Chemistry Commons^™

Radicals, Metals And Magnetism, David J R Brook

Faculty Publications, Chemistry

The interaction between unpaired electrons governs many physical properties of materials. Although in a fundamental sense the interaction is simple, a full understanding of the interaction in molecular systems is complicated by the presence of other bonding and non-bonding electrons. The resulting many body problem is very challenging. Nevertheless, much qualitative understanding can be obtained from applying simple molecular orbital theory and considering only the partly filled orbitals. The resulting model can be used to describe existing diradical and metal-radical systems and also has predicative value in the search for molecular magnets and design of nanoscale devices.

Effects Of Curing Temperature On The Leachability Of Lead Undergoing Solidification/Stabilization With Cement, Michael A. Janusa

Faculty Publications

Curing temperature was found to dramatically affect the amount of waste leached from a solidified waste/cement matrix between 2 and 40°C. Using lead nitrate as a model waste, samples cured for 7,14, and 28 days at a cure temperature of 40°C leached very little lead (1-3 mg/liter), while at a cure temperature of 2°C samples leached approximately 25 times more lead (20-90 mg/liter). The results indicate that curing temperature is a very crucial variable to consider when solidifying waste with cement if maximum stabilization is to be achieved.

Effects Of Particle Size And Contact Time On The Reliability Of Toxicity Characteristic Leaching Procedure For Solidified/Stabilized Waste, Michael A. Janusa

Faculty Publications

Inconsistency in leaching results using the Toxicity Characteristic Leaching Procedure (TCLP)indicates that the procedure should contain specific guidance with respect to the following parameters: ( 1 ) minimum particle size, (2) contact time limit between leachant and waste. Experimental datas how that there is approximately a 50% decrease in the amount of waste leached when a minimum particle size of 8 mm is applied. Results indicate that as the contact time between leachant and waste increases, the amount of waste leached increases drastically. The results suggest that restrictions should be set on these two parameters for TCLP results to be …

Palladium-Catalyzed Carboxylation Of Allyl Stannanes And Carboxylative Coupling Of Allyl Stannanes And Allyl Halides [Abstract], Russell J. Franks

Faculty Publications

The reaction of allyl stannanes with CO₂ to form stannyl carboxylates (esters) is catalyzed by Pd(PR₃)₄ complexes. Thus, R₃SnCH₂CH=CH₂ [R=Me and Ph]are converted to R₃SnO₂ CCH₂CH=CH₂ and R₃SnO₂CCH=CHCH₃ under 33 atm of CO₂ (70°C, THF) in moderate to excellent yield in the presence of 8 mol% Pd(PPh₃)₄ ; polycarboxylation of diallyldibutyltin and tetraallyltin also is effected, producing the respective di- and tetracarboxylates, Bu₂Sn(O₂CCH₂CH=CH₂)₂ and Sn(O₂CCH …

Vibrational Sum Frequency Spectroscopy Of Surfactants And Phospholipids Monolayers At Liquid-Liquid Interfaces, B. L. Smiley, R. A. Walker, D. E. Gragson, T. E. Hannon, G. L. Richmond

Chemistry and Biochemistry

Work from our laboratory on vibrational sum frequency spectroscopic investigations of molecular ordering at the carbon tetrachloride-water interface is reviewed. Simple charged surfactants adsorbed at the liquid-liquid interface are seen to induce alignment of interfacial water molecules to a degree which is dependent on the induced surface potential. Saturation of water molecule alignment occurs at a surfactant surface concentration corresponding to a calculated surface potential of approximately 160 mV. In complementary studies, the relative degree of hydrocarbon chain ordering within monolayers of symmetric phosphatidylcholines of different chain lengths is inferred by the relative signal contributions of the methyl and methylene …

Exo- And Endo-Tricarbonyl[(4b,5,6,7,8,8a-Η)-Cis-N-Methyl-2,3,4,4a,9,9a-Hexahydro-1h- Carbazole]Chromium(0), Nigam Rath, F. Pigge, Shiyue Fang

Chemistry & Biochemistry Faculty Works

Acid-mediated hydride reduction of tricarbonyl([eta]6-N-methyl-1,2,3,4-tetrahydrocarbazole)chromium(0) affords either the cis-fused exo-hexahydrocarbazole chromium(0) complex {[Cr(C13H17N)(CO)3], (I)} exclusively, or a separable mixture of (I) and the endo-isomer {[Cr(C13H17N)(CO)3], (II)}, depending upon the choice of hydride donor. The conformations of the hexahydrocarbazole systems differ in the orientation of the indoline moiety with respect to the saturated hexahydrocarbazole rings. The isolation of the exo isomer is unusual, as this complex arises via reaction at the sterically more hindered endo face of the coordinated ligand.

