Chemistry and Chemical Engineering.

Chair: Timothy J. Ward, Millsaps College

Vice-chair: John Pojman, University of Southern Mississippi

THURSDAY MORNING

Chandeleur

Session A

9:30 EFFECT OF REHYBRIDIZATION ON THE ELECTRONIC STRUCTURE OF SINGLE-WALLED CARBON NANOTUBES

Mark Hamon (1)*, Mikhail E. Itkis (2), Sandip Niyogi (2), and Robert C. Haddon (2), (1) Millsaps College, Jackson, MS 39210, and (2) University of California, Riverside, CA

Single-walled carbon nanotubes (SWNTs) are expected to have a rich chemistry and the development of this subject will make available a unique set of materials. We have shown that chemical processing of short (100-300 nm in length), SWNTs allows the preparation of stable organic solutions of these materials. Related routes to soluble SWNTs have been reported, together with approaches involving sidewall functionalization. In order to systematize the chemistry of SWNTs, it is necessary to develop analytical tools for the detection and identification of the different species of SWNTs. Raman spectroscopy and near-infrared (NIR) spectroscopy have already been very useful in this regard.

9:45 AQUEOUS SOLVENT EFFECTS ON THE REGIOSELECTIVITY OF THE SINGLET OXYGEN ENE REACTION OF A SUBSTITUTED SULFIDE, SULFOXIDE, AND SULFONE 

Ben Brock* and Kristina L. Stensaas, Millsaps College, Jackson, MS 39210

The singlet oxygen photooxidations of 2,3-dimethyl-2-butenyl p-nitrophenyl sulfide, 1-[(p-nitrophenyl)sulfinyl]-2,3-dimethyl-2-butene, and 1-[(p-nitrophenyl)sulfonyl]-2,3-dimethyl-2-butene were conducted in deuterated chloroform, methanol-[d.sub.4], and aqueous methanol-[d.sub.4] mixtures. Proton nuclear magnetic resonance spectroscopy was utilized to monitor the product distribution in each reaction. The results indicate that the strong hydrogen bonding capability of water affects the regiochemistry of each reaction.

10:00 COMPETITIVE OXIDATIONS OF BENZYL TRISULFIDE AND SUBSTITUTED ARYL DISULFIDES

Seema Ahuja* and Kristina L. Stensaas, Millsaps College, Jackson, MS 39210

The competitive oxidations of dibenzyl trisulfide and various substituted aryl disulfides utilizing meta-chloroperoxy-benzoic acid will be discussed. Bis-p-acetylphenyl disulfide, bis-p-methylphenyl disulfide, and bis-p-methoxyphenyl disulfide were all oxidized in competition with benzyl trisulfide. The relative rates were determined using proton nuclear magnetic resonance spectroscopy. The results indicate that bis-p-acetyl-phenyl disulfide, which contains an electron-withdrawing group, is not competitive with the dibenzyl trisulfide. Both of the disulfides containing electron-donating groups, bis-p-methylphenyl disulfide and bis-p-methoxyphenyl disulfide reacted differently. Bis-p-methylphenyl disulfide was oxidized much slower than benzyl trisulfide whereas bis-p-methoxyphenyl disulfide was oxidized faster. We have attributed these results to several factors including the difference in oxidative reactivity between aryl and alkyl sulfides, the sulfur chain length effect, and the alkyl substitution effect.

10:15 IRREVERSIBLE PHOTOOXIDATION USING NSUBSTITUTED HETEROAROMATIC SYSTEMS

Wolfgang H. Kramer* and Ian R. Gould, Millsaps College, Jackson, MS 39210, and Arizona State University, Tempe, AZ 85287

The efficiency of photoinduced one-electron transfer reactions is often low due to return electron transfer in the initially formed radical-ion pair. The use of N-alkoxy-hetero-aromatic compounds (Ar[N.sup.+]-OR) avoids the return electron transfer process completely. Excitation of these compounds results in cleavage of the N-O bonds, and the formation of the radical cation of the parent heterocycle. This radical cation can be used to irreversibly oxidize an electron donor. In this work we have studied the synthesis, photo-chemistry and photo-physics of a series of A[r.sup.+]-OR for use as irreversible photooxidants. Transient absorption and product analysis studies reveal that the quantum efficiencies for cleavage in the excited singlet state are indeed high, with in-cage recombination being probably the only energy wasting process. Compounds that cleave efficiently, with oxidizing abilities to 2 V vs SCE, and with absorptions as long as 450 nm have been identified. The cleavage fragments can be used to oxidize or nick DNA. Changing the oxidation potential of the radical cation with substituents can help select the mechanism of biomolecule cleavage.

[GRAPHIC OMITTED]

10:30 Break

10:45 ENHANCED CAPILLARY LC-MS2 DETERMINATION OF BIOGENIC AMINES BY PRE-COLUMN DERIVATIZATION WITH 7-FLUORO-4-NITROBENZOXADIAZOLE (NBD-F)

Yi-Ming Liu* and Yaru Song, Jackson State University, Jackson, MS 39217

This presentation describes a capillary LC-MS2 determination of biogenic amines enhanced by pre-column derivatization with 7-fluoro-4-nitrobenzoxadiazole (NBD-F). Biogenic amines including histamine, tryptoamine, N-methylsalsolinol, and agmatine were studied. The NBD-biogenic amine derivatives were characterized by using tandem mass spectrometry and found to be mono-substituted except the one formed from N-methylsalsolinol which was di-substituted. The derivatives could be quantitatively enriched on 20 X 0.25 mm capillary column packed in house with 5 mm silica particles. In an electrospray ionization source, the fragmentation of these derivatives was effective and produced characteristic daughter ions. Agmatine was taken as the model compound for studying the analytical figures of merit. Detection limit was found to be 4.5 X [10.sup.-9] M agmatine and a linear calibration curve with an r2 value of 0.9996 was obtained in the range from 1 X [10.sup.-8] to 1 X [10.sup.-5] M agmatine. Tissue samples of rat brain, stomach, and intestine were analyzed. Minimum sample pre-treatment was needed and each LC-MS2 run was completed within 5 min. The highest level of agmatine was found in the stomach.

11:00 QUANTITATION OF BACTERIA VIA CAPILLARY ELECTROPHORESIS

Geoff Stone, David Smith, Bryant Jones, Stacy Ponder, Daisy Hamburg, Robert Nevins, and Timothy Ward*, Millsaps College, Jackson, MS 39210

Identifying and quantization bacteria and other microorganisms is a difficult problem that is becoming increasingly important. The traditional method for characterizing microorganisms is by isolation of pure cultures. Compounding this problem is the fact that sample analysis is slow, thus limiting the number of samples that can be analyzed in a given time. At the present time, there are no reliable and easy to perform techniques for separating, identifying and quantization of intact microorganisms. Recently, a number of groups have explored the possibility of applying the technique of capillary electrophoresis in order to separate intact microorganisms such as bacteria and viruses. The application of this technique to this particular field of study would be advantageous, because it allows the bacteria to remain intact while being analyzed quickly and efficiently with broad applicability. In general, microorganisms tend to be amphoteric, containing multiple charges thus ideally suiting them for analysis by electrophoresis. We discuss the relevant characteristics associated with microorganisms that must be carefully controlled to achieve a useful separation as well as parameters affecting quantitation.

