Physical Sciences and Mathematics Commons^™

Changes In Reproductive Morphology And Physiology Observed In The Amphipod Crustacean, Melita Nitida Smith, Maintained In The Laboratory On Polluted Estuarine Sediments, John T. Tanacredi Ph.D., B. Borowsky, P. Aitken-Ander

Faculty Works: CERCOM (1977-2016)

An earlier study showed that the amphipod crustacean Melita nitida Smith maintained on sediments dosed with waste crankcase oil developed physiological and morphological abnormalities. Most notably, mature females developed abnormal setae along the edges of their brood plates. The present study was conducted to determine whether similar abnormalities might be induced in animals maintained on polluted field sediments containing petroleum by-products among other toxic substances. In the laboratory, heterosexual pairs were maintained on three sediments taken from Jamaica Bay (New York) plus one control sediment and one toxic substratum (Ulva lactuca (L.) thalli). The results mirrored the results of …

Fabrication And Evaluation Of Boron-Doped Cvd Diamond Microelectrodes, Song Pang

Chemistry & Biochemistry Theses & Dissertations

The electrochemical behavior of boron-doped diamond microelectrodes has been studied in acetonitrile solutions containing two redox couples using cyclic voltammetry. One test system is 1-2.5 mM ferrocene, containing 0.1 M Tetrabutyl ammonium hexafluorophosphate (TBAH). This well-known reversible redox system involves only one electron transfer with little or no change in the solvation sphere and no breakage/formation of chemical bonds. Another test system is a 1 mM S₂Mo₁₈0₆₄^4- solution containing 0.1 M HCIO₄. This is one of the most complicated redox systems. In the presence of acid, electrons are usually transferred consecutively and …

Evaluation Of Solid Phase Extraction Followed By Supercritical Fluid Elution Of Semi-Volatile Organic Compounds In Toxicity Characteristic Leachates, William Edward Corl Iii

Chemistry & Biochemistry Theses & Dissertations

The Environmental Protection Agency (EPA) developed the toxicity characteristic leaching procedure (TCLP) to determine the potential for unknown wastes to leach haz.ardous constituents into the environment. Methods currently being used for the extraction of semi-volatile organic compounds from aqueous TCLP leachates involve acid/base partitioning into methylene chloride. The concentrated extract is then analyzed by gas chromatography/mass spectrometry (GC/MS). The methods are either timeconsuming or labor intensive and they generate significant volumes of haz.ardous wastes themselves. Considering the haz.ards and disposal costs of methylene chloride wastes, great interest has been elicited by the EPA in other extraction techniques which would reduce …

Comparison Of The Dichlorination Of Organic N-Chloramines By Caroate And By Bisulfite: A Kinetic Study, Said H. Lubbad

Chemistry & Biochemistry Theses & Dissertations

Bisulfite is commonly used to dechlorinate chlorinated municipal wastewater. However, several studies suggest that bisulfite is not effective in dechlorinating N-chlorinated amino components of wastewater. The purpose of this study was to investigate the effectiveness of an alternate dechlorinating agent, caroate (peroxysulfate), and to compare its rate of dechlorination of three different types of chloramines with that of bisulfite.

Four N-chlorinated amino compounds were investigated: N-chlorodiethylamine, N­ chloroalanylphenylalanine, N-chloroglycylphenylalanine, and N-[2-(N'-chloroimino)­ propanoyl]phenylalanine. These compounds were selected from different families of N­ chloramines to study the effect of structure on dechlorination by both caroate and bisulfite. At pH …

Speciation Of Selenium In Serum, Alice Tsapayi-Musapatike

Chemistry & Biochemistry Theses & Dissertations

We investigated the separation of selenoprotein P and extracellular (serum) glutathione peroxidase using a concanavalin A affinity column. We were able to show that the method does not adequately separate serum glutathione peroxidase from selenoprotein P because human glutathione peroxidase binds strongly to the column. We also found that albumin can interfere with measurement serum of glutathione peroxidase activity when hydrogen peroxide is used as the substrate. When t-butyl hydroperoxide was used as the substrate, less than 10% of the measured activity was due to the presence of albumin. We also found that the pH of the elution buffer plays …