Method For The Synthesis Of Α-Oxranyl Amino Acids, David B. Berkowitz, Michelle L. Pedersen

Department of Chemistry: Faculty Publications

The present invention is related to a novel class of decar-boxylase enzyme inhibitors consisting of α-oxiranyl amino acids and derivatives thereof and a method of synthesizing Such compounds.

The Total Synthesis Of A Conformationally Constrained Organophosphorus Analog Of Acetycholine, Justin Mergott '98

Honors Projects

We propose the total synthesis of a conformationally constrained organophosphorus analog of acetylcholine (5, Scheme 5). This compound will contain two crural centers, one being the phosphorus atom and the other being the pyrrolidine ring carbon beta to the phosphorus atom. The chiral beta carbon is conformationally constrained because it is part of the pyrrolidine ring. Studies with such a compound should allow us to make substantial progress towards the clarification of the stereospecificity of AChE inhibition by OP compounds and eventually help us understand more about the structure of the AChE active site. The synthesis begins with Cbz-L-proline methyl …

Pyrrolic Compounds, Michael J. Therien, Stephen Dimagno

Department of Chemistry: Faculty Publications

Novel methylpyrroles are provided, as well as processes for their preparation.

The Synthesis And Characterization Of Monometallic And Bimetallic Pd-Pnp Complexes, Lorinda Asmus

Honors Theses, 1963-2015

The bridging ligand, 2-[bis(diphenylphosphino)methyl]pyridine (PNP), is ideal for synthesizing mono- and bi-metallic catalysts due to its potential to be bidentate (P-P or P-N) or tridentate and its ability to bind to one or more metals. Three Pd-PNP complexes, [Pd(PNP)₂]⁺² (1) and two complexes resulting from the removal of one or two methine pronouns (2 and 3), have been synthesized. The removal of one methine proton changes the PNP bidentate binding mode. In complex 1 and 3, the two PNP ligands are P-P bound. However, upon the removal of one methine proton, one …

Synthesis And Characterization Of A Trypsin Inhibitor, Eric L. Schneider

Honors Theses, 1963-2015

Inhibitors of biological enzymes are frequently produced by mimicking the molecular structure of the enzyme's natural substrate. Because of the extensive studies that have already been performed on the trypsin enzyme, its natural substrates and its mode of interaction with them are well understood. By finding an easily synthesized molecule to inhibit the trypsin enzyme, college level laboratory experiments could be designed and integrated into organic chemistry and biochemistry courses. In this project, a possible trypsin inhibitor molecule, 4-fluorobenzylaimine, was chosen based on its similarity to the natural trypsin substrates and because it has been predicted through computational studies to …

On-Road Remote Sensing Of Automobile Emissions In The Chicago Area: Year 1, Peter J. Popp, Gary A. Bishop, Donald H. Stedman

Fuel Efficiency Automobile Test Publications

No abstract provided.

Final Technical Report For Its For Voluntary Emission Reduction: An Its Operational Test For Real-Time Vehicle Emissions Detection, Gary A. Bishop, Donald H. Stedman, R. Bruce Hutton

Fuel Efficiency Automobile Test Publications

No abstract provided.

1998 Preliminary Snowmobile Emission Survey In Yellowstone National Park, Gary A. Bishop, Donald H. Stedman

Fuel Efficiency Automobile Test Publications

No abstract provided.

Environmental And Botanical Controls On Peatification - A Comparative Study Of Two New Zealand Restiad Bogs Using Py-Gc/Ms, Petrography And Fungal Analysis, Tomasz K. Kuder, Michael A. Kruge, J C. Shearer, S L. Miller

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

This study shows that chemical properties of two restiad species, Empodisma minus and Sporadanthus traversii, may contribute to their success as peat-formers in a climate of the North Island of New Zealand which is not conducive to raised mire development. Unlike Sphagnum, the equivalent northern hemisphere peat-former, restiads possess lignin in their tissues. In addition, the presence of non-lignin polyphenols (including tannins and phenolic acids) in restiads may be an important factor in peat formation due to the allelopathic decay retardation. Patterns of degradation of plant biopolymers have been examined and the pathway of degradation of monocotyledons (loss …

A Molecular Evaluation Of Contaminants And Natural Organic Matter In Surface Sediments From Western Lake Ontario, Michael A. Kruge, Prasanta K. Mukhopadhyay, C.F. Michael Lewis

