Physical Sciences and Mathematics Commons^™

Synthesis Of Cyclopropanes Via Organoiron Methodology: Preparation Of 2-(2′-Carboxy-3′-Ethylcyclopropyl)Glycine, Kamil Godula, William A. Donaldson

Chemistry Faculty Research and Publications

A route to 1,2,3-trisubstituted cyclopropanes has been developed. The relative stereochemistry at the three cyclopropane centers is established by nucleophilic attack on the pentadienyl ligand on the face opposite to iron and subsequent oxidatively induced reductive elimination with retention of configuration. This methodology was applied to the synthesis of 2-(2′-carboxy-3′-ethylcyclopropyl)glycines. The diastereomeric glycine dimethyl esters are separable as their diphenylmethylene imines.

The conformationally restricted glutamate analogs (2S,1′S,2′S,3′R)- and (2R,1′S,2′S,3′R)-ECCG's 5a and5b were prepared in five steps (17 and 15% yield, respectively) from (pentadienyl)Fe(CO) …

Photooxidation Of Polymeric-Inorganic Nanocomposites: Chemical, Thermal Stability And Fire Retardancy Investigations, Adams Tidjani, Charles A. Wilkie

Chemistry Faculty Research and Publications

Nanocomposites of polypropylene-graft-maleic anhydride/clay and polypropylene/clay were prepared by melt blending using two different approaches. X-Ray diffraction results showed an intercalated structure. Samples of nanocomposites were exposed to UV light under atmospheric oxygen and their photo-oxidative stability was studied using FTIR and UV spectroscopy. The consequences of this photo-oxidation on the thermal stability and fire retardant performance of the nanocomposites were also addressed from thermogravimetry analysis and Cone calorimetry.

Xps Characterization Of Friedel-Crafts Cross-Linked Polystyrene, Jiangqi Wang, Jianxin Du, Hongyang Yao, Charles A. Wilkie

Chemistry Faculty Research and Publications

The combination of a difunctional alkylating agent, either hydroxymethylbenzyl chloride or α,α′-dichloroxylene with polystyrene or high-impact polystyrene together with a Friedel-Crafts catalyst, 2-ethylhexyldiphenylphosphate, and an amine to react with hydrogen chloride has been studied by X-ray photoelectron spectroscopy. The results confirm what had been suggested from previous investigations using thermogravimetric analysis; cross-linking of the polymer occurs as the temperature is raised and the alcohol-containing alkylating agent gives a greater amount of cross-linking than does the dichloro compound.

Noncovalent Binding Of The Halogens To Aromatic Donors. Discrete Structures Of Labile Br2 Complexes With Benzene And Toluene, Alexandr V. Vasilyev, Sergey V. Lindeman, Jay K. Kochi

Chemistry Faculty Research and Publications

Precise molecular structures resulting from the noncovalent interaction of Br₂ with benzene (and toluene) reveal the unusual localized bonding to specific (one or two) carbon centers in prereactive complexes leading directly to the transition states for electrophilic aromatic brominations.

An Xps Investigation Of Thermal Degradation And Charring Of Cross-Linked Polyisoprene And Polychloroprene, Jianwei Hao, Charles A. Wilkie, Jiangqi Wang

Chemistry Faculty Research and Publications

Our interest in butadiene-containing polymers had led to an investigation of the thermal degradation of polyisoprene, PIP, and polychloroprene, PCP. The connection between cross-linking and thermal stability through an examination of PIP and PCP has been reported. Like the course of thermogravimetric analysis (TGA) the cross-linking and charring of polymers subjected to heat can also be experimentally observed as function of temperatures by the pseudo-in-situ XPS (X-ray Photoelectron Spectroscopy). Data acquisition of C1s spectra as function of temperature permits us to explore: (1) the extent of cross-linking and/or carbon accumulation of systems of PCP and PIP with/without initiators, BPO and …

The Thermal Stability Of Cross-Linked Polymers: Methyl Methacrylate With Divinylbenzene And Styrene With Dimethacrylates, Fawn Marie Uhl, Galina F. Levchik, Sergei V. Levchik, Caroline Dick, John J. Liggat, C.E. Snape, Charles A. Wilkie

