3x√3r 30 Cl/Ni(111) Determined Using Low-Temperature Angle-Resolved-Photoemission Extended Fine Structure, Li-Qiong Wang, Z. Hussain, Z. Q. Huang, A. E. Schach Von Wittenau, Dennis W. Lindle, D. A. Shirley

Chemistry and Biochemistry Faculty Research

A surface structural study of the √3 × √3 R30° Cl/Ni(111) adsorbate system was made using low-temperature angle-resolved photoemission extended fine structure. The experiments were performed along two emission directions, [111] and [110], and at two temperatures, 120 and 300 K. The multiple-scattering spherical-wave analysis determined that the Cl atom adsorbs in the fcc threefold hollow site, 1.837(8) Å above the first nickel layer, with a Cl-Ni bond length of 2.332(6) Å, and an approximate 5% contraction between the first and the second nickel layers (the errors in parentheses are statistical standard deviations only).

Reductive Cleavage Of Cyclopentadienylmanganese Tricarbonyl, Mani S. Iyer

Masters Theses

Since the isolation of ferrocene in 1951, it has been shown to behave like benzene and may be acylated, sulfonated, metalated, and arylated. Like benzene, it also resists hydrogenation.

Daniel Trifan and Louis Nicholas (1957) were the first to show that ferrocene can be smoothly degraded by lithium and ethylamine. The isolation of free cyclopentadienyl ion on hydrolysis of the reaction mixture indicates that the cleavage leads initially to cyclopentadienyl lithium salt. A similar procedure applied to cyclopentadienylmanganese tricarbonyl also resulted in the formation of cyclopentadienyl lithium salt. This, when added to ferrous chloride, gave ferrocene. This technique can be …

Selected Studies On Certain Iron Sandwich Complexes, Mashitah M. Yusoff

Masters Theses

In these studies, the synthesis of [2.3](1,3)cyclopentadiendoparacyclophane was attempted. Like ferrocene and [2.2]paracyclophane, it is expected to exhibit transannular π-electronic interaction throughout its molecular structure and therefore, one dimensional semiconductivity.

The preparation of dialkylferrocenes had resulted in complex inseparable mixtures. Due to the fluxional nature of its intermediates, their conversion to stable Diels-Alder adducts would facilitate analysis. In this project, certain Diels-Alder adducts of bis-cyclopentadienyliron dicarbonyl intermediates were prepared for analysis.

Very few transition metal complexes of pyrrole are currently known. [2.2](2,5)Pyrroloparacyclophane was perceived to be stable especially as a part of an iron sandwich complex. The final phase …

An Analytical Representation Of The Lowest Potential Energy Surface For The Reaction O(3 P)+Hcl (X  1Σ+)→Oh(X  2Π)+Cl(2 P), H. Koizumi, George C. Schatz, Mark S. Gordon

Mark S. Gordon

We present a new analytical representation of the lowest 3 A‘ energy surface for the reaction O(3 P)+HCl(X  1Σ+)→OH(X  2Π)+Cl(2 P). This surface is derived by fitting a b i n i t i o calculations, and adjustments are made to the barrier height so that rate constants derived from accurate quantum scattering calculations match the room temperature thermal rate constants. Contributions to thermal and state resolved rate constants arising from reaction on the lowest 3 A’surface are also considered. Comparisons of thermal and state resolved rate constants with experiment are good except at high temperature where the 3 A’ …

Change Of Magnetic Properties Of Th₂Fe₁₇ Due To Interstitial Solution Of C And N, T. H. Jacobs, Gary J. Long, Oran Allan Pringle, Fernande Grandjean, K. H. Buschow

Chemistry Faculty Research & Creative Works

The changes in magnetic and crystallographic properties in the series Th₂Fe₁₇C_x and Th₂Fe ₁₇N_x have been studied. The changes in the latter series were also studied by ⁵⁷Fe Mössbauer spectroscopy. The ultimate enhancements of the saturation moments in these series are 13% and 24%, respectively. This is much larger than observed previously in the corresponding rare-earth compounds, although the Curie temperature enhancements are of comparable magnitude. In the Th-Fe-C system a novel compound of the BaCd ₁₁ type was found, having a Curie temperature around 370 K.

