Chemistry and chemical engineering.

Chair: David Creed, University of Southern Mississippi

Vicechair: John H. O'Haver, University of Mississippi 

THURSDAY MORNING

Ship Isle Room

9:00 AB INITIO STUDIES OF SILICON ALPHA EFFECT ON THE INTRAMOLECULAR RING-OPENING REACTIONS OF EPOXYSILANES

Lovell O. [Agwaramgbo.sup.1*], Hinda [Ahmed.sup.1], Glake Hill, [Jr..sup.1], and Jerzy [Leszczynski.sup.2], [Tougaloo.sup.1] College, Tougaloo, MS 39174, and [Jackson.sup.2] State University (2), Jackson, MS 39217

Intramolecular nucleophilic substitution reactions are controlled by many factors:- transition state energy, proximity of the reacting functional groups, and the size, energy & stability of the ring product. For the cyclization of [omega]-aminoalkyl bromides, the reaction of 1-Amino-4-bromobutane, which gave a five-membered ring was more reactive than the reaction of 1-Amino-5-bromopentane which gave a six-membered ring. In order to investigate the influence of an [alpha]-silyl group in the energetics of the these intramolecular nucleophilic substitution reactions, we conducted the ab initio studies of compounds 1-4 below. The results showed that the trimethylsilyl group had an overriding influence over the controlling factors stated above in controlling the cyclization reactions of the systems studied. HO-([CH.sub.2])n-Br: Compound 1; n = 4; Compound 2; n = 5; Compound 3 = 1,1-disubstituted epoxide; Compound 4 = 1,2-disubstituted epoxide. Acknowledgements: 1. a = Tougaloo College, Tougaloo, MS; b = Jackson S tate University, Jackson, MS; c = Computational Center For Molecular Structures and Interactions. 2. Funding for this project was provided by NFS CREST Program 3. Chemistry Department, Tougaloo College

9:20 USING LASER LINE DEFLECTION AND SHADOWGRAPHY TO DETERMINE THE EXISTENCE OF ISOTHERMAL FRONTAL POLYMERIZATION OF METHYL METHACRYLATE, ITS FRONT POSITION, AND ITS FRONT WIDTH

Lydia L. [Lewis.sup.*] and John A. Pojman, University of Southern Mississippi, Hattiesburg, MS 39406

Isothermal Frontal Polymerization (IFP) is a process that is used to produce gradient materials, such as gradient refractive index materials (GRINs) and organic optical limiters (OOLs). IFP is a self-sustaining propagating polymerization resulting from an increased rate of reaction (the Trommsdorff effect), which is a result of a viscous region created at the interface of a polymer seed and a monomer/thermal initiator solution. The optical detection methods of laser line deflection (LLD) and shadowgraphy were used to examine the systems without disturbing them. The systems were examined to determine if a front exists and to determine the resulting front position, width, and velocity with respect to time. Solutions of 2.00 mM 2,2'- azobisisobutyronitrile in methyl methacrylate with poly(methyl methacrylate) seeds of 3 million molecular weight were examined. These systems exhibit frontal behavior at 45-50[degrees]C, propagate approximately 0.6 cm in 8 hours, have a front width ranging from 0.3 to 1.0 cm, and ex hibit an increased front velocity ranging from 0 to 1.5 cm/hr during the front.

9:40 THE EFFECTS OF pH ON THE SOLUBILITY OF ALUMINUM OXIDE AND KAOLIN 

Kristi [Budzinski.sup.*] and David L. Wertz, University of Southern Mississippi, Hattiesburg, MS 39406

Aluminum oxide and kaolin's solubility were tested in solutions over a range of pH = 2 to pH = 7. The purpose of this experiment is to determine the optimum pH at which aluminum oxide and kaolin have the highest solubility. The solution consisted of nitric acid diluted to the desired pH along with either a weighed amount of kaolin or aluminum oxide as the solute. The aluminum oxide and kaolin were stirred overnight; then each was filtered from the solution and dried. Once the samples dried completely, a spectrum from X-ray fluorescence was used to determine the concentration of aluminum and/or silicon in each sample. The X-ray fluorescence machine has an internal control that corrects for the x-rays emitted by the rhodium tube. In order to compare findings, the ratio of aluminum peak to rhodium peak area was calculated for the aluminum oxide solutions. In addition to the aluminum peak/ rhodium peak ratio, an aluminum peak/ silicon peak ratio was computed for the kaolin samples. The aluminum oxide solutions sh ow a decreasing aluminum peak/ rhodium peak ratio, suggesting that the aluminum oxide is becoming more soluble as the pH increases. The kaolin solutions do not reveal substantial change in the aluminum peak/ rhodium peak ratio, suggesting that kaolin does not respond to changes in acidity.

10:00 PHOTOCHEMISTRY AND PHOTOPHYSICS OF MODEL COMPOUNDS CONTAINING BISARYL CINNAMATE CHROMOPHORES

Rabih O. [Al-Kaysi.sup.*] and David Creed, The University of Southern Mississippi, Hattiesburg, MS 39406

Liquid crystalline polymers (LCP) containing aryl cinnamate pendant groups exhibit a wide range of photochemical and photophysical behavior which depends on the phase type and chromophore aggregation in the polymer film. The UV-spectrum of an LCP in the solid state is blue shifted, due to ground state aggregation effects, with respect to that in a good solvent. The photochemistry is also different when a film and a solution sample of the LCP are irradiated at 366 nm. Compounds such as 1 containing two aryl cinnamate chromophores were synthesized and characterized. The UV-spectra of these model compounds were collected in solution and as dilute dispersions in a polymer matrix. Their photochemistry was also investigated and similar trends to those in the polymer film were observed. Irradiation at 366 nm of a dilute dispersion of 1 in hydrogenated polystyrene (H-PS) showed predominant 2+2 cyclo-addition when compared to model compound 2 in H-PS.