11:15 BINDING ENERGIES OF MONOVALENT AND DIVALENT CATIONS WITH TNT 

Laura Lewis* and David H. Magers, Mississippi College, Clinton, MS 39058

Trinitrotoluene is considered a teratogen and mutagen and therefore a major environmental hazard when it seeps into ground water. And yet, TNT is prevalent at artillery ranges, bomb sights, and anywhere explosives are used for any purpose, military or civil. The only current EPA-approved method for remediating TNT from soil is incineration, which is quite expensive. Other treatments are currently being investigated involving base hydrolysis of TNT. However, little is know about the mechanism of this reaction. Base hydrolysis always occurs in the presence of high concentrations of monovalent and divalent cations. Studies have shown that the intermediates of the alkaline hydrolysis of TNT can occur through radicals that have been observed in tight associated with monovalent cations. In the present study, we began our investigation of this process by calculating the binding energy of TNT to such cations using SCF and density functional methods (DFT). The ground-state geometry and the corresponding electronic energy of trinitrotoluene, the energies of the Li, Na, K, Mg, and Ca cations, and the optimum geometries and energies of a TNT dimer with each cation were calculated. In these initial computations, each cation and dimer combination yielded a different optimized structure. Each of these is currently being used as a starting point for further geometry optimizations of the other four cations with TNT dimer, thus yielding up to five possible structures for each system. In each case, the most stable will be used to determine the binding energy. Every computation is being performed at both the SCF and DFT levels of theory with two basis sets: 3-21G(d) and 6-31 G(d,p). We gratefully acknowledge the support of NSF EPSCoR (EPS-0132618).

11:30 CONVENTIONAL STRAIN ENERGY OF DIMETHYLSUBSTITUTED CYCLOBUTANES AND THE GEM-DIMETHYL EFFECT

Ashley L. Ringer* and David H. Magers, Mississippi College, Clinton, MS 39058

The gem-dimethyl effect is the acceleration of cyclization by substituents in the chain and is often used in organic synthesis as a ring-closing effect. In the current study, calculations on methylcyclobutane, 1,1-dimethylcyclobutane, 1,2-dimethylcyclobutane, and 1,3 dimethylcyclobutane are performed to determine if this effect is at least in part a thermodynamic effect caused by lower strain energy or entirely a kinetic effect that lowers the activation barrier for the cyclization reaction. 1,1-dimethylcyclobutane is a four-membered carbon ring with gem-dimethyl substituents. Optimum equilibrium geometries, harmonic vibrational frequencies, and corresponding electronic energies are computed for all pertinent molecular systems using SCF theory, density functional theory (DFT), and second-order perturbation theory (MP2). Comparisons are made between the conventional strain energy of cyclopropane and cyclobutane, methylcyclobutane, and the dimethyl-substituted cyclobutanes. Preliminary SCF and DFT calculations indicate that 1,1-dimethylcyclobutane is approximately 3 to 3.5 kcals/mol less strained than methylcyclobutane, which in turn is 3 to 3.5 kcals/mol less strained than cyclobutane. One hypothesis suggests that the strain energy is lower because the methyl groups have more freedom to move in the ring than in the open chain. Thus, there appears to be at least some thermodynamic component to the gem-dimethyl effect. The study continues by calculating conventional strain energies for the 1,2- and the 1,3-dimethyl substituted cyclobutanes. Additionally, the optimum geometries of the cyclic systems are examined, particularly noting the bonding angles in the rings, to study the relevance of geometry to the gem-dimethyl effect. We gratefully acknowledge the support of NSF EPSCoR (EPS-0132618).

THURSDAY AFTERNOON

Chandeleur

Session A

1:30 CONVENTIONAL STRAIN ENERGY IN THE DIAZETIDINES, DIPHOSPHETANES, THIAZETIDINES, AND THIAPHOSPHETANES

Patricia Honea*, Ashley L. Ringer, and David H. Magers, Mississippi College, Clinton, MS 39058

The conventional strain energies for the cis and trans conformations of 1,2-diazetidine, 1,3-diazetidine, 1,2-diphosphetane, and 1,3-diphosphetane together with the 1,2- and the 1,3- isomers of thiazetidine and thiaphosphetane are determined within the isodesmic, homodesmotic, and hyperhomodesmotic models. Optimum equilibrium geometries, harmonic vibrational frequencies, and corresponding electronic energies are computed for all pertinent molecular systems using SCF theory, second-order perturbation theory (MP2), and density functional theory. The DFT functional employed is Becke's three-parameter hybrid functional using the LYP correlation functional. Two basis sets, both of triple zeta quality on valence electrons, are employed: 6-311G (d,p) and 6-311+G(2df,2pd). Additionally, single point coupled-clustered calculations using the optimized MP2 geometries and the larger of the two basis sets, are used to investigate the effects of higher-order electron correlation. Finally, the calculated strain energies are compared to those of cyclopropane, cyclobutane, azetidine, phosphetane, 1,2-oxazetidine, and 1,3-oxazetidine. We gratefully acknowledge support from NSF EPSCoR (EPS-0132618).

1:45 CONFORMATIONAL ENERGETICS OF NAPHTHYLQUINOLINES

Margie Lovell*, David H. Magers, and Gary Reid Bishop, Mississippi College, Clinton, MS 39058

Naphthylquinoline derivatives satisfying hypothesized structural criteria for triplex DNA selectivity have been designed and synthesized. Proposed structural characteristic criteria promoting intercalation between bases of triplex DNA include: (i) a large aromatic surface area, (ii) an unfused flexible ring system, (iii) cationic, and (iv) crescent shape. Previous high-throughput competition dialysis experiments provided additional insights by demonstrating that the replacement of the secondary amine function found in the lead compound termed LS8 with an ether oxygen linkage greatly increased selectivity towards triplex DNA. Those experiments have been extended to include two additional compounds containing either a sulfur containing thiol or amide linkage. Here we present results from computational studies designed to examine the dynamic flexibility of the naphthylquinoline sidechain for the four compounds containing amine, ether, thiol, or amide linkages. Calculations are performed to determine the energy of each compound with varying dihedral angles between the side chain and the naphthylquinoline. Beginning from optimized geometries, the specific dihedral angle is frozen at 10-degree increments for values between 0 and 360 degrees and the rest of the structure is reoptimized to yield the energy barrier of the side-chain rotation and the approximate dihedral angle at which the top of the barrier lies. Calculations are performed using semiempirical theory, SCF theory, and density functional theory. We gratefully acknowledge the support of NSF EPSCoR (EPS-0132618).

2:00 THE THEORY AND USE OF LASER LINE DEFLECTION TO MONITOR ISOTHERMAL FRONTAL POLYMERIZATION 

Lydia Lee Lewis* and John A. Pojman, Millsaps College, Jackson, MS 39210, and University of Southern Mississippi, Hattiesburg, MS 39406

Isothermal Frontal Polymerization (IFP) is a method of converting monomer into polymer via a self-sustained propagating reaction zone that occurs when a solution of monomer and thermal initiator diffuse into a polymer seed creating a viscous region. Polymerization occurs in both the monomer solution and in the viscous region but occurs faster in the viscous region because of the Trommsdorff effect. As more monomer solution diffuses into the viscous region, new polymer forms, and a propagating, self-sustaining reaction occurs. IFP is used to produce gradient refractive index materials, which are materials containing a change in their refractive indices, e.g. fiber-optic cables for local-area networks. During the reaction, propagating isothermal fronts contain refractive index gradients as a result of the monomer solution diffusing into the polymer seed and the subsequent reacting front. These refractive-index gradients make detection of the reaction zone impossible with the naked eye. Laser line deflection, light deflection through use of a line laser, has been developed to determine the position of the reaction zone within these systems. In addition, a mathematical algorithm has been developed to quantitatively determine the propagation distances as well as the front velocities and gradient profiles. The experimental apparatus and mathematical algorithm are discussed as well as their limitations, advantages, experimental and analytical error, and future directions of this field.

2:15 LIMITATIONS OF ISOTHERMAL FRONTAL POLYMERIZATION

Christopher A. Harris (1)*, Lydia Lee Lewis (1), and John A. Pojman (2), (1) Millsaps College, Jackson, MS 39210, and (2) University of Southern Mississippi, Hattiesburg, MS 39406

Isothermal Frontal Polymerization (IFP) is a directional polymerization that occurs when monomer and thermal initiator diffuse into a polymer creating a viscous region. The rate of polymerization in this viscous region is higher than in the solution of monomer and thermal initiator because of the Trommsdorff, or gel, effect, resulting in a propagating front. To determine the experimental conditions at which IFP occurs, systems of the monomer/polymer seed system of methyl methacrylate/poly(methyl methacrylate) were examined using the thermal initiator 2,2'-azobisisobutyrolnitrile (AIBN). These systems were run at various AIBN concentrations and cure temperature ranges to determine the limits at which homogeneous polymerization of the monomer solution occurred before front propagation could begin. Front propagation did not occur for solutions of 0.03% (wt/V) AIBN concentration above cure temperatures of 90 [degrees]C. This concentration limit increased with decreasing temperature until it was discovered that propagation occurred for saturated solutions at temperatures below 50 [degrees]C. For the conditions at which IFP occurred, the propagation distance was 0.6 [+ or -] 0.15 cm regardless of initiator concentration and cure temperature.

