Chemistry Commons^™

Organic N-Chloramines: Chemistry And Toxicology, Frank E. Scully, Jr., Maxwell A. Bempong

Chemistry & Biochemistry Faculty Publications

The stability of aqueous solutions of organic N-chloramines, suspected of contaminating chlorinated water, has been studied. Two factors influence the decomposition of solutions of N-chloropiperidine and N-chlorodiethylamine: a spontaneous decomposition and photodecomposition. Since solutions of these compounds are relatively long-lived, a need for an analytical method for their identification is discussed. A new method is described which involves reaction of organic N-chloramines with arenesulfinic acid salts. The method gives high yields of stable arenesulfonamides. Several toxicological studies of N-chloropiperidine are described. The compound is mutagenic by Ames assay in Salmonella typhimurium strain TA 100 and does not require metabolic activation …

High Performance Liquid Chromatographic Analysis Of Biogenic Amines, Thais Edwina Ahrendt Keegan

Chemistry & Biochemistry Theses & Dissertations

The objectives of this research were to develop a sensitive method for separation and quantitation of biogenic amines and to apply that procedure by monitoring neurochemical changes resulting from stimuli to the test system.

Primary aromatic amines were derivatized with o-phthalaldehyde-mercaptoethanol prior to chromatography, Separation of the fluorescent adduct was achieved using a μBondapak/ phenyl reversed-phase column and a two-step gradient of methanol:0.08 M acetic acid, pH J.O. Fluorescence was monitored using a J40 nm excitation energy and an emission filter which transmits radiation greater than 400 nm (50% T at 418 nanometers).

Following optimization of the chromatographic conditions, studies …

Studies Of The Reorientational Relaxation Of Pyridine In Water By Depolarized Rayleigh Light Scattering, C. H. Wang, Scott L. Whittenburg, P. A. Lund, D. H. Christensen

Chemistry and Biochemistry Faculty Publications

The depolarized Rayleigh spectra of aqueous solutions of pyridine have been studied using a high‐finesse Fabry–Perot interferometer as a function of temperature and concentration. The Rayleigh relaxation times are found to have a complex concentration and viscosity dependence. The classical Stokes–Einstein–Debye equation for molecular reorientation breaks down in this system. The Rayleigh relaxation time of pyridine molecules is not determined by the macroscopic shear viscosity of the solution. The specific interaction due to the formation of hydrogen bonds between pyridine and water molecules plays a very important role in affecting the relaxation time. At a fixed temperature the plot of …

Adaptative Alteration In Phospholipid Composition Of Plasma Membranes From A Somatic Cell Mutant Defective In The Regulation Of Cholesterol Biosynthesis, Michael Sinensky

Faculty Publications, Biological Sciences

A somatic cell mutant (CR1) of a Chinese hamster ovary cell (CHO-K1) which has previously been shown to be defective in the regulation of cholesterol biosynthesis accumulates more cholesterol than the parental cell line in plasma membranes. Although such an increase in membrane cholesterol should lead to an increase in the order parameter of these membranes, as measured with an electron spin resonance spin probe, the order parameters of mutant and wild-type plasma membranes are identical--apparently because of an adaptive alteration in membrane phospholipid composition. The phospholipid compositions of mutant and wild-type cell plasma membranes are compared and the mutant …

The Association Of 5.8 S With 28s Ribosomal Rna, Nandita Banerjee

Chemistry & Biochemistry Theses & Dissertations

5.8S rRNA is a low molecular weight ribosomal RNA which is noncovalently bonded to the larger ribosomal subunit 28S rRNA; through its 3' end and through its 5' end. This interaction is an integral part of the ribosome, and plays an important role in the ribosome structure and function.

There is a high degree of homology between the 5.8S rRNA primary structures of rat, turtle and chicken. The base sequence of rat 5.8S rRNA differs only in one position from that of turtle and in three positions fr.om that of cl1.icken. Tl1ere is a single purine substitution at the 5' …

Heating-Effect Minimization In Dye Lasers, Kenneth Lee Matheson, James M. Thorne

Faculty Publications

Optical pumping of dye lasers deposits heat nonuniformly in the active medium. Because the refractive index of a liquid or gas is a function of temperature, gradients are created which refract the laser beam. This effect is sometimes serious enough to quench laser action. In this paper, we evaluate the effects caused by optical pumping with a coaxial flashlamp and suggest ultraviolet absorbers and wavelength shifters as materials for minimizing the problem

Pulling The Wool Off, Department Of Agriculture, Western Australia

Journal of the Department of Agriculture, Western Australia, Series 4

The Department of Agriculture has begun a three year project to study the potential for "chemical shearing" or, more correctly, biological defleecing.