10:20 Break

10:30 INFLUENCE OF AMINO SUBSTITUENTS ON THE ENERGETICS OF ETHIDIUM-DNA COMPLEX FORMATION

Nicholas B. [Hammond.sup.*], Nicola C. Garbett, and David E. Graves, University of Mississippi, University, MS 38677

The complex formed between ethidium bromide and nucleic acids has provided a paradigm for the study of DNA binding agents for the last four decades. These studies have provoked considerable interest in the field of the design of pharmacologically active drugs over the past three decades and generated novel compounds that are effective in the inhibition of DNA and RNA polymerases, topoisomerases, and other DNA modifying enzymes that are critical targets in the treatment of cancer. Although the interactions of ethidium with DNA have been well characterized, many questions remain regarding the role that the amino substituents (located at positions 3 and 8 on the phenanthridine ring) play in the intercalative binding process. The studies described here seek to examine the influence of each of these amino substituents on the energetics and thermodynamic mechanism(s) associated with complex formation. Specifically, we have examined the parent ethidium along with three analogs (the 8-amino-5ethyl-6-phenyl phenanthra dinium chloride; 3-amino-5-ethyl-6-phenyl phenanthradinium chloride; and the 3,8-desamino-5-ethyl-6-phenyl phenanthradinium chloride. This systematic evaluation of DNA binding energetics as determined by optical spectroscopies and isothermal titration calorimetry (ITC) demonstrates that both the placement and/or position of the amino substituents on the intercalating chromophore of the intercalating drug plays a pivotal role in dictating the thermodynamic mechanism(s) of the interactions of these compounds with DNA.

10:50 AFFINITY PURIFICATION OF BOVINE PITUITARY GLUTAMINYL CYCLASE 

Kyle F. [Lott.sup.*], Graham Weaver, Stephanie Misquitta, Rachell Booth, and Robert Bateman, University of Southern Mississippi, Hattiesburg, MS 39406

Glutaminyl cyclase (QC) is a soluble protein of the mammalian secretory pathway and catalyzes the formation of the pyroglutamyl group at the amino terminus of many bioactive secretory peptides. Although this enzyme has been cloned and expressed in both bacteria and insect cells, little is known about posttranslational processing of the natural tissue form of QC. We have therefore sought to develop a rapid and high yield method of purifying QC from bovine pituitary. This has been achieved by use of anion exchange chromatography followed by affinity chromatography on a dye column. The talk will discuss the purification procedure as well as characterization of the purified enzyme.

11:10 ENZYME MONITORING FOR DETECTION OF PROSTATE CANCER

DeGail [Hadley.sup.*] and Charles Henry, Mississippi State University, Mississippi State, MS 39762

Prostate cancer is one of the leading causes of death in American men. Studies have implicated the enzyme, Cathepsin B (CB), as playing an important role in the metastasis of prostate cancer. In this study, capillary electrophoresis was used to develop a method to study prostate cancer by monitoring the activity of the CB enzyme. The limit of detection for the product and the substrate was 1 [micro]M. In addition, the amount of product yielded from the enzymatic reaction was found to be time dependant. Future goals are to further optimize the enzyme analysis method, determine the reaction kinetics, and monitor CB activity in prostate epithelial cells.

11:30 AN INVESTIGATION INTO THE SEQUESTERING CAPACITY OF WASHED WOMBAT POWDER FOR HEAVY METAL IONS AND HALIDE SALTS IN AQUEOUS SOLUTIONS

Callie [Bounds.sup.*] and David L. Wertz, University of Southern Mississippi, Hattiesburg, MS 39406

The purpose of this project was to determine if washed WOMBAT powder could be used as a sequestering agent for heavy metal ions and halide salts in aqueous solutions, to quantify the amount of each element retained on the powder, and to assess if the sequestered ions could be removed from the powder. WOMBAT powder is a byproduct of tires that is obtained through the Wertz Oxidative Molecular Bombardment at Ambient Temperature process. The WOMBAT powder was first washed and filtered to remove any naturally occurring metal ions from the surface of the powder. The WOMBAT powder was treated with solutions of mercuric chloride, potassium bromide, cupric chloride, calcium sulfate, and cobalt nitrate. The treated WOMBAT powder was allowed to air dry. A sample of washed but untreated WOMBAT powder was used as a control. Standards composed of activated carbon and each of the salts were made to evaluate how much of each element was retained by the powder. The treated WOMBAT powder was washed in distilled water to remov e the metal ions and halides from its surface. X-ray fluorescence was used to analyze all of the samples. The results indicate that the WOMBAT powder can successfully sequester heavy metal ions and some halides from solution and that these ions can be effectively removed from the WOMBAT powder.

THURSDAY AFTERNOON

Ship Isle Room

1:30 DOWN TO EARTH MICROGRAVITY EXPERIMENTS, PART I: THE BENEFITS OF CLASSROOM-BASED DROP EXPERIMENTS

Nicholas J. [Carter.sup.*], Brian D. Zoltowski, Kayce Leard, Kristi Budzinski, Christina Watters, William J. Ainsworth, and John A. Pojman, University of Southern Mississippi, Hattiesburg, MS 39406

Classroom-based drop experiments possess the capabilities of demonstrating the usefulness of microgravity research to a large audience. Being conceptually simple and cost effective they are ideal for high school and undergraduate education levels. In order to determine the effectiveness of drop experiments, the following three systems were studied: A postage scale, a candle, and a plasma sphere. The results of the latter were confirmed over a larger time scale aboard the KC-135 aircraft. It was determined that the drop experiments were simple and provided meaningful data.

