Physical Sciences and Mathematics Commons^™

Microemulsion Characterization By The Use Of A Noninvasive Backscatter Fiber Optic Probe, Rafat R. Ansari, Harbans S. Dhadwal, Michael Cheung, William V. Meyer

Chemical, Biomolecular, and Corrosion Engineering Faculty Research

This paper demonstrates the utility of a noninvasive backscatter fiber optic probe for dynamic light-scattering characterization of a microemulsion comprising sodium dodecyl sulfate/1-butanol/brine/heptane. The fiber probe, comprising two optical fibers precisely positioned in a stainless steel body, is a miniaturized and efficient self-beating dynamic light-scattering system. Accuracy of particle size estimation is better than +/- 2%.

Electronegativity And Bond Type 2. Evaluation Of Electronegativity Scales, Gordon Sproul

Faculty Publications

No abstract provided.

Tribological Characteristics Of Perfluoropolyether Liquid Lubricants Under Sliding Conditions In High Vacuum, Masabumi Masuko, William R. Jones Jr, Larry S. Helmick

Science and Mathematics Faculty Publications

Tribological characteristics of three PFPE's (Fomblin Z, Demnum, and Krytox) were studied under high vacuum using a four-ball apparatus with 440C steel specimens. Fomblin Z and Demnum exhibited initial scuffing-like high friction whereas Krytox did not. Steady state friction with Fomblin Z was the lowest among the three oils. Frictional values for Demnum and Krytox were almost the same. The lowest wear rate in air was provided by Krytox regardless of load, and low wear rates in vacuum at high load were achieved with Krytox and Demnum. Results are explained by reactivity and pressure-viscosity characteristics of the oils.

A Neutron Diffraction And Mössbauer Effect Study Of The Magnetic Properties Of Pr₂Fe₁₇ And Pr₂Fe₁₇N₂.₆, Gary J. Long, Oran Allan Pringle, Fernande Grandjean, William B. Yelon, K. H. Buschow

Chemistry Faculty Research & Creative Works

The neutron diffraction powder patterns of Pr₂Fe₁₇ and Pr₂Fe₁₇N_2.6 have been measured at 295 K and refined within the Th₂Zn₁₇ structure type to give the structural changes which occur upon nitrogenation; changes which include a 6.4% expansion of the unit cell volume. The Mössbauer spectra of Pr ₂Fe₁₇ and Pr₂Fe₁₇N_2.6 have been measured between 85 and 295 K and analyzed with a model which is based on the Wigner-Seitz cell environment of each iron site, the basal orientation of the magnetization, and …

Variability In Growth And Age Structure Among Populations Of Ribbed Mussels, Geukensia Demissa (Dillwyn) (Bivalvia: Mytilidae), In Jamacia Bay, New York (Gateway Nra), David R. Franz, John Tanacredi Ph.D.

Faculty Works: CERCOM (1977-2016)

Growth rates, body weight, density and biomass of ribbed mussels, Geukensia demissa (Dillwyn), were determined at Spartina alterniflora marsh-flat sites in Jamaica Bay, New York (Lower Hudson Estuary). Cumulative growth and annual growth increments varied but rates were lower at sites within the central bay relative to peripheral sites. Local variability both in size at Ring-1 and size-specific annual growth rates probably account for the variability in cumulative length. No pattersn were noted in frequency distributions of shell size but congruence in age structure was observed among neighboring sites in some areas of the bay. Mussel densities were greater within …

Characterization Of Combustion Profiles Of Co-Fired Coal/Biomass/Limestone Samples By Tg And Tg/Ftir, Erik Jon Hutchinson

Masters Theses & Specialist Projects

Recent concerns over declining landfill space and a renewed interest in waste-to-energy technologies have increased the possibilities of co-firing different types of fuels in fluidized bed combustion systems. Fluidized bed combustion systems are idea for co-firing because of their ease in heat conversion and ability to burn a wide range of fuels. Additionally, thermal analytical techniques can be used to screen fuel blends for the fluidized bed combustion systems at a lower cost than directly firing the fuel blends in pilot systems. Three coals, three different municipal solid wastes (MSW), one limestone were combined into nine series of binary fuel …