2:30 Break

2:45 THE SYNTHESIS OF A POLYMERIC INHIBITOR FOR USE IN ISOTHERMAL FRONTAL POLYMERIZATION

Evan L. Underwood* and Lydia Lee Lewis, Millsaps College, Jackson, MS 39210

Isothermal Frontal Polymerization is a self-sustaining, directional polymerization that occurs when a solution of monomer and thermal initiator come in contact with a polymer seed and create a viscous region where a higher polymerization rate, the gel effect, occurs. Monomer and thermal initiator continue to diffuse into this viscous region, and the polymer reaction proceeds in a vertical direction until homogeneous polymerization of the monomer on top of the front stops the front. To prolong the lifetime of the front, polymeric inhibitors of sufficient size to prevent diffusion into the forming polymer matrix have been utilized. The free-radical scavenger 2,2'-6,6'-tetramethyl-1-piperidinyloxy has effectively prevented the polymerization of methyl methacrylate and has been incorporated onto a polymer backbone through the addition of substituted 2,2'-6,6'-tetramethyl-1-piperidinyloxy to low molecular-weight poly(methyl methacrylate). The polymeric inhibitor has been characterized through IR. Preliminary studies of the polymeric inhibitor's effectiveness show prolonged front behavior for fronts using the thermal initiator 2,2'-azobisisobutyronitrile with the monomer methyl methacrylate and poly(methyl methacrylate) seeds.

3:00 DETERMINATION OF THE EFFECT OF OXYGEN AND INHIBITOR ON AN ISOTHERMAL FRONTAL POLYMERIZATION SYSTEM VIA LASER LINE DEFLECTION

Daniel Antrim (1)*, Svetlana I. Evstratova (1,2), and John A. Pojman (1), (1) University of Southern Mississippi, Hattiesburg, MS 39406, and (2) Rostov State Pedagogical University, Rostov-on-Don, Russia

Isothermal Frontal Polymerization (IFP) is a form of frontal polymerization that requires a polymer seed in order for a front to form. The seed is dissolved by the monomer forming a viscous region where polymerization occurs much faster than in the bulk of the solution--the newly formed polymer is likewise dissolved; thus propagating the reaction as a front. The purpose of this study is to more accurately characterize the IFP system--specifically, the effect of oxygen and inhibitor concentration on the front's velocity and propagation distance. For the oxygen study, a solution of monomer with initiator was flushed with oxygen for varying time periods before being poured into the reaction vessel. For the inhibitor study, solutions containing monomer with initiator and varying concentrations of inhibitor (2,2-diphenyl-1-picrylhydrazyl) were analyzed. Laser line deflection--an optical technique sensitive to refractive index gradients--was used to determine the position and velocity of the front. Results indicate that oxygen increases both propagation distance and velocity of the front by inhibiting bulk polymerization and by forming peroxides that increase polymerization in the viscous region. Results of the inhibitor study will be compared to modeling.

3:15 CONVENTIONAL STRAIN ENERGY IN UNSATURATED FOUR-MEMBERED RINGS

Shelley S. Huskey* and David H. Magers, Mississippi College, Clinton, MS 39058

In order to study the effect of unsaturation on the ring strain in small cyclic molecules, the conventional strain energies for cyclobutene, azetidine-1-ene, phosphetane-1-ene, azetidine-2-ene, and phosphetane-2-ene are determined within the isodesmic, homodesmotic, and hyperhomodesmotic models. Optimum equilibrium geometries, harmonic vibrational frequencies, and corresponding electronic energies are computed for all pertinent molecular system using SCF theory, second-order perturbation theory, and density functional theory (DFT). The DFT functional employed is Becke's three-parameter hybrid functional using the LYP correlation functional. Two basis sets, both of triple-zeta quality on valence electrons, are employed: 6-311G(d,p) and 6-311+G(2df,2pd). Finally, the calculated strain energies are compared to those of cyclopropane, cyclobutane, azetidine, and phosphetane. We gratefully acknowledge support from NSF EPSCoR (EPS-0132618).

3:30 CONVENTIONAL STRAIN ENERGY IN SMALL HETEROCYCLES OF CARBON AND SILICON

Crystal Coghlan*, Shelley S. Huskey, and David H. Magers, Mississippi College, Clinton, MS 39058

The conventional strain energies for three- and four-membered heterocycles of carbon and silicon are determined within the isodesmic, homodesmotic, and hyperhomodesmotic models. Optimum equilibrium geometries, harmonic vibrational frequencies, and corresponding electronic energies are computed for all pertinent molecular systems using SCF theory, second-order perturbation theory (MP2), and density functional theory. The DFT functional employed is Becke's three-parameter hybrid functional using the LYP correlation functional. Two basis sets, both of triple zeta quality on valence electrons, are employed: 6-311G (d,p) and 6-311+G(2df,2pd). Finally, the calculated strain energies are compared to those of cyclopropane, cyclobutane, oxaziridine, azetidine, phosphetane, diazetidine, and diphosphetane. We gratefully acknowledge support from NSF EPSCoR (EPS-0132618).

3:45 Divisional Business Meeting in Chandeleur

THURSDAY MORNING

Petit Bois

Session B

9:30 SEQUESTRATION OF TOXIC METALLIC IONS BY TIRE-DERIVED POWDER FROM THE WOMBAT PROCESS

Donald D. Bratton III* and David L. Wertz, University of Southern Mississippi, Hattiesburg, MS 39406

Toxic metal ions, such as copper, lead and mercury pose a serious ecological threat to humans, animals and vegetation if leaked into the environment. The WOMBAT process, an environmentally sound method of recycling tires into a viable fuel, produces a black powder derived from scrap tires. Third-party analysis of powder obtained from the WOMBAT process revealed that the tire-derived powder had the potential to sequester toxic metal ions. The purpose of the study was to determine to what extent WOMBAT powder could sequester a toxic metal ion, copper(II) chloride. A solution of aqueous copper(II) chloride was prepared to which tire-derived powder was added to and mixed overnight. UV-visible spectra of the solution and X-ray fluorescence spectra of the separated and dried powder confirmed a significant increase in copper ion concentration within the WOMBAT powder as well as a significant decrease in copper ion concentration in solution. XRF analysis also showed no significant alteration in the composition of the powder other than the increase in copper.

9:45 AN ANALYSIS OF THE BONDING CAPABILITIES OF WOMBAT POWDER WITH VARIOUS METALS

Veronika G. Viner* and David L. Wertz, University of Southern Mississippi, Hattiesburg, MS 39406

Scrap tires have littered landfills worldwide for years. Despite appearing to be useless garbage, scrap tires actually are a source of potentially valuable material and have been recycled for many useful applications. One potential application is to recycle the tires for previous metals such as copper. The Wertz oxidative method for processing scrap tire residual, shredded rubber scraps attached to steel wire, produces a powder that is known as WOMBAT powder. This powder was combined with first a copper salt and then with five different metals, calcium, cobalt, copper, mercury and lead in a solution in order to determine which metals would react with the powder and form bonds with it. These solutions were then filtered, dried and combusted before being analyzed with an x-ray diffractometer and x-ray fluorescence spectrometer. From x-ray fluorescence, it was found that a medley of metals, including mercury and copper, reacted with the WOMBAT powder. These results show that scrap tire residual are potentially useful material for obtaining valuable metals such as copper.