1:50 DOWN TO EARTH MICROGRAVITY EXPERIMENTS: PART II VERIFICATION OF PLASMA BEHAVIOR IN MICROGRAVITY

Brian D. [Zoltowski.sup.*], Nicholas J. Carter, Kayce Leard, Kristi Budzinski, Christina Watters, William J. Ainsworth, and John A. Pojman, University of Southern Mississippi, Hattiesburg, MS 39406

Classroom-based drop experiments possess the capability of demonstrating the usefulness of microgravity research to a large audience. Being conceptually simple and cost effective they are ideal for high school and undergraduate education levels. In order to determine the effectiveness of drop experiments, the following three systems were studied: A postage scale, a candle, and a plasma sphere. The results of the latter were confirmed over a larger time scale aboard the KC-135 aircraft. It was determined that drop experiments are simple and provided meaningful data.

2:10 SYNTHESIS OF LIQUID CRYSTALLINE STILBENE DIOL MONOMERS AND STILBENE POLYESTERS

Holly R. [Williams.sup.*], Alline P. Somlai, and David Creed, University of Southern Mississippi, Hattiesburg, MS 39406

Thermotropic liquid crystalline polymers (LCP) have different phases (mesophases) that can be observed at different temperatures. The photochemistry and photophysics of these polymers are quite dependent on the phase type and organization of the rigid rod parts on the polymers, the mesogens, which are also the chromophores for light absorption. Stilbenes are fluorescent rigid rod mesogens that undergo several photochemical reactions including 2 + 2 photocycloaddition and trans-cis photoisomerization. We have synthesized several stilbene diol monomers, of general structure 1, R = [([CH.sub.2]).sub.n] OH, which have been copolymerized with substituted malonyl chlorides to produce photoreactive low Tg co-polyesters with room temperature mesophases. The monomers were synthesized from trans-4,4'-stilbene dicarboxylic acid, 1, R = H, via the acid chloride which was converted to the ethyl ester, 1, R = [CH.sub.3][CH.sub.2]. The latter was reacted with diols of general structure HO [([CH.sub.2]).sub.n] OH using titan ium tetraisopropoxide as a transesterification catalyst to afford monomers 1, R = [([CH.sub.2]).sub.n]OH. The monomers were characterized by NMR, IR, and UV-Vis spectroscopy, and elemental analysis, then reacted with malonyl dichlorides to form the co-polyesters (work supported by the NSF REU program).

2:30 PHOTOCHEMISTRY AND PHOTOPHYSICS OF SOME MAIN CHAIN LIQUID CRYSTALLINE STILBENE POLYESTERS

Alline P. [Somlai.sup.*] and David Creed, University of Southern Mississippi, Hattiesburg, MS 39406

The photochemistry and photophysics of a main chain liquid crystalline homopolymer and two copolyesters containing the trans-4,4'-dialkoxystilbene dicarboxylate chromophore have been examined. The homopolymer has a high and narrow mesophase temperature range between 165[degrees]C and 177[degrees]C. The stilbene copolyesters contain butyl or ethyl malonate repeat units that lowered the transition temperatures compared to the homopolymer and resulted in room temperature polymer mesophases. Irradiation of polymer cast films at 313 nm leads to the formation of cyclobutane adducts and polymer crosslinking. UV-Vis spectroscopy shows the disappearance of the aggregated stilbene chromophore with a simultaneous increase in absorption at 250 nm. FT-IR also shows the decrease of trans-stilbene peaks at 702 and 668 [cm.sup.-1] and a new peak emerging at 718 [cm.sup.-1]. Subsequent 254 nm irradiation results in the loss of 250 nm absorption, regeneration of structured stilbene absorption above 300 nm but with no indicatio n of aggregate formation, and a decrease in the IR band at 718 [cm.sup.-1]. These changes are consistent with cyclobutane photocleavage back to stilbene. The homopolymer cast film has only excimer-like emission centered at 450 nm. The intensity of the emission decreases with increasing temperature. The copolyester containing the butyl malonate repeat unit also gives the excimer-like emission, but in contrast to the homopolymer, an increase in temperature gives monomer-like emission and decreased excimer-like emission.

2:50 Break

3:00 NUMERICAL SIMULATIONS OF TRANSIENT INTERFACIAL PHENOMENA IN MISCIBLE FLUIDS

John A. [Pojman.sup.*], Vitaly Volpert, Rozenn Texier-Picard, and Nicholas Bessonv, University of Southern Mississippi, Hattiesburg, MS 39406, and University of Lyon 

To study theoretically interfacial (capillary) phenomena in miscible fluids, we consider a continuous medium with a composition gradient. We describe it with the model consisting of the heat and diffusion equations with convective terms and of the Navier-Stokes equations with an additional volume force written in the form of the Korteweg stresses arising from nonlocal interaction in the fluid. It is proportional to the square of the composition gradient with the proportionality coefficient depending on temperature. We carry out numerical simulations of this model and show that the capillary force can cause convection in the initially quiescent liquid. For physically realistic values of parameters the liquid motion, though decreasing rapidly in time, can probably be observed experimentally. The proportionality coefficient, k, is the same square gradient parameter in the Cahn-Hilliard theory for diffuse interfaces and for phase separation. We estimate it on the basis of measurements from spinning drop tensiomet ry and light scattering for two systems: poly(dodecyl acrylate)/dodecyl acrylate and glycerin/water. Because concentration and temperature gradients also cause buoyancy-induced convection, experiments must be performed in weightlessness. Therefore, long term, high quality weightlessness is required to test the predictions of the modeling, and we propose a photo-polymerization system to create the concentration and temperature gradients. Transient Interfacial Phenomena in Miscible Polymer Systems (TIPMPS) and a Microgravity Science Glovebox experiment, Miscible Drop in Microgravity (MDMG) are both planned for the International Space Station.