Solvent-Induced Interactions Between Hydrophobic And Hydrophilic Polyatomic Sheets In Water And Hypothetical Nonpolar Water, Kenichiro Koga, Xiao Cheng Zeng, Hideki Tanaka

Xiao Cheng Zeng Publications

Hydrophobic and hydrophilic interactions are two major intermolecular forces between hydrophobic nonpolar and hydrophilic polar sites of macromolecules or materials surfaces in solvents. To further understand these two interactions at the microscopic level, an idealized polyatomic model is devised, which includes hydrophobic, hydrophilic, and partially hydrophilic polyatomic planar square molecular sheets. The hydrophobic molecular sheet is composed of the Lennard-Jones particles while the hydrophilic molecular sheet consists of positive and negative charge sites. In the framework of the extended reference interaction site model integral equation theory the solvent-induced interactions (or the potential of mean forces) between two parallel molecular sheets …

A High Level Theoretical Investigation Of The Cyclic Hydrogen Fluoride Trimer, Gregory S. Tschumper, Yukio Yamaguchi, Henry F. Schaefer

Chemistry Faculty Research & Creative Works

A high-level ab initio theoretical investigation of the cyclic hydrogen fluoride trimer was carried out. The structures of the hydrogen fluoride monomer, dimer, and trimer were fully optimized at the coupled-cluster level of theory including single, double, and perturbatively applied connected triple excitations [CCSD(T)] using three large basis sets. Geometrical parameters, dipole moments, harmonic vibrational frequencies, infrared intensities, and total energies are reported for each equilibrium structure. Changes in bond lengths and shifts in HF stretching frequencies relative to the monomer, as well as the dissociation energies corresponding to various fragmentation pathways, are given for the dimer, trimer, and their …

Preparation Of Organometallic Complexed Sugars:  Hetero Diels−Alder Reactivity Of Tricarbonyl(Formyltrimethylenemethane)- Iron, Paul J. Kleindl, William Donaldson

Chemistry Faculty Research and Publications

No abstract provided.

Synthesis Of [15n,15n‘]-N,N,N‘,N‘-Tetramethyl- Ethylenediamine And Its Use In Solvation Studies Of [6li]-N-Butyllithium., Delia Waldmüller, Barbara Kotsatos, Michael Nichols, Paul Williard

Michael A Nichols

No abstract provided.

40. Otto Vogl, Joseph C. Salamone

Otto Vogl

No abstract provided.

The Effect Of Protein Environment And Ring Substitution On The Electrostatic Charges, Dipole Moment, And Ultraviolet Spectra Of Flavin, Jared Berger

Honors Theses

Old Yellow Enzyme is an interesting protein clue to its involvement in many biochemical systems, such as bioluminescence and degradation of variety of substrates. The flavin mononucleotide (FMN) is the active site of the protein. The FMN is an isoalloxazine ring with a phospholipid tail, which attaches to the protein through a phosphate group and hydrogen bonding in the hydrophilic section of the ring system. My research is a theoretical, computational calculation, which uses Spartan, a quantum mechanical calculation program, to determine how the dipole moment and electrostatic charges change upon the substitution of the FMN and within the protein …

Molecular Recognition Of Blunt-Ended Dna, Michael D. Farwell

Honors Theses

Many important enzymatic and physical processes occur specifically at the ends of DNA molecules. The goal of this project was to develop a molecule that would be an effective probe of the chemistry a. the ends of DNA. To do this, ethidium bromide, a well-known intercalation (a molecule that binds between DNA base pairs), was blocked to intercalation with bulky t-butyl groups. We proposed that this new molecule would preferentially bind to blunt-ended DNA, where there is much less steric hindrance. The synthesized molecule was characterized by NMR, Fluorescence, UV/Vis, and Mass Spectroscopy. Supporting data were acquired through fluorescence lifetime …

Methylene Blue Doped Sol-Gels Preparation And Application As Fiber-Optic Fluorescence Sensors, Dawn M. Landry

