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Contents

IDENTIFICATION OF FATTY ACIDS FOUND IN CORAL AND THEIR SYMBIOTIC ZOOXANTHELLAE. Juliet Bock and Mark Teece.

CHEMOTAXONOMIC STUDIES OF EUPHORBIA SPECIES FROM SOUTH AFRICA AND THE CANARY ISLANDS. Patrick Bowen and Jose-L. Giner

THE EFFECTS OF DROUGHT STRESS ON THE ACCUMULATION OF EPICUTICULAR WAXES ON LEAF TISSUE OF NICOTIANA GLAUCA. Kimberly D. Cameron1, Mark A. Teece2, and Lawrence B. Smart1.

INVESTIGATION OF LIGHT INTENSITY EFFECTING CHLOROTIC BEHAVIOR AND GROWTH IN AMERICAN CHESNUT CLONES GROWN IN VITRO. Jason Corwin, Sharon Bickel, Michael Satchwell,Gregory Boyer and Charles Maynard.

THE EFFECTS OF IRON ON THE GROWTH OF THE RED TIDE ALGA, Alexandrium tamarense. Katherine Duarte, Elizabeth Patchett, Mike Satchwell and Gregory L. Boyer

A FUNDAMENTAL PROBLEM IN ATMOSPHERIC CHEMISTRY. Melissa Ferenac and Theodore S. Dibble

FLUORESCENT PEPTIDE ANALOGS OF HIV-1 PROTEASE CLEAVAGE SITES. Amanda Fusco, Susan Young and Neil Price.

PROGRESS IN THE DEVELOPMENT OF CELLULOSE REINFORCED NANOCOMPOSITES. Maren Grunert and William Winter.

MICROPARTICLE DISPENSERS FOR THE CONTROLLED RELEASE OF INSECT PHEROMONES. Patrick J. Hennessy, Arthur J. Stipanovic and Francis X. Webster.

STRUCTURE EFFECTS ON ISOMERIZATION RATES: ETHERS AND ESTERS. Andrew S. Holloway and Theodore S. Dibble.

APPLICATION OF STABLE NITROGEN ISOTOPES TO STUDY PROTEIN STRESS AND METABOLISM. Andrew S. Holloway and Mark A. Teece

RECOVERY OF TRACE POLLUTANTS FROM AMBIENT WATERS USING THE TRACE ORGANICS PLATFORM SAMPLER (TOPS). Donald J. Hughes and John P. Hassett, Faculty of Chemistry, SUNY College of Environmental Science and Forestry, Syracuse, NY; and Simon Litten, Division of Water, NYS Dept. of Environmental Conservation, Albany, NY.

SEQUCING PEPTIDES USING THE NEW 600 MHZ NMR SPECTROMETER. David J. Kiemle1 and Gregory. L. Boyer21Analytical and Technical Services and 2 Faculty of Chemistry, SUNY College of Environmental Science and Forestry, Syracuse, NY 13210.   (djkiemle@syr.edu, glboyer@esf.edu ).

THE IMPORTANCE OF DIET TO AID IN THE CONSERVATION OF SEA TURTLES. Cynthia Lawniczak and Mark Teece, Faculty of Chemistry, 437 Jahn Lab, SUNY College of Environmental Science and Forestry, Syracuse, NY 13210.

HIGHLY DENSITY-CHARGED MOLECULE HEXANE HEXAACID. Nabila Lehachi, SUNY College of Environmental Science and Forestry, Syracuse, NY 13210

NEW CARBON MATERIALS BASED ON MPPO FOR DOUBLE LAYER CAPACITORS. Han Liu, Suoding Li, Youxin Yuan and Israel Cabasso, Polymer Research Institute, State University of New York - CESF, Syracuse, NY 13210.

MACROMOLECULE-INDUCED CLUSTERING AND CONTINUUM PERCOLATION. Sheng-Li Ma and Avik P. Chatterjee, Department of Chemistry, Jahn Laboratory, SUNY College of Environmental Science and Forestry, Syracuse, NY 13210.

DEVELOPMENT OF AN ENZYME ASSAY FOR FERRIC CHELATE REDUCTASE ACTIVITY IN WHOLE CELLS OF THE BROWN TIDE ALGA AUREOCOCCUS ANOPHAGEFFERENS.  Nicole M. Martin and Gregory L. Boyer, Faculty of Chemistry, 341 Jahn Lab, State University of New York College of Environmental Science and Forestry,  Syracuse, NY 13210.  (nmmartin@mailbox.syr.edu, glboyer@esf.edu)

THE CHARACTERIZATION OF ELECTRORHEOLOGICAL FLUIDS AND THE MODIFICATION OF VARIOUS PHYSICAL PROPERTIES. Harold O'Grady and co-author Dr. Arthur Stipanovic, Faculty of Chemistry, 230 Jahn Lab, SUNY College of Environmental Science and Forestry, Syracuse, NY 13210.

INDIVIDUAL PARTICLE ANALYSIS OF SUSPENDED SOLIDS IN CATSKILL/DELAWARE RESERVOIR SYSTEM. Feng Peng and Dr. David L. Johnson, Department of Chemistry, 439 Baker Lab, SUNY College of Environmental Science and Forestry, Syracuse, NY 13210.

EFFECT OF ALUMINUM, ZINC AND CHROMIUM ON THE GROWTH AND SIDEROPHORE FORMATION IN THE MYCORRHIZAL FUNGI WILCOXINA MIKOLAE. Jonelle Penschow, Guozhang Zou, Mike Satchwell and Gregory L. Boyer, Faculty of Chemistry, 341 Jahn Lab, SUNY College of Environmental Science and Forestry, Syracuse, NY 13210.

OPTIMIZATION OF A PROTEIN PHOSPHATASE INHIBITION ASSAY (PPIA) FOR DETECTION AND QUANTIFICATION OF MICROCYSTINS. Toan V. Tran, and Gregory L. Boyer, Faculty of Chemistry, 341 Jahn Lab, SUNY College of Environmental Science and Forestry, Syracuse, NY 13210.

TUNICAMYCIN BIOSYNTHESIS IN RESISTANT (TUNR) AND NON-RESISTANT (TUNNR) STREPTOMYCES LYSOSUPERIFICUS: EIGHT NEW TUNICAMYCINS. Billyana Tsvetanova and Dr. Neil Price, Department of Chemistry, 336 Jahn Lab, SUNY College of Environmental Science and Forestry, Syracuse, NY 13210.

NEW APPROACHES TO COUPLING SERINE PEPTIDES TO PROTEINS: PREPARATION OF A STABLE HAPTEN OF FERRICROCIN. Tzu-Pin Wang and Gregory L. Boyer, Department of Chemistry, SUNY-CESF, Syracuse, NY 13210.