A Study Of The Chlorination Products Of Methionine In Model Solutions And In Wastewater, D. Scott Winters

Chemistry & Biochemistry Theses & Dissertations

Model solutions of the amino acid methionine were chlorinated to seven chlorine-to-nitrogen (Cl₂/N) molar ratios. After 30 minutes, the solutions were analyzed by high performance liquid chromatography (HPLC). At a Cl₂/N molar ratio of 1, methionine sulfoxide was found to be the main product. At Cl₂/N molar ratios ≥ 2, a mixture of methionine sulfoxide, methionine sulfone, an unidentified sulfoxide (product 1), and N-chloro-3-(methylsulfonyl) propionaldimine are formed. These products were identified by comparison to synthesized standards which were characterized by ¹H-NMR and ¹³C-NMR nuclear magnetic resonance spectroscopy, ion trap mass spectroscopy, …

The Isolation And Identification Of Polyphenolics From Grape Seeds And Their Activity Towards Specific Cell Lines, Joseph A. Reddy

Chemistry & Biochemistry Theses & Dissertations

Grape seed extract is being marketed in France for cardiovascular use and skin care. The active constituents of both these drugs are certain polyphenols called procyanidins. A similar seed extract has now been obtained from Virginia Chardonnay grape seeds. Ten of the major components in this extract have been isolated in their pure form by the semi-preparative HPLC separation on a YMC ODS-AQ (Octadecylsilane-AQ) column. The ODS-Aq column has been shown to have a better resolving capacity compared to the Spherisorb ODS (Octadecylsilane) column previously described in the literature. This has been attributed to the ODSAQ support which has both …

Hexameric Lithium Phenolate: Crystal Structures And Lithium-7 Quadrupole Coupling In Solid And Solution Phases., Lloyd Jackman, Deniz Cizmeciyan, Paul Willard, Michael Nichols

Michael A Nichols

No abstract provided.

Formation Of O-Tyrosine And Dityrosine In Proteins During Radiolytic And Metal-Catalyzed Oxidation, Thomas G. Huggins, Mary C. Wells-Knecht, Nicholas A. Detorie, John W. Baynes, Suzanna R. Thorpe

Faculty Publications

To evaluate their usefulness as chemical indicators of cumulative oxidative damage to proteins, we studied the kinetics and extent of formation of ortho-tyrosine (0-Tyr), dityrosine (DT), and dityrosine-like fluorescence (Ex = 3 17 nm, E,,, = 407 nm) in the model proteins RNase and lysozyme exposed to radiolytic and metalcatalyzed (H20z/Cu2+) oxidation (MCO). Although there were protein-dependent differences, o-Tyr, DT, and fluorescence increased coordinately during oxidation of the proteins in both oxidation systems. The contribution of DT to total dityrosine-like fluorescence in oxidized proteins varied from 2-10070, depending on the protein, type of oxidation, and extent of oxidative damage. In …

Oxidized Amino Acids In Lens Protein With Age: Measurement Of O-Tyrosine And Dityrosine In The Aging Human Lens, Mary C. Wells-Knect, Thomas G. Huggins, Daniel G. Dyer, Suzanne R. Thorpe, John W. Baynes

Faculty Publications

The concentrations of ortho-tyrosine (o-Tyr) and dityrosine (DT) were measured in noncataractous human lenses in order to assess the role of proteinoxidation reactions in the aging of lens proteins. The measurements were conducted by selected ion monitoring-gas chromatography/mass spectrometry using deuterium-labeled internal standards, which provided both high sensitivity and specificity for the quantitation of o-Tyr and DT. Between ages 1 and 78 years, the o-Tyr concentration in lens proteins varied from 0.3 to 0.9 mmol of o-Tyr/mol of Phe (n = 19), while DT ranged from 1 to 3 mumol of DT/mol of Tyr (n = 30). There were no …