Honors Theses

The goal of this thesis project was to create a Methylene Blue (MB) doped sol-gel fiber-optic fluorescence sensor. Ideally this sensor would be capable of detecting changes in sulfite concentration in solution continuously and reversibly. In aqueous solution, MB, a redox indicator, is converted from a bright blue color to the colorless leuco-MB species upon exposure to sulfite or other reducing agents. This reaction is reversible in the presence of an oxidizing agent Therefore, if MB can be immobilized properly, it would make a suitable reversible indicator for the sulfite anion in solution. The method of MB immobilization employed in …

Comparison Of Outgassing And Surface Reactivity Of Graphic Substrates, Philip Ross Tavernier

Honors Theses

Materials constructed of carbon are widely used in applications requiring high emissivity at temperatures above 1300°C. The ability to transmit heat efficiently makes these materials an excellent choice for use with x-ray tubes. However, heating carbon substrates to high temperatures also leads to thermal desorption of surface bound species. The release of these species increases the total vapor pressure inside sealed x-ray tubes. Our present study considers the outgassing of these carbon substrates as a function of temperature, as a result of their reactivity towards oxygen, carbon monoxide, carbon dioxide, and water vapor. By modeling the factors that influence outgassing …

Design, Synthesis, And Characterization Of Short Salt And Non-Salt Bridged Peptides, Clark K.N. Choi

Honors Theses

Peptides with secondary characteristics such as α-helices are among the most important structures in nature. Previous studies from Baldwin and coworkers have shown that short alanine-based peptides with specific salt spacing adopt helical conformations. In the study of helix formation, we have synthesized our versions of alanine- and glutamine-based peptides with (i, i + 4) and (i, i + 5) salt spacing. The design of the salt bridge is most suitable when it contains (i, i + 4) salt spacing. The rational is that the (i, i + 4) salt spacing yields a value close to 3.6, the number of …

Kinetics And Mechanism Of Chromium Hexacarbonyl Photochemistry Using Flash By Photolysis, Marina Zaydman

Honors Theses

Chromium hexacarbonyl, Cr(CO)6, has been shown to be a very effective photochemical catalyst for many reactions, such as the 1,4- hydrogenation and 1 ,4-hydrosilation of conjugated 1 ,3-dienes resulting in the formation of a cis alkene product in greater than 99% yield. Although much research has been done on the reactions which Cr(CO)6 catalyzes, not much data exists on the reactions of photochemically created fragments of Cr(CO)6 , such as Cr(CO)6. This study focuses on the reactivity of organotransition metal intermediates with the goal of contributing to the growing database of the reactions involving the photochemistry of Cr(CO)6. Particular emphasis …

A Computational Study Of The Inclusion Processes Of Cyclodextrins And Cyclodextrin Polymers, James A. Best

Honors Theses

Cyclodextrins (CDs) are molecules that are composed of glucopyranose rings. Cyclodextrins can be formed from either 6, 7, or 8 glucopyranose units yielding, α-, β-, or y-Cyclodextrins respectively. Cyclodextrin polymers (COPs) can occur when glyceryl linkers are added to the previously mentioned cyclodextrins. CDs and COPs are hydrophilic, yet contain a hydrophobic cavity. This cavity allows for the binding of numerous guest molecules. Some practical purposes resulting from the host-guest interactions can be seen in cosmetology, food science, and pharmacy. Using the MacroModel Interactive Molecular Modeling System Version 5.0 we studied the binding of guest molecules to α-, β-, and …

The Crystallation Of Estrogen-Binding Protein From Candida Albicans, Chia-En Chen

Honors Theses

In the past decade scientists have discovered that the pathogenic fungus Candida albicans contains a highly specific estrogen-binding protein (EBP). Since it is known that the use of estrogen-containing compounds causes one to be more prone to infection by this organism, it is hypothesized that this estrogen system may have a role in infection. Understanding the structure and function of EBP would be helpful in developing treatments for infection by C. albicans. One way to approach the structure and function question of any protein is to crystallize the protein and solve its structure using X-ray diffraction. In the past few …

A Binding Investigation Of Fluorescence\Probes And Cyclodextrin Derivatives, Sara L. Mcintosh