The Conformational Potential Energy Surface Of Glycine: A Theoretical Study, Jan H. Jensen, Mark S. Gordon

Mark S. Gordon

The conformational potential energy surface of nonionized glycine has been studied by using ab initio (6-310*, ST0-20) and semiempirical (AM1, PM3) methods. The MP2/6-31G*/ /RHF/6-310* potential energy surface was then used to calculate the Boltzmann equilibrium distribution and kinetics of conformational interconversion at various temperatures. The results of this study are compared to previous computational and experimental investigations of gas-phase glycine.

Structures And Bonding Of Group Iv Sulfur And Oxygen Propellane Derivatives, Kiet A. Nguyen, Marhsall T. Carroll, Mark S. Gordon

Mark S. Gordon

The RHF, ROHF, and GVB structures and energetics of group IV 2,4,5-trioxa[l.l.l]metallapropellanes, 2,4,5- trithia [ l.l.l]metallapropellanes, and their bicyclopentane analogues have been determined from ab initio molecular orbital theory by using both the 6-31G(d) basis set for all-electron calculations and the valence basis set with effective core potentials (ECP) developed by Stevens, Basch, and Krauss. Although they have extremely short bridgehead distances, these species possess fairly large natural orbital occupation numbers in the lowest unoccupied molecular orbitals, indicating significant diradical character. Structures and other properties determined by ECP calculations are in good agreement with the 6-31 G(d) all-electron calculations.

Ua66/7/2 Hilltopper News, Wku Chemistry

WKU Archives Records

Newsletter created by and about the WKU Chemistry department.

Thermal Characterization Of Carbon Monoxide Oxidation Catalysts Using Thermogravimetric Analysts And Differential Scanning Calorimetry, Rene A. Bartgis

Chemistry & Biochemistry Theses & Dissertations

Catalysts composed of platinum and/or palladium on tin (IV) oxide supports, with and without silica gel, as well as catalysts composed of gold on manganese oxide, have been developed for the recombination of carbon monoxide and oxygen to form carbon dioxide for use in carbon dioxide lasers. A thermogravimetric method and a differential scanning calorimetric method have been developed for the thermal characterization of these catalysts. The mass loss data and the enthalpy changes determined as the catalysts lost water were then related to existing activity data for these catalysts. No relationship was found between the thermal data and the …

Reactions Of Aqueous Chlorine With Valine In Model Solutions And In Wastewater, Erika Forrer Mccormick

Chemistry & Biochemistry Theses & Dissertations

Solutions of the amino acid valine were chlorinated to seven chlorine-to-nitrogen mole (Cl/N) ratios and analyzed by high performance liquid chromatography, gas chromatography/mass spectroscopy, infrared spectroscopy, and nuclear magnetic resonance spectroscopy. The chlorination products found were N-chlorovaline, isobutyraldehyde, isobutyronitrile, and N-chloroisobutyraldimine. Their product distribution depends on the level of chlorination and pH. The main products identified at the lower CI/N mole ratios were N-chlorovaline and isobutyraldehyde, whereas at the higher CI/N mole ratios isobutyronitrile and N-chloroisobutyraldimine were identified as the main products. The concentration and the chlorination products of valine in municipal wastewater were also determined. The chlorination products of …

Reply To "Comment On 'Kinetic-Energy Density Functional For A Special Shape-Invariant Potential Of A One-Dimensional Two-Level System'", Jiushu Shao, John J. Stezowski

John J. Stezowski Publications

For a harmonic potential, which is the special shape-invariant potential discussed in our paper [1], the relation between the ground state and the first-excited-state wave functions [Eq. (2)] should be . . .

Therefore, we have shown that one cannot find a closed form of the kinetic-energy density for the harmonic oscillator.