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

Pyrolysis-gas chromatography-mass spectrometry (Py-GC/MS) analysis of bottom sediment from Lake Ontario was shown to be effective in assessing organic contaminants, especially attractive as it is a rapid technique requiring little sample preparation. Pyrolyzates of samples richer in organic matter (OM) were relatively enriched in aliphatic hydrocarbons and pyrrolic nitrogen compounds, while leaner samples were more aromatic and pyridinic. Alkylbenzene and alkylphenol distributions in the pyrolyzates were most compatible with derivation from aquatic (algal, bacterial) OM. The organonitrogen compounds indicated the presence of degraded proteinaceous material from aquatic sources and/or sewage. Normal and polycyclic aromatic hydrocarbon distributions indicate, at least in …

Petrographic And Chemical Properties Of Carboniferous Resinite From The Herrin No. 6 Coal Seam, John C. Crelling, Michael A. Kruge

Department of Earth and Environmental Studies Faculty Scholarship and Creative Works

Resinite is a naturally occurring substance found in coal and derived from original plant resins. It is ubiquitous in North American coals and comprises 1 to 4% by volume of most Illinois coals. It has been commercially exploited in the western USA for use in adhesives, varnishes and thermal-setting inks. The major objectives of this study were: (1) to separate resinite macerals from the Herrin No. 6 coal seam and to carefully verify, by petrographic and fluorescence microspectrophotometric methods, that the separated material was indeed resinite; (2) to characterize the chemical composition of the separated resinite by Py–GC–MS techniques; and …

Fuel Cells, Frederick J. Munster Jr.

Maine Collection

Fuel Cells

by Frederick J. Munster Jr.

Edited by: Mr. Christopher Carroll

Maine Department of Economic Development, Augusta, Maine, 1998.

Contents: Hydrogen / Hydrogen Safety / Electrolysis / Electrolyzers / History of Fuel Cells / How Fuel Cells Operate / Fuel Cell Types / Fuel Cell Electrochemistry / Power Systems / Fuel Cells in Transportation / Hydrogen Powered Internal Combustion Engines / Home, Garden, Education and Industry / For More Information / Glossary / References

Biophysical Studies Of The Spectrin Sequence Motif, Denise M. Lusitani

Dissertations

No abstract provided.

Remote Sensing Of Commercial Aircraft Emissions, Peter J. Popp, Donald H. Stedman

Fuel Efficiency Automobile Test Publications

No abstract provided.

Generation Of Intense Excimer Radiation From High-Pressure Hollow Cathode Discharges, Ahmed El-Habachi, Karl H. Schoenbach

Bioelectrics Publications

By reducing the diameter of the cathode opening in a hollow cathode discharge geometry to values on the order of 100 μm, we were able to operate these discharges in noble gases in a direct current mode up to atmospheric pressure. High-pressure discharges in xenon were found to be strong sources of excimer radiation. Highest intensities at a wavelength of 172 nm were obtained at a pressure of 400 Torr. At this pressure, the vacuum ultraviolet (VUV) radiant power of a single discharge operating at a forward voltage of 220 V and currents exceeding 2 mA reaches values between 6% …

Alternatives To Nitroprusside, William T. Hiscock

Honors Theses

Any transition metal nitrosyl complex may release nitric oxide and thus has potential as a vasodilator. Nitroprusside, Na2[Fe(CN)5(NO)], is currently used, but dosages are limited because of the potential release of cyanide. Research in our group has been directed towards the synthesis of iron and ruthenium complexes containing the nitrosyl ligand and polypyridyl coligands such as 2,2-dipyridyl (bpy) and 2,2': 6',2"-terpyridine (tpy). These coligands are much less toxic than cyanide. Both [(bpy)(tpy)Fe(NO)]3+ and [(bpy)(tpy)Ru(NO)]3+ have been synthesized and characterized using infrared and ultraviolet spectroscopy, conductivity, and magnetic susceptibility. Along with the search for other possible polydentate coligands, is the search …

Approaches And Methodologies For The Synthesis Of Aromatic Natural Products, Christina A. Goudreau

Honors Theses

Chemists have been captivated by the ability of most natural products to exhibit biological activity which in effect has made them very attractive to pharmaceutical companies. Many over-the-counter drugs such as aspirin were first extracted from natural products and are now an integral part of most of our lives. More importantly, certain drugs such as taxol, which is used to treat breast cancer, initially came from the bark of a yew tree. Extracting these substances from their natural source and using them medicinally at the demand of the consumers would result in the destruction of the natural habitat. Oftentimes, the …

Reactions Of Modified Silica Gel Surfaces With Organometallic Compounds: Enhancing Olefin Polymerization Catalysts, Richard E. Diebel Iii

Masters Theses

Pretreated silica gels with distinct silica surfaces containing either isolated silanols, vicinal silanols, siloxanes, or some combinations of the three, were reacted with several organometallic compounds to determine how each compound reacted with the different silica surface species. The organometallic compounds used were trimethylaluminum, triethylaluminum, diethylaluminum chloride, ethylaluminum dichloride, methylaluminoxane, dibutylmagnesium, and bis-cyclopentadienyl dimethyl zirconium.