3:20 MEASURING CONVECTION IN MISCIBLE POLYMER SYSTEMS USING PARTICLE IMAGE VELOCIMETRY (PIV)

William J. [Ainsworth.sup.*] and John A. Pojman, University of Southern Mississippi, Hattiesburg, MS 39406

Convective fluid motion created by the formation of a miscible polymer/monomer interface and induced thermal gradients can be measured using particle image velocimetry (PIV). PIV uses a sheet of laser light passing through a sample to illuminate neutrally buoyant tracer particles that scatter the laser light and follow the convective motion. The miscible polymer/monomer interfaces were created by the photopolymerization of half of the sample using a high intensity fiber optic UV light source and a sharp mask in a process very similar to photolithography. Studies have been carried out involving the formation of the interface and the creation of thermal gradients within the interface by heating the sample. Video images of the reactions and the resultant fluid flow were analyzed using particle tracking software provided by NASA. From the vector data, we can determine the magnitude and direction of the induced fluid flow, and generate vector maps of the fluid motion under different experimental conditions. The ex perimental data will be used to develop a numerical simulation of the Effective Interfacial Tension Induced Convection (EITIC) caused by the formation of an interface between two miscible fluids. This method will be used as part of a flight investigation aboard the International Space Station to investigate the miscible polymer systems in the absence of buoyancy driven convection.

3:40 EFFECT OF SUPPORTING ELECTROLYTE ON ION TRANSPORT THROUGH ION EXCHANGE POLYMERS

Lois [Zook.sup.*] and Johna Leddy, Delta State University, Cleveland, MS 38733, and University of Iowa, Iowa City, IA 52242

While often ignored, changing electrolyte concentration and/or ion size can change the effective diffusion of redox species in cast polymer films. Effective diffusion is defined as a combination of extraction and physical diffusion of a redox moiety within the polymer. Electrochemical experiments employing the techniques of cyclic voltammetry and rotating disk voltammetry can be used to separate out the extraction coefficient, K, and the physical diffusion parameter, D, for a redox probe. The effects of ion size and electrolyte concentration on the effective diffusion of a redox probe in the ion exchange polymer Nafion will be discussed. Preliminary results for the study of the redox probe Tris(2,2'-bipyridyl)dichlorruthenium(II)hexahydrate, (RuTrisBypy), indicate that both the size of the supporting electrolyte and the concentration of the electrolyte alter the effective diffusion. In a study of electrolyte concentration, the physical diffusion parameter, D, for RuTrisBypy decreased as the electrolyte concen tration increased, while the extraction coefficient, K, initially increased to a maximum value, then began to decrease. In a study of ion size, the diffusion coefficient for RuTrisBypy decreased as the hydrated radius of the electrolyte increased, and the extraction coefficient increased with increasing electrolyte size. Once one understands how both these parameters, K and D, change with the choice of electrolyte, one can better tailor diffusion through polymer films for specific applications.

4:00 QUANTITATIVE ANALYSIS OF ALUMINUM CONTENT OF SOIL, ROOT, AND GREEN SAMPLES FROM A NATIONAL GUARD FIRING RANGE

David L. Wertz and Amanda C. [Winters.sup.*], University of Southern Mississippi, Hattiesburg, MS 39406

This research is designed to determine the degree to which reaction byproducts from firings of multiple launch rocket systems (MLRS) accumulate in the environment. Powdered aluminum is a reactant in the ignition, and both aluminum and aluminum oxide are produced. One sample each of soil, roots, and greens are taken from predetermined sites at varying distances from, and positions relative to, the firing point. These samples are washed (in the case of roots and greens), dried, ground to a fine powder, and analyzed using x-ray fluoroscopy. The peak areas of several different elements (including aluminum) are measured. Data from samples taken both before and after test firings are compared, and all results are expressed as an aluminum:silicon ratio. Research is still in progress--analysis of "before" samples is being performed, and preparations are being made for processing of "after" samples. Preliminary data indicate that aluminum is already present in most of the soil and root samples, albeit in small quantit ies (possibly due to the abundance of clay in the area). No aluminum has been measurable in the green samples.

4:20 Divisional Business Meeting

FRIDAY MORNING

Ship Isle Room

8:20 Divisional Poster Session

LEACHABLE LEAD IN SMALL ARMS FIRING RANGE SOILS

Natalie M. [Ballard.sup.*], Barbara Tardy, and Jefretha Christian, Alcorn State University, Lorman, MS 39096, and Waterways Experiment Station, Vicksburg, MS

Lead contamination is of great concern because of its adverse effects on human health. Lead is a heavy metal that is toxic to humans and animals. Its extensive use and widespread dispersal in the environment have resulted in numerous lead contaminated soils. The health concern with lead contaminated soils mostly arises from plant contamination by soil particles, solids, and dust ingested by humans and grazing animals. It is very important to minimize adverse lead impacts on the environment. Reducing lead solubility and bioavailability in contaminated soils without removing the soil is one of the issues involved in reducing the effects of lead on the environment. The U.S. Army operates Small Arms Firing Ranges (SAFRs) at various locations in and outside the United States. The ranges are used for munitions training for military personnel. In operation for a number of years these ranges are contaminated with spent munitions, lead bullets, and other metal contaminants. Although SAFR projectiles primarily contain lead, copper, and antimony, lead is by far the most toxic. Soil samples were collected from three sites: Fort Polk located in Louisiana, a SAFR in New Orleans, Louisiana and a site located in Kodiak, Alaska. Soil samples removed from several SAFRs have shown that lead in the munitions degrade and corrode producing lead particles that are not physically removable from the surrounding soil. Notwithstanding other metal contaminants, corrosion, and degradation of spent bullets producing lead particles that may be come mobile is the greatest environmental concern. The U.S. Army Engineer Research and Development Center (ERDC) is conducting studies on soils from three ranges to assist in providing strategies for remediation and management practices at various SAFR sites.