Electrochemical Synthesis of Polysilanes. Xinwei Wang, Youxin Yuan and Israel Cabasso*, Polymer Reasearch Institute, State University of New York CESF, Syracuse, New York 13210.

The laser induced fluorescence (LIF) excitation spectra of 3-pentoxy and tert-pentoxy radicals and the kinetic study of 2-butoxy radicals.  Deng Wei, Chuji Wang, Liat Shemesh, Michael Lilien, David R. Katz, Gregory Gawinski, and Theodore S. Dibble, Faculty of Environmental and Forest Chemistry, 121 Jahn Laboratory, SUNY College of Environmental Science and Forestry, Syracuse, NY 13210.

DETECTION OF THE CYANOBACTERIAL TOXIN, ANATOXIN-A, IN NATURAL WATERS. Xingye Yang and Gregory L Boyer, State University of New York, College of Environmental Science and Forestry, Syracuse, NY 13210.

SAMPLING FOR POLYCYCLIC AROMATIC HYDROCARBONS USING A PASSIVE IN-SITU CONCENTRATION EXTRACTION SAMPLER. Kate Zakharov, Jocelyn M. Polito, John P. Hassett, Faculty of Chemistry, 435 Jahn Laboratory, SUNY College of Environmental Science and Forestry, Syracuse, NY.

STUDIES ON STIMULI RESPONSIVE FLUIDS BASED ON MODIFIED CELLULOSE MATERIALS. Shengbin Zhang, Arthur Stipanovic and William T. Winter, Department of Chemistry and the Cellulose Research Institute, Jahn Laboratory, SUNY College of Environmental Science and Forestry, Syracuse, NY 13210.


Abstracts

IDENTIFICATION OF FATTY ACIDS FOUND IN CORAL AND THEIR SYMBIOTIC ZOOXANTHELLAE. Juliet Bock and Mark Teece, Faculty of Chemistry, 417 Jahn Lab, SUNY College of Environmental Science and Forestry, Syracuse, NY 13210.

Coral reef ecosystems provide essential nutrients to surrounding marine life despite their nutrient poor locations. They retain these nutrients through their efficient system of recycling. Corals are composed of communities of simple colonial organisms called polyps. Polyps contain the coral's symbiotic algae, the zooxanthellae. It is the translocation of nutrients between the coral and the zooxanthellae that make its system of recycling nutrients so efficient. The coral feeds heterotrophically by capturing prey and autotrophically by receiving translocated products of photosynthesis from the zooxanthellae. A combination of fatty acid and stable isotope analysis can indicate the role that zooxanthellae play in the nutrition and general health of the coral. Fatty acid analysis of Acropora palmata, a branching coral, shows similar lipid compounds in both the zooxanthellae and coral host. Specifically, C14, C16, C18:0, C18: 2 and C18: 3 fatty acids were found to be present in the organic matter of the Acropora palmata coral and zooxanthellae. Additionally, C18: 1 and C18: 4 fatty acids were found in the animal but not in the zooxanthellae, suggesting that these compounds were synthesized by the animal. Further analysis by stable isotope mass spectrometry will determine the identity of translocated fatty acids.

 

CHEMOTAXONOMIC STUDIES OF EUPHORBIA SPECIES FROM SOUTH AFRICA AND THE CANARY ISLANDS. Patrick Bowen, Dept of Environmental & Forest Biology, and Jose-L. Giner, Dept of Chemistry SUNY College of Environmental Science & Forestry

The genus Euphorbia is widely distributed in the arid zones of the southern hemisphere. These plants produce latex, a defensive milky secretion that is rich in various triterpenoid and 4a-methyl steroid compounds. The triterpenoid and 4a-methyl steroid components of the latex of euphorbias from southern Africa and the Canary Islands were analyzed with the intent of discerning taxonomic differences among species widely separated in space. Individual compounds were isolated using a regimen of extraction, thin layer chromatography (TLC), and high pressure liquid chromatography (HPLC) and identified using proton nuclear magnetic resonance (1H-NMR). Relatedness among the plants was determined based upon the presence and relative proportions of various triterpenoid and 4a-methyl steroid compounds.

 

THE EFFECTS OF DROUGHT STRESS ON THE ACCUMULATION OF EPICUTICULAR WAXES ON LEAF TISSUE OF NICOTIANA GLAUCA. Kimberly D. Cameron1, Mark A. Teece2, and Lawrence B. Smart1. 1Faculty of Environmental and Forest Biology; 2Faculty of Chemistry, SUNY College of Environmental Science and Forestry, Syracuse, NY 13210

Nicotiana glauca plants that have been subjected to periodic drying in a growth chamber display a glaucous appearance on the leaf surface suggesting that one way N. glauca plants respond to drought stress is by increasing cuticular wax deposition. In this work we have used low kV scanning electron microscopy (SEM) to observe the epicuticular wax on the adaxial surface of leaves. Plants that have been periodically dried exhibit an increase in wax load over time, over both epidermal cells and guard cells. We have also extracted the methylene chloride soluble surface lipids from the adaxial and abaxial surfaces of N. glauca leaves and used GC and GC-MS to identify and quantify components of the wax. We have identified C28-C31 alkanes as well as C24, C26, and C28 alcohols. Of all the alkanes extracted, triacontane (C31 alkane) was found in the highest proportion. To determine the effects of drought stress on the accumulation of specific components in the cuticular waxes we have also analyzed the epicuticular wax from plants that have been periodically dried. Here we present a comparison of wax extracted from plants that have been well watered vs. plants that have been subjected to periodical drying. This work was supported by the McIntire-Stennis program of the U.S.D.A.

 

INVESTIGATION OF LIGHT INTENSITY EFFECTING CHLOROTIC BEHAVIOR AND GROWTH IN AMERICAN CHESNUT CLONES GROWN IN VITRO. Jason Corwin1, Sharon Bickel1, Michael Satchwell2,Gregory Boyer2 and Charles Maynard1, 1Faculty of Forestry and 2Faculty of Chemistry, 217 Marshall Hall, SUNY College of Environmental Science and Forestry, Syracuse, NY 13210.

