Chemistry Commons^™

Excimer Emission From Cathode Boundary Layer Discharges, Mohamed Moselhy, Karl H. Schoenbach

Bioelectrics Publications

The excimer emission from direct current glow discharges between a planar cathode and a ring-shaped anode of 0.75 and 1.5 mm diameter, respectively, separated by a gap of 250 μm, was studied in xenon and argon in a pressure range from 75 to 760 Torr. The thickness of the “cathode boundary layer” plasma, in the 100 μm range, and a discharge sustaining voltage of approximately 200 V, indicates that the discharge is restricted to the cathode fall and the negative glow. The radiant excimer emittance at 172 nm increases with pressure and reaches a value of 4 W/cm² for …

Chemical Vapor Deposited Diamond Films For Self-Referencing Fiber Optic Raman Probes [Erratum], Sacharia Albin, Jainli Zheng, Bing Xiao, John B. Cooper, Robert B. Jeffers, Sonia Antony

Chemistry & Biochemistry Faculty Publications

No abstract provided.

Measurement Of Proton Transfer Reaction Rates In A Microwave Cavity Discharge Flowing Afterglow, George M. Brooke Iv

Physics Theses & Dissertations

The reaction rate coefficients between the hydronium ion and the molecules ethene (C₂H₄), propene (C₃H₆), 1-butene (C₄H₈) and hydrogen sulfide (H₂S) were measured at 296 K. The measured reaction rates were compared to collision rates calculated using average dipole orientation (ADO) theory. Reaction efficiency depends primarily upon the proton affinity of the molecules. All the measurements were obtained using the newly developed microwave cavity discharge flowing afterglow (MCD-FA) apparatus. This device uses an Asmussen-type microwave cavity discharge ion source that is …

Argon Eximer Emission From High-Pressure Microdischarges In Mental Capillaries, R. Mohan Sankaran, Konstantinos P. Giapis, Mohamed Moselhy, Karl H. Schoenbach

Bioelectrics Publications

We report on argon excimer emission from high-pressure microdischarges formed inside metal capillaries with or without gas flow. Excimer emission intensity from a single tube increases linearly with gas pressure between 400 and 1000 Torr. Higher discharge current also results in initial intensity gains until gas heating causes saturation or intensity drop. Argon flow through the discharge intensifies emission perhaps by gas cooling. Emission intensity was found to be additive in prealigned dual microdischarges, suggesting that an array of microdischarges could produce a high-intensity excimer source.

Comparison Between The Ultraviolet Emission From Pulsed Microhollow Cathode Discharges In Xenon And Argon, Isfried Petzenhauser, Leopold D. Biborosch, Uwe Ernst, Klaus Frank, Karl H. Schoenbach

Bioelectrics Publications

We measured the dynamic I–V characteristics and vacuum ultraviolet (VUV) emission lines of the second continuum in xenon (170 nm) and argon (130.5 nm) from pulsed microhollow cathode discharges (MHCD). For pulse lengths between 1 and 100 μs the dynamic I–V characteristics are similar in both inert gases. Only the time variation of the VUV emission line at 170 nm for xenon can be related to the dimer excited states. In argon the energy transfer between the Ar*₂ dimers and the oxygen impurity atoms is responsible for a qualitatively different time behavior of the resonance line at 130.5 nm. …

Chemical Vapor Deposited Diamond Films For Self-Referencing Fiber Optic Raman Probes, Sacharia Albin, Jianli Zheng, Bing Xiao, John B. Cooper, Robert B. Jeffers, Sonia Antony

Chemistry & Biochemistry Faculty Publications

Diamond thin films grown by the microwave plasma enhances chemical vapor deposition (CVD) process have been investigated as an internal reference in fiber optic remote Raman sensing. The growth parameters have been optimized for diamond thin films on quarts substrates using a gas mixture of methane, carbon dioxide, and hydrogen. The resulting films exhibit essentially no Raman spectral background while exhibiting a strong Raman peak at 1332 cm^-¹. The films are used as an internal reference in the quantitative measurement of chemical concentration using remote fiber optic Raman sensing. Internal referencing is accomplished by normalizing all spectral intensities …

Chromium Tolerant Microbial Communities From The Chesapeake Bay Watershed, Kristine L. Lowe, Ruth E. Fliflet, Tony Ly, Brenda J. Little, Joanne Jones-Meehan