COMPARING METHODS OF ASSESSING TOXICITY TESTING OF LEAD AND ARSENIC IN WATER

Andrea J. [Kelley.sup.*] and Chandra S. Theegala, Alcorn State University, Alcorn State, MS 39096, and Southern University, Baton Rogue, LA 70813

Daphnia magna are small freshwater crustaceans that are commonly called "water fleas." The reproduction rate and survival rate of the organisms were tested when contaminants were introduced to the organisms environment. Studies showed that arsenic and lead decreased the survival rate when exposed to the contaminants longer than four hours. The organisms' survival rate was high in concentrations of arsenic for more than 96 hours. Lead appeared to be more lethal to D. magna at concentrations of 0.25 ppm to 1.00 ppm. Reproduction did not take place in lead concentrations. Arsenic did reproduce in 0.50 ppm concentrations only. The respirometer was able to detect the oxygen consumption and carbon dioxide production of the organisms in non-contaminated water and water contaminated with 0-5 ppm of lead and arsenic. The respirometer results were compared and contrasted with the acute (short term or static test) results.

ANALYSIS OF GLUCOSE IN THE HYDROLYZATE FROM SAWDUST

Centeria Cornellius (1), Esmeralda Fuentes (2), and Ken S. [Lee.sup.*] (1), (1.) Jackson State University, Jackson, MS 39217, and (2.) Brackenridge High School, San Antonio, TX 78210

In the project to produce ethanol from the sawdust via acid-hydrolysis and fermentation, the determination of concentration of glucose and other organic components in the hydrolyzate is necessary for optimizing the process. However the analysis with HPLC is not feasible due to the high concentration of sulfuric acid. Therefore we use the Seliwanoff reagent for determining of actual concentration of glucose of the hydrolyzate. Since it gives dark red color after that resorcinol reacts with 5-hydroxymethylfurfural (HMF), which is the dehydration product of glucose, the calibration line has been made from the series of known concentrations of glucose. Total concentration of glucose of sample was determined from the line via standard addition method. Total concentration of glucose in hydrolyzate was 7.5%. We have proposed the double analysis to calculate the actual glucose concentration, because the conversion from glucose to HMF needs heat and at room temperature the conversion is not occurred. Difference betwee n results from two analysis, with heat and without heat, can be the actual concentration of glucose in the hydrolyzate. This project is supported by DOE EPSCOR, Grant #DE-FG0200ER45830.

AERIAL DRIFT DETERMINATION OF HERBICIDES WITH ANALYSIS BY HPLC AND AA

April [Robinson.sup.*] (1), Jason Corbitt (1), Candice Scott (1), Andrew Steele (1), Marcus Steele (1), Shawanda Wilson (2), Phelesia Foster (3), Dennis Elmore (3), and Lowrey Smith (3), (1.) Delta State University, Cleveland, MS 38733; (2.) Mississippi Valley State University, Itta Bena, MS 38930; and (3.) Application Technology Research Unit, USDA-ARS, Stoneville, MS 38776

The Environmental Protection Agency and Mississippi Department Environmental Quality suspended aerial application of the herbicide, glyphosate, for three months during Spring, 2001, due to the damage to non-glyphosate resistant crops created by the wide application glyphosate the previous year. This study examines the horizontal drift of the herbicide, glyphosate, and a tracer, rubidium, as they are applied from an aerial and tractor platform. Spray droplets were collected at selected sampling sites on flat Mylar sheets, drinking straws, and cotton strings. The droplets were removed from each of these collection devices using HPLC grade ethanol or reverse osmosis water. Subsequently, the glyphosate samples were analyzed with a Waters LC Module 1 controlled by Waters Millenium 2000 software. The Rb samples were analyzed by a Perkin Elmer 5000Z electrothermal atomic absorption spectrophotometer. A grid of the spray area and adjacent drift impacted area will be presented.

CHIRAL HPLC BEHAVIOR OF HYDROXYLATED AND METHOXYLATED DOPAMINE DERIVATIVES

Kenneth D. [McMurtrey.sup.*], Eron Schellinger, Anthony Pittman, Chris Strawbridge, and John G. McCoy, University of Southern Mississippi, Hattiesburg, MS 39406

1-Methyltetrahydroisoquinoline derivatives of dopamine have been suggested to play possible roles in the development of human maladies including both alcoholism and Parkinson's disease. One but not both of the two possible stereoisomers is thought to have pharmacological activity. This paper examines the effects of phenolic and methoxyl substituents at the 6- and 7- positions of the 1,2,3,4-tetrahydroisoquinoline molecule on HPLC resolution of the above stereoisomers.

GC-FID ANALYSIS OF THE DEGRADATION OF SURFACTANTS IN WATER BY FENTON'S REAGENT

Abul B. Kazi, William C. Mahone, and Naci [Powell.sup.*], Mississippi Valley State University, Itta Bena, MS 38941

In continuation of our previous studies on the use of Fenton's reagent for the remediation of organic pollutants in water, we are currently studying the effectiveness of Fenton's oxidation reaction for the removal of surfactants in water. Preliminary results obtained from GC-FID analysis of the chloroform extracts of untreated and treated samples in water indicate that Fenton's reagent is very efficient in removing most of the components, particularly the more volatile components of surfactants in water.

REMOTE SENSING OF VOLATILE LIQUIDS

William C. Mahone and Joi [Sawyer.sup.*], Mississippi Valley State University, Itta Bena, MS 38941

Remote Sensing is the technique of acquiring information about an object without actually coming in contact with the object. This information comes in the form of electromagnetic radiation. New technology is allowing applications of remote sensing technology in a variety of ways. There are a variety of factors that can influence the incoming distribution of frequencies and intensities of radiation that is registered as a return spectral profile. These can be reflectance from a surface or absorption or emission of radiation by gas molecules that occupy the space between the sensor and the reflector. The object of our investigation is to use remote sensing to analyze a vapor flux between the reflector and the sensor. If successful this technique could be used to remotely analyze hazardous spill sites or chemical warfare agents.