Although difficult to work with, our laboratory contains a large number of chestnut shoots grown in vitro, or in tissue culture, for genetic engineering. Recently a significant number of individuals exhibited chlorosis. A possible factor was the varying light intensities from each rack of lights within the light bench. Light intensity on the different shelves was tested. Three intensities were selected and labeled as low (40.69mmol s-1m-2 per mA), intermediate (83.19mmol s-1m-2 per mA) and high (137.97 mmol s-1m-2 per mA). Three clones of American chestnut (Castanea dentata) were chosen to represent the various sources of stock plants. The first, M3 x M4 Clone 4, is derived from pure American chestnut embryos. The second is Iowa #2, and is seedling derived from a pure American chestnut. Douglas is a seedling-derived culture that is a hybrid between an American chestnut and a Chinese chestnut (Castanea mollissima). Each light intensity contained four cubes of each clone. Every 4 weeks for 2 months the shoots were measured for height and tested for chlorophyll and pheophytin, a chlorophyll break down product. The embryonic clone (M3 x M4 Clone 4) grew well under all intensities, showing growth of over a centimeter per month in each light intensity. The long term testing showed no comparable difference in growth. Iowa #2 showed decreasing heights as light intensity increased as well as possible long term stunted growth. Douglas exhibited a high affinity to the intermediate intensity, growing as much as 3 cm on the average. Over the long term, Douglas grew 2 times taller in the intermediate compared to the high intensity light. Plantlet leaves were used for chlorophyll extraction and evaluation with a Beckman DU640 spectrophotometer. Analysis of all three clones under all three light intensities showed a correlation of higher light intensity with a decrease in chlorophylls a and b. In conclusion, a light level between 40.69 and 83.19 mmol s-1m-2 per mA is favored for optimal growth and vigor of plantlets.

 

THE EFFECTS OF IRON ON THE GROWTH OF THE RED TIDE ALGA, Alexandrium tamarense. Katherine Duarte, Elizabeth Patchett, Mike Satchwell and Gregory L. Boyer, Faculty of Chemistry, 341 Jahn Lab, SUNY College of Environmental Science and Forestry, Syracuse, NY 13210 (esfkat@yahoo.com, elpatche@syr.edu, glboyer@esf.edu ).

The red tide alga, Alexandrium tamarense, is a toxin-producing dinoflagellate which can cause ecological and economic damage. During a red tide bloom, the abundance of the organism turns the water a red color and produces several toxins. These toxins will accumulate in shellfish feeding on the algae. Consumption of these toxic shellfish causes a condition known as paralytic shellfish poisoning or PSP, which can be fatal to humans, shore birds and other marine life. Very little is known about those factors that cause a red tide. These blooms can re-occur annually in an area or show up in a new area and not be seen again for several years. We are trying to determine the role of the environmental iron concentration in the growth of this organism. To investigate this, Alexandrium tamarense is grown in polycarbonate flasks containing artificial seawater with a series of iron concentrations between 0 and 11uM added iron. Growth was measured by in vivo fluorescence. Cultures grew well on 1 and 11uM added iron but showed signs of limitation at levels below these concentrations. Cells showed some acclimation to different concentrations of added iron, suggesting that the cells were capable of storing excess iron. A detailed analysis of their initial growth rates and maximal cell yields using different artificial and natural chelators is currently in progress. To determine how these cells obtain their needed iron, their ferric chelate reductase activity was measured on whole cells using the assay developed by Nicole Martin in our laboratory. FCR is an enzyme used to reduce iron and increase its bioavailability. This enzymatic activity was present in iron-deficient cells and showed little preference for NADPH over NADH. Further characterization of this activity is currently in progress.

 

A FUNDAMENTAL PROBLEM IN ATMOSPHERIC CHEMISTRY. Melissa Ferenac and Theodore S. Dibble, Department of Chemistry, SUNY- College of Environmental Science and Forestry, Syracuse, NY 13210.

ROOo and NO react to form ROONO, which is an unstable molecule with a very short lifetime. ROONO will either isomerize to RONO2 or break apart to form an alkoxy radical, ROo, and NO2. Isomerization may also result in the eventual formation of an alkoxy radical and a nitrite molecule by photolysis of RONO2 if the photolysis occurs before RONO2 is stabilized by collisions. Once stabilized, RONO2 may travel significant distances before it reacts to form an alkoxy radical. The concentration of alkoxy radicals in the troposphere (0-12 km in altitude) strongly influences ozone concentrations at lower altitudes. This ozone is not contributing to the protective layer of ozone at 15 km, but is contributing to global warming and urban smog. If ROONO breaks apart, then air quality will be adversely affected in the area local to the source of ROOo. If ROONO forms RONO2, then ozone may be produced hundreds of miles away. It is important to know the fate of ROONO to plan smog reduction in urban areas and assess effects of different types of pollution sources. The activation energies for isomerization and decomposition of ROONO largely determine which reaction is more likely. Activation energies are determined by the energies of the transition states of reactions. We are using computational chemistry programs to find the transition state for the isomerization of peroxynitrous acid to nitric acid: HOONO ® HONO2. This reaction may be important in its own right in explaining certain observations about the pressure dependence of the OH + NO2 reaction. Furthermore, transition state geometries for this isomerization and the isomerization of larger ROONO compounds should be similar, and this geometry will be used as a building block for determining the transition states for the atmospherically relevant isomerization reactions.

 

FLUORESCENT PEPTIDE ANALOGS OF HIV-1 PROTEASE CLEAVAGE SITES. Amanda Fusco*, Susan Young and Neil Price*, *Dept. Chemistry, Jahn Lab, SUNY-ESF, Syracuse, NY and Bio-Tech Imaging, Inc., Frederick, MD

The HIV protease is expressed as a part of the viral Gag-Pol polyprotein, and is unusual in being able to selectively hydrolyze Phe-Pro (FP) and Tyr-Pro (YP) sequences. Indeed, three of the eight consensus sequences cleaved by HIV-1 protease involve F/T-Pro bonds, and most strategies for the design of drugs against the HIV protease are based on transition state analogs of these cleavage sites. Here we report the synthesis of a series of fluorescent peptidyl analogs of the HIV-1 protease FP/TP cleavage sites using a solution phase approach with N-dansylated and O-benzoyl protected residues in the presence of 1,3-dicyclohexylcarbodiimide. Selective deprotection with TFA affords good yields of fluorescently-tagged peptides that have been characterized by reverse-phase HPLC with diode array detection (DAD) and coupled electrospray MS. Bio-Tech Imaging, Inc. has developed a receptive cell line (OCL) that will be used in an infectivity reduction assay to determine the efficacy of these drugs to inhibit infection by a IIIB strain isolate of HIV-1. The end point determination will be measured using BTI's HIV-1 Cell Separation Kit.

 

PROGRESS IN THE DEVELOPMENT OF CELLULOSE REINFORCED NANOCOMPOSITES. Maren Grunert and William Winter, Cellulose Research Institute and Department of Chemistry, SUNY-ESF, 121 Edwin C. Jahn Laboratory, Syracuse, NY 13210.