10:00 A STUDY OF THE VALUE-ADDED PRODUCTS OF THE WOMBAT REACTION

Kate Vigour*, Giselle Schnaubelt, Tara Craft, and David L. Wertz, University of Southern Mississippi, Hattiesburg, MS 39406

A study of the used WOMBAT fluid produced by the WOMBAT tire recycling process was conducted. The used WOMBAT fluid was effectively used four times, which proved the smallest ratio of tire to WOMBAT fluid was 1:5. The spent fluid was neutralized and the potassium nitrate was crystallized. These crystals were used in the production of WOMBAT fertilizer. They were analyzed and compared to commercial Miracle-Gro fertilizer using x-ray spectrometry. Three types of plants were used to compare the WOMBAT fertilizer along with the commercial Miracle-Gro fertilizer. After weekly fertilization, the fully-grown plants were analyzed. The Miracle-Gro fertilizer produced the best results. However, the WOMBAT fertilizer produced better results than the plants grown in the absence of fertilizer. A base composition was developed based on the information obtained from this research.

10:15 ENVIRONMENTAL X-RAY ANALYSIS ON SOIL AND VEGETATION EXPOSED TO SCRAP TIRE CHIPS

Holly R. Williams* and David L. Wertz, University of Southern Mississippi, Hattiesburg, MS 39406

Pieces of scrap tire and steel were deposited in the ground and the area was examined to determine if any metals from the tire chips were leaching into the ground. Vegetation commonly cultivated in Mississippi was also planted in a garden exposed to tire chips. X-ray fluorescence was used to monitor the soil samples over a tri-monthly basis. We found that concentrations of the elements found in the scrap tires and steel increased after a period of time; however some elements concentrations decreased over time. The cause of this may be due to bacteria in the soil. This study demonstrates that tires that are landfilled have the potential for increased toxicities to be incorporated into the ground and surrounding area.

10:30 Break

10:45 TEACHING AND LEARNING CHEMISTRY WITH THREE-DIMENSIONAL MOLECULAR MODELS

Robert C. Bateman, Jr., University of Southern Mississippi, Hattiesburg, MS 39406

Science teachers have long used three dimensional models for helping students learn about the three-dimensional world. Some familiar examples are the foaming clay volcano and topographic maps of geology and the molecular model sets of chemistry. Recently students have been able to utilize computer graphics with interactive images and animations to assist with learning in a variety of science disciplines. This presentation will review the use of three-dimensional molecular models in chemistry education, with a discussion of the various possible approaches to using these tools along with their pedagogical strengths and pitfalls. Emphasis will be on the mental models generated by the use of physical and computer graphic models of both small molecules and macromolecules.

11:00 INTERFACIAL BEHAVIOR OF HYDROPHOBINS, A UNIQUE CLASS OF PROTEINS

Sonya D. Benson*, Chang K. Hong, and Sarah E. Morgan, University of Southern Mississippi, Hattiesburg, MS 39406

An understanding of how natural polymers such as proteins adsorb onto various substrates is extremely important. The surface and interfacial behavior of these biopolymers including their adhesion and wettability characteristics determines where and how proteins and other biopolymers are used within their respective organisms. Therefore, detailed surface characterization of both the protein and substrate is required to understand the nature of protein behavior at surfaces and interfaces. A prediction of the adhesion and wettability behavior of hydrophobins, the most surface active proteins known to date, is determined using surface energy and solid/liquid interfacial tension theory. The surface energy and surface tension of hydrophobin Sc3 isolated from the wood-rotting fungus Schizophyllum commune is determined using contact angle measurements. Contact angle measurements are obtained via the sessile drop technique using a range of solvents and substrates of varying polarity. A prediction of the adhesion and wettability behavior of Sc3 is made using methods and theories developed by Fowkes and Owens and Wendt. Atomic force microscopy is used to study the surface topography and morphology of Sc3 deposited onto substrates of differing polarity.

11:15 METHYLENE KETALS AS BICHROMOPHORIC MODEL COMPOUNDS FOR LIQUID CRYSTAL-LINE POLY(ARYL CINNAMATES)

Stacy R. Burton* and David Creed, University of Southern Mississippi, Hattiesburg, MS 39406

UV-Vis spectra of pure films of liquid crystalline (LC) polymers are almost invariably perturbed relative to those of simple model compounds in solution. We have been using several approaches to modeling the interchromophore interactions and perturbed electronic spectra of LC poly(aryl cinnamates). Ketals of methanal of general structure ArOC[H.sub.2]OAr have a flexible 'spacer' group, -OC[H.sub.2]O-, that should allow for maximum interchromophore interactions of the pendent aryl groups. Reaction of alkyl 4-hydroxycinnamate esters with C[H.sub.2]C[l.sub.2] in N,N-dimethyl acetamide in the presence of [K.sub.2]C[O.sub.3] affords high yields of the bichromophoric compounds. These bichromophoric model compounds have been characterized by NMR, IR, and UV-Vis measurements. They show perturbed UV-Vis spectra but these spectra are unlike those seen in the LC polymers possibly reflecting significant perturbation of the cinnamate absorption spectrum by the polar effect of the OC[H.sub.2]O substituent.

11:30 DEMONSTRATION AND QUANTIFICATION OF THE EFFECTIVE INTERFACIAL TENSION IN AN ISOBUTYRIC ACID/WATER SYSTEM VIA SPINNING DROP TENSIOMETRY

Colin Whitmore*, Rosie Parker, Brian Zoltowski, and John A. Pojman, University of Southern Mississippi, Hattiesburg, MS 39406

The existance of an effective interfacial tension (EIT) in a miscible solution is demonstrated and quantified. This is done by analyzing a binary system of isobutyric acid (IBA) and water with a spinning drop tensiometer (SDT). A solution of IBA and water is injected into a SDT set at a temperature below their demixing temperature. Here, two immiscible phases exist. The temperature of the tensiometer is then raised above the demixing temperature to make the two phases miscible. After allowing thermal equilibrium to be achieved, the EIT is measured though two methods. Rapidly lowering the rate of rotation causes the drop to break up via the Rayleigh-Tomottika instability. This provides definitive evidence of the EIT, and allows for a method through which its value is calculated. The value so obtained is compared to that derived from the static drop via the Vonnegut formula. Acknowldments: NASA's Microgravity Materials Science Program grants NAG8-1466 and NAG8-1858

THURSDAY AFTERNOON

Petit Bois

Session B

1:30 MOLECULAR DESIGN FOR NONLINEAR OPTICAL MATERIALS

Paresh Ray, Jackson State University, Jackson, MS 39217

In this presentation I want to emphasis mainly on the design strategy to maximize the Nonlinear Optical (NLO) properties of organic molecules. Series of push-pull neutral, ionic and Octupolar molecules are investigated to establish the structure/NLO- property relationships by carrying out the ab initio (HF/6-31G*) calculations of the molecular first hyperpolarizability (a). The solvent effects on the NLO properties are studied by using the self-consistent reaction field (SCRF) method. It is found that Bond Length Alternation (BLA), Donor-Acceptor properties, Ionic Strength and Solvent polarity are the main factors to be considered for designing nonlinear optical materials. We also compare our theoretical results with the experimental values wherever available in the literature, reported by us or other groups.

1:45 PRODUCTION OF INITIATOR-CORE MICROCAPSULES AND ANALYSIS OF THEIR RELEASE PROPERTIES

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

Certain polymerization reactions are often designed to take place through a triggered release of an initiator and/or accelerator that has been enclosed in microcapsules that are dispersed throughout the reaction medium. These microcapsules can be designed to release their core contents through a variety of ways, including mechanical rupture, heat-triggered release, and slow release by gradual diffusion of the core out of the capsule shell. An in-depth study has been designed to examine the production of initiator-core microcapsules by various microencapsulation techniques, and to examine their release properties as both a dry powder and in storage in a liquid monomer medium. The examination of the release properties will give insight as to which types of microcapsules are best applied to certain polymerization applications.

