Chemistry Commons^™

Origins Of The Quantum Efficiency Duality In The Primary Photochemical Event Of Bacteriorhodopsin, Robert R. Birge, Leonore A. Findsen, Albert F. Lawrence, Mark Masthay, Chian-Fan Zhang

Chemistry Faculty Publications

Experimental and theoretical evidence is presented which suggests that two distinct forms of light-adapted bacteriorhodopsin may exist. We propose that these two forms have characteristic photocycles with significantly different primary quantum yields. INDO-PSDCI molecular orbital procedures and semiempirical molecular dynamics simulations predict that one ground state geometry of bR undergoes photochemistry with a primary quantum yield, Φ1, of ~ 0.27, and that a second ground state geometry, with a slightly displaced counterion, yields Φ1 ~ 0.74. This theoretical model is supported by the observation that literature measurements of Φ1 tend to fall into one of two categories- those that observe …

Incorporation Of A Product Of Mevalonic Acid Metabolism Into Proteins Of Chinese Hamster Ovary Nuclei, Michael Sinensky, L. A. Beck, T. Hosick

Faculty Publications, Biological Sciences

We have examined the nuclear localization of isoprenylated proteins in CHO-K1 cells labeled with [14C]mevalonate. Nuclear proteins of 68, 70, and 74 kD, posttranslationally modified by an isoprenoid, are also components of a nuclear matrix-intermediate filament preparation from CHO cells. Furthermore, the 68-, 70-, and 74-kD isoprenylated polypeptides are immunoprecipitated from cell extracts with two different anti-lamin antisera. Based on exact two-dimensional comigration with lamin B, both from rat liver lamin and CHO nuclear matrix-intermediate filament preparations, and its immunoprecipitation with anti-lamin antisera, we conclude that the 68-kD isoprenylated protein found in nuclei from [14C]mevalonate-labeled CHO cells is lamin B. …

The Synthesis Of 2-Aryl-3-Fluoroalkoxy-1-Propenes And Some Potentially Useful Reaction Of These Systems, Joan E. Brown

Retrospective Theses and Dissertations

This report discusses research involving the fluoroalkoxylation of 2-arylprop-1-en-3-yltrimethylammonium iodides and the useful synthetic application of the adducts formed. The present work includes: 1) reactions of several 2-arylprop-1-en-3-yltrimethylammonium iodides with the sodium salt of 2,2,2-trifluoroethanol; 2) reactions of several fluoroalkoxy alcohols with 2-(4-bromophenyl)prop-1-en-3-yltrimethylammonium iodide; and 3) the oxidation of 2-(4-chlorophenyl)-3-(2,2,2-trifluoroethyoxy)-1-propene using the Lemieux/von Rudloff reagent. This report reveals the experimental conditions and procedures used as well as spectral and physical data of all new compounds synthesized. Explanation is offered for a possible mechanism for the formation of these compounds and recommendations for future research are given.

Preparation Of Geminal Diflourodienes, Antonio Landavazo

Retrospective Theses and Dissertations

This report discusses research involving the preparation of germinal difluorodienes. Free radical addition of dibromodifluoromethane to 1-hexene and cyclohexene was performed, followed by a double dehydrohalogenation to yield 1,1-difluoro-1,3-heptadiene and 3-(difluoromethylene)cyclohexene, respectively. NMR, IR, and mass spectral data were obtained and presented as groundwork for further research. A study comparing the free radical initiators, benzoyl peroxide and 2,2’-azobis-(2-methyl)proprionitrile (AIBN) was included, showing neither as ideal initiators for the free radical additions performed. The relative stabilities of the bromodifluoromethyl and the difluoroiodomethyl radicals were approximated. A Diels-Alder reaction of 1,1-difluoro-1,3-heptadiene with 4-phenyl-1,2,4-triazoline-3,5-dione produced the expected [4 + 2] cycloadduct in good …

Hydration Of Propylene To Isopropanol, Nehemiah Diala

Retrospective Theses and Dissertations

The hydration of propylene to isopropanol was investigated. The first part of this study concerned the direct hydration reaction in various liquid phase systems in the presence of sulfuric acid or p-toluenesulfonic acid. The second part in a two-stage process in which propylene was contacted with excess acetic acid to form isopropyl acetate; the ester was then hydrolyzed to isopropyl alcohol and acetic acid.