Structural Changes And Enhancements In Dnase I Footprinting Experiments?, Jerry Goodisman, James C. Dabrowiak

Chemistry - All Scholarship

In footprinting experiments, an increase in DNA cleavage with addition of ligand to a system may be due to a ligand-induced structural change. Ligand binding also enhances cleavage by displacing the cleavage agent from ligand-binding sites, thus increasing its concentration elsewhere. The theory and characteristics of this mass-action enhancement are given, and it is shown how it may be recognized. Results of DNase I footprinting of small oligomers, with actinomycin D as ligand, are analyzed to reveal which enhancements are due to mass action, and which can reasonably be ascribed to structural changes. Patterns in the footprinting plots from our …

Site-Specific Binding Constants For Actinomycin D On Dna Determined From Footprinting Studies, Jerry Goodisman, Robert Rehfuss, Brian Ward, James C. Dabrowiak

Chemistry - All Scholarship

We report site-specific binding constants for the intercalating anticancer drug actinomycin D (Act-D), binding to a 139-base-pair restriction fragment from pBR 322 DNA. The binding constants are derived from analysis of footprinting experiments, in which the radiolabeled 139-mer is cleaved using DNase I, the cleavage products undergo gel electrophoresis, and, from the gel autoradiogram, spot intensities, proportional to amounts of cleaved fragments, are measured. A bound drug prevents DNase I from cleaving at -7 bonds, leading to decreased amounts of corresponding fragments. With the radiolabel on the 3’ end of the noncoding strand (A-label), we measured relative amounts of 54 …

Predicted Enthalpies Of Formation For Methyl-Substituted Silaethylenes And Disilenes, Jerry A. Boatz, Mark S. Gordon

Mark S. Gordon

Enthalpies of formation of the methyl-substituted silaethylenes (CH3).H2_,Si=CH2 (n = 1, 2) and disilenes (CH3),.H~i=Si(CH3),H:~-m (n, m = Q-2) are predicted by using isodesmic reactions which relate the compound of interest to the parent silaethylene (H2Si=CH2) or disilene (H~i=SiH2), for which accurate enthalpies of formation have recently been determined. In turn, the enthalpies of formation of these methyl-substituted compounds are used in conjunction with homodesmic reactions to reevaluate the enthalpies of formation of the silicon-substituted cyclobutenes C.Si4-0H6 (n = Q-4).

Low Pressure Chemical Vapor Deposition (Lpcvd) Of Silicon Carbide From Diethylsilane, Yi-Tong Shi

Theses

The depositions of amorphous and cubic-crystal SiC from a new chemical vapor deposition source, diethylsilane(DES), have been studied. Amorphous SiC thin films and crystalline cubic-SiC materials have been deposited on silicon wafers at temperature lower and higher than 850C, respectively. The activation energy and a reaction mechanism involving the production and subsequent desorption of diethylsilene has been suggested, which explains the observed deposition dependency with the temperature and reactor pressure. A model based on the polymerization of DES is offered and the deposition rate is found to be the result of a large number of simultaneously occuring deposition processes for …

Surface Tension Of A Charged And Polarized System, Jerry Goodisman

Chemistry - All Scholarship

Usually, the formula for the surface tension of a planar charged and polarized interface is obtained from that for a system involving only short-range forces, y = - dz [p - px(z)] by replacing the tangential pressure p , by p , + E2/8u. Problems with this include (a) p, is no longer explicitly defined, (b) the electrostatic stress term E2/8 pi is not correct in general but only if polarization is proportional to density of polarizable species, (c) the derivation of the formula in terms of p and p, involves calculating the work to expand a volume containing the …

Liquid Phase Electrochemistry At Ultralow Temperatures, Royce W. Murray, Stanton Ching, John T. Mcdevitt, Stephen R. Peck