2:00 POLYMER-DISPERSED AQUEOUS MATERIALS

Kayce Leard-Aultman (1)*, Dana N. Ho (2), John A. Pojman (1), Douglas Wicks (1), and Charles Hoyle (1), (1) University of Southern Mississippi, Hattiesburg, MS 39406, and (2) Kentucky State University 

The focus of this study is to prepare hydrophobic polymeric materials in which the aqueous phase is distributed throughout the polymer matrix as droplets. The resulting material could respond to magnetic fields, electric fields, or volatile compounds, depending on the composition of the aqueous phase. Preliminary experiments involve preparation of microemulsion solutions of Aerosol-OT, Dodecyl acrylate, and water. The surfactant, Aerosol-OT is employed to encapsulate the aqueous molecules within a surfactant monolayer, and the films are created via photopolymerization. Exposure to ultraviolet light of approximately 30 mW/c[m.sup.2] produces a thin film of opaque polymer. The opaque characteristic of the thin film suggests that aqueous droplets have been distributed throughout the polymeric material, because for the material to be cloudy the droplets must be larger than a wavelength of light. It is known that the droplets can aggregate to different degrees, and it may be possible to follow the evolution of droplet coalescence by imaging the films after different amounts of exposure to UV light. The appearance of the films will alternate from opaque to transparent, depending on the environment in which the material is contained, and a polymer thin film responsive to humidity and water in the air has been created. The current goal is to develop the most accurate and effective imaging technique for viewing the droplets within the matrix. Presently, phase contrast microscopy has been successful in proving that the droplets are there, but other imaging techniques will be used to gather measurements of the actual droplet size.

2:15 MISCIBLE FLUIDS IN MICROGRAVITY (MFMG)

John A. Pojman (1)*, Nick Bessonov (2), and Vitaly Volpert (2), (1) University of Southern Mississippi, Hattiesburg, MS 39406, and (2) Universite Lyon I, France

We use a 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 performed simulations of drops and streams of miscible fluids and showed that it is possible for transient phenomena to occur that are similar to that observed with immiscible fluids. Specifically, we show that an aspherical drop can spontaneously become spherical and that a stream of a fluid can exhibit a Rayleigh instability. We also simulated a miscible drop migrating in a temperature gradient. The MFMG experiment is a zero-upmass experiment to be performed with Russian honey and water on the International Space Station.

2:30 Break

2:45 DETERMINING VISCOSITY NONINVASIVELY USING FLUORIMETRIC TECHNIQUES

Sammy Popwell*, Kayce Leard-Aultman, Victor Wyatt, Joshua U. Otaigbe, and John A. Pojman, University of Southern Mississippi, Hattiesburg, MS 39406

A noninvasive method of measuring viscosity during the adiabatic photopolymerization of dodecyl acrylate is being developed for use in an experiment on the international space station. The goal is to achieve viscosity measurements by monitoring the increase in intensity of pyrene and the ratio of monomer to excimer fluorescence of bis-pyrene. The fluorescence of both are being measured as a function of polymer concentration and temperature in an attempt to correlate the fluorescence intensity and viscosity.

3:00 INVESTIGATING SPIN MODE PATTERNS IN SPHERICALLY PROPAGATING POLYMERIZATION FRONTS

Hitish Nathani*, Sammy Popwell, and John A. Pojman, University of Southern Mississippi, Hattiesburg, MS 39406

Frontal Polymerization involves the conversion of monomer to polymer via a localized reaction zone that propagates through an unreacted solution of monomer and initiator. This study focuses on the expansion of three-dimensional frontal polymerization systems in which spin modes migrate around the periphery of the front. Spin modes are unique dynamical patterns caused by thermal instabilities. The viscosity dependence of spin modes in the frontal polymerization of Trimethylolpropane ethoxylate triacrylate, 1,6-hexanediol diacrylate (HDDA), and Aliquat Persulfate (thermal initiator) have been studied. Silica gel was added to increase the viscosity of the solution. It has been determined that the appearance of spin patterns decrease with increased viscosity, thus spin modes in polymerization systems are viscosity dependent. Spherically-propagating frontal polymerization and indications of spin modes in high viscosity have been achieved.

3:15 INVESTIGATION OF FRONTAL POLYMERIZATION IN A THIOL-ENE SYSTEM

Alford Perryman, University of Southern Mississippi, Hattiesburg, MS 39406

Thiol-ene thermo initiator proceeds via a sequential radical propagation/chain transfer mechanism that leads to polymer and network formation much like a step growth polymerization. Thiol-enes are advantageous over traditional acrylate systems in that they exhibit low oxygen inhibition during cure and have the ability to form thin and thick cures. The frontal polymerization of the Thiol-ene allows conversion of the monomers into polymer via localized reaction propagation. In this study, the velocity and temperature profiles of a frontal polymerized Thiol-ene system were determined. Thiol-ene frontal polymerization is new, so determining these dependencies is essential for determining the potential applications.

3:30 FRONTAL POLYMERIZATION IN THIOL-ENE AND THIOL-ACRYLATE SYSTEMS

Birsen Varisli, University of Southern Mississippi, Hattiesburg, MS 39406

We demonstrate for the first time frontal polymerization with a thiol-ene system. We studied Pentaerytrytol Triallyl Ether (PTE) and Trimethylolpropane tris (3-mercaptopropionate) (TT1) with Luperox 231 as a free-radical peroxide initiator. We determined the front velocity as a function of the initiator concentration and the ratio of PTE:TT1. A stoichiometric ratio produced the maximum front velocity. Nonstoichiometric ratios produced nonplanar modes of propagation, so called, 'spin modes.' We also studied a mixed thiol-diacrylate system in which the thiol significantly reduced the inhibition from dissolved oxygen.

3:45 Divisional Business Meeting in Chandeleur

FRIDAY MORNING

Chandeleur

8:45 Divisional Poster Session

PREPARATION OF SALSOLINOL STEREOISOMERS USING CHIRAL HPLC TO MONITOR SEPARATIONS

Bradley Cheek, Chris Strawbridge, John McCoy, and Kenneth McMurtrey*, University of Southern Mississippi, Hattiesburg, MS 39406

In this paper a racemic mixture of salsolidine (the methoxy derivative of salsolinol) was separated into its two enantiomers using D- and L-tartaric acid, which separated (+)-salsolidine into R-salsolinol and S-salsolinol, respectively. Racemic salsolidine was combined with D-tartaric acid and methanol added to the mixture. One of the diastereomeric salts, S-salsolidine-D-tartrate was obtained and purified by Crystallization. The R-salsolidine-D-tartrate salt, which is relatively soluble in methanol, was extracted into chloroform from a basic solution giving salsolidine as predominantly the R-isomer. This was mixed with L-tartaric acid and was recrystallized from methanol to give the purified R-salsolidine. The two isolated stereoisomers were then demethylated in refluxing concentrated HBr to give the two salsolinol stereoisomers. S-(-)-salsolinol-HBr was obtained in 97.7% purity and R-(+)-salsolinol-HBr in 98.8% purity as measured by reversed-phase HPLC using sulfated [beta]-cyclodextrin as modifier in the mobile phase. Polarized light measurements indicated that these measurements of optical purity was essentially correct.

THE PURIFICATION OF ESTRONE SULFATASE 

Marie Winston (1)*, Theodore S. Widlanski (2), and Cheri Stowell (2), (1) Alcorn State University Alcorn State, MS 39096, and (2) Indiana University, Bloomington, IN 47401

Included with in a human placenta are many diverse proteins. Among those proteins are membrane proteins. These membrane proteins are comprised of an enzyme known as estrone sulfatase. Breast tumors produce increasing levels of estrone sulfatase activity, and a majority of breast tumors are estrogen dependent. Therefore, the purification and isolation of membrane proteins containing estrone sulfatase is vital to producing chemotherapeutic intervention in breast cancer. Purification of these membrane proteins that house estrone sulfatase can be accomplished by several methods including chromatography separation and electrophoresis. Here, the chromatography separation method is employed. However, there are many forms of chromatography separation. The form used here is ion exchange chromatography. This purification was carried out to extract membrane proteins out of a human placenta in order to gain access to the estrone sulfatase activity level in which these proteins exhibit. Although future chemotherapeutic advancements for breast tumors are not known at this time, the results of this purification showed promising levels of estrone sulfatase activity.