Cellulose nanocrystals and topochemically trimethylsilylated cellulose nanocrystals were prepared from bacterial cellulose. The crystals were characterized by FTIR and CP/MAS NMR spectroscopy, x-ray diffraction, and transmission electron microscopy. The surface derivatization was investigated as a function of reaction time. The trimethylsilylation appeared to be completed after 18 hours. Nanocomposites were prepared with crosslinked polydimethylsiloxane as matrix and unreacted or surface trimethylsilylated cellulose crystals as particulate phase. The nanocomposites were characterized by dynamic mechanical analysis. A reinforcement with respect to the pure matrix was observed for both the composite with unreacted and the composite with trimethylsilylated crystals. The extent of reinforcement depended strongly on temperature, oscillation frequency and surface chemistry of the particulate phase.

 

MICROPARTICLE DISPENSERS FOR THE CONTROLLED RELEASE OF INSECT PHEROMONES. Patrick J. Hennessy, Arthur J. Stipanovic and Francis X. Webster, Department of Chemistry, SUNY College of Environmental Science and Forestry, 230 Jahn Laboratory, One Forestry Drive, Syracuse, NY 13210, USA. <E-mail: pahennes@syr.edu>

Pheromones play a very important role in the world of insects. In most cases, females will emit pheromones to attract a male to mate. For many insects, the specific mating pheromone has been characterized and can now be synthesized in large quantities in the laboratory. This allows us to use these synthetic pheromones in monitoring pest population, mass trapping, and in mating disruption. The main focus of this project is to try and improve upon existing controlled release technology used for mating disruption. Currently, dispensers used for mating disruption are relatively large, non-biodegradable, and require application by hand. In this project, micron-sized biodegradable pheromone dispensers have been fabricated and release rates studied using an "aeration" procedure as well as Thermal Analysis (TGA, DSC). Preliminary work with microcrystalline cellulose (MCC) particles has shown that the evaporation rate for the Gypsy and Codling Moth pheromones can be modified through adsorption of these compounds onto the cellulosic substrate. To further control evaporation rate, MCC particles can be coated with biodegradable polymers, including cellulose derivatives and other polysaccharides.

 

STRUCTURE EFFECTS ON ISOMERIZATION RATES: ETHERS AND ESTERS. Andrew S. Holloway and Theodore S. Dibble, 421 Jahn Lab, SUNY College of Environmental Science and Forestry, Syracuse, New York 13210.

The reactions of alkoxy radicals have a very important part in chemistry of the troposphere because of their role in smog formation during the degradation of organic compounds. Three main pathways alkoxy radicals may undergo are reaction with O2, decomposition, and isomerization. Very little information on isomerization is currently available, however, it is quite important. Isomerization of alkoxy radicals leads to prompt production of two molecule of O3, whereas the O2 reaction leads to only one molecule of O3. Studies have been done on the degradation pathways of similar molecules such as methyl-tert-butyl ether, dimethyl ether and diethyl ether, but products of the isomerization reaction were either not detected, could not be analyzed, or were neglected in the analysis. The goal of this project is to learn how an internal oxygen affects the isomerization rate of small alkoxy radicals. Standard quantum chemistry methods are applied to several short chain etheric and esteric compounds, which are models for the larger compounds of greater atmospheric interest.

 

APPLICATION OF STABLE NITROGEN ISOTOPES TO STUDY PROTEIN STRESS AND METABOLISM. Andrew S. Holloway and Mark A. Teece, Faculty of Chemistry, 415 Jahn Lab, SUNY College of Environmental Science and Forestry, Syracuse, New York 13210.

Urea and uric acid are the byproducts of protein metabolism in terrestrial mammals. The concentrations of these two compounds in the system will vary depending on the protein metabolism and catabolism rates. Rates can change as the result of the system undergoing stress. However, the change in concentration may be low enough such that it is below the detection limit of standard analytical methods. Because of this, we will study the stable isotopic fractionation of nitrogen species to measure the concentration change. Although N14 and N15 have the same physical and chemical properties, on an isotopic level, N14 reacts faster because it is isotopically light; it has one less neutron than N15. Variations in this ratio can be detected before there is a measurable change in urea and uric acid concentrations. If we know what the "ambient" fractionation is, we can determine when the system is experiencing stress because the fractionation will change. This change can then be related to an increase or decrease in protein metabolism in organisms. The potential applications of this stable isotope technique are far ranging including use in animal physiology and ecology.

 

RECOVERY OF TRACE POLLUTANTS FROM AMBIENT WATERS USING THE TRACE ORGANICS PLATFORM SAMPLER (TOPS). Donald J. Hughes and John P. Hassett, Faculty of Chemistry, SUNY College of Environmental Science and Forestry, Syracuse, NY; and Simon Litten, Division of Water, NYS Dept. of Environmental Conservation, Albany, NY.

A popular system for measuring trace organics in ambient waters uses glass fiber filters, followed by XAD resin, a styrene-divinylbenzene copolymer. The Trace Organics Platform Sampler (TOPS) is such a system, designed and fabricated by the New York State Department of Environmental Conservation. The filtered solids and resin-bound fractions are operationally defined as "particulate" and "soluble," respectively. We have evaluated the TOPS with respect to its ability to fully capture soluble trace organic compounds, including dieldrin, DDT, and PCBs. In experiments using two XAD columns in series it was found that the "soluble" trace organics are incompletely captured. This data was used to estimate overall extraction efficiencies: the observed capture of individual PCB congeners by the first column ranged from nearly 100% to under 50%, while dieldrin and chlordane averaged 50 to 56%. It is likely that actual efficiencies are lower, due to the loss of compounds beyond the second column. The relationship with octanol-water partition coefficient was found to be complex. Efficiencies generally decreased with increasing hydrophobicity. Also, waters with high dissolved organic matter tended to have the poorest extractability. Taken together, this supports the hypothesis that dissolved organic matter is interfering with the extraction of hydrophobic compounds.

 

SEQUCING PEPTIDES USING THE NEW 600 MHZ NMR SPECTROMETER. David J. Kiemle1 and Gregory. L. Boyer21Analytical and Technical Services and 2 Faculty of Chemistry, SUNY College of Environmental Science and Forestry, Syracuse, NY 13210.   (djkiemle@syr.edu, glboyer@esf.edu ).

As part of the construction of the new Jahn Laboratory for Chemical Research, SUNY-ESF has invested in the acquisition of several pieces of major chemical instrumentation. This instrumentation opens up new opportunities and approaches for the solving basic biological problems.  Here we describe the use of the new Bruker AVANCE 600 MHz NMR spectrometer for the sequencing of small peptides using pulse field gradients.