A REINVESTIGATION ON THE USE OF AN ACIDIC [H.sub.2][O.sub.2] SOLVENT SYSTEM IN THE CHEMICAL-DISSOLUTION ANALYSIS OF FLY ASH

Matt [Myers.sup.*], Myron Hutson, and Marcus Steele, Delta State University, Cleveland, MS 38733

Noncrystalline components greatly influence the physical and chemical activity of materials and complicate the identification of crystalline phases. Our research group (1) identified an acidic hydrogen peroxide solvent mixture that competes favorably with sodium hydroxide in removing the noncrystalline materials in complex samples. However, the exact mechanism was not established. Hydrogen peroxide is a strong oxidizing agent in acidic solutions ([E.sup.0])= +1.77 V). The purpose of this study was to evaluate the effectiveness of selected acids (HCI, [HNO.sub.3] [H.sub.2][SO.sub.4], [CH.sub.3]COOH) in the solvent mixture. We will show that [H.sub.2][O.sub.2]-[H.sub.2][SO.sub.4]is the most effective solvent mixture in the dissolution of noncrystalline materials in a fly ash sample. A Siemens D5000 x-ray diffractometer was used to examine the crystallinity of the various samples. V. L. [Pate.sup.1] and M.L. Steele, "Studies on the Selective Dissolution of Fly Ash." National Student Affiliate Poster Session, 197th N ational ACS Meeting, Dallas, TX, April, 1989.

DRYING CHARACTERISTICS AND OXYGEN TRANSPORT IN DREDGED SEDIMENTS

Alma [Jackson.sup.*] and Clint Williford, University of Mississippi, University, MS 38677

To maintain and improve waterborne navigation, about four hundred million cubic yards of sediment are dredged each year by different industries in the United States. Port dredging is done to create and maintain sufficient water depth so that ships and boats can move safely through bodies of water. The Environmental Protection Agency detected that the sediments are contaminated and that river and harbors will require remediation. Presently, the New York Harbor is the largest sediment cleanup technology-testing program in the United States. This study in the New York Harbor dredged sediment is carried out to determine the drying characteristics of the sediment in the confined disposal facilities. Confined disposal facilities are an open body of land that has been cleared to serve as repositories for contaminated sediments. The tasks of this project included investigating the sediment pore water evaporation, shrinkage, pore collapse, and other physical characteristics when additives are added to the sediment. In addition, measurements such as the redox conditions and oxygen penetration in the sediment were also conducted in this research.

SCREENING FOR LIGNIN IN MICROBIAL CONSORTIA

O.L. [Griffin.sup.*] and Alfred Mikell, Alcorn State University, Alcorn State, MS 39069, and University of Mississippi, University, MS 38677

The study of lignin, the second most abundant of all organic compounds on Earth and the most complex, has significant importance to biologists and chemists alike. However, to engineers in industries such as paper and pulp production, the degradation of lignin is far more vital. Therefore, research is necessary on the biodegradability of lignin within vascular plants. The objectives of this investigation were to isolate fungi from environments suspected of harboring organisms with lignin degrading activity, to characterize the fungi consortia using direct and indirect methods, and to establish the lignin degrading activity of the consortia. Using various plants as substrates within inoculated environments, it was established that succession occurs within these environments and that the results of direct and indirect methods do not necessarily have to coincide.

CATALYTIC DECOMPOSITION OF PCDD/F

Zakiya [Nicks.sup.*], Slawomir Lomnick, and Barry Dellinger, Louisiana State University, Baton Rogue, LA

Catalytic oxidation is one of the most efficient forms of destroying polychlorinated-p-dioxins and polychlorinated furans (PCDD/F). Because these chemicals are considered toxic, the government is focusing much concern on lowering the emissions of dioxins produced by industries. This study describes the studies on iron oxide catalyst supported on alumina, silica, and titania for dioxin destruction. As a model compound for dioxins, 2-Chlorophenol was used due to its structural similarities to dioxins. We found that iron oxide depends significantly on the supports used in studied reaction. Of the three catalysts tested, iron oxide supported on titanium oxide exhibited the highest conversion. The preparation method of the catalyst also alters the activity of the catalyst. The sol-gel preparation method gave much higher conversion of 2-chlorophenol than the impregnated method. Also, the introduction of promoters (Ca) enhanced the performance of the catalyst.

AQUEOUS SOLVENT EFFECTS ON THE REGIOCHEMISTRY OF THE SINGLET OXYGEN ENE REACTIONS OF ANGELIC ACID AND TIGLIC ACID SALTS

Anisha [Bajaj.sup.*] and Kristina L. Stensaas, Millsaps College, Jackson, MS 39210

Photooxidations of tiglic acid and angelic acid salts with singlet oxygen were carried out in aqueous deuterated solvents and water/methanol mixtures. Deuterated solvents were used to increase the lifetime of singlet oxygen thereby decreasing reaction times. Proton nuclear magnetic resonance spectroscopy was used to monitor the product formation in each reaction. The results indicate that the product regioselectivities of these substrates deviate from the corresponding esters. We attribute this behavior to a hydrogen bonding interaction between the salts and the solvent which is not available to the esters.

DESIGN AND SYNTHESIS OF AGMATINE DERIVATIVES AS INHIBITORS OF THE MAMMAL AGMATINASE

Eric McClendon (1), Eric Carlton (2), Gregory Vaughn (1), John Piletz (3), and Ken S. [Lee.sup.*] (1), (1.) Jackson State University, Jackson, MS 39217; (2.) Arkansas School of Math and Science, Jonesboro, AK 72404; and (3.) University of Mississippi Medical Center, Jackson, MS 39216

Agmatine is a product of the mammal enzyme, decarboxylase, on L-arginine. It is also known to depress the production of nitrogen oxide in the brain, but it will be degraded with agmatinase and diamine oxidase. In this study, we design and attempt to synthesize a series of agmatine derivatives in order to test them as inhibitors of the mammal agmatinase. The proposed pathway to make the agamtine derivatives is: (1) Michael reaction of HCN on methyl vinyl ketone, (2) Converting ketone to oxime, (3) Reduction of oxime and nitrile groups to amine, (4) Coupling reaction with cyanoamine. Changing the methyl vinyl ketone with various substituents allows us to prepare several agmatine derivatives. The details of the reaction scheme and the experimental results will be discussed.