An Emulsion Dye Laser, Kenneth Lee Matheson, James M. Thorne

Faculty Publications

A laser dye which is insoluble in water has been dissolved in hexane and emulsified in a water matrix. When pumped with a nitrogen laser, this mixture was observed to lase. The emulsion is superior to a simple hexane solution because the excellent thermo-optical properties of the water matrix help prevent refractive-index gradients from degrading laser performance. This is a useful characteristic for flash-pumped dye lasers, laser-pumped dye lasers, and liquid filters. Another type of solvent system, a critical solution, is also discussed. For certain dyes, a critical solution has even better thermo-optical properties because of its ability to absorb …

Light Scattering Studies Of Transverse Sound Wave And Molecular Motion In Benzonitrile, Scott L. Whittenburg, C. H. Wang

Chemistry and Biochemistry Faculty Publications

The zero‐frequency shear wave dip appearing in the depolarized Rayleigh spectrum in benzonitrile has been studied as a function of concentration and temperature. The solution study was carried out at constant viscosity equal to the viscosity of liquid benzonitrile at each temperature. The result indicates that the presence of shear wave fine structure does not depend on the collective orientational fluctuations. The orientational and vibrational relaxation times of benzonitrile were measured at various concentrations and temperatures. The orientational relaxation times show no concentration dependence at any temperature, suggesting that the pair correlation is negligible at all concentrations. The orientational relaxation …

Light Scattering Studies Of Rotational And Vibrational Relaxations Of Acetonitrile In Carbon Tetrachloride, Scott L. Whittenburg, C. H. Wang

Chemistry and Biochemistry Faculty Publications

The rotational and vibrational relaxation times of acetonitrile–carbon tetrachloride solutions were investigated as a function of concentration, viscosity, and temperature using depolarized Rayleigh and Raman scattering. Using a Fabry‐Perot interferometer and single frequency laser source, we have shown that reliable results for the single particle orientational correlation times (τ_s) for CH₃CN can be obtained by carrying out a concentration dependent depolarized Rayleigh scattering study. Raman scattering was shown to yield inconsistent results for τ_s in CH₃CN. At constant viscosity, it was found that the Rayleigh scatteringrelaxation time (τ_Ray) of CH_{3 …}

Intermolecular Potential Surfaces From Electron Gas Methods. Ii. Angle And Distance Dependence Of The A’ And A” Ar–No(X^2ii) Interactions, Glen C. Nielson, Gregory A. Parker, Russell T. Pack

Faculty Publications

Angle dependent intermolecular potential energy surfaces for the two states (2A’ and 2A”) that arise from the interaction of ground (X^2II) state NO with Ar are calculated using the electron gas model to obtain the short range interactions. The average and difference of the two interaction energies are fit to analytic forms convenient for use in scattering calculations and joined smoothly onto the long range van der Waals potential previously determined. The results, which appear to be of useful accuracy, and the applicability of the electron gas model to such open shell–closed shell interactions are discussed.

A Review Of The Limnology Of And Water Quality Standards For Lake Mead, Charles R. Goldman

Publications (WR)

1. The waters of Las Vegas Bay, a heavily utilized recreational resource, receive discharges from a variety of municipal and industrial waste sources. The U.S. Environmental Protection Agency has determined, on the basis of numerous studies, that the present water quality violates state and federal standards and constitutes a public nuisance. Consultants have advised the Sewage and Wastewater Advisory Committee that rapid abatement of the alleged pollution conditions can be achieved by an advanced wastewater treatment (AWT) plant.

2. The major problems in Las Vegas Bay are an objectionable water color, excessive turbidity, noxious odors, and oxygen depletion in certain …

A Comparison Of The Rough Sphere Rotational Diffusion Model With Experimental Results For Liquid Methyl Iodide, Dane R. Jones, Scott L. Whittenburg, C. H. Wang

Chemistry and Biochemistry Faculty Publications

No abstract available.

Esr Study Of Free Radicals In Irradiated Single Crystals Of Potassium Hydroxylamine Disulfonate, B. J. Wilson, Robert W. Holmberg

Faculty Publications

Two free radicals formed when single crystals of potassium hydroxylamine disulfonate are irradiated with gamma rays at 77degrees K were studied by ESR. The ESR spectra result from a predominant center (radical A) exhibiting large 14N and 1H hyperfine splittings and from lesser amounts of Fremy's radical [O-dotN(SO3)2-2]. The g and hyperfine tensors of these radicals have been evaluated and are discussed. Radical A, whose identity remains in doubt, may be regarded as the precursor to Fremy's radical; on warming its lines decay and those of Fremy's radical are formed. Lines from radical A decrease in strength and those of …

Van Der Waals Interactions Of Carbon Monoxide, Gregory A. Parker, Russell T. Pack

Faculty Publications

Pade approximant methods and experimental frequency dependent polarizabilities are used to calculate reliable van der Waals C6 coefficients for the interaction of CO with He, Ne, Ar, Kr, Xe, H, Li, Na, K, Rb, Cs, H2, N2, O2, CO2, and CO. Error bounds are given for the C6 coefficients and for the CO oscillator strength sums.