Chemistry Faculty Publications

Fluid electrolyte solutions based on mixtures of butyronitrile (PrCN) and ethyl chloride (EtCl) with or as electrolyte freeze below −180°C and provide excellent media for cryogenic electrochemical experiments. A 1:2 mixture of PrCN and EtCl exhibits the best combination of freezing point and ionic conductivity for ultralow temperature electrochemistry. Diffusion coefficients for bis(pentamethylcyclopentadienyl) iron are measurable by potential step chronoamperometry down to −160°C using a conventionally sized electrode, but the resistivity of the solvent mixture is such that potential sweep voltammetry benefits from the use of microdisk (10 and 25 μm diam Pt) or microband (0.2 μm wide Au) electrodes. …

Stabilization Of Β Positive Charge By Silicon, Germanium, Or Tin, Kiet A. Nguyen, Mark S. Gordon, Gen-Tai Wang, Joseph B. Lambert

Mark S. Gordon

Ab initio molecular orbital theory is used to study the β effect of carbon, silicon, germanium, or tin on the carbenium ions in H2R'MCH2CHR+ (R' = H; R = H, CH3). The relative stabilization energies of carbenium ions provided by M (M = C, Si, Ge, Sn) were determined by calculating the energy change in an isodesmic reaction using MP2/3-21G(d) (at SCF /3-21G* geometries) and MP2/6-31G(d) (at SCF /6- 31G(d) geometries) wave functions. The magnitude of the β effect is predicted to increase in the order C < Si < Ge < Sn. For R = H, the nonvertical cyclic structure is favored for the cations, whereas methyl substitution appears to stabilize the vertical acyclic arrangement.

Ab Initio Study Of Some Methylene And Silylene Insertion Reactions, David R. Gano, Mark S. Gordon, Jerry A. Boatz

Mark S. Gordon

The theoretical barriers and reaction energetics have been determined, using ab initio calculations at the MP4/6-3IG(d) level, with 3-2IG* geometries, for the insertions of methylene and silylene into the X-Y bonds of ethane, methylsilane, disilane, and cyclopropane and into the X-H bonds of disilane and ethane. A correlation was observed between barrier heights and lengths of substrate bonds. The largest barriers were observed for methylene and silylene inserting into the C-C bonds of ethane. The barriers became successively lower for the C-Si and Si-Si bonds. Steric interactions thus appear to be a major factor in determining barrier heights. The observed …

Nature Of The Si-N Bond In Silatranes, Mark S. Gordon, Marshall T. Carroll, Jan H. Jensen, Larry P. Davis, Larry W. Burggraf, R. Martin Guidry

Mark S. Gordon

Both ab initio and semiempirical calculations are used to investigate the structure and bonding in substituted silatranes. In agreement with gas-phase experiments, which fmd Si-N distances that are 0.25-0.35 A longer than those in the crystal phase, the Si-N distance (for example, in methylsilatrane) is predicted to be much larger than that observed in the crystal. Nonetheless, a bond critical point is found between Si and N, suggesting the existence of an Si-N bond in these compounds. It is found that the energy cost for constraining the Si-N distance in hydroxysilatrane to a value similar to that observed in the …

Expression Of Biologically Active Human Corticosteroid Binding Globulin By Insect Cells: Acquisition Of Function Requires Glycosylation And Transport, Jayasri Ghose-Dastidar, J. B. Alexander Ross, Reza Green

Chemistry and Biochemistry Faculty Publications

Human corticosteroid binding globulin (hCBG) is a 50- to 55-kDa serum glycoprotein that binds cortisol and progesterone with high affinity. To map the steroid-binding domain and to investigate the folding pathways of hCBG, we have established an expression system based on infection of insect cells with a recombinant baculovirus encoding hCBG. Infected Spodoptera frugiperda (Sf9) cells secrete immunoreactive hCBG at high levels (16-24 pmol per 10⁶ cells per 40 h), and the recombinant protein binds cortisol with an affinity and specificity equivalent to that of human serum-derived hCBG. Thus, this system has the potential to provide large amounts of …