Impact-Parameter-Selected Two-Proton Intensity Interferometry For 36ar + 45sc At E/A=80 Mev, M. A. Lisa, C. K. Gelbke, W. Bauer, P. Decowski, W. G. Gong, E. Gualtieri, S. Hannuschke, R. Lacey, T. Li, W. G. Lynch, C. M. Mader, Graham F. Peaslee, T. Reposeur, A. M. Vander Molen, G. D. Westfall, J. Yee, S. J. Yennello

Faculty Publications

The momentum dependence of the two-proton correlation function is studied for central and peripheral Ar36+45Sc collisions at E/A=80 MeV. Calculations with the Boltzmann-Uehling-Uhlenbeck transport theory reproduce well the measured momentum dependence of the correlation functions for central collisions, but underpredict the momentum dependence for peripheral collisions.

The Cytotoxic Effect Of Tropical Plants On Human And Rat Hepatoma Cells, Mark Tafazoli

Honors Capstone Projects and Theses

No abstract provided.

Sources And Emission Time Scales In E/A=50 Mev 129xe + Natcu Reactions, D. R. Bowman, Graham F. Peaslee, N. Carlin, R. T. De Souza, C. K. Gelbke, W. G. Gong, Y. D. Kim, M. A. Lisa, W. G. Lynch, L. Phair, M. B. Tsang, C. Williams, N. Colonna, K. Hanold, M. A. Mcmahan, G. J. Wozniak, L. G. Moretto

Faculty Publications

Velocity distributions and fragment-fragment correlation functions have been measured as a function of charged particle multiplicity for Xe129+natCu collisions at E/A=50 MeV. With increasing multiplicity, the velocity distributions evolve from a pattern exhibiting targetlike and projectilelike sources to an anisotropic distribution centered near the projectile-target center-of-mass velocity. Emission times extracted from the correlation functions are consistent with the decay of a projectilelike source in low multiplicity collisions, but the time scale for fragment emission in the high multiplicity collisions is too short for a separation of sources to occur.

Synthesis Of N-Boc-3-Azabicyclo[3.3.0]Octan-7-One Via Reductive Pauson-Khand Cyclization And Subsequent Conversion To A Novel Diazatricyclic Ring System, Daniel Becker, Daniel L. Flynn

Chemistry: Faculty Publications and Other Works

An intramolecular reductive Pauson-Khand reaction of the hexacarbonyldicobalt complex of N-(tert-butyloxycarbonyl)allylpropargylamine under dry-state adsorption conditions directly afforded the saturated N-BOC-3-azabicyclo[3.3.0]octan-7-one when the reaction was performed under an inert atmosphere. This bicyclic ketone was converted in several steps to the novel octahydro-1-azeto[2′,3′:3,4]cyclopenta[1,2-C]pyrrole ring system as confirmed by single crystal X-ray analysis.

Experimental And Computational Studies Of Four-Coordinate Aluminum: The Reaction Of Aluminates And Acids, Robert Damrauer, Michèle Krempp, Niels H. Damrauer, Michael W. Schmidt, Mark S. Gordon

Mark S. Gordon

The gas-phase reactions of trimethylaluminates with a variety of acids are considered from both an experimental and computational perspective. The experimental work involves product and kinetic studies of ten aluminates, [(CH3hAlX]- (X= H, CH3, NH2, OH, F, SiH3, PH2, SH, Cl, and OCH3). Both X and methyl cleavage pathways are observed in these reactions. X cleavage occurs with several aluminates (X = H, NH2, OH, and PH2), in contrast to the thermochemical predictions of ab initio computations performed at the MP2/6-31 ++G(d,p) level. These indicate that methyl cleavage is favored in the reaction of nine aluminates (OCH3 was not computed) …

The Selective Oxidation Of Dihydrosilanes, Paul B. Gansle Jr.