Chemistry Faculty Research and Publications

Cross-linking of polymers is frequently presumed to enhance the thermal stability of polymer systems. Methyl methacrylate has been reacted with divinylbenzene and styrene with various dimethacrylates. These systems have been characterized by gel content, swelling ratio, infrared spectroscopy, thermal analysis, TGA/FT-IR, and solid state NMR. Both systems show enhanced thermal stability and char formation. This is most pronounced in the cases of methyl methacrylate with divinylbenzene and styrene with bisphenol A dimethacrylate.

Fire Properties Of Polystyrene-Clay Nanocomposites, Jin Zhu, Alexander B. Morgan, Frank K. Lamelas, Charles A. Wilkie

Chemistry Faculty Research and Publications

Polystyrene−clay nanocomposites have been prepared using a bulk polymerization technique. Three new “onium” salts have been used to prepare the nanocomposites, two are functionalized ammonium salts while the third is a phosphonium salt. By TGA/FTIR, both ammonium and phosphonium treatments have been shown to degrade by a Hofmann elimination mechanism at elevated temperatures. TGA/FTIR showed that the phosphonium treatment is the most thermally stable treatment when compared to the two ammonium salts. The nanocomposites were characterized by X-ray diffraction, transmission electron microscopy, strength and elongation at break, as a measure of the mechanical properties, thermogravimetric analysis, and cone calorimetry. The …

Thermal Degradation Of Pvc In The Presence Of Polystyrene, Qiang Yao, Charles A. Wilkie

Chemistry Faculty Research and Publications

The thermal degradation of poly(vinyl chloride) (PVC) and blends of PVC with polystyrene has been studied using thermogravimetric analysis coupled to Fourier transform infrared spectroscopy. The degradation of PVC commences at weak links by an ionic pathway, but there is evidence to suggest the presence of a radical pathway at high temperatures. While there is some chemical interaction between PVC and polystyrene, the principal mode of stabilization is a physical process.

Studies On The Mechanism By Which The Formation Of Nanocomposites Enhance Thermal Stability, Jin Zhu, Fawn Marie Uhl, Alexander B. Morgan, Charles A. Wilkie

Chemistry Faculty Research and Publications

Polystyrene−clay and polystyrene−graphite nanocomposites have been prepared and used to explore the process by which the presence of clay or graphite in a nanocomposite enhances the thermal stability of polymers. This study has been designed to determine if the presence of paramagnetic iron in the matrix can result in radical trapping and thus enhance thermal stability. Nanocomposites were prepared by bulk polymerization using both iron-containing and iron-depleted clays and graphites, and they were characterized by X-ray diffraction, transmission electron microscopy, thermogravimetric analysis, and cone calorimetry. The presence of structural iron, rather than that present as an impurity, significantly increases the …

Group Invariant Solutions In Mathematical Physics And Differential Geometry, Ian M. Anderson, Mark E. Fels, Charles G. Torre

All Physics Faculty Publications

This is a brief overview of our work on the theory of group invariant solutions to differential equations. The motivations and applications of this work stem from problems in differential geometry and relativistic field theory. The key feature in our theory is that we allow for non-transverse symmetry group actions, which are very common in applications.

White Dwarfs In Common Proper Motion Binary Systems: Mass Distribution And Kinematics, Nicole M. Silvestri, Terry D. Oswalt, Matt A. Wood, J. Allyn Smith, I. Neill Reid, Edward M. Sion

Publications

We present the mass distribution, gravitational redshifts, radial velocities, and space motions of white dwarf stars in common proper motion binary systems. The mass distribution we derive for the 41 DA white dwarfs in this study has a mean of 0.68 ± 0.04 M_Ꙩ. This distribution has a slightly higher mean and larger dispersion than most previous white dwarf studies. We hypothesize that this is due to a higher fraction of cool (average T_eff ̴ 10,000 K), hence old, white dwarfs in our sample. Our results indicate that samples made up of predominantly cool, old white dwarf stars …

Fact Sheet, Yale University Office Of Institutional Research

Fact Sheets

No abstract provided.