These reacted silica gels were analyzed using diffuse reflectance infrared Fourier transform spectroscopy and ICP-AES elemental analysis. CH/Metal ratios were calculated using specific peaks in the IR spectra to elucidate the surface bonded species. Elemental analysis was used to determine how much metal was bonded …

Characterization Of An All-Optical Device Based On Organic Materials, Hans-Martin Keller, Mark Andreas Bader, Gerd Marowsky

Turkish Journal of Chemistry

We present numerical and first experimental results for an all-optical switching device. The device consists of a periodically modulated nonlinear waveguide, where so-called gap solitons stabilize the switching process. The fabrication of Bragg gratings in different polymeric films, e.g. poly(phenylene vinylene), polydiacetylene or polystyrene by excimer laser photoablation was tested. In preparation of further experiments numerical calculations were performed to characterize the device under realistic conditions, including position dependent index modulations and absorption losses. In further time-dependent simulations the transition from the reflecting to the transparent state was investigated in detail. As a main result, the threshold intensity turns out …

Phthalocyanines And Related Compounds: Subunits For The Preparation Of Molecular Materials, J. Garcia, A. Gonzalez, A. Gouloumis, E.M. Maya, M.D. Perez, B.D. Rey, P. Vazquez, T. Torres

Turkish Journal of Chemistry

The design, synthesis, structural and physical characterization and engineering, and the study of the electrical conductivity and the nonlinear optical properties of phthalocyanines and molecular substances related to them, such as subphthalocyanines, hemiporphyrazines and triazolephthalocyanines were reviewed.

Azobenzene Side-Chain Liquid Crystalline Polyesters With Outstanding Optical Storage Properties, S. Hvilsted, M. Pedersen, N.C.R. Holme, P.S. Ramanujan

Turkish Journal of Chemistry

A flexible azobenzene side-chain liquid crystalline (SCLC) polyester architecture employed for reversible optical storage is described. The modular design allows four structural parameters to be individually modified. These parameters: {\em i}- the methylene side-chain spacer length, {\em ii}- the substituent on azobenzene, {\em iii}- the methylene main-chain segment length, and {\em iv}- the polyester molecular mass, all influence the optical storage properties. A general synthetic route to novel mesogenic azobenzene diols comprising parameters {\em i} and {\em ii} is outlined. Polyesters with molecular masses (parameter {\em iv}) up to 100,000 are routinely obtained by melt transesterification of the novel diols …

Poly(3-Alkylthiophene) Modifications, A. Bolognesi

Turkish Journal of Chemistry

No abstract provided.

Electrically Conductive Polymer Grafts Prepared By Electrochemical Polymerization Of Pyrrole Onto Poly[(Methyl Methacrylate)-Co-(2-(N-Pyrrolyl) Ethyl Methacrylate)] Electrodes, Nuran Balci, Ural Akbulut, Levent Toppare, Dietmar Stanke, Manfred L. Hallensleben

Turkish Journal of Chemistry

Pyrrole was grafted on poly[(methyl methacrylate)-co-(2-(N-pyrrolyl) ethyl methacrylate)] (PMMA-co-PEMA) using constant potential electrolyses. The thermal stability of PMMA-co-PEMA was improved as a result of electrochemical grafting with pyrrole. The electrochemical behavior of the films was studied by cyclic voltammetry. Pyrrole was found to be electroactive on PMMA-co-PEMA electrodes.

Dimerization Of Pyrrole, Mine Yurtsever, Ersin Yurtsever

Turkish Journal of Chemistry

Accurate ab-inito quantum mechanical calculations of pyrrole dimers are reported. The thermodynamical stabilities of dimers with $\alpha - \alpha, \alpha - \beta$, and $\beta - \beta$ type linkages are compared in order to predict the possibilities of branching in polypyrroles. Calculations employing large basis sets and including electron correlation effects predict the $\alpha - \alpha$ dimers as the most stable form. However, an $\alpha - \beta$ type bonding requires only 1.5-2.0 kcal/mol, and the energy necessary to introduce a $\beta - \beta$ type bond is 3.6-4.0 kcal/mol. These values show that a high degree of branching is possible even at …