Honors Theses

The synthesis of drugs and natural products in enartiomerically pure form is a growing area of research. Our laboratory is currently working on synthetic methodologies that would facilitate the production of compounds in such a form. The approach we are taking is to use chiral silanes as templates for the stereochemical control of organic reactions. In order to do this, however, we must first synthesize these silanes enantiomerically pure. This project focuses on the synthesis of chiral silanes by selective oxidation of prochiral dihydrosilanes to yield directly, or by further transformations, halohydrosilanes. These halohydrosilanes can in turn, be used as …

Construction Of A Compact, Versatile Diode Laser Spectrometer And Characterization Of Dye-Surfactant Interactions, Marc Alexander Unger

Honors Theses

A compact diode laser spectrometer has been designed and built. A diode laser serves as a light source. The sample holder was designed to allow the mounting of optical filters and focusing optics. These optical filters differentiate between transmitted, scattered, and fluorescent light. A photodiode transduces one of these optical signals to a current signal. The electronics were designed to perform current to voltage conversion, amplify the signal, and filter out noise. Further processing and display are performed by a "Virtual Instrument", which is a computer program designed to simulate a physical instrument. Design methodology for the mechanical/optical, electronic, and …

The Development And Testing Of An Instrument For Doing Fast Time-Resolved Infrared Spectroscopy And The Study Of Dimanganese Decacarbonyl Using Uv/Vis And Ftrir Spectroscopic Techniques, Steven Wells Kinne

Honors Theses

Over the past three years at Union College, an instrument has been developed that can be used to probe the mechanisms of the photochemistry of transition metal carbonyl compounds. When these complexes are activated with photons, one or two carbonyl ligands are removed from the complex, opening these sites for chemical bonding. Thus, the coordinatively unsaturated species become catalytically active, and can catalyze a wide variety of organic reactions. The intermediates in these catalytic cycles tend to be short-liver lifetimes are usually less than one second), and therefore special instrumnetation must be developed in order to directly observe these intermediates …

Existence Of High-Order Superlattices In Orientationally Ordered C_{60}, J. E. Fischer, D. E. Luzzi, K. Kniaź, A. R. Mcghie, D. A. Ricketts-Foot, W. R. Romanow, Gavin B. M. Vaughan, Dayin Li, Allan L. Smith, Robert M. Strongin, M. A. Cichy, Laurent Bard, Amos B. Smith Iii

Chemistry Faculty Publications and Presentations

We correlate the presence or absence of high-order modulated structures in solid C₆₀ with the differential scanning calorimetry signature of the orientational ordering transition and other diagnostic data. We have searched for, but not observed, the 2a face-centered cubic structure recently observed in low-temperature electron and single-crystal x-ray diffraction. We conclude that the intrinsic ground state is the previously reported simple cubic structure [space groupPa3¯, a(14 K)=14.06 Å], and that other structures may be stabilized by defects or impurities.

Coherence Peak And Superconducting Energy Gap In Rb_{3}C_{60} Observed By Muon Spin Relaxation, R. F. Kiefl, W. A. Macfarlane, K. H. Chow, S. Dunsiger, T. L. Duty, T. M. S. Johnston, J. W. Schneider, J. Sonier, Laurent Brard, Robert M. Strongin, J. E. Fischer, Amos B. Smith Iii

Chemistry Faculty Publications and Presentations

Muon spin relaxation resulting from spin exchange scattering of endohedral muonium (μ+e-) with thermal electronic excitations has been observed in the fullerene superconductor Rb₃C₆₀. The temperature dependence of T₁^-1 shows a coherence peak just below T_c and can be fit to the conventional Hebel-Slichter theory for spin relaxation in a superconductor with a broadened BCS density of states. The average energy gap for electronic excitations, Δ/k_B=53(4) K or 2Δ/ k_BT_c=3.6(3), is consistent with the BCS weak coupling limit.