Virginia Journal of Science

Chromium tolerant bacteria were enumerated from portions of the Chesapeake Bay watershed and examined for their potential to reduce Cr(VI). Water and sediment samples were collected from various locations in Baltimore Harbor and Bear Creek, as well as Sandy Point State Park in Maryland and the Anacostia River in Washington, DC. Samples were spread onto agar plates with CrO₄^2- (5 ppm) as the sole terminal electron acceptor. Plates were incubated anaerobically and colony forming units (CFU) enumerated. CFU arising on minimal-CrO₄^2- medium ranged from 10³-10⁴ mL^-1 or g^-1 and community estimates …

Styrene Monomer Solubility In Artificial And Natural Seawaters Of The Lower Chesapeake Bay, Eric Joseph Miller

Chemistry & Biochemistry Theses & Dissertations

Used for making a variety of plastic products, styrene monomer is an aromatic hydrocarbon frequently shipped in bulk quantities through the Port of Hampton Roads, Virginia. Despite its common use around the world and its high aquatic toxicity, little research has been conducted on the chemical's aqueous solubility and reactions during a major spill. In this study, the solubility of styrene monomer was measured in artificial seawater and natural waters collected from four sites on the lower Chesapeake Bay and Elizabeth River. The samples represented a range of different water chemistries in terms of salinity (13.8 — 29.0%) and the …

Production Of A Monoclonal Antibody Against Benzo[Α]Pyrene Diol Epoxide Dna Adducts, Brian Peden Austin

Chemistry & Biochemistry Theses & Dissertations

Benzo[α]pyrene is a ubiquitous pollutant produced from the incomplete combustion of organic material such as fossil fuels. It is found in the workplace, urban air, drinking water, and the food supply. Recently, it has been proposed that benzo[α]pyrene may be the causative agent in the formation of lung adenocarcinomas among some Taiwanese women exposed to cooking oil fumes without adequate ventilation. In this study, calf thymus DNA was modified in vitro with benzo[α]pyrene-diol epoxide (BPDE) to a level consistent with that found in biological samples. This DNA of low modification was used as an immunogen in the production of a …

Electrical Network-Based Time-Dependent Model Of Electrical Breakdown In Water, R. P. Joshi, J. Qian, K. H. Schoenbach

Bioelectrics Publications

A time-dependent, two-dimensional, percolative approach to model dielectric breakdown based on a network of parallel resistor–capacitor elements having random values, has been developed. The breakdown criteria rely on a threshold electric field and on energy dissipation exceeding the heat of vaporization. By carrying out this time-dependent analysis, the development and propagation of streamers and prebreakdown dynamical evolution have been obtained directly. These model simulations also provide the streamer shape, characteristics such as streamer velocity, the prebreakdown delay time, time-dependent current, and relationship between breakdown times, and applied electric fields for a given geometry. The results agree well with experimental data …

Production Of A Novel Copper-Binding Ligand By Marine Synechococcus (Cyanobacteria) In Response To Toxic Concentrations Of Copper, Arunsi C. Brown, Andrew S. Gordon

Virginia Journal of Science

Marine Synechococcus spp. are extremely sensitive to copper toxicity. Some strains have been shown to produce high-affinity, extracellular ligands of unknown structure which form complexes with free cupric ion. They are also known to produce metallothioneins (MT) in response to cadmium and zinc stress. In the present study, marine Synechococcus PCC 73109 (Agmenellum quadruplicatum BG-1) (Van Baalen) was exposed to three concentrations of CuSO₄ for various times. Size exclusion chromatography, atomic absorption spectrophotometry, and reverse phase HPLC were used to isolate an intracellular copper binding ligand of low molecular weight (< 6,500 Da). The ligand was detected after exposure to ≥ 8 μM CuSO₄ for 2 hr in BG-11 medium. …

Resonant Energy Transfer From Argon Dimers To Atomic Oxygen In Microhollow Cathode Discharges, M. Moselhy, R. H. Stark, K. H. Schoenbach, U. Kogelschatz

Bioelectrics Publications

The emission of atomic oxygen lines at 130.2 and 130.5 nm from a microhollow cathode discharge in argon with oxygen added indicates resonant energy transfer from argon dimers to oxygen atoms. The internal efficiency of the vacuum-ultraviolet (VUV) radiation was measured as 0.7% for a discharge in 1100 Torr argon with 0.1% oxygen added. The direct current VUV point source operates at voltages below 300 V and at current levels of milliamperes.