The Reaction Of 2-Arylprop-1-En-3-Yltrimethylammonium Iodides With Sulfur Nucleophiles And Useful Synthetic Applications Of These Adducts, Steven J. Duranceau

Retrospective Theses and Dissertations

This report discusses research involving the reactions of 2-arylprop-1-en-3-yltrimethyl ammonium iodides with sulfur nucleophiles and the useful synthetic applications of the adducts formed. The present work may be subdivided into four sections: 1) reactions of several 2-arylprop-1-en-3-yltrimethylammonium iodides with benzenethiol; 2) reactions of several 2-arylprop-1-en-3-yltrimethylammonium iodides with the sodium salt of benzenesulfinic acid; 3) reactions of several 2-arylprop-1-en-3-yltrimethylammonium iodides with 2-mercapto-1-methyl imidazole; and 4) oxidation of 2-aryl-3-phenylthio-1-propenes and 2-aryl-3-phenylsulfonyl-1-propenes using sodium perborate. This report outlines the experimental conditions and procedures responsible for the synthesis of these products; in addition, this report describes the physical properties, NMR and IR spectra of …

A Theoretical Investigation Of The One– And Two–Photon Properties Of Porphyrins, Mark Masthay, Leonore A. Findsen, Brian M. Pierce, David F. Bocian, James S. Lindsey, Robert R. Birge

Chemistry Faculty Publications

The one‐ and two‐photon properties of free base porphin, free base porphin dianion, and the 2,4‐substituted diformyl and divinyl analogs of these molecules are studied using a semiempirical SCF‐MO formalism (CNDO‐π‐SCF‐MO‐PSDCI) including extensive single and double configuration interaction. Strongly two‐photon allowed states are predicted to lie in the Soret region as well as in the region between the Soret and visible bands. A number of the two‐photon allowed states in the Soret region are predicted to have two‐photon absorptivities exceeding 100×10−50 cm4 s molecule−1 photon−1. The calculations indicate that the visible (Q) states are well characterized by the …

Flow Injection And Photometric Determination Of S(Iv) In Rainwater With Pararosaniline, Frank A. Hedgecock

Retrospective Theses and Dissertations

The photometric pararosaniline (pRA) method for determination of S(IV) has been adapted to flow injection sample processing (FIA). Prominent features of the method include a limit of detection of 0.010 ppm of dissolved sulfur dioxide and a sampling rate of 20 per hour. The concentration range investigated was 0.010 to 0.200 ppm S0₂. Sequential samples were collected from two rainstorms and SO₂ concentrations were measured for 19 samples. The suppression of interference by Cr(III), Mn(II), and Fe(III) using 1,2-cyclohexylenedinitrilotetraacetic acid (CDTA) and ethylenediaminetetraacetic acid (EDTA) was investigated. A comparison of the adapted FIA method and its parent …

The Use Of Scheffe-Equivalent Equations To Predict Physical Properties Of Neoprene, Cheng Y. Loh

Retrospective Theses and Dissertations

The goal of this study is to find a more organized and directed approach to build models for mixture systems. An attempt is made to generate and then compare Scheffe (mixture) models with those generated by McGee using the ‘conventional’ method for neoprene data. The models are judged on their ability to predict physical properties of neoprene by comparing the following: predicted and actual values by inspection; the calculated % error of prediction; the squared multiple correlation coefficients; adjusted squared multiple correlation coefficients; the Fisher statistic and significance probability. Scheffe models do not have an intercept term and test statistics …

Ion Selective Electrodes Based On Aza- Substituted Crown Ethers, Lisa Ann Wellington

Retrospective Theses and Dissertations

A cation-responsive electrode system has been developed which incorporates aza-substituted crown ethers as ligands. In a novel application, uncomplexed crown ethers were used in the pelletized form for ionic transport. Electrodes have been produced which can be conditioned for a particular ion and following their use, be reconditioned and reused for other ions. Preparation method and lifetime studies are included.

The responses of two crown ethers with plasticizers were evaluated for thirteen representative cations. The concentration range covered in each evaluation was 1 x 10^-1 to 1 x 10^-7 M. For those ions exhibiting Nernstian or near-Nernstian response, …

New Synthetic Applications Of Enaminoketones, Timothy J. Buck

Retrospective Theses and Dissertations

This report discusses research concerning synthetic applications of enaminoketones. The work may be divided into four parts as follows: a) replacement of the dimethylamino group of certain enaminones by other amine groups through a simple procedure; b) formation of 3-alkyl-pyrazoles; c) formation of 2-amino-4-alkyl-pyrimidines; d) synthesis and subsequent reduction of iminium salts. The starting materials (E-1-(N,N-dimethylamino)-1-alkene-3-ones) have been condensed with hydrazine and guanidine to form pyrazoles and pyrimidines, respectively. The same starting materials have been reacted with POCl₃ in CH₂Cl₂ to produce chlorovinyliminium salts. These have then been reacted in situ with reducing agents to produce …