Can Long-Term Variability In The Gulf Stream Transport Be Inferred From Sea Level?, Tal Ezer

CCPO Publications

Recent studies by Sturges and collaborators suggest a simple, but powerful, technique to estimate climatic changes in the transport of the Gulf Stream from the difference between the oceanic sea level calculated with a simple wind-driven Rossby wave model and the observed coastal sea level. The hypothesis behind this technique is tested, using 40 years of data (1950 to 1989) obtained from a three-dimensional Atlantic Ocean model forced by observed surface data. The analysis shows that variations in sea level difference between the ocean and the coast are indeed coherent with variations of the Gulf Stream transport for periods shorter …

Reconstructing Basin-Scale Eulerian Velocity Fields From Simulated Drifter Data, M. Toner, A. C. Poje, A. D. Kirwan, C. K. R. T. Jones, B. L. Lipphardt, C. E. Grosch

CCPO Publications

A single-layer, reduced-gravity, double-gyre primitive equation model in a 2000 km x 2000 km square domain is used to test the accuracy and sensitivity of time-dependent Eulerian velocity fields reconstructed from numerically generated drifter trajectories and climatology. The goal is to determine how much Lagrangian data is needed to capture the Eulerian velocity field within a specified accuracy. The Eulerian fields are found by projecting, on an analytic set of divergence-free basis functions, drifter data launched in the active western half of the basin supplemented by climatology in the eastern domain. The time-dependent coefficients are evaluated by least squares minimization …

Future Marine Zooplankton Research- A Perspective, Marine Zooplankton Colloquim 2, Eileen E. Hofmann, John M. Klinck

CCPO Publications

During the Second Marine Zooplankton Colloquium (MZC2) 3 issues were added to those developed 11 yr ago during the First Marine Zooplankton Colloquium (MZC1). First, we focused on hot spots, i.e., locations where zooplankton occur in higher than regular abundance and/or operate at higher rates. We should be able to determine the processes leading to such aggregations and rates, and quantify their persistence. Second, information on the level of individual species, even of highly abundant ones, is limited. Concerted efforts should be undertaken with highly abundant to dominant species or genera (e.g., Oithona spp., Calanus spp., Oikopleura spp., Euphausia superba …

Wind And Gulf Stream Influences On Along-Shelf Transport And Off-Shelf Export At Cape Hatteras, North Carolina, Dana K. Savidge, John M. Bane Jr.

CCPO Publications

Along-shelf transports across three cross-shelf lines on the continental shelf near Cape Hatteras have been calculated from moored current meter data over a continuous 24 month period in 1992-1994. The along-shelf convergence has been used to infer off-shelf export. Transport and transport convergence have been related to wind and Gulf Stream forcing and to variability in sea level at the coast. The along-shelf transport variability is primarily wind-driven and highly correlated with sea level fluctuations at the coast. Both winds and along-shelf transport exhibit a near-annual period variability. Along shelf transport is not well correlated with Gulf Stream offshore position. …

Observations Of Intratidal Variability Of Flows Over A Sill/Contraction Combination In A Chilean Fjord, Arnoldo Valle-Levinson, Fernando Jara, Carlos Molinet, Doris Soto

CCPO Publications

Underway velocity measurements were carried out for the first time in a Chilean fjord using an acoustic Doppler velocimeter with the purpose of elucidating the intratidal variability of flows through a pass, Paso Galvarino. The pass included a sill, where the bottom sloped by roughly 30%, and a coastline contraction of -90%. The relatively small dimensions of the pass allowed for rapid sampling of the flow evolution throughout the tidal cycle. The backscattered sound signal from the velocimeter and from an echo sounder were used to describe the vertical excursions of the pycnocline throughout the domain and to identify regions …

Future Research Vessels, Larry P. Atkinson

CCPO Publications

The academic research vessel fleet in the United States is embarking on a great experiment. By 2004 we will know if SWATH vessels such as the Mlo Moana and the possible built Woods Hole Oceanographic Institution coastal SWATH have such great advantages that all future vessels will be of SWATH design. Or, we will find that the two hull forms have distinct niches and the fleet will evolve with a strategic mix. Regardless of the Mure hull form research vessels will grow in size to accommodate advanced technology and the people to run and maintain it. The research vessel will …