THE DIFFERENCES BETWEEN FRESH AND DRIED BACOPA MONNIERI

Padma Venkat (1), Bettaiya Rajanna (2), Preeti Sudha (1), and Roger Holloway (2)*, (1) Foundation for Revitalization of Local Health Traditions (FRLHT), Bangalore, India, and (2) Alcorn State University, Alcorn State, MS 39096

This research was carried out by the author in association with the scientists at Foundation for Revitalization of Local Health Traditions (FRLHT), Bangalore, India, in summer 2003 as part of Minority International Research Training (MIRT) program. A major goal of FRLHT is to revitalize traditional local health cultures and practices by challenging to demonstrate their contemporary relevance to serve the country's present and future health care needs. According to Charak Samhita, a classical Ayruvedic text, Bacopa monnieri has been a part of Indian culture since the time of Atharva-ved. A naturally occurring herb, Bocopa monnieri has been used to treat mental diseases and as a nerve tonic. The use of Bacopa monnieri in Indian Ayurvedic medicine for memory enhancement goes back 3000 years or more. Both fresh (green and wet) and dried form of the plant are used. The purpose of this study was to evaluate the differences or similarities in the medicinal characteristics between fresh and dried Bacopa monnieri plant. The morphological characteristics of the plant was authenticated and described with the help of a qualified botanist. Plants were harvested and stored in the laboratory at appropriate temperature. Prescribed samples of plant material were selected from the original stock. Laboratory tests for morphological description, foreign organic matter content, moisture, total ash, acid insoluble ash, water soluble extract, alcohol soluble extract and bacoside content were performed. Thin Layer Chromatography (TLC) was used for identification and finger printing. (Supported by NIH/FIC/MIRT # 5 T37 TW00132)

ANALYSIS OF ENTEROSTATIN IN CEREBROSPINAL FLUID AND RAT BRAIN BY HPLC-MS/MS

Kristina Vaughn*, Yi-Ming Liu, and Yaru Song, Jackson State University, Jackson, MS 39217

Obesity has been linked to mechanical, metabolic, and physiological adverse public heath effects. Although some cases of obesity are linked to hereditary factors, high fat consumption remains the chief contributor to the large obese population. Enterostatin, a group of neuropeptides, have been correlated with reduction of high fat intake. Enterostatin is produced in the gastric mucosa and small intestine. Enterostatins include several pentapeptides, [Val-Pro-Asp-Pro-Arg (VPDPR), Val-Pro-Gly-Pro-Arg (VPGPR), and Ala-Pro-Gly-Pro-Arg (APGPR)], which are found in varying abundances in the human cerebrospinal fluid and rat brain. The purpose of this study is to effectively determine the dominant form of enterostatin in human cerebrospinal fluid and rat brain using high performance liquid chromatography coupled with mass spectrometry analysis. Other aspects include determining solution makeup for the bioactive form of APGPR, by analyzing APGPR in various compositions. Samples obtained by the laboratory were resolved on a C18 reversed-phase column using a ternary mobile phase consisting of methanol, acetonitrile, and water. These samples were analyzed with HPLC coupled with Mass spectrometry detection. Analysis demonstrates that APGPR is the dominant form of enterostatin in human cerebrospinal fluid and rat brain. The levels of APGPR were 98.3 [+ or -] 16.3 ng/ml of human cerebrospinal fluid and 30.1 [+ or -] 12.6 ng/g wet tissue of rat brain sample. This research was supported by NIMH-COR grant MH-16926.

PHOTOCHEMICAL DEGRADATION OF NITRO POLYCYCLIC AROMATIC HYDROCARBONS

Generique Stewart*, Jian Yan, Lei Wang, and Hongtao Yu, Jackson State University, Jackson, MS 39217

Polycyclic Aromatic Hydrocarbons (PAHs) are a class of widely spread mutagenic and tumorigenic environmental contaminants. Nitro-polycyclic aromatic hydrocarbons (nPAHs) are derivatives of PAHs, and contain two or more fused aromatic rings made of carbon and hydrogen atoms. They are formed as a result of incomplete combustion of organic material both from natural events and human activities. N-PAHs are of primary concern because most of them are more carcinogenic than their parent PAHs, and also display a great degree of mutagencity. They occur in the environment in the vapor phase or absorbed to particulate matter. Photochemical reaction rate of 6-nitrochrysene (6-NC), 1,3-dinitropyrene (1,3-DNP), 1,6-dinitropyrene (1,6-DNP), 1,8-dinitropyrene (1,8-DNP), 1-nitropyrene (1-NP), and 2-nitropyrene (2-NP) were studied. The samples were premixed in methanol, diluted to a desired concentration with acetonitrile/water (80/20), then irradiated by UVA light (144 J/c[m.sup.2].h). The degradation of each compound was monitored by RP-HPLC. The peak intensity was recorded and plotted versus irradiation time, Ln [A] = Ln [A]0 -kt, to obtain reaction rate constant k and then degradation half-life, t1/2 = 0.693/k. 1,3-, 1,6-, and 1,8-DNP and 1- and 2-NP have half-lives of 60, 15, 20, 18, and 23 min, respectively. Photoproducts of all the above nitro-PAHs are being investigated. This research is supported by Army Research Office for student stipend and NIH SCORE S06GM08047.

THE ACCURATE CALCULATION OF RO-VIBRATIONAL EIGENENERGIES OF HOD

Jennifer L. Curry* and Joseph A. Bentley, Delta State University, Cleveland, MS 38733

We report the accurate calculation of ro-vibrational eigenenergies of the ground electronic state of the HOD molecule. The Radau coordinate system ([R.sub.1], [R.sub.2], [theta]) is employed. 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--this leads to a sparse Hamiltonian matrix. A primitive angular basis set is constructed which diagonalizes the rotational (J > 0) kinetic energy operator; subsequently, this basis is contracted through a series of diagonalizations of smaller Hamiltonian matrices. The final Hamiltonian matrix is then constructed out of this contracted angular basis set. The eigenvalues of this matrix are then obtained by using the Implicitly Restarted Amoldi Method (IRAM) which is part of a recently developed numerical package (ARPACK) designed to solve large scale eigenvalue problems.

SYNTHESIS AND ANALYSIS OF PHTHALOCYANINE DYES THAT ABSORB AT 680 TO 780 NM

Terry Jones (1)*, Amber J. Countryman (2), Guifa Su (2), and Robert P. Hammer (2), (1) Delta State University, Cleveland, MS 38733, and (2) Louisiana State University, Baton Rouge, LA

Phthalocyanines (Pcs) are near-IR fluorescence dyes, which have widespread biological and chemical applications due to their large extinction coefficients and good fluorescent quantum yields. Additionally, they have excellent chemical and photochemical stability. Absorbance and fluorescence can be altered easily by changing ring substituents or the metal center (Zn, Sn, Ga, Al, etc.). The downside is that the Pc dyes are hydrophobic and water insoluble. There have been experiments, however, which have found some water-soluble tetra- and octa-substituted Pcs by adding groups like sulfonates, carboxylates, or phosphonates. The overall goal of this research is to find near-IR fluorescent dyes to allow a multiplex of analytical methods. There are many different derivatives of the phthalocyanine dyes. Our synthesis of the dyes involved making and purifying a precursor, a phthalonitrile, and using it to synthesize a Pc. We synthesized our octasubstituted Pc by following similar procedures used to make other tetra- and octasubstituded dyes in the past. Zinc was used as the metal center for the dye, and the substituents were alkenes. The dye, 1,4,8,11,15,18,22,25-octakis(3-butenyloxy)phthalocyanine, was purified by column chromatography. The procedure gave high yields and pure products. Further tests were run to oxidize the substituent groups on the Pc without changing the entire structure of the Pc. These tests are run to determine if the dye will have a near-IR absorbance with different substituent groups, like carboxylic acids or esters. Finally, the Pcs were characterized by proton NMR, UV-VIS (200-800nm), and by measuring fluorescence and the lifetime.