Sequencing peptides is done in several distinct experiments.  First, one must identify the signals associated with the individual amino acid residues.  In step one, the individual proton and carbon signals are obtained using a simple 1-D proton and carbon NMR spectrum.  Those hydrogen’s that are adjacent to each other are identified using a 2-D experiment referred to as a COSY.  For other hydrogen’s in the same amino acid residue, their connectivity within the specific amino acid can be determined using a TOCSY experiment.  Carbon signals are assigned using a DEPT experiment that tells the number of protons attached to each carbon.  Further confirmation of those signals is obtained using a HMQC experiment that links each carbon to protons directly attached to that carbon.  By combining the results of these five experiments, a clear picture of the signals from each individual amino acid residues and their “R” group is obtained.  The proton on the amide linkage of the peptide bond can be included in this same connectivity pattern by running the experiment in a mixture of 90% distilled water and 10% deuterated water.  This sets us up for the next stage; namely linking the different amino acid residues together in their proper sequence.  An HMBC experiment will link this amide proton of the peptide bond with its adjacent carbonyl carbon.  The same experiment will link the >CHR proton of the adjoining amino acid residue with the same carbonyl carbon.  This allows us to tell which amino acids are adjacent to each other.  Confirmation of this assignment is obtained using a ROESY experiment.  This experiment tells us what “R” groups (including their >CHR proton) are nearby in 3-dimensional space.  Once you have assigned two residues, you simply move down the peptide chain and assign the next residue. This technique will be illustrated using the model tetrapeptide: Valine-Glycine-Serine-Glutamate.  The entire sequencing experiment took a single weekend using a 5 mg sample and was totally non-destructive.  The entire peptide was recovered after the experiment by simply removing the water. 

 

THE IMPORTANCE OF DIET TO AID IN THE CONSERVATION OF SEA TURTLES. Cynthia Lawniczak and Mark Teece, Faculty of Chemistry, 437 Jahn Lab, SUNY College of Environmental Science and Forestry, Syracuse, NY 13210.

Sea turtle populations around the world are declining, perhaps as a result of destruction of their foraging areas. However, little is known of the dietary needs of turtles, particularly during reproduction and breeding. In this study, the red-bellied turtle is used as a model to determine the importance of diet in producing a healthy hatchling. Initially, metabolic processes that occur during turtle hatchling development within the egg are examined in order to understand how nutrients from the mother are passed on to the hatchling. Then it can be determined which of these are essential for growth and development. To do this, the organic components from the yolks of eggs at different stages in embryonic development were analyzed to observe the changes that occur. Preliminary results indicate that C16 monounsaturated fatty acids are present in large amounts initially, but are rapidly utilized within 36 days. The organic extracts will be further characterized into specific lipid classes to get a more detailed picture of the metabolic and chemical processes which occur during development. The future goal is to determine the essential dietary contents of both freshwater and sea turtles during the gestation period.

 

HIGHLY DENSITY-CHARGED MOLECULE HEXANE HEXAACID. Nabila Lehachi, SUNY College of Environmental Science and Forestry, Syracuse, NY 13210

Hexane hexa acid is a molecule that contains four different chiral centers. That makes this compound consist of six diestereomers: two Miso and four pairs of enantiomers. My work consists of separating these six different diestereomes by recrystallizing the crude in diethyl ether using different techniques. This involve a great work of proton and carbon thirteen NMR.

 

NEW CARBON MATERIALS BASED ON MPPO FOR DOUBLE LAYER CAPACITORS. Han Liu, Suoding Li, Youxin Yuan and Israel Cabasso, Polymer Research Institute, State University of New York - CESF, Syracuse, NY 13210

Double layer capacitors are energy storage devices which can store more energy (20-200 times) than conventional capacitors. Since there is no chemical reaction involved, the double layer capacitors can discharge the stored energy much faster than conventional rechargeable battery and their cycle life is much longer. B.E. Conway, et al., described the application of double layer capacitor modules in EV as a load-leveling device for batteries. Similar concept can also be applied to EVs based on fuel cells. (Demonstration will be set up during the poster session to show the combination of double layer capacitors and PEM fuel cells in the EVs.) Carbon-carbon composites have long been adopted as the major form of double layer capacitor electrodes. Compared to other forms, such as polymer/carbon composites, carbon-carbon composites have higher electrical conductivity and they are easier to control during the fabrication processes of the capacitors. Carbon/carbon composites based on poly(phenylene oxide) (PPO), in forms of carbon fiber reinforced carbon paper and carbon particle based pellets (CPBP), has been developed and are fabricated in this laboratory. PPO derived polymeric carbon has some unique properties comparing to other common polymeric carbons, such as phenolic resin based carbons. The PPO based polymeric carbon shows good electric conductivity (i.e. better than 16 s/cm) at relatively low heat treatment temperatures (i.e. less than 900 oC). Without further activation treatment, the PPO polymeric carbons have high specific surface area (i.e. more than 500 m2/g), which fits the requirements for effective double layer capacitors, other energy storage devices and adsorption related applications. Since the PPO based polymeric carbon has relatively high surface area without any further treatments, the PPO based carbon electrode has a specific capacitance of 22 F/g. The phenolic resin based electrodes performed poorly in the tests. Capacitors based on PPO carbons achieved ~60 F/g after further activation with metal hydroxides.

Acknowledgements. This work has been supported by Polymer Research Institute, State University of New York - ESF, and by Niagara Mohawk Corporation, Gas Division, Syracuse, NY.

 

MACROMOLECULE-INDUCED CLUSTERING AND CONTINUUM PERCOLATION. Sheng-Li Ma and Avik P. Chatterjee, Department of Chemistry, Jahn Laboratory, SUNY College of Environmental Science and Forestry, Syracuse, NY 13210.

In recent years, traditional methods of liquid-state theory have been applied to understand the formation of percolating networks in fluids composed of small, spherical molecules. We investigate a generalization of this approach to a two-component fluid composed of hard spheres and either flexible or rigid rod-like macromolecules within the Percus-Yevick approximation. The threshold density at which the spheres form a percolating network is studied as a function of the relative size ratio between the spheres and macromolecules, and the macromolecular packing fraction. Correlations with the macromolecule-induced second virial coefficient between the spheres are examined, and compared with predictions based on the adhesive hard sphere model. The threshold density for sphere percolation is found to depend strongly on macromolecular architecture and size disparity, and in all cases is significantly greater than would be expected based on the adhesive sphere model with matched sphere-sphere second virial coefficients. Significant discrepancies are found with respect to an effective one-component model in which the spheres alone are represented explicitly, with the macromolecules accounted for at the level of an effective induced pair potential.