White Dwarfs In Open Clusters: New Tests Of Stellar Evolution And The Age Of The Galaxy, Ted Von Hippel

Publications

White dwarf cooling theory and very deep observations in star clusters provide a new tool to test stellar evolution theory and time scales. In particular, white dwarf cooling theory is now testing the degree of enhanced core mixing in stars with turnoff ages of 1 to 2 Gyr. More generally, I show the good overall agreement between white dwarf and modern isochrone ages over the range 0.1 to 4 Gyr.

Break Out Session: The Future Of White Dwarf Observing, Ted Von Hippel

Publications

On Thursday, June 15, 2000 the conference participants joined on of four afternoon break out sessions. Our break out session was charged with addressing the the following questions: Astronomy is changing. Eight to ten meter telescopes looking towards the edge of the Universe will dominate the astronomical landscape. Queue scheduling, large surveys, and the current emphasis towards the red end of the spectrum will also affect us. What consequences do these changes imply for our field? How can we convince telescope assignment committees to grand observing time to proposers from our community?

Characterization Of Solvent-Extractable Hydrocarbons From Airborne Particulates And Street Dust Of Kuala Lumpur, Nasr Yousef M. J. Omar

Student Works (2000-2009)

The solvent-extractable hydrocarbons were identified in PM 10 airborne particles and roadside soil particles collected at eight locations in the city center and the suburb of Kuala Lumpur, Malaysia during the period from November 1998 to January 1999. Airborne particles were collected using high-volume PM1o sampler on glass fiber filters over 24 h average sampling period. After ultrasonic agitation with dichloromethane, the extracts were concentrated and fractionated on an alumina-silica column into three major fractions (aliphatics, aromatics and polar compounds). The aliphatics and aromatics fractions were then subjected to gas chromatography-mass spectrometric (GCMS) analysis. The major hydrocarbons identified in these …

Eddy Structures Induced Within A Wedge By A Honing Circular Arc, C. P. Hills

Articles

In this paper we outline an expeditious numerical procedure to calculate the Stokes flow in a corner due to the rotation of a scraping circular boundary. The method is also applicable to other wedge geometries. We employ a collocation technique utilising a basis of eddy (similarity) functions introduced by Moffatt (1964) that allows us to satisfy automatically the governing equations for the streamfunction and all the boundary conditions on the surface of the wedge. The circular honing problem thereby becomes one-dimensional requiring only the satisfaction of conditions on the circular boundary. The advantage of using the Moffatt eddy functions as …

Eddies Induced In Cylindrical Containers By A Rotating End Wall, Christopher Hills

Articles

The flow generated in a viscous liquid contained in a cylindrical geometry by a rotating end wall is considered. Recent numerical and experimental work has established several distinct phases of the motion when fluid inertia plays a significant role. The current paper, however, establishes the nature of the flow in the thus far neglected low Reynolds number regime. Explicitly, by employing biorthogonality relations appropriate to the current geometry, it is shown that a sequence of exponentially decaying eddies extends outward from the rotating end wall. The cellular structure is a manifestation of the dominance of complex eigensolutions to the homogeneous …

Structural, Magnetic, And Mössbauer Spectral Study Of Er₂Fe₁₇ And Its Hydrides, Fernande Grandjean, Olivier Isnard, Dimitri Hautot, Gary J. Long

Chemistry Faculty Research & Creative Works

The structural and magnetic properties of the Er₂Fe₁₇H_x compounds, where x is 0, 1, 2, 3, and 3.8, have been investigated by means of powder x-ray diffraction, thermal and ac magnetic susceptibility measurements, and iron-57 Mössbauer spectroscopy. The Er₂Fe₁₇H_x compounds crystallize in the hexagonal P6₃/mmc space group with the Th₂Ni₁₇-like structure, a structure which has both an iron-rich stoichiometry and disorder of the erbium and iron-iron 4f-4f dumbbell sites. The increase in the lattice parameters, the magnetic ordering temperature, the saturation magnetization, and the …