Accumulation Of Maillard Reaction Products In Skin Collagen In Diabetes And Aging, Daniel G. Dyer, John A. Dunn, Suzanne R. Thorpe, Karen E. Bailie, Timothy L. Lyons, David R. Mccance, John W. Baynes

Faculty Publications

To investigate the contribution of glycation and oxidation reactions to the modification of insoluble collagen in aging and diabetes, Maillard reaction products were measured in skin collagen from 39 type 1 diabetic patients and 52 nondiabetic control subjects. Compounds studied included fructoselysine (FL), the initial glycation product, and the glycoxidation products, N epsilon-(carboxymethyl) lysine (CML) and pentosidine, formed during later Maillard reactions. Collagen-linked fluorescence was also studied. In nondiabetic subjects, glycation of collagen (FL content) increased only 33% between 20 and 85 yr of age. In contrast, CML, pentosidine and fluorescence increased five-fold, correlating strongly with age. In diabetic patients, …

Investigation Of Electron Transfer From Carbonylmetallate Anions To Electron Acceptors, Joseph Kofi Agyin

Masters Theses

This study investigated electron transfer potential of the carbonyl-metallate anions cyclopentadienylirondicarbonyl and methylcyclopentadienyliron-dicarbonyl anions to the electron acceptors 2,2-dinitropropane, 1,1-dinitrocyclohexane, $\alpha$,p-dinitrocumene, methyl cyclopentadienyl-mercury(II) chloride and iodide.

The findings from this study indicated that: (a) the expected products could not be obtained from reactions of the anions with the dinitro-substrates, and (b) the mercurials reacted with the anions but the expected products, (ferrocene and methylferrocene), was the minor product and an unexpected (methyl) cyclopentadienylirondicarbonylmercury(II)-chloride or iodide was the major product.

Maillard Reaction Products And Their Relation To Complications In Insulin-Dependent Diabetes Mellitus, David R. Mccance, Daniel G. Dryer, John A. Dunn, Karen E. Bailie, Suzanne R. Thorpe, John W. Baynes, Timothy J. Lyons

Faculty Publications

Glycation, oxidation, and browning of proteins have all been implicated in the development of diabetic complications. We measured the initial Amadori adduct, fructoselysine (FL); two Maillard products, N epsilon-(carboxymethyl) lysine (CML) and pentosidine; and fluorescence (excitation = 328 nm, emission = 378 nm) in skin collagen from 39 type 1 diabetic patients (aged 41.5 +/- 15.3 [17-73] yr; duration of diabetes 17.9 +/- 11.5 [0-46] yr, [mean +/- SD, range]). The measurements were related to the presence of background (n = 9) or proliferative (n = 16) retinopathy; early nephropathy (24-h albumin excretion rate [AER24] > or = 20 micrograms/min; n …

An Elementary Reaction Model For Thermal Decomposition Of Cf2cl2 In A H2 Atmosphere And Experimental Studies On Oxidation Of Ch3oh Plus Ch4 Under Fuel Rich, Stoichiometric And Fuel Lean Conditions, Cheng Guo

Theses

Pyrolysis of CF₂CL₂ in an atmosphere of H₂, has been studied in a tubular flow reactor, 723 to 873 K. Overall eaction conversion proceeds via loss of Cl with CHF₂CL formation, then loss of the second Cl atom and CH₂F₂ product. Initiation occurs by unimolecular Cl atom loss. Subsequent chain propagation steps rapidly generate active H atoms which abstract Cl atoms, but abstraction of fluo-rine atoms by atomic hydrogen is slow at the temperatures of this study.