 

DEVELOPMENT OF AN ENZYME ASSAY FOR FERRIC CHELATE REDUCTASE ACTIVITY IN WHOLE CELLS OF THE BROWN TIDE ALGA AUREOCOCCUS ANOPHAGEFFERENS.  Nicole M. Martin and Gregory L. Boyer, Faculty of Chemistry, 341 Jahn Lab, State University of New York College of Environmental Science and Forestry,  Syracuse, NY 13210.  (nmmartin@mailbox.syr.edu, glboyer@esf.edu)

There are two main acquisition strategies for iron in the plant kingdom.  One involves the secretion by the cell of small iron-binding compounds that serve to chelate iron and increase its solubility.  The other strategy involves a membrane-bound reducing enzyme called ferric chelate reductase (FCR).  FCR serves to reduce iron to its more soluble Ferrous (Fe II) form and also increases its availability to the organism.  Previous experiments1 have shown that the brown tide alga Aureococcus anophagefferens uses this latter approach, i.e. FCR, to obtain its needed iron.  This FCR activity is constitutively expressed and can use either NADH or NADPH as its source of electrons.  These experiments were done by grinding cells to prepare active enzyme extracts.  We were interested to see how the whole cell FCR activity would compare to these previous results using cell extracts.  FCR activity was measured by incubating buffered cells with ferric HEDTA (an iron-III source), NAD(P)H and the iron-II detection reagent ferrozine. The absorbance of ferrozine was monitored at 562 nm over 10 min and the enzyme rate determined by linear regression. Optimal results required 10 mM added ferric HEDTA and 1 mM NAD(P)H.  Using these conditions, changing the number of cells added to the assay mix resulted in a corresponding change in measured enzyme activity.  At higher concentrations of iron or nucleotide, the non-enzymatic reduction of iron obscured the measurement of any enzymatic reduction of iron.  This whole cell activity was characterized for its substrate kinetics and showed a nucleotide preference of NADPH over NADH.  These results are similar to those previously observed using extracts of FCR from Aureococcus anophagefferens.

1 D. B. Nichols, (2000) Iron and nitrogen utilization in the brown tide alga, Aureococcus anophagefferens.  M.S. thesis, SUNY-CESF.

THE CHARACTERIZATION OF ELECTRORHEOLOGICAL FLUIDS AND THE MODIFICATION OF VARIOUS PHYSICAL PROPERTIES. Harold O'Grady and co-author Dr. Arthur Stipanovic, Faculty of Chemistry, 230 Jahn Lab, SUNY College of Environmental Science and Forestry, Syracuse, NY 13210.

Electrorheological fluids exhibit a unique physiochemical property in that they can be transformed to a semi-solid upon the application of a voltage. This transformation occurs on a millisecond time scale, is reversible, and is directly proportional to the applied voltage: typically 1000 to 3000 volts per millimeter of fluid. As a result, ER fluids can be exploited in a number of vibration dampening or force transmission applications. ER fluids are generally comprised of electrically polarizable particles dispersed in a non-conducting base fluid. The effectiveness of an ER fluid is based primarily on optimizing the particle and base fluid properties. In this study, the rheology of commercially available and "developmental" ER fluids was tested using a parallel plate rheometer in which controllable factors such as the shear rate and level of voltage were used for comparing fluids in terms shear stress, viscosity, etc., which are important application parameters. Experimental results for semi-conducting carbon particles in a hydrocarbon-based fluid will be shown. The experimental data indicated that there is a direct correlation of ER effectiveness for each carbon sample and the level of conductivity within the fluid.

 

INDIVIDUAL PARTICLE ANALYSIS OF SUSPENDED SOLIDS IN CATSKILL/DELAWARE RESERVOIR SYSTEM. Feng Peng and Dr. David L. Johnson, Department of Chemistry, 439 Baker Lab, SUNY College of Environmental Science and Forestry, Syracuse, NY 13210.

Suspended solids in water column are the cause for observed turbidity (Tn), an important water quality criterion. Since there is a linear relationship between turbidity and total particle cross sectional area per unit volume (PAV) [1], it is possible to predict turbidity from measured PAV. Scanning Electron Microscopy (SEM) equipped with X-ray microanalysis is able to measure not only the PAV but also the X-ray compositions of the particles. By classifying particles into generic geochemical types according to their elemental compositions, we can apportion turbidity to different particle types, such as clay, quartz, and diatom. This technique of individual particle analysis (IPA) is employed in our research to measure PAV for six New York City drinking water reservoirs. We have found that a simple linear model can explain more than 85% of the variability for over 350 observed turbidity values. More importantly, turbidity can be apportioned to different particle types. This is extremely useful for the water quality management, as it provides information for particle source and origin. The temporal and spatial trends for generic particle types are direct evidence for relating both the internal (chemical precipitation and primary production) and external (tributary transport) impacts to the system.

1. Treweek, G.P. and J.J. Morgan (1980). Prediction of suspension turbidities from aggregate size distribution. In: M.C. Kavanaugh and J.O. Leckie (eds.) Particulates in water, advances in chemistry series No. 189, American Chemical Society, Washington, D.C.

 

EFFECT OF ALUMINUM, ZINC AND CHROMIUM ON THE GROWTH AND SIDEROPHORE FORMATION IN THE MYCORRHIZAL FUNGI WILCOXINA MIKOLAE. Jonelle Penschow, Guozhang Zou, Mike Satchwell and Gregory L. Boyer, Faculty of Chemistry, 341 Jahn Lab, SUNY College of Environmental Science and Forestry, Syracuse, NY 13210.

The mycorrhizal fungus Wilcoxina mikolae produces the small peptide siderophore, ferricrocin, under iron-limiting conditions. This peptide solubilizes iron and promotes its uptake by the organism. In addition to forming complexes with iron, ferricrocin also forms stable complexes with other metals. This complex formation may be an artifact of the siderophore chemistry. It may also protect the organism against heavy metal toxicity by lowering the "free" metal concentration. If so, then siderophore formation should be beneficial to Wilcoxina exposed to increased concentrations of heavy metals. Alternatively, if the siderophore-metal complex is recognized by the uptake receptor, then siderophore production would increase the toxicity of the metal by providing an alternate route for metal uptake. To test these hypotheses, pure cultures of Wilcoxina mikolae were grown in defined culture using trace metal clean techniques. Iron-replete (10 µM) and iron-limited cultures were grown in the presence of 0, 0.1 and 0.5 mM aluminum; 0, 0.5 and 5.0 mM zinc; or 0, 0.01, 0.1 and 1 mM chromium. Samples from each treatment were harvested weekly for eight weeks. Growth was measured as dry weight and siderophore formation was determined using the HPLC 55Fe-binding assay. For all treatments, growth was significantly less in iron-limited, as compared to, iron-replete cultures. The higher concentrations of both zinc and chromium were toxic to the cell and totally inhibited growth. At lower concentrations, addition of both chromium and zinc stimulated siderophore production in the -Fe cultures. However this stimulation did not result in an increase or decrease in growth, suggesting that formation of the siderophore-metal complex did not significantly change the movement of metal into the cell. In contrast, the addition of higher concentration of aluminum increased the growth of iron-replete cultures and, inhibited the growth of iron-limited cultures. Aluminum did affect the siderophore production with decreased levels of siderophore formation at the higher aluminum concentration. While suggesting that siderophore- mediated uptake may be important for the uptake of Al, aluminum does not induce siderophore synthesis. Further studies are in progress. Supported by the USDA Soils and Soil Biology Program.