Xenon Excimer Emission From Pulsed Microhollow Cathode Discharges, M. Moselhy, R. H. Stark, K. H. Schoenbach, U. Kogelschatz

Bioelectrics Publications

By applying electrical pulses of 20 ns duration to xenon microplasmas, generated by direct current microhollow cathode discharges, we were able to increase the xenon excimer emission by more than an order of magnitude over direct current discharge excimer emission. For pulsed voltages in excess of 500 V, the optical power at 172 nm was found to increase exponentially with voltage. Largest values obtained were 2.75 W of vacuum-ultraviolet optical power emitted from a single microhollow cathode discharge in 400 Torr xenon with a 750 V pulse applied to a discharge. Highest radiative emittance was 15.2 W/cm². The …

Analysis Of Wine For Penicillin, Gary Morris, James Yuan, Roy Williams

Chemistry & Biochemistry Faculty Publications

This study addresses the question of whether the antibiotic Penicillin, which is produced by the common mold Penicillium notatum, could possibly become a contaminate of wine during the fermentation process. The significance of this study is related to the potential health effects this agent might produce in those consumers who have an allergic response to Penicillin. It has been estimated that between 6% and 8% of the American population is subject to this type of allergic response. A method is developed for the detection of penicillin in wines using high-pressure liquid chromatography. We demonstrate that penicillin G hydrolyzes rapidly …

Stm And Electrochemical Investigation Of Homoepitaxial Boron-Doped Cvd Diamond Films, John B. Cooper, Jason A. Moulton, Sacharia Albin, Bing Xiao

Chemistry & Biochemistry Faculty Publications

Homoepitaxial growth of boron-doped CVD diamond films was carried out on (100) and (111) oriented substrates. Atomic resolution images were obtained for both (100) and (111) surfaces using scanning tunneling microscopy. STM images reveal the presence of a 2x1-monohydride reconstruction for the untreated (100) surface and a lxl reconstruction for the untreated (111) surface. No other atomically resolved reconstructions were observed under a wide range of growth conditions. Non-aqueous electrochemical investigations were carried out on the films exhibiting atomically resolved reconstructions. Evidence for potential-induced surface-reconstruction and surface chemical modification of the (100) 2xl-monohydride surface has been observed.

Meso-1, 2-Bis (Methylazo)-1, 2-Diphenylethane, Craig A. Bayse, Barry K. Carpenter, Rudy L. Luck

Chemistry & Biochemistry Faculty Publications

The title compound, meso-1,2-bis(methyldiazenyl)-1,2-diphenylethane, C16H18N4, is arranged in a disordered manner around an inversion point. The N—N atom distances in the azo group of 1.192 (8) and 1.195 (8) Å, and the C—C atom distances in the ethylene moiety at 1.512 (8) and 1.503 (8) Å in the two models [refined to 51.7 (6) and 48.3 (6)% occupancies] were not significantly different.

Boron-Doped Homoepitaxial Diamond (100) Film Investigated By Scanning Tunneling Microscopy, Bing Xiao, Weihai Fu, Sacharia Albin, Jason Moulton, John Cooper

Electrical & Computer Engineering Faculty Publications

Conducting epitaxial diamond films of high quality are essential for many diamond studies and diamond electronic device fabrication. We have grown boron-doped epitaxial diamond films on type Ila natural diamond (100) substrates by microwave plasma chemical vapor deposition. A gas mixture of H₂/CH₄ was used. Boron doping was done by placing solid sources of pure boron in the microwave plasma. Homoepitaxial films with atomic smoothness were achieved under the following growth conditions: substrate temperature 900 °C, gas pressure 40 Torr, and gas flow rates of H₂/CH₄ = 900/7.2 seem. The growth rate was 0.87 …

Fourier Transform Raman Spectroscopy For Process Control In The Petroleum Industry, Kent Lawson Wise

Chemistry & Biochemistry Theses & Dissertations

As early as 1950, Raman spectroscopy was proposed as a method to determine aromatics and olefins in hydrocarbon mixtures. Until recently, extensive use of Raman spectroscopy in the characterization of hydrocarbons has not been practical due to several limitations. One early limitation to Raman analysis was the absence of a high intensity and stable excitation source. This problem has been overcome with the advent of lasers. Another limitation was the presence of fluorescence in hydrocarbon fuels when excited by visible lasers. However, the development of Fourier-transform Raman spectrometers now allows Raman spectra to be collected using near-IR lasers (e.g …