SYNTHESIS AND CHARACTERIZATION OF METAL COMPLEXES OF BENZIL DIPHENYLTHIOSEMICARBAZONE

Brian [Napolion.sup.*], Booker Spurlock, and Ramaiyer Venkatraman, Jackson State University, Jackson, MS 39204

Copper(II), cobalt(II), lead(II), nickel(II), and palladium(II) complexes of benzil Di-N4 phenylthiosemicar-bazone, (BDPTSC) have been prepared and characterized by conductance, magnetic moment, IR, UV-VIS, and NMR spectral data. From the experimental data cobalt, copper and palladium complexes exhibit a square planar geometry where as nickel shows an octahedral symmetry with two water molecules. The ligand is found to form an 1:1 type complex with all the metals.

SYNTHESIS AND STRUCTURAL CHARACTERLZATION OF TERNARY COMPLEXES OF COPPER(II), CHROMIUM(II), AND LEAD(II) WITH DI AND MONO CARBOXYLIC ACIDS AND AROMATIC DIAMINES

Ramaiyer [Venkatraman.sup.*], Mira Walker, Julian Magee, Brian Napolion, and Joseph A. Cameron, Jackson State University, Jackson, MS 39204

Ternary complexes of divalent metal ions (copper(II), cadmium(II)and lead(II)) with mono or dicarboxylic acid (levulinic acid and malonic acid) and aromatic diamines (2,2' bipyridyl, 4,4' dimethylbipyridyl, neocuproine) have been prepared and characterized by conductance measurements, electronic, IR, and NMR spectra. Thermal analysis and magnetic behavior for all the compounds were studied. The solid complexes isolated are in the M/acid/Diamine molar ratio 1:1:1 [M(II) Cu, Cd, and Pb; Acid = malonic; Diamine = neocuproine].

INVESTIGATION OF THE STEROCHEMICALLY DETERMINING STEP IN THE SQUARATE ESTER CASCADE

Ken S. [Lee.sup.*], Ashton T. Hamme, and Leo A. Paquette, Jackson State University, Jackson, MS 39217

The study of the sterochemically determining step of the squarate ester cascade reaction was achieved by isolating two diasteromers of a squarate adduct after monoaddition of an ion with a chiral carbon. Each diastereomer was independently reacted with a second alkenyl anion which lead to the isolation of the same polycyclic compound after the cascade reaction took place. Since the same compound was isolated from two unique diastereomers, the stereodefining step must arise from a common octatetraene intermediate.

OXONIUM ION FORMATION FROM ISOXAZOLIDINES

Ken S. [Lee.sup.*], Erick Ellis, and Ashton T. Hamme, Jackson State University, Jackson, MS 39217

A number of different isoxazolidines were synthesized from the addition of nitrones to propargylic alcohol systems. These isoxazolidines were subjected to acidic conditions to determine if the isoxazolidine system was stable to acidic conditions. After some of the isoxazolidines were protonated, a rearrangement occurred through an oxonium ion intermediate to form a unique spirocyclic system.

PROTEIN INTERACTIONS RELATED TO PROTEIN CRYSTALLIZATION

Kristen M. [Demoruelle.sup.*] and W. William Wilson, Mississippi State University, Mississippi State, MS 39762

The osmotic second virial coefficient, B, has been found to identify protein interactions in experimental solution conditions that are favorable for protein crystallization. The values of B describe how the protein molecules interact with each other. When solution conditions for a certain protein produce a B value falling in the crystallization slot (-2 to -8' [10.sup.-4] mol ml [g.sup.-2]), it is concluded that these conditions are favorable for protein crystallization because the proteins have the proper attraction between themselves to produce protein crystals. This work shows data collected for lysozyme, ESA, and VSV N protein solutions. The data include graphs which show conditions favorable for crystal growth along with conformation by actual ESA crystal growth under the identified optimal conditions.

RESEARCH IN FLUOROUS MEDIA

Neil [Stowe.sup.*], Joseph Thrasher, Alfred Waterfeld, and Greg Szulezewski, University of Alabama, Tuscaloosa, AL 35487

Krytox oils are stable liquids with low vapor pressure. A high vacuum system will be used to measure the vapor pressure of Krytox. Vapor pressure can be linked to volatility. This will help DuPont to determine specific applications for homologues of Krytox.

HIGHLY EXCITED RO-VIBRATIONAL EIGENSTATES OF HOCl

Amy [Creel.sup.*] and Joseph A. Bentley, Delta State University, Cleveland, MS 38733

We report the accurate calculation of high-lying rovibrational eigenstates of the ground electronic state of hypochlorous acid, HOCI. The Jacobi coordinate system is used. The discrete variable representation (DVR) [Z. Bacic and J.C. Light, Annu. Rev. Phys. Chem. 40, 469 (1989)] is used as a basis for both radial coordinates leading to a sparse Hamiltonian matrix. The diagonalization-truncation method is used to give a contracted set of angular basis functions. The eigenvalues are then obtained by using the Implicitly Restarted Arnoldi Method (IRAM). This is part of a recently developed numerical package (ARPACK) designed to solve large scale eigenvalue problems. The energies are calculated using a new potential energy surface for HOC1 [S. Skokov, K.A. Peterson, and J.M. Bowman, Chem. phys. Lett. 312, 494 (1999)].

NORMAL FREQUENCIES OF ISOBUTANE AND ISOBUTANE-[d.sub.8]: COMPARISON OF THEORETICAL AND EXPERIMENTAL RESULTS

Chandra M. [Pathak.sup.*] (1), M.K. Shukla (2), and Jerzy Leszczynski (2), (1.) Alcorn State University, Alcorn State, MS 39096, and (2.) Jackson State University, Jackson, MS 39217

The structure and vibrational spectra of isobutane and isobutane-[d.sub.8] have been theoretically investigated in detail. Since both isobutane and isobutane-[d.sub.8] are gases at room temperature, the study provided a unique opportunity to compare the theoretically computed vibrational frequencies with those observed by one of us (CMP) in the gas phase. In the present work, different levels of theories such as HF, DFT(B3LYP), MP2, and CCD were applied employing the 6-311 G(d,p) basis set. One of the isomers has a real minimum structure while the other represents saddle point on the corresponding potential energy surface. A detailed comparative study between the theoretically calculated frequencies and the experimentally observed ones, both in isobutane and isobutane-[d.sub.8] will be presented.