Spectrophotometric Determination Of Propranolol As Cu(Ii), Ni(Ii) And Co(Ii) Dithiocarbamate Complexes, Ayşegül Gölcü, Mustafa Dolaz, Selahatti̇n Seri̇n

Turkish Journal of Chemistry

A spectrophotometric method was developed for the determination of the beta adrenergic blocking drug propranolol. The method was based on the formation of Cu(II), Ni(II) and Co(II)-dithiocarbamate complexes from the secondary amine group of propranolol with carbondisulfide (CS_{2}) and the acetate salts of the metals in ammonia medium. The method was applied to the analysis of propranolol tablets and the results were statistically compared with those obtained by the official method using t- and F-tests. There was no significant difference between the mean values and the precisions of the two methods at the 95% confidence level.

Design, Construction And Testing Of A Portable Electronic Speckle Pattern Interferometry System For Contouring Applications, Tara J. Kneafsey

Masters

Optical surface metrology techniques offer many advantages over conventional methods. Some of these advantages include a greater sensitivity and a whole field analysis that is non-contract. They also offer greater lateral and vertical resolution and are not subject to electromagnetic influence. Despite these many advantages, there has been reluctance in industry to adopt these techniques. This reluctance can be attributed to the use of high-power lasers which are considered dangerous, the expense of the systems and complicated operation and analysis procedures. The objective of the research described in this thesis was to utilise recent developments in laser diodes, data acquisition …

Null String In Curved Backgrounds, Sergey Nikolaevich Roshchupkin

Turkish Journal of Physics

We consider null string in curved backgrounds. Some exact solutions of the classical equations of motion and of the constraints for the null string in a large class of cosmological backgrounds are found.

The Langmuir Properties Of A Mixed Copolysiloxane Monolayer, Rifat Çapan, Tim H. Richardson, David Lacey

Turkish Journal of Physics

A family of linear copolysiloxanes [1-3] substituted with side chains containing carboxylic head groups has been synthesised. The Langmuir properties of the mixed monolayer at the water-air interface has been studied using a single layer Langmuir trough. The area per molecule for the mixed monolayer is calculated theoretically and experimentally. This study has not only shown that there is an excellent agreement between theoretical and experimental values, but has also shown that this mixed monolayer at the water-air interface can be transferred as a monolayer onto a solid substrate.

Power Connector, Stephen L. Clark, Joseph B. Shuey, Jose L. Ortega, John B. Brown Iii

Mathematics and Statistics Faculty Research & Creative Works

A pair of mating connectors includes a receptacle having an insulative housing and at least one conductive receptacle contact with a pair of spaced walls forming a plug contact receiving space. The plug connector has an insulative housing and at least one conductive contact having a pair of spaced walls which converge to form a projection engageable in the plug receiving space of the receptacle contact. In each case, the spaced walls are joined by a bridging structure that unites the walls. The plug and receptacle contacts are retained in the respective housings by engagement of opposed lateral edge portions …

Corrected Article: Exclusive Electroproduction Of ᵠ Mesons At 4.2 Gev [Physical. Rev. C 63, 065205, (2001)], M. Bektasoglu, L. Ciciani, G. E. Dodge, T. A. Forest, C. E. Hyde-Wright, S. E. Kuhn, L. M. Qin, F. Sabatié, L. B. Weinstein, Et Al., The Clas Collaboration

Physics Faculty Publications

We studied the exclusive reaction ep → e' p' ᵠ using the ᵠ →K⁺K^- decay mode. The data were collected using a 4.2 GeV incident electron beam and the CEBAF Large Acceptance Spectrometer (CLAS) at the Thomas Jefferson National Accelerator Facility. Our experiment covers the range in Q² from 0.7 to 2.2 GeV²and W from 2.0 to 2.6 GeV. Taken together with all previous data, we find a consistent picture of ᵠ production on the proton. Our measurement shows the expected decrease of the t slope with the vector-meson formation time c Δ t …