Van Der Waals Interactions Of Ii-State Linear Molecules With Atoms. C6 For No(X 2Π) Interactions, Glen C. Nielson, Gregory A. Parker, Russell T. Pack

Faculty Publications

Formulas are derived for the van der Waals Cn coefficients for the interaction of a diatomic molecule in a II electronic state with an S-state atom. Two triatomic states arise from the degenerate IIstate. The average of the two energies has the usual Legendre polynomial (PL) angular dependence, but the difference in energies of the two states is shown to have associated Legendre polynomial (PML with M=2) angular dependence. Procedures for including spin orbit coupling are included, and the extension to interactions of Delta- and Phi-state molecules is discussed. Values of the spherical part of the C6 coefficients for the …

Comment On ''Inelastic Scattering In Atom-Diatomic Molecule Collisions. I. Rotational Transitions In The Sudden Approximation'', Russell T. Pack

Faculty Publications

It is argued that conflicting approximations in a recent paper [J. R. Stallcop, J. Chem. Phys. 61, 5085 (1974)] render the resulting theory invalid.

Close Coupling Test Of Classical And Semiclassical Cross Sections For Rotationally Inelastic Ar-N2 Collisions, Russell T. Pack

Faculty Publications

Accurate quantum mechanical close coupling (CC) integral cross sections are reported for rotationally inelastic Ar-N2 collisions at room temperature using an empirical intermolecular potential. These cross sections are used to test the infinite order sudden (IOS) approximation and the results of several methods [classical trajectories (CT), full sudden (SA), generalized phase shift (GPS), and classical limit generalized phase shift (CGPS)] as reported in the preceding paper by Pattengill. The IOS approximation works very well for cross sections involving low rotational states. The CT method works well for all the cross sections examined, justifying the popular belief that the rotational motion …

Erratum: On Improved Wkb (Uniform Asymptotic) Quantum Conditions, Dunham Corrections, The Langer Modification, And Rkr Potentials, Russell T. Pack

Faculty Publications

In Eqs. (28) and (29) p should be changed to t.

Rotationally Inelastic Molecular Scattering. Computational Tests Of Some Simple Solutions Of The Strong Coupling Problem, Thomas P. Tsien, Gregory A. Parker, Russell T. Pack

Faculty Publications

Partial cross sections (opacity functions) for rotational transitions in atom-diatom collisions are computed in the infinite-order sudden (IOS) approximation and compared with accurate close-coupling (CC) calculations. Agreement is good in the dominant coupling (small total angular momentum J) region. Simple methods for calculating integral inelastic cross sections are discussed, and it is found that accurate cross sections can often be computed very simply, even when large numbers of channels are coupled together, by using IOS or first-order sudden (FOS) approximations for small J and CC or exponential Born (EBDW) methods for large J.

I. An Isothermal Titration Microcalorimeter. Ii. Importance Of Micronutrients In Nutrition. Iii. Zinc Bibliography, John Willard Gardner

Theses and Dissertations

I. An isothermal titration microcalorimeter having a colume of 4 ml and capable of temerature control to ±2 x 10-5°C is described. Major components include a constant temperature water bath controlled to ±3 x 10-4°C, a platinum reation vessel, and an isothermal control circuit consisting of constant Peltier thermoelectric cooling and variable Joule heating controlled by a thermistor in an AC Wheatstone bridge circuit. The calorimeter was tested by measuring the heat of ionization of water and was found to produce data accurate to ± 0.1% where small samples are used such as in the investigation of many biological systems.

Final Report On Interrelationships Between Chemical, Physical And Biological Conditions Of The Waters Of Las Vegas Bay Of Lake Mead, James E. Deacon, Richard W. Tew

Publications (WR)

This program was a status study of the interaction between Las Vegas Wash, an enriched stream, and Las Vegas Bay, a wedge shaped arm of one of the world's deeper reservoirs. The program centered primarily on identification and counting of planktonic algae from several points in Las Vegas Bay. Additional work on nutrient enrichment of water samples was conducted to aid in interpretation of algal distribution related to nutrient input. Examination of a variety of physical, chemical, and biological parameters, both at many surface points in the bay, as well as in vertical profile, was also accomplished and further aided …

On Improved Wkb (Uniform Asymptotic) Quantum Conditions, Dunham Corrections, The Langer Modification, And Rkr Potentials, Russell T. Pack

Faculty Publications

An improvement to the WKB quantum condition for the rotation-vibration levels of diatomic molecules, known empirically to give RKR potentials of increased accuracy and to account for the Dunham correction Y00, is derived using uniform asymptotic methods. The role of the Langer transformation in this problem is also discussed.