Copper Complexation And Speciation In The Western South And Equatorial Atlantic Ocean, John A. Consolvo

Chemistry & Biochemistry Theses & Dissertations

Presented here are the first data on copper complexation and speciation in the South Atlantic Ocean. Samples were collected at six vertical profile stations and along the surface (1m) transect during the 1996 IOC Baseline Contaminant Survey. Copper complexation measurements were made for the surface transect (1m) samples and three of the six vertical profile stations (1m - ~500m) using differential pulse anodic stripping voltammetry (DPASV) with a thin mercury film, rotating glassy carbon disk electrode (TMFRGCDE).

A strong organic copper complexing ligand (L₁; log K' _cuL1/cu2+ > 11. 8 ± 0 .4) was detected in 57% of all …

Investigations On The Use Of Ion Mobility Spectrometry For Clinical Chemistry Applications, Henri Parson Patten

Theses and Dissertations in Biomedical Sciences

The major objective of this research is to examine ion mobility spectrometry as a rapid screening tool for specific application to clinical chemistry research and laboratory use. Methodology was developed for target analytes representing several classes of physiologically active substances, including anesthetics, illicit drugs, and their metabolites. The IMS characteristics of animal tissues and other compounds such as amino acids and proteins were determined. Quality assurance and control procedures were developed for specific quality data objectives. Criteria were established relating to use of IMS for assessing the precision and accuracy of data, qualitative screening, and semi-quantitative analyses.

It was found …

Binding Of Pb And Zn To Aluminium Oxide And Proton Stoichiometry, Wing H. Leung, A. Kimaro

Virginia Journal of Science

The interaction of Pb and Zn with Al₂O₃ in aqueous solution was studied as a function of pH and metal ion concentration. Results indicated the complexation of metal ions by oxide surfaces is strongly pH dependent; the extent of adsorption is a function of pH with an abrupt change within approximately 2 pH units. The adsorption of Pb and Zn on aluminium oxide can be interpreted in terms of a surface complexation formed by association with one surface AlOH group, thus releasing one bound hydrogen ion. -AlOH + M²⁺ = -AlOM⁺ + H⁺ . …

Jeffress Research Grant Awards

Virginia Journal of Science

Announcements of the Jeffress Research Grants that have been awarded in 1999.

Microhollow Cathode Discharge Excimer Lamps, Karl H. Schoenbach, Ahmed El-Habachi, Mohamed M. Moselhy, Wenhui Shi, Robert H. Stark

Bioelectrics Publications

Microhollow cathode discharges are high-pressure, nonequilibrium gas discharges between a hollow cathode and a planar or hollow anode with electrode dimensions in the 100 μm range. The large concentration of high-energy electrons, in combination with the high-gas density favors excimer formation. Excimer emission was observed in xenon and argon, at wavelengths of 128 and 172 nm, respectively, and in argon fluoride and xenon chloride, at 193 and 308 nm. The radiant emittance of the excimer radiation was found to increase monotonically with pressure. However, due to the decrease in source size with pressure, the efficiency (ratio of excimer radiant power …

Humic Substances As Interferences In The Analysis Of Nitrite In Water, Stephanie Ann Tebault

Chemistry & Biochemistry Theses & Dissertations

Humic substances are of current interest because of their roles in environmental processes involving pollutants. It is also becoming recognized that humic substances may interfere in analysis of environmental samples though the possible adverse effects do not appear to be fully appreciated. The present effort focuses on determining whether humic materials interfere in the analysis of nitrite in water using the Griess reaction. This is a well-known reaction using nitrosation to gjve a diazonium salt followed by coupling with an appropriate reagent to form a dye. This colorimetric method continues to be applied in the laboratory and the field for …

Zinc Speculation And Ligand Fluxes In Chesapeake Bay And Elizabeth River Pore Waters, Duncan Glover Byers

Chemistry & Biochemistry Theses & Dissertations

Presented here are the first data on the vertical concentrations, complexation, speciation, and fluxes of total dissolved zinc and zinc complexing ligands, and zinc speciation in sediment pore waters in the Chesapeake Bay and Elizabeth River, Virginia.