10:10 Break

Divisional Talks Resume

10:20 VISCOSITY DEPENDENCE OF SPIN MODES IN FRONTAL POLYMERIZATION OF MULTIFUNCTIONAL ACRYLATES

Kayce [Leard.sup.*], Sarah Tompkins, and John A. Pojman, The University of Southern Mississippi, Hattiesburg, MS 39406

Frontal polymerization involves the conversion of a monomer into a polymer through thermal initiation. Our study focused on the expansion of two-dimensional and three-dimensional fronts in a frontal polymerization system where spin modes migrated around the front as it propagated. Spin modes are regions of high temperature that migrate in a helical pattern ahead of the front. The intention of this study was to determine the behavior of a front as it undergoes linear propagation in two-dimensional fronts and propagation from the center of a sphere outward in three-dimensional fronts. We studied the viscosity dependence of spin modes in the frontal polymerization of pentaerythritol tetraacrylate (PETAC), ammonium persulfate (thermal initiator), and dimethyl sulfoxide (DMSO). Silica gel was added to the system to make the solution more viscous. It has been determined that the appearance of spin patterns decreases with increased viscosity, thus spin modes in polymerization systems are viscosity dependent. Spheric al polymerizations and indications of spin modes in high viscosity systems have also been achieved.

10:40 METHOD FOR DETERMINING VISCOSITY OF UNKNOWN SAMPLES

Roger D. [Holloway.sup.*] (1), John A. Pojman (2) and William J. Anisworth (2), (1.) Alcorn State University, Alcorn State, MS 39096, and (2.) University of Southern Mississippi, Hattiesburg, MS 39406

A combination of these methods (fluorometric and viscometer) was used to determine viscosity. This method was used to characterize pyrene, a multi-ringed hydrocarbon compound. A concentration 1.0 x [10.sup.-7] M of pyrene in dodecyl acrylate was used in fluorescence experiments to determine the fluorometric intensity. Viscosity data were obtained by using a Brookfield Viscometer (viscosity vs. temperature). The fluorescence data together with viscosity measurements were used to attempt to construct a standard curve of known viscosity verses fluorescence intensity ratio, so that the viscosity of unknown samples can be determine easily.

11:00 WIDE ANGLE X-RAY SCATTERJNG STUDY OF THE EFFECT OF ORGANIC LIQUIDS ON THE LAYERING OF PITTSBURGH #8 COAL

Eric Ryan [Smith.sup.*] and David L. Wertz, University of Southern Mississippi, Hattiesburg, MS 39406

The effects of organic liquids of differing polarities on Pittsburgh #8 coal were examined using wide-angle x-ray scattering techniques. Eight organic liquids were mixed with 2-3 gram samples of coal. After 7-9 days, X-ray scattering spectra were taken from 2 Theta values of 5 degrees to 90 degrees and the spectra were converted to reciprocal space, q. The peak of the untreated coal lies within the 1.0-2.0 [A.sup.-1] range of reciprocal space, which translates to an average distance between layers of ~4.2 A. The effect of the solvents ranged from producing a more pronounced peak at the same reciprocal space range to shifting the peak. The data was used to examine the molecular-level interactions that the coal was undergoing, such as hydrogen-bonding.

11:20 CONTROLLED INITIATION OF POLYMERIZATION REACTIONS USING MICROENCAPSULATION TECHNIQUES

Brian H. [McFarland.sup.*] and John A. Pojman, University of Southern Mississippi, Hattiesburg, MS 39406

The polymerization of a monomer upon addition of an initiator and an accelerator often takes place in an almost instantaneous fashion. The ability to control the time and manner in which these polymerizations take place would offer advantages in storage and in use of these polymerizations in certain applications. This can be accomplished by microencapsulation. Microencapsulation allows a component of the polymerization reaction to be separated from the other components by means of trapping it in a chemical shell. This shell can be removed at the desired time of the user by means such as mechanical shearing, dissolving, and by thermally melting the shell. This releases the core material and the polymerization can then take place. Current methods of microencapsulation being studied include complex coacervation, interfacial polymerization, and in situ polymerization. The effectiveness of each method of microencapsulation is studied, as well as the effectiveness of each method of releasing the core material.

11:40 DETERMINATION OF OXIDATIVE TOLERANCE AND CHARACTERIZATIONS OF MICROORGANISMS FROM SWIMMING POOLS AND SPAS

Regina [Covington.sup.*] and Alfred Mikell, University of Mississippi, University, MS 38677

Water contamination is a popular basis for infection, illness, and death among people today. It is an ordeal that prompts millions to buy faucet filters and bottled water. These extra steps of caution are reasonable when considering that one cannot assess the quality of water merely by observing it. Moreover, crystal clear water can contain some of the most lethal microorganisms known today. These microorganisms usually live in the intestinal tract and are excreted through a bowel movement. As a means of safety, chlorination has been used to combat such creatures through oxidative methods. Unfortunately, microorganisms, particularly those living in swimming pools and spas, have developed antioxidant defense systems that can help them maintain homeostasis and thus continue to live and grow. As a result of this evolution, waterborne pathogens can cause diseases from skin infections to gastrointestinal diseases. Alternative methods of water disinfection are currently being used to compensate for the antioxidant defense systems evolved in microorganisms. Under the conditions that evolved defense systems tolerate present and future resources of water disinfection, water contamination will be the most prominent killer of mankind.