On The Mechanism Of Low-Temperature Termolecular Atomic Recombination, Russell T. Pack, Richard L. Snow, Wesley D. Smith

Faculty Publications

A simple theory of gas-phase termolecular atomic recombination kinetics is presented which treats the bound-complex (BC) mechanism in a fashion which parallels the Roberts, Bernstein, and Curtiss resonance theory of the energy-transfer (ET) mechanism. The ET rate constant has a low temperature maximum, but the BC rate constant does not. The contributions of the two mechanisms to the low-temperature recombination of hydrogen atoms, with He, Ar, and H2 as third bodies, are estimated and compared. The presence (absence) of a low-temperature maximum in the observable total rate constant is determined by absence (presence) of bound vibrational levels of the hydrogen-third …

Micronutrients And Biological Patterns In Lake Mead, Hasan K. Qashu, Lorne G. Everett, J. S. Carlson, Bureau Of Reclamation

Publications (WR)

Progressive increases in concentration of dissolved solids in the Colorado River water from Lake Powell to Imperial Dam seem to alter plankton dynamics and biological productivity of the river. Also, changes in biological productivity and micronutrients concentrations occur within the same reservoir. Development of a digital simulation model to predict micronutrients concentrations and biological productivity is necessary for diagnosing changes in plankton population and effluent-carrying capacity of the system. The objectives of the study are: (1) to determine trace metal balance at different locations in Lake Mead, (2) to measure biological productivity and conduct plankton population counts at each sampling …

High-Pressure Phase Studies On Sodium–Potassium Alloys, D. Ray Anderson, J. Bevan Ott, Rex J. Goates, H. Tracy Hall

Faculty Publications

The solid–liquid phase diagrams were investigated to 60 kbar for elemental sodium, potassium, and various sodium–potassium alloys. The data for Na and K are in general agreement with those of earlier workers. In the alloy system the temperatures of both the peritectic and eutectic halts increase as the pressure increases, but with different slopes, so that the two invariant points merge at approximately 35 kbar. Above this pressure, two halts are again observed. One increases with increasing pressure, and the other decreases with increasing pressure up to 55 kbar, where it abruptly starts increasing again. Melting points for samples in …

The Enzymatic Oxidation Of Aldehydes By Xanthine Oxidase, Duane Beal Gregory

All Master's Theses

As early as sixty years ago, the existence of an enzyme from mammalian tissues which catalyzed the oxidation of xanthine and hypoxanthine was recognized. The name given the enzyme was derived from its earliest recognized action, hence xanthine oxidase. Although little is known about the biological functions of the enzyme, the high affinity shown for xanthine and hypoxanthine may indicate that these are the most significant substrates biologically.

Asymptotic Evaluation Of Wkb Matrix Elements. Ii. Use Of Langer's Uniform Asymptotic Wavefunctions, Wesley D. Smith, Russell T. Pack

Faculty Publications

An improvement in a previous procedure for the analytic asymptotic evaluation of integrals arising in the quantum-mechanical theory of inelastic molecular collisions is presented. The integrals are evaluated using Langer's uniform asymptotic wavefunctions and the higher-order saddle-point or steepest-descents method. It is found that the Langer functions give no better results than WKB functions, but the higher-order steepest-descents corrections produce a marked improvement. The result is a simple method for evaluating a large class of integrals with an error of 0.1%-2.1%.

Quasilattice Interpretation Of The Thermodynamic Properties Of Mixing Of Binary Alkali-Metal Systems, J. Bevan Ott, J. Rex Goates

Faculty Publications

Quasilattice theory was applied to heats of mixing in the six systems formed from the binary combinations of Na, K, Rb, and Cs. The alkali-metal systems are particularly well suited for a critical test of the quasi-crystalline assumption since the theoretical model for these systems is relatively simple and the thermodynamic data are fairly complex. Very good fits of the heat-of-mixing data were achieved by assuming that the larger atom in the binary system covered multiple sites on the quasilattice. The values of the empirically determined constants appear to fit the physical significance accorded to them by the quasilattice model. …

Expectation Values Of Simple Correlated Helium-Atom Wavefunctions, Thomas P. Tsien, Russell T. Pack

Faculty Publications

In this Note we present the results of a calculation of the expectation values of a number of one- and two electron properties of the ground-state helium atom using two very simple correlated wavefunctions.