AN AB INITIO STUDY OF C-H ... O HYDROGEN BONDING IN PEPTIDE MODELS

Amy Rowe, Delta State University, Cleveland, MS 38733

Hydrogen bonding involving the alpha carbon of a peptide backbone occurs frequently in proteins. Due to the lack of knowledge about the strength of these weak hydrogen bonds, however, the importance and function they serve in proteins is ambiguous--high level ab initio calculations performed on n-formy lalanine-amide and acetamide offer evidence of a hydrogen interaction between the alpha carbon of alanine with the carbonyl oxygen of acetamide. The geometries for n-formyl-alanine-amide and acetamide were optimized using density functional theory (DFT) at the BLYP level and 3-21G, 6-31G*, and 6-311G** basis sets. Scans of the CH ... O hydrogen bond distance at varying C-H ... O bond angles were computed at the 6311G**/MP2 level. Results show that the binding energies of some of the C-H ... O hydrogen interactions have sufficient strength. Therefore, C-H ... O hydrogen bonding and may be considered a factor in protein structure and function.

SURFACE ANALYSIS OF PLURONIC-TREATED SURFACES USING CONTACT ANGLE TESTING METHODS

Fayth Davis*, Shay Thigpen*, Sonya D. Benson, Chang K. Hong, and Sarah E. Morgan, University of Southern Mississippi, Hattiesburg, MS 39406

Pluronics are tri-block copolymers that contain poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) segments. Their surfactant abilities and compatibility in the human body make them of interest for potential biomedical applications. Studies show that the copolymer self-assembles onto a substrate depending on the characteristic of the substrate. For example, if the substrate is hydrophobic, the PPO segment of the Pluronics will adhere to the substrate, while the PEO segments remain to render the surface hydrophilic. We utilized contact angle measurements to analyze the surfactant properties of Pluronics when deposited onto hydrophobic substrates, including polystyrene and Teflon. Pluronics solutions of varying molecular weights and concentrations were evaluated. Effects of application method, concentration, polymer type and molecular weight on deposited films were explored. Varying levels of surface modification were observed.

GROWTH AND ISOLATION OF THE HYDROPHOBIN SC3 SECRETED BY THE WOOD-ROTTING FUNGUS SCHIZO-PHYLLUM COMMUNE

Ashley Grant*, Jeremy Yarbrough*, Sonya D. Benson, Chang K. Hong, Gordon C. Cannon, Charles L. McCormick, and Sarah E. Morgan, University of Southern Mississippi, Hattiesburg, MS 39406

Hydrophobins are a unique class of proteins discovered in the mid 1980s. These proteins exhibit remarkable self-assembly and high surface activity. The hydrophobin Sc3 secreted by the wood-rotting fungus Sc3 is the most surface active protein known to date and is highly studied for potential use in technical, cosmetic, pharmaceutical, and biomedical applications. Before the self-assembly and surface-active behavior of Sc3 can be analyzed, it must be isolated from the fungus Schizophyllum commune. The growth of the fungus and subsequent isolation of the protein Sc3 has proven to be significantly challenging to date with approximately 2 mg to 60 mg of Sc3 isolated from one liter of growth medium. We have chosen to explore various growth mediums and protein isolation methods and techniques to obtain consistent and increased yields of the hydrophobin Sc3. We have studied the effect of varying concentrations of sugar, amino acids, and salts to the growth medium of Schizophyllum commune. In addition, we have also explored the use of various protein separation techniques including hydrophobic interaction chromatography to obtain more highly purified yield of the hydrophobin Sc3.

STRUCTURAL AND THEORETICAL STUDY OF BERBERINE HEMISULFATE BY NMR AND COMPUTATIONAL CHEMISTRY

Sharon Hurley, Ming-Ju Huang, and Ken S. Lee*, Jackson State University, Jackson, MS 39217

The structure of berberine hemisulfate was analyzed by NMR Spectroscopy. A series of spectra of 1D and 2D NMR including long-range coupling were taken for the analysis. Every carbon and hydrogen was assigned based on the spectra taken and their chemical shifts were compared with other report. The structure of berberine has been fully optimized by ab initio methods. The [.sup.1]H and [.sup.13]C NMR chemical shifts of berberine hemisulfate were calculated by means of GIAO and other methods. The results from theoretical calculations were compared with experimental data for chemical shifts. The structure of berberine in the solid state was compared with our theoretical molecular properties.

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DETERMINATION OF CHROMIUM CONCENTRATION IN THE ACID-HYDROYZATE FROM SAWDUST BY ATOMIC ABSORTION SPECTROSCOPY.

Lenore Hicks, Delphine Woody, and Ken S. Lee*, Jackson State University, Jackson, MS 39217

In the project to produce ethanol from the sawdust via acid-hydrolysis and fermentation, the extruder made of stainless steel with a high concentration of sulfuric acid was used for hydrolysis of sawdust. High concentration of sulfuric acid erodes the metal and releases metal ions into the acid-hydrolyate in the process of hydrolysis. Therefore it is necessary to analyze metal ions in the solution. Especially the chromium ion needs to be determined, since this ion can harm the fermentation process later. The paste from the extruder was treated with water in a 1:1 weight ratio and the solution was analyzed by Atomic Absorption spectroscopy (AA). The analysis indicated that the solution had 20 ppm of chromium ion. The project is supported by DOE EPSCOR.

SYNTHESIS, STRUCTURAL, AND THEORETICAL STUDY OF AGMATINE DERIVATIVES VIA CYANOAMINE

Ken S. Lee (1)*, G.B. Yi (2), Ming-Ju Huang (1), and Lenore Hicks (1), (1) Jackson State University, Jackson, MS 39217, and (2) University of Mississippi Medical Center, Jackson, MS 39216

Two agmatine derivatives, (3-aminopropyl)guanidine and (trans-4-aminocyclohexyl)guanidine, were synthesized from cyanoamine and the corresponding diamines. [.sup.1]H and [.sup.13]C NMR were used to confirm the structures of the two products. The structures of synthesized agmatine derivatives were fully optimized by ab initio methods. The [.sup.1]H and [.sup.13]C NMR chemical shifts were calculated by means of GIAO and other methods. The results from theoretical calculations were compared with experimental data for chemical shifts.

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CHEMCAL EXCITATION OF TiO IN DIFFUSION FLAME

Chandra M. Pathak, Alcorn State University, Alcorn State, MS 39096

Electronic excitation of molecular species such as [C.sub.2], formed in the flame produced by burning butane in air, has been fairly well known. The study of such flames have yielded spectroscopic data of considerable interest and importance involving both the ground state and the upper electronic states of the molecules formed in the flames. The present study was undertaken in the expectation that under appropriate conditions of excitation in a diffusion flame, a diatomic or a tri-atomic species can be formed in an excited state and an electronic transition to a lower state may give rise to a new electronic band system in the molecule formed in the flame. Diffusion flames have in the past given rise to a number of new electronic band systems of several species as a consequence of the highly exothermic elementary reactions occurring in such systems which produce overpopulations of certain excited states, yielding emission that would be unobservable under thermal excitation. Four new electronic band systems were observed in the emission spectrum of a lowpressure diffusion flame of TiC[l.sub.4] plus oxygen burning in potassium vapor. The new systems, all if which lie in the ultraviolet region, are attributed to TiO. Two of them have also been observed in emission from a TiB[r.sub.4][O.sub.2]-K flame. One system appears to involve transition to the ground, [X.sup.3][DELTA][.sub.r] state. The lower state of the other three systems seems to be the low-lying singlet state of TiO. The new bands permit two new excited states to be located with some certainty : a triplet state at 32,000 c[m.sup.-1] and a [.sup.1][SIGMA] state at 30,970 c[m.sup.-1].