 

OPTIMIZATION OF A PROTEIN PHOSPHATASE INHIBITION ASSAY (PPIA) FOR DETECTION AND QUANTIFICATION OF MICROCYSTINS. Toan V. Tran, and Gregory L. Boyer, Faculty of Chemistry, 341 Jahn Lab, SUNY College of Environmental Science and Forestry, Syracuse, NY 13210. (glboyer@esf.edu)

Microcystins are a family of hepatotoxic peptides. They are produced by a large number of unicellular cyanobacteria included the common Microcystis aeruginosa and are serious health risk to human beings (1). In 1999, the World Health Organization adapted 1 mg microcystin-LR per liter as the maximum microcystin concentration allowable in drinking waters. Key to enforcing this standard is the ability to detect microcystins at this low concentration. Microcystins are a family of more than 60 related peptides and instrumental techniques, such as LCMS, often fail to give an integrated value for all the toxic compounds. Microcystin-LR, one of the most common hepatotoxins, binds irreversibly and inhibits the activity of protein phosphatase 1 and 2A (2). This suggests that this assay could be used as a screen for total microcystin activity in water samples. To test this assay and develop conditions for its use in our laboratory, human recombinant protein phosphatase 1 was purchased from Boehringer-Mannheim and its activity with the artificial phosphate substrate para-nitrophenyl phosphate (pNPP) was tested using a microtiter plate reader. The enzyme showed a pH optimum near 7.5 and its activity was dependent on both the substrate and enzyme concentration. Addition of microcystin-LR inhibited the enzyme with an IC-50 (concentration that gives 50% inhibition) about 24 mg/L. The lowest detection limit is 1 ug/L. The assay sensitivity and the linear portion of the standard curve were dependent upon the amount of protein phosphatase used. When less protein phosphatase was used, the sensitivity of the PPIA increased and the range of linearity of the calibration curve decreased. When more protein phosphatase was used, the sensitivity of the PPIA decreased and the linear portion increased. These results suggest that the inhibition protein phosphatase is a viable assay for microcystins. Experiments to compare its activity on several different microcystin variants are in progress. This assay will be used as part of a statewide screening program for microcystins in drinking water this coming summer.

(1) Chorus, I. and Bartram, J. (1999) Toxic Cyanobacteria in Water; A guide to their public health consequences, monitoring and management. WHO. (2) Carmichael, W.W. and An, J. (2000) Using the protein phosphatase inhibition assay (PP1A) for detection of microcystins and nodularins, Natural Toxins, submitted.

 

TUNICAMYCIN BIOSYNTHESIS IN RESISTANT (TUNR) AND NON-RESISTANT (TUNNR) STREPTOMYCES LYSOSUPERIFICUS: EIGHT NEW TUNICAMYCINS. Billyana Tsvetanova and Dr. Neil Price, Department of Chemistry, 336 Jahn Lab, SUNY College of Environmental Science and Forestry, Syracuse, NY 13210.

Streptomyces lysosuperificus is a fungus-like soil bacterium that produces a nucleoside antibiotic called tunicamycin. Tunicamycin is known to inhibit the polyprenolphosphate-N-acetylhexosamine-1-phosphate translocase enzyme family as a transition state analogue. Therefore, it blocks the first step in protein N-glycosylation in eukaryotes and the assembly of cell wall peptidoglycan in bacteria. However, tunicamycin is not a single compound but a mixture of structurally similar compounds that differ only in the nature of the N-linked acyl chain. We have developed electrospray ionization (ES) mass spectrometric techniques to assign the tunicamycin structural variants in the picomolar range. The application of in-line reverse-phase high performance liquid chromatography-electrospray MS (HPLC-ESMS) resulted in the identification of eight new tunicamycins. In addition, several strains of S. lysosuperificus were selected with different antibiotic sensitivities using a tunicamycin agar diffusion bioassay. The application of HPLC-ESMS to culture supernatants and cellular extracts of these lines indicates that tunicamycin resistance can be uncoupled from its biosynthesis.

 

NEW APPROACHES TO COUPLING SERINE PEPTIDES TO PROTEINS: PREPARATION OF A STABLE HAPTEN OF FERRICROCIN. Tzu-Pin Wang and Gregory L. Boyer, Department of Chemistry, SUNY-CESF, Syracuse, NY 13210.

Ferricrocin (FCR) is a hexapeptide and a strong iron chelator produced by fungi. FCR contains a serine residue that is the principle target for coupling the peptide to proteins for antibody preparation. Several derivatives of this serine hydroxyl were prepared including the FCR-hemisuccinate, FCR-hemiadipate, tosyl FCR, FCR N-aminoethylsuccinamide, FCR N-aminoethyladipamide, and the diFCR adipate. Use of succinic anhydride, or a Steglich esterification using the free acid, were both effective for coupling the serine to carboxylic acids. The resulting ester linkage was unusually labile in both aqueous buffer and in anhydrous DMF. To avoid this problem, FCR was converted to tosyl FCR in a low yield (10%). This tosyl derivative will then be displaced with an amine to form the more stable amide linkage. Work is in progress to optimize the yield of tosyl FCR and to displace it with different amines.

 

Electrochemical Synthesis of Polysilanes. Xinwei Wang, Youxin Yuan and Israel Cabasso*, Polymer Reasearch Institute, State University of New York CESF, Syracuse, New York 13210

Polysilanes are a class of polymers with continuous silicon-silicon linkages. It can be used for production of semi-conducting electronic devices. The most general synthetic pathway of polysilanes is the Wurtze coupling reaction of dichlorosilanes with a sodium dispersion in toluene at reflexing temperature. However, this method is complex and moisture sensitive, due to alkali metal, as well as formation of large amounts of metal chlorides as byproducts. Over the past several years, attention has been paid to the electro-reduction route. In this method, platinum was used as the cathode and mercury, or copper, as the anode. Hitherto, this method produced di, tri, oligomers, or very low molecular weight of polysilanes with poor yield.

Reported herein is the electrolysis of dichlorosilane based on Al-Metal electrodes that is shown to yield high molecular weight polysilanes in a relatively high current efficiency. Polymers with molecular weight more than 100,000 have been produced.

The mechanism of the electrochemical synthesis of polysilanes had been proposed. During electrolysis, chlorosilane species in the vicinity of cathode surface accepts one electron and then excludes a Cl- ion to form a silyl radical. Subsequently, the silyl radical may couple with another radical, forming a Si-Si bond, or it could accept another electron to generate a silyl anion that then attacks Cl-Si- containing species to form polysilane via nucleophilic substitution. Since the proposed polymerization mechanism involves silyl radical and anion intermediates, low temperature that can stabilize anionic reactive sites and then enlarges the reaction probability of the species of this type, results in high molecular weight. Sonication aids to refresh the electrode surface and facilitates the mass transfer of reactants, results in an improved current efficiency and molecular weight.