Some Useful Synthetic Applications Of Gold's Reagent, John T. Gupton

Chemistry Faculty Publications

While looking for some appropriate research projects, I had been impressed by and interested in the work of Danishefsky¹ and others² regarding the use of "Eschenmoser's salt" (1). During the course of a literature search on an industrial project, we came across an article by Gold,³ which described the preparation of a rather interesting vinylogous iminium salt (2). The name assigned to this compound was [3-(dimethylamino)-2-azaprop-2-en-1-ylidene]dimethylammonium chloride. This terminology seemed a little cumbersome for routine discussions so we adopted the name "Gold's Reagent" for compound 2. Although the reagent had been prepared³ in 1960, very little …

High‐Resolution Ν1 Spectrum Of Propyne: Application Of A Microcomputer‐Controlled Infrared‐Acoustic Color Center Laser Spectrometer, E. Kyrö, Shannon Lieb, J. W. Bevan

Scholarship and Professional Work - LAS

Development of a microcomputer‐controlled infrared‐acoustic color center laserspectrometer capable of scanning in 100 cm⁻¹ sections over the wavelength range 2.2–3.3 μm with a resolution of 0.01 cm⁻¹ (300 MHz) is reported. Application of the spectrometer to investigation of the ν₁spectrum of propyne is demonstrated.

Pressure Dependence Of Fluorescent And Photolytic Interferences In Ho Detection By Laser-Excited Fluorescence, Thomas M. Hard, Robert J. O'Brien, T. B. Cook

Chemistry Faculty Publications and Presentations

In the measurement of HO concentrations by laser-excited fluorescence, expansion of the sampled air offers a way to reduce fluorescent and photolytic interference by other species. The decrease in [HO] upon expansion is balanced by an increase in HO fluorescence yield over a wide range of pressures. Background air fluorescence is reduced if the responsible species have fluorescence yields higher than those of HO. Preliminary experiments indicate that most of the fluorescence observed in laboratory air is due to such species. Upon expansion, the suppression of fluorescent interference can be no greater than the reduction in pressure, whereas the suppression …

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 …

Gas Phase Hydrogen Permeation In Alpha Titanium And Carbon Steels, Donald L. Johnson, Kiritkumar K. Shah, Bruce H. Reeves, Vijay L. Gadgeel

Department of Chemistry: Faculty Publications

Commercially pure titanium rods were machined into hollow cylinders and gas-phase permeation and diffusion measurements obtained with a quadrupole residual gas analyzer at temperatures between 400-800°C and pressures between 0.533 and 266.6 Nrn^-2. Pressure dependence measurements established that phase boundary reactions as well as lattice diffusion control the transport process. Lag-time data yield excellent agreement with the diffusivity data of Wasilewski and Kehl and Papazoglou and Hepworth for the case where phase boundary reactions are taken into account. The best value of the diffusivity is D = 2.1 x 10^-2 exp (-50,40O/RT). Analysis of lag-time data reveals …

New Header Treatment Aids Weevil Control, J H. Moulden

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

A new insecticide formulation supplied in high pressure cylinders simplifies weevil control in headers.

Simplified Sheep Skin Tanning, Department Of Agriculture, Western Australia

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

Most people would agree that a white sheepskin rug adds a touch of luxury to any home.

The following method will produce dressed, woolly sheep skins with chemicals and equipment available to any householder.

Magnesium Ion Inhibition Of Calcium Carbonate Precipitation And Its Relation To Water Quality, John J. Hassett

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

The effect of Mg⁺⁺ ion on the solubility of calcium carbonate was determined using P. K. Weyls "carbonate saturometer."

The amount of calcium carbonate precipitated or dissolved was measured for five series of waters when equilibrated with solid carbonate.

It was found that the effect of Mg⁺⁺ ion on solubility depend upon the nature of the solid phase: surface area, coprecipitated Mg⁺⁺, minerology, etc.

Pure low area calcite showed an increase in solubility which could be explained by ion-pair formation, while its other carbonates departed from this behavior.

Progress In Weed Control, Department Of Agriculture, Western Australia

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

In May, 1967, the "Journal of Agriculture" printed a special issue on weed control, with the emphasis on chemicals for weed control in cereal crops.