Honors Theses

Cyclodextrins (CDs) are cyclical carbohydrates composed of repeating glucopyranose units. The three most common CDs, α-, β-, or y-, contain 6, 7 and 8 glucopyranose units, respectively, and have hydrophilic exteriors, which makes them water soluble. CD polymers (CDPs) have been synthesized, containing glyceryl link, between CD units. These polymers are more water soluble than their monomer counterparts. CDs and CDPs, because of their hydrophobic interior cavities, form inclusion complexes with various molecules, including aromatics. This latter property is one we have investigated using fluorophores, including naphthalenes and pyrene. We have shown, through absorption spectral and fluorescence lifetime data, that …

Numerical Modeling Of Self-Propagating Polymerization Fronts: The Role Of Kinetics On Front Stability, Stanislav E. Solovyov, Victor M. Ilyashenko, John A. Pojman

Faculty Publications

Frontal propagation of a highly exothermic polymerization reaction in a liquid is studied with the goal of developing a mathematical model of the process. As a model case we consider monomers such as methacrylic acid and n-butyl acrylate with peroxide initiators, although the model is not limited to these reactants and can be applied to any system with the similar basic polymerization mechanism. A three-step reaction mechanism, including initiation, propagation and termination steps, as well as a more simple one-step mechanism, were considered. For the one-step mechanism the loss of stability of propagating front was observed as a sequence …

Breakdown Of The Independent Particle Approximation In High-Energy Photoionization, E. W. B. Dias, H. S. Chakraborty, P. C. Deshmukh, S. T. Manson, Oliver Hemmers, P. Glans, D. Hansen, H. Wang, S. B. Whitfield, Dennis W. Lindle, R. Wehlitz, Jon C. Levin, I. A. Sellin

Environmental Studies Faculty Publications

The independent particle approximation is shown to break down for the photoionization of both inner and outer nℓ (ℓ>0) electrons of all atoms, at high enough energy, owing to interchannel interactions with the nearby ns photoionization channels. The effect is illustrated for Ne 2p in the 1 keV photon energy range through a comparison of theory and experiment. The implications for x-ray photoelectron spectroscopy of molecules and condensed matter are discussed.

Estimation Of Groundwater Velocities From Yucca Flat To The Amargosa Desert Using Geochemistry And Environmental Isotopes, Ronald L. Hershey, Steve Y. Acheampong

Publications (WR)

Geochemical modeling techniques were applied to groundwater flowpaths from Yucca Flat on the Nevada Test Site (NTS) to the Amargosa Desert, south of the NTS to estimate groundwater flow velocities for independent comparison to velocities calculated by other methods. The groundwater flowpaths examined considered flow in the carbonate aquifer beneath Yucca and Frenchman flats mixing with flow from carbonate aquifers east and southeast of the NTS and discharging at wells south of the NTS border. The approach used the computer codes WATEQ4F and NETPATH to calculate chemical speciation, determine the saturation state of mineral phases, and simulate mixing and the …

Synthesis Of Biologically Active Substituted Chalcones, Kiel Steven Hoff

Masters Theses

Two different synthetic routes to poly-hydroxylated chalcones are investigated. The wittig synthesis and protection of the hydroxyl functionalities by forming the methyl ether followed by the base catalyzed Claissen-schmidt reaction and then deprotection were investigated. It was demonstrated that the protection-condensation- deprotection route was more efficient. The antiviral activity of 2,2', 4' - trihydroxychalcone against the HIV virus is also presented.

The Electrochemical Oxidation Of Organic Selenides And Selenoxides, Michael D. Ryan, Jiyi Yau, Michael Hack

Chemistry Faculty Research and Publications

The electrochemical oxidation of alkyl and aryl selenides was investigated in acetonitrile. The oxidation of diphenyl selenide and di(4‐methylphenyl) selenide led primarily to the formation of their respective selenoxides, which were identified by exhaustive coulometric oxidation and and analysis of the products. The selenoxide itself was not observed in the cyclic voltammetry of the selenide for two reasons: first, the protonation of the selenoxide by the acid formed from the reaction of water with the cation radical and second, the formation of a selenoxide hydrate. The formation of the hydrate with diphenyl selenoxide was verified by isolation of the dimethoxy …

Syntheses And Characterizations Of Unsymmetrical Porphyrins As Photosensitizers For A Solid-State Solar Cell, Yinping Zhao