  

The laser induced fluorescence (LIF) excitation spectra of 3-pentoxy and tert-pentoxy radicals and the kinetic study of 2-butoxy radicals Deng Wei, Chuji Wang, Liat Shemesh, Michael Lilien, David R. Katz, Gregory Gawinski, and Theodore S. Dibble, Faculty of Environmental and Forest Chemistry, 121 Jahn Laboratory, SUNY College of Environmental Science and Forestry, Syracuse, NY 13210.

Alkoxy radicals are central intermediates in the tropospheric degradation of volatile organic compound. The fate of alkoxy radicals in the atmosphere influence the yield of ozone, air toxicant, and organic aerosol in polluted air. Therefore, understanding and modeling the alkoxy radicals chemistry in the atmosphere are of crucial importance for environmental chemists. The laser induced fluorescence (LIF) excitation spectra of 3-pentoxy and tert-pentoxy ((CH3)2C(O·)(C2H5)) radicals are obtained for the first time in our lab. The experiments were carried out in the wavelength range 345-400 nm by laser photolysis of corresponding pentyl nitrites at 355 nm. All spectra are extensively structured, and the band corresponding to the C-O stretching mode is tentatively identified for both compounds.   The minimum excitation energies (the transition origins) of the these electronic absorptions were tentatively assigned at 26437±5 cm-1 (378.2 nm) for 3-pentoxy and 25491±10 cm-1 (392.3 nm) for tert-pentoxy; these values are consistent with values previously determined for other alkoxy radicals of similar size and structure.  New observations from LIF experiments on 10 additional large alkoxy radicals in the range from 335 to 400 nm are reported. Temperature dependent rate constant measurements over the range 203-283K are reported for the reactions 2-butoxy with 2-butylnitrite and NO. Preliminary values of the rate constants for the removal of 2-butoxy are k=2.26*10-11exp(-0.80 kcal mol-1/RT) cm3/s with 2-butylnitrite and k=6.4*10-12exp(0.75 kcal mol-1/RT) cm3/s with NO.

 

DETECTION OF THE CYANOBACTERIAL TOXIN, ANATOXIN-A, IN NATURAL WATERS. Xingye Yang and Gregory L Boyer, State University of New York, College of Environmental Science and Forestry, Syracuse, NY 13210. (xyang02@mailbox.syr.edu, glboyer@esf.edu)

Blooms of toxic cyanobacteria and their secreted toxins are responsible for the intoxication of human beings and domestic stock that occurs throughout the world. Several different types of cyanotoxins, including hepatotoxins, neurotoxins, cytotoxins, and dermatoxins are reported to be present in cyanobacterial blooms. Little is known about the occurrence of these compounds in New York State and its drinking waters. A toxic cyanobacteria outbreak in Lake Champaign last year resulted in the deaths of several dogs. Anatoxin-a, a frequently occurring cyanotoxin, was the compound present in this Lake Champaign outbreak. This toxin is difficult to measure in natural samples however a fluorometric HPLC method for determining its level has been described in the literature1. In this method, the toxin is first extracted from cells using methanol and then these water samples, together with purified standards, are derivatized with NBD-F (4-Fluoro-7-nitrobenzofurazan). After derivatization, anatoxin-a can be analyzed by HPLC using a fluorescent detector. The efficiency of extraction and derivatization can be calculated by using an internal standard, methyl pipecolinate, spiked into the samples at the time of extraction. This method is currently being used to analyze catfish aquaculture ponds that appear to be suffering from cyanobacteria-related fish kill and is being developed for later use this summer in monitoring New York State recreational and drinking waters. Suspicious anatoxin-a peaks presented in HPLC chromatograms, i.e, peaks whose retention times are within the range retention times of anatoxin-a standards, will be confirmed by additional analysis using LCMS. (This work is supported by New York Sea Grant).

Structure of anatoxin-a

1 James et al. (1997) Anatoxin-a in Irish freshwater and cyanobacteria determined using a new fluorometric liquid chromatographic method. Toxicon 35:963-971.

 

SAMPLING FOR POLYCYCLIC AROMATIC HYDROCARBONS USING A PASSIVE IN-SITU CONCENTRATION EXTRACTION SAMPLER. Kate Zakharov, Jocelyn M. Polito, John P. Hassett, Faculty of Chemistry, 435 Jahn Laboratory, SUNY College of Environmental Science and Forestry, Syracuse, NY

Many hydrophobic pollutants of environmental concern are found in low concentrations in natural waters, so low that conventional grab samples can not detect them. PISCES is a passive in-situ concentration extraction sampler. It provides a time averaged sample of the water of interest and allows lower detection limits than grab samples. PISCES concentrates hydrophobic organic compounds by diffusion from the water, across a polymer membrane and into a reservoir of organic solvent. The sampling rate of PISECES for compounds varies by their identity and depends on the temperature and degree of turbulence. The higher the temperature the faster compounds enter the PISCES. Calibrations for rate that PISCES samples polycyclic aromatic hydrocarbons (PAH) have been performed for naphthalene, anthracene, phenanthrene, acenaphthene and acenaphthylene. Sampling rates are in the range of 0.5L to 1 L per day for field samplers with 57 cm2 membrane areas, with the lower rates at lower temperatures.

 

STUDIES ON STIMULI RESPONSIVE FLUIDS BASED ON MODIFIED CELLULOSE MATERIALS. Shengbin Zhang, Arthur Stipanovic and William T. Winter, Department of Chemistry and the Cellulose Research Institute, Jahn Laboratory, SUNY College of Environmental Science and Forestry, Syracuse, NY 13210.

Stimuli responsive fluids (SRFs) are an emerging class of 21st century "smart materials" that are capable of reversibly transforming themselves, on a millisecond time scale, from the liquid to solid state in response to changes in external electrical or magnetic fields. This effect enables the mechanical properties of a device, such as an automotive shock absorber, to be continually adjusted in real-time in response to input stimuli such as irregular road surfaces, thereby creating safer and more energy-efficient vehicles and equipment. SRFs applications in ultrafast, computer-controlled machines and virtual reality are also emerging. SRFs are typically composed of solid, electrically or magnetically polarizable particles dispersed in a fluid medium usually a mineral oil or silicon fluid. Derivatized cellulose fibers and microcrystalline particles can be formulated into either electrorheological or magnetorheological fluids (ERFs, MRFs) depending on the derivatization process. In this poster, preliminary results on the electrorheological performance of a series of ionically substituted cellulose particles will be compared to several commercially available ERFs.


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