This month, just two years later, enough new information has accumulated to warrant publication of another "theme" issue, this time with important articles on weed control in pastures, chemical firebreaks and chemical ploughing, as well as weed control in linseed and cereal crops.

Experiments On The Inactivation Of Zinc By The Mineral Fractions Of The Soil, John J. Hassett

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

Zinc deficiency, in many cases, is closely related to organic matter decomposition. DeRemer and Smith (1964) studied the effects of decomposing sugar beet tops on the reactions of Zn⁶⁵ in a Portneuf soil. They found that with time the Zn⁶⁵ associated with lime minerals, exchangeable, and water soluble fractions of the soil decreased, while that found with the organic and mineral fractions increased. This increase in the mineral fraction is of particular interest, since the majority of the Zn⁶⁵ was found to be with this fraction after a period of time. They also showed that the increase …

Polarography Of Selected Metal Ions In Anhydrous Aliphatic Diamines, Frederick William Foss Jr.

University of the Pacific Theses and Dissertations

A search of the literature revealed that no study has sought to measure and compare the polarographic solvent properties of the anhydrous aliphatic diamines. In fact, there has been no reported instance of the use of anhydrous 1,3-propanediamine or 1,4-butanediamine in any electro- chemical system.

The Effect Of Chelates On Phosphorus Availability And Mobility, Salah Ahmed Tahoun

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

Soil-phosphorus relations and plant-phosphorus relations have attracted the interest of many investigators since Liebig introduced his famous theory about the importance of the mineral matters to the plant in 1840. It was soon realized that phosphorus nutrition was a problem not easily solved for two reasons. 1. The added phosphorus fertilizers, soon after soil application are converted by some reactions in the soil to complex compounds far less soluble, consequently less available to the plant. Conclusions about this process led to controversial debates until it was discovered that a general statement covering all soils was impossible since the reactions involved …

The Effect Of Moisture And Temperature On Transformation Of Applied Ammonium Sulfate In Several Western Soils, Lloyd Richard Hossner

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

The conversion of ammonia nitrogen to nitrite and nitrate forms of nitrogen has aroused much attention in the past and continues to receive much of the energy of the present day researcher.

Phosphorus Status Of Genola Soils In Utah, Warren E. Bendixen

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

With increasing pressure on economical production of crops, more fertilizers are being applied to the soil each year to increase crop yields. Economical production of crops with applications of fertilizer requires an evaluation of the essential elements of the various crops so applications of fertilizer will not exceed the law of diminishing returns.

Because varying soil, moisture, and climatic conditions influence the response to added fertilizers, some workers (18, 26, 38) have contended that the only reliable way of determining the fertilization needs of a crop is to conduct a trial on the particular farm. The length of time involved …

The Mineral Content Of Various Sections Of Some Plants As Influenced By Conditions Associated With Lime-Induced Chlorosis, Hyrum Del Var Petersen

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

The so-called "lime-induced" chlorosis has been recognized for many years as a problem where plants are grown on calcareous soils. The characteristics associated with lime-induced chlorosis are the same as those associated with iron deficiency chlorosis--interveinal yellowing of the leaves at the meristemic region combined with reduced vigor of the plant as a whole. Lime-induced chlorosis is unique in that the iron content of both chlorotic plant and the soil do not always show a deficiency in iron when chemically analyzed. This leads to the theory that iron is inactivated in both the soil and plant.

Although no single factor …

Citrus Growers : Don't Blow Up Your Colouring Rooms, Department Of Agriculture, Western Australia

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

THERE have been several dangerous incidents associated with the use of acetylene in citrus colouring chambers recently, and growers are warned to take care when using this explosive gas.

Specific Gravities And Fluidity Factors Of Glaze Slips, E. S. Amos

Journal of the Arkansas Academy of Science

No abstract provided.

Simple Ignition Furnaces, L. B. Roberts, J. C. Hackney

Journal of the Arkansas Academy of Science

No abstract provided.

The Synthesis And Certain Chemical Properties Of Several Aromatic Fluorides, Horst G. Schneider

Bachelors’ Theses

The preparation of organic fluorides, until only recently, had been seriously curtailed not only because of the difficulty experienced in their synthesis, but also due to the lack of information with regard to their physical and chemical properties. With the investigation of their characteristics, their great importance was for the first time fully realized. A concerted search was made for new modes of their preparation. That this search was rewarded is shown in part by the synthesis of several aromatic fluorides as a portion of this thesis.