Dissertations and Theses

Solar light is the most important source of regenerative energy and represents mankind's only inexhaustible energy source. One of today's most promising tools to make use of solar energy is its direct conversion into electrical energy in a photovoltaic cell. The practical use of these solar cells depends on the price of the devices and therefore of the obtained energy. The conventional silicon cells, although efficient, are expensive for common consumer applications. The Grätzel cell is a photovoltaic system for harvesting the sun's energy that operates at about 10-15% overall efficiency, like a conventional solar cell, but does it at …

Effects Of Tunneling Electrons And Local Field On Nanometer Region Solid / Liquid Interfacial Reactions ——Potential Controlled Stm Induced Nanoscale Modification Of H Terminated Si(111) Surfaces, Zhaoxiong Cai Xiongwei Xie, Caihui Shi, Bingwei Mao, Zhaowu Tian

Journal of Electrochemistry

H terminated n Si(111) surface was found to be etched in 0.5% HF solution in nanometer scale while scanning the STM tip when the substrate potential was somehow lower than the open circuit potential at tunneling condition of V b=+1.0 V (tip positive), I t=1 nA. Much more stable Si surface was achievable at potentials much more negative than the open circuit potential (such as 500 mV negative to OCP) under the same tunneling condition. Furthermore, the etching rete at less negative potential was found to be somehow related to the tunneling current. These results indicate that the STM induced …

Mechanism And Texture Of Ni Mo Alloy Electrodeposition, Ling Huang, Shukai Xu, Jaoning Tang, Fangzu Yang, Shaomin Zhou

Journal of Electrochemistry

Ni Mo alloy deposits with (111) preferred orientation was obtained in a solution of 0.22 mol/L NiSO 4·6H 2O, 0.06 mol/L Na 2MoO 4·2H 2O and 0.3 mol/L Na 3C 6H 5O 7·2H 2O in temperature from 25℃ to 50℃,and current densities ranged from 10 mA·cm -2 to 30 mA·cm -2 . The electrodeposition of Ni Mo alloy was studied by cylic voltammetry and potential step experiment. It was shown that Ni Mo alloy is formed by mechanism involving progressive nucleation followed by three dimensional growth of the metal centres. The complex plane impedance plots indicate codeposition of Ni Mo …

Electroluminescence Of Photoelectrochemically Etched N + Si, Guozheng Li, Chengqian Zhang, Xiumei Yang

Journal of Electrochemistry

Porous silicon with micrometer size pores, which is made on n + Si by photoelectrochemically etched, has electroluminescent property. Each monochromic intensity and wavelength range of luminescent spectra depend on polarized potential. The intersity and the stability of cathodic electroluminescence is high than those of anodic one. Voltammetric behavior before quenching indicated that the electrochemical reactions of some surface species are involved in except the reduction of S 2O 2- 8, which leads to radiative recombination. The energy band diagram based on n + Si (E g=1.1 eV)/PS(E g=1.8 eV) junction is proposed.

Study On The Preparation, Properties And Applications Of The Polymer/Graphite Composite Electrode, Guohua Chen, Jinrui Xu

Journal of Electrochemistry

The graphite AS composite electrodes, which show high electric conductivity, high mechanical strength and operationl stability, were prepared by filling and extruding the AS copolymer with graphite powder. It exhibited a substantial hydrogen overvoltage and small residual current in different electrolytes, as compared with glassy carbon electrode. The electrode was applied to the determination of traces of Pb 2+ in mineral water, Ag + in waste water and In 3+ , Cu 2+ , Pb 2+ , Cd 2+ in zinc ore, and showed high stability, reproducibility and selectivity. Owing to the existence of abundant polar functioal groups on the …

The Influence Of Dextran And Its Anion Derivates On The Electrofusion Of Barley Protoplasts, Wang Wei, Jiang Zhiyu

Journal of Electrochemistry

The influence of dextran and its anion derivates (blue dextran, cibacron blue dexran, fluoresceinythiocarbamoyl dextran) on the electrofusion of barley protoplasts has been investigated. It was found that as a kind of neutral surface active agent, dextran could promote the electrofusion, but these anion derivates could decrease the electrofusion yield. The phenomena were discussed from the view of adsorption of additives on the cell membrane.