Sediment pore waters were collected in mid and southern Chesapeake Bay in November 1997 and in the Elizabeth River (Pinner's Point) in March, April, and July 1998. Flux experiments were conducted in Elizabeth River sediment cores in April and July 1998. [TDZn] and zinc complexation were determined using differential pulse anodic stripping voltammetry at a hanging mercury drop electrode (DPASV-HMDE).

[TDZn] in the …

Synthesis And Crystal Structure Of Tetrachloro (1,10-Phenanthroline) Platinum (Iv), Robert M. Granger Ii, Jill N. Granger, Kelly Del Campo, Molly B. Becherer, Phillip E. Fanwick

Virginia Journal of Science

We report the crystal structure determination of tetrachloro( l,10-phenan­throline)platinum(IV). X-ray data indicate there is little steric repulsion between the cx.-hydrogens on the phenanthroline ligand and the chloride ligands in the equatorial plane.

Trans-Resveratrol Inhibits Calcium Influx In Thrombin-Stimulated Human Platelets, Yuliya Dobrydneva, Roy L. Williams, Peter F. Blackmore

Chemistry & Biochemistry Faculty Publications

1 The phytoestrogenic compound trans-resveratrol (trans-3,5,4'-trihydroxystilbene) is found in appreciable quantities in grape skins and wine. It has been shown that both products rich in trans-resveratrol and pure trans-resveratrol inhibit platelet aggregation both in vivo and in vitro. However the mechanism of this action still remains unknown.

2 An essential component of the aggregation process in platelets is an increase in intracellular free Ca²⁺ ([Ca²⁺]_i). Ca²⁺ must enter the cell from the external media through specific and tightly regulated Ca²⁺ channels in the plasma membrane. The objective …

Aneuploidy Frequencies In Semen Fractions From Ten Oligoasthenoteratozoospermic Patients Donating Sperm For Intracytoplasmic Sperm Injection, Jerome Pfeffer, Myung-Geol Pang, Stanton F. Hoegerman, Christopher J. Osgood, M. W. Stacey, Jacob Mayer, Sergio Oehninger, William G. Kearns

Biological Sciences Faculty Publications

Objective: To determine aneuploidy frequencies in pellet and swim-up semen fractions from 10 infertile men with severe oligoasthenoteratozoospermia (OAT) who were donating sperm for intracytoplasmic sperm injection and to determine whether the swim-up isolation method would successfully separate aneuploid from haploid sperm.

Design: Prospective study.

Setting: Infertility clinic and molecular genetics laboratory.

Patient(s): Ten patients with severe OAT.

Intervention(s): Cytogenetic analyses by fluorescence in situ hybridization to determine aneuploidy frequencies for chromosomes 1, 13, 18, 21, X, and Y in sperm from swim-up and pellet fractions.

Main Outcome Measure(s): Gametic aneuploidy was scored in sperm fractions separated by the swim-up …

Chemical Modification Of Cvd Diamond Electrodes, Robert Matthew Johnson

Chemistry & Biochemistry Theses & Dissertations

The micro-array behavior of boron doped CVD diamond thin film electrodes has been studied in acetonitrile containing two redox couples. The analytical technique employed in these studies was cyclic voltammetry. One system is 0.4 mM ferrocene containing 0.1 M tetrabutylammonium hexafluorophosphate (TBAH). This reversible redox system is not only well-known, but also involves only one electron transfer with no breakage/formation of chemical bonds, thus making it a simple system for analysis. The second test is 0.8 mM cobaltocenium hexafluorophosphate, with 0.4 mM ferrocene as an internal standard. Unlike ferrocene, which is neutral initially, cobaltocenium is positively charged, and is reduced …

Determination Of The N-Terminal Amino Acid Residues On Polypeptides In Secondary Wastewaters, Edward L. Creecy

Chemistry & Biochemistry Theses & Dissertations

The N-terminal amino acid residues on polypeptides and proteins were determined in wastewaters prior to chlorination. The terminal amino groups'ere first derivatized with the well known derivatizing agent dansyl chloride, and then the resulting dansyl amino acid hydrolyzed from the peptide chain by a propionic acid/ hydrochloric acid mixture. The resulting dansyl amino acids were then separated and detected using reversed phase high performance liquid chromatography with fluorescence detection. The majority of N-terminal residues detected were the more polar amino acids. Concentrations ranged from 1 x 10^-10 to 3 x 10^-7 moles/liter. It is suggested that the shorter …