A small mechanism, about 35 elementary reaction steps, and a thermodynamic data base …

Photochemistry Of Nitrous Acid And Nitrite Ion, Kathryn E. Shanks '93

Honors Projects

Research is currently underway to elucidate the photochemical decomposition mechanism of nitrous acid and nitrite ion in aqueous and non-aqueous media. The quantum yield of the photochemical disappearance of nitrous acid and nitrite, as a function of pH and nitrous acid/nitrite ion concentration ratios, was examined. Spectroscopic studies have been done with nitrite ion in various aprotic organic solvents. Similar work has been started with molecular nitrous acid that was produced in aqueous solution and then extracted into organic solvents. These organic solvents were employed in order to study the quantum yield with respect to NO2- and HONO without the …

Development Of New Methods For Assessing Solidification/Stabilization Of Hazardous Waste Using Solid-State Nuclear Magnetic Resonance Techniques (Ph.D Dissertation, Lsu), Michael A. Janusa

Faculty Publications

New methods for assessing solidification/stabilization (S/S) of hazardous waste using solid-state nuclear magnetic resonance are developed for the purpose of diagnosing on a microscopic level the performance of S/S as a hazardous waste disposal technique. There are four techniques developed and described in this dissertation: (1) Solid-state deuterium NMR spectroscopy is used to determine if a particular deuterated organic waste is effectively solidified/stabilized and to determine the lower limit of the bond strength between the waste and the cement matrix; (2) Constant time pulsed field gradient ^ NMR spectroscopy is tested on a liquid waste encapsulated within a solidified matrix …

A Neutron Diffraction And Mössbauer Effect Study Of The Magnetic Structure Of Y₂(Fe₁₋ₓmnₓ)₁₄B, Gaya Kanishka Marasinghe, Oran Allan Pringle, Gary J. Long, William Joseph James, William B. Yelon, Fernande Grandjean

Physics Faculty Research & Creative Works

The magnetic structures of a series of Y₂(Fe _1-xMn_x)₁₄B samples, with x equal to 0.03, 0.10, 0.25, and 0.37, have been studied by powder neutron diffraction and Mössbauer spectroscopy. Y₂(Fe_0.97Mn _0.03)₁₄B and Y₂(Fe_0.9Mn _0.1)₁₄B are ferromagnetic at both 295 and 85 K, Y ₂(Fe_0.63Mn_0.37)₁₄B is paramagnetic at both 295 and 85 K, whereas Y₂(Fe_0.75Mn _0.25)₁₄B is paramagnetic at 295 K and is partially ordered at …

Unusual Thermal Stability Of A Site-Ordered Mc60 Rocksalt Structure (M=K, Rb, Or Cs), Q. Zhu, O. Zhou, J. E. Fischer, Andrew R. Mcghie, W. R. Romanow, Robert M. Strongin, M. A. Cichy, Amos B. Smith Iii

Chemistry Faculty Publications and Presentations

X-ray diffraction and differential scanning calorimetry of M_xC₆₀, with x∼1 and M=K, Rb, or Cs, reveal an unusual T-dependent phase sequence. A low-symmetry ground state is found, while the high-T limit is an ordered rocksalt structure in which only the octahedral sites are occupied. The unusual high-T stability of this ordered phase is attributed to the entropy of molecular orientational disorder and/or thermal disorder of the alkali-metal ions within the octahedral sites. Unique to K_xC₆₀ with x≥1.4, we find at intermediate temperatures an fcc site-disordered lattice gas …

Examination Of Fat Oxidation Products By Ft-Nmr & Ft-Ir, De Chen

Masters Theses & Specialist Projects

Edible oils are easily oxidized when used for frying. Oxidation originates with double bonds present in unsaturated fatty acids. A new NMR method is presented which offers potential for determining the products of oil oxidation. High resolution fourier transform nuclear magnetic resonance (FT-NMR) and fourier transform infrared (FT-IR) spectroscopy have found increasing use in biochemistry. One pure fat, trioleoylglycerol, was heated at 160°C in the presence of air Samples were taken for FT-NMR and FT-IR analyses at 4, 10. 20. 25, 35, 50, 70 and 100 hours. Proton, Carbon-13 and several types of two-dimensional FT-NMR spectra were obtained using a …