THE INTERACTION OF URIC ACID AND METAL CATIONS

R.N. Allen*, M.K. Shukla, and Jerzy Leszczynski, Jackson State University Jackson, MS 39217

A detailed investigation of the interaction of urate with L[i.sup.+], N[a.sup.+], and [K.sup.+] were carried out using a variationperturbation energy decomposition scheme defining sequence of approximate intramolecular interaction energy model. The geometries of urate metal complexes were optimized using Density Functional Theory Becke-3 parameter Lee, Yang, Parr (B3LYP) level employing the 6-311++G(d,p) basis set. The nature of potential energy surfaces was ascertained by harmonic vibrational frequency analysis. Our results show that the most electronegative area of the urate molecule is the N3 site which has the strongest affinity for metal cations.

SYNTHESIS AND CHARACTERIZATION OF TIN(IV) COMPLEXES OF DI-2-PYRIDYL [.sup.4]N-ETHYL AND [.sup.4]N--PHENYL THIOSEMICARBAZONE

Ramaiyer Venkatraman, Jackson State University, Jackson MS 39217

[alpha]-N-heterocyclic acetyl and formyl thiosemicarbazones and their metal complexes have been known for their cytotoxicity and inhibiting activity against DNA synthesis under controlled conditions. Under this class, several derivatives of formyl and acetylpyridines and their metal complexes bearing 4N mono and 4N4N-disubstituted compounds have been extensively studied. Due to their biological significance and proven capabilities as antifungal, anti-neoplastic and antilukemic agents, herein we present the synthesis, structure and characterization of some tin(IV) complexes of di-2-pyridyl ketone thiosemicarbazone, and their 4N-ethyl and phenyl derivatives. The ligands and complexes were characterized by FTIR, [.sup.1]HNMR, UV-Visible spectroscopic methods. The nature of these complexes was analyzed on the basis of their electrical conductivity measurement.

Divisional Talks

10:30 PREPARING OLIGOMERS OF MANDELIC ACID TO BE TESTED FOR ANTI-HIV ACTIVITY

Jelani Griffin (1)*, Victor Wyatt (2), and John A. Pojman (2), (1) Jackson State University, Jackson, MS 39217, and (2) University of Southern Mississippi, Hattiesburg, MS 39406

Mandelic acid, [C.sub.8][H.sub.8][O.sub.3], is an antiseptic commonly used for urinary tract infection. However, further research has shown that when reacted with sulfuric acid, the product can inhibit the replication of HIV-1. The racemic (+) or (-) mandelic acid was reacted with toluenesulfonic acid and benzene for synthesis using the Dean-Stark trap apparatus. Through mandelide synthesis, the product was obtained and characterized using gel permeation chromatography(GPC). From GPC analysis, it was determined that when synthesized, products are dimers rather than trimers. The R,R, S,S, and R,S oligomers were sent to the New York Blood Center to be test the anti-HIV-1 antiviral activity of the 3 compounds. They all were inactive. At the highest level used, 1.5 mg/ml, there was a slight reduction of virus production. No effect was seen at 0.75 mg/ml and higher 2-fold dilutions. The compounds also did not inhibit the binding of the virus surface protein to a soluble form of the cellular receptor.

10:45 INVESTIGATION ON SUICIDE INACTIVATION OF CHLOROPEROXIDASE

Jianping Xu*, Wei Lin* and Xiaotang Wang, Jackson State University, Jackson, MS 39217

Chloroperoxidase (CPO) is a highly versatile heme enzyme that catalyzes the transformation of a broad range of substrates. CPO catalyzes chlorination, epoxidation, hydroxylation and asymmetric sulfoxidation reactions at the expense of [H.sub.2][O.sup.2] or ROOH Many of these reactions, especially epoxidation of alkenes, can lead to enantiomerically enriched chiral products. Despite the extensive research on CPO catalyzed alkenes epoxidation, little is known about the mechansism of these reactions. A few mechanisms were proposed; all of them involved a key oxoiron intermediate. It is believed that the native enzyme(CPO)reacts with hydrogen peroxide to generate an oxoiron(IV) porphyrin cation radical species during both epoxidation and sucide inactivation. To confirm this mechanism, we investigated the CPO catalyzed epoxidation of allybenzene. The experiments were conducted with and without KCN. Without KCN, CPO was converted to an inactive green species which was consistent with previous reports. As evidenced by the red-shift 410 nm (to 418 nm) of the optical spectra of CPO. With the addition of KCN, the band red-shifted to 439 nm from original 400 nm, then quickly blue-shifted to 418 nm after the addition of hydrogen peroxide. It is well known that C[N.sup.-] is a more powerful ligand to F[e.sup.3+], the sixth ligand position of F[e.sup.3+] in active site must be occupied by C[N.sup.-] and this would prevent the formation of an oxoiron(IV) porphyrin cation radical species. The fact that CPOCN also afford the formation of green pigment of with allylbenzene suggests that there is alternative path to convert CPO to green species. This preliminary result showed that current mechanism on suicide inactivation via oxoiron(IV) intermediate deserves further investigation, at least for CPO catalyzed epoxidation of allybenzene.

11:00 MOLECULAR-LEVEL MIXING OF NOVEL POLYMER NANOBLENDS

Joshua U. Otaigbe, Eric Taylor, Dave Rhoades, and Denise Beitia*, University of Southern Mississippi, Hattiesburg, MS 39406

Molecular-level mixing of reactive polymers is an economic technique use to produce new polymers with enhanced properties and particular structures. A novel method was employed to prepare nanostuctured blends (nanoblends) of polypropylene (PP)/Polyamide 6 (PA6) and polypropylene (PP)/Polycarbonate (PC) using a Thermo Haake polydrive batch mixer. This research presents the system utilized to compatibilized PP/PA6 and PP/PC blends at different weight percents via in situ polymerization and in situ compatibilization. The PA6 and PC were synthesized via ring opening polymerization of [epsilon]-caprolactam (monomer of polyamide 6) and cyclic carbonate respectively. The torque measurements of the polydrive revealed that compatibilization took place in the reaction of the materials generating grafting polymers. The melting and crystallization rates of the PP/PA6 blend and the thermodynamic stability behavior of the PP/PC blend were studied using differential scanning calorimeter (DSC). This analysis determined that PP/PC blend crystallize fast a low temperature and PP/PA6 indicative that the level of compatibilization affects crystallization kinetics. The dynamic mechanical properties and thermomechanical behavior of these blends were accomplished by standard dynamic mechanical analysis (DMA). This study is able to indicate compatibilization on these blends leading to the improved of mechanical properties and the preparation of nanoscale polymer blends.

11:15 SYNTHESIS OF NOVEL STIMULI-RESPONSIVE, WATER-SOLUBLE NORBORNENE BASED MONOMERS FOR RING OPENING METATHESIS POLYMERIZATION

David Rankin* and Andrew B. Lowe, University of Southern Mississippi, Hattiesburg, MS 39406

Ring Opening Metathesis Polymerization (ROMP) is a variation of olefin metathesis in which the metal-catalyzed redistribution of carbon-carbon double bonds of strained cyclic alkenes leads to a ring-opened unsaturated polymer. The synthesis of norbornene-based monomers for ROMP is described. The monomers described are new functional, stimuli-responsive, water-soluble norbornene derivatives. The tertiary amine, 4-(2-dimethylaminoethyl)-4-azatricyclo[5.2.1.0]dec-8-ene-3,5-dione (DMAEATDD), is readily prepared from the reaction of N,N-dimethylethylenediamine with 4-oxa-tricyclo[5.2.1.0]dec-8-ene-3,5-dione. This monomer is particularly useful as a precursor to many novel stimuli-responsive cationic and zwitterionic monomers. We have derivatized DMAEATDD with both benzyl chloride and 1,3-propanesultone to yield the corresponding cationic and sulfopropylbetaine derivatives for aqueous ROMP. We have also started the synthesis of novel water-soluble Ru-alkylidene complexes, which will be used for the synthesis of novel stimuli-responsive polymers via ROMP.