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Mechanistic Studies On The Preparation Of The Hantzsch’S Base From Ethyl Acetoacetate And Chloromethylmethyl Ether, Huo-Jin Hsieh

Dissertations and Theses @ UNI

Dihydropyridines, which were first studied by Hantzsch in 1882, now bear his name. A new synthesis of Hantzsch 's base, 2,6-dimethyl-3,5-dicarboethoxy-l ,4- dihydropyridine (lb), was discovered. The preparation of Hantzsch's base (lb) from new starting materials, ethyl acetoacetate (3) and chloromethylmethyl ether (4), was described. Ethyl acetoacetate was reacted with sodium amide in liquid ammonia followed by chloromethylmethyl ether to form the 2,6-dimethyl-3,5-dicarboethoxy1,4-dihydropyridine (lb) in 84% overall yield. Compound (lb) was further identified by its oxidation to the corresponding pyridine, 2,6-dimethyl-3,5-dicarboethoxypyridine ( 11 b) by glacial acetic acid. A mechanism for the formation of the compound ( 1 b) was …

Nuclear Magnetic Resonance Study Of Antigen-Antibody Complexes, Including Sequence Specific Assignments And Structural Analysis Of Neurophysin As An Antigen Model, Elisar Jamil Barbar

Dissertations and Theses

The interaction between molecules is essential in a wide range of biological processes. A detailed knowledge of these interactions is necessary for understanding these processes. Among the systems that involve important interactions is the immune system. NMR spectroscopy has a large number of spectral parameters that were used in this work to study antibody-antigen interactions. These same parameters were also used to begin a structural analysis of a medium-sized protein, neurophysin, that has important interactions with neurohormones, and served here as a model antigen. A set of ligands differing in size and charge was designed and used to probe the …

Computational Neural Networks In Chemistry: Model Free Mapping Devices For Predicting Chemical Reactivity From Molecular Structure, David Wayne Elrod

Dissertations

Computational neural networks (CNNs) are a computational paradigm inspired by the brain’s massively parallel network of highly interconnected neurons. The power of computational neural networks derives not so much from their ability to model the brain as from their ability to learn by example and to map highly complex, nonlinear functions, without the need to explicitly specify the functional relationship. Two central questions about CNNs were investigated in the context of predicting chemical reactions: (1) the mapping properties of neural networks and (2) the representation of chemical information for use in CNNs.

Chemical reactivity is here considered an example of …

Identification Of The Nd Δ And Σ States And The 1,3Φ←←X  3Σ− G Transition Of O2 By Resonant Multiphoton Ionization, Robert J. Yokelson, R. J. Lipert, W. A. Chupka

Chemistry and Biochemistry Faculty Publications

Spectra of the 3dRydberg state region of O₂ have been obtained by two‐photon resonant ionization of the ground electronic state. By varying the rotational distribution and radiation polarization, all observed bands were identified and attributed to excitation of Σ, Δ, and Φ states. Earlier assignments were corrected. The Δ and Φ assignments are complete while the Σ assignments are so far incomplete.

Identification Of The Ns And Nd Rydberg States Of O2 For N=3–5, Robert J. Yokelson, R. J. Lipert, W. A. Chupka

Chemistry and Biochemistry Faculty Publications

The 4s‐3d and 5s‐4dRydberg complexes of diatomic oxygen have been studied by (2+1) resonance‐enhanced multiphoton ionization of the X  ³∑ _g ⁻ ground state of O₂. We have located and identified at least two vibrational levels of each of the following states: Three of four expected 4sσ Π states; all four expected 5sσ Π states; 18 of 22 expected 3d states (with only the states of the 3dσ orbital remaining unobserved); and 5 of the 10 predicted 4dπ states. State assignments …

Use Of High-Energy Radiation For Degradation Of Environmental Pollutants, Robert D. Guthrie, Manjiri Patwardhan

KWRRI Research Reports

The purpose of this project was to explore the advantages and/or limitations of high-energy radiation treatment as a method for degrading organic pollutants, particularly aryl halides, in an aqueous medium. We have done analyses of ⁶⁰Co-irradiated samples and kinetic studies using pulsed electron beams. For aryl halides containing no more than two fused rings, the main products detected are those of simple halogen replacement by hydrogen, although the amount of aryl halide destroyed was always greater than the total amount of products detected. To accomplish halogen replacement by H, the reaction solvent may not be pure water but must …

The Immunosuppressive And Toxic Effects Of Fk-506 Are Mechanistically Related: Pharmacology Of A Novel Antagonist Of Fk-506 And Rapamycin, Francis J. Dumont, Mary Jo Staruch, Samuel L. Koprak, John Siekierka, C. Shirley Lin, Richard Harrison, Tonya Sewell, Victoria M. Kindt, Thomas R. Beattie, Matthew Wyvratt, Nolan H. Sigal

Department of Chemistry and Biochemistry Faculty Scholarship and Creative Works

FK-506 inhibits Ca2+-dependent transcription of lymphokine genes in T cells, and thereby acts as a powerful immunosuppressant. However, its potential therapeutic applications may be seriously limited by several side effects, including nephrotoxicity and neurotoxicity. At present, it is unclear whether these immunosuppressive and toxic effects result from interference with rehted biochemical processes. FK-506 is known to interact with FK-binding protein-12 (FKBP-12), an abundant cytosolic protein with cis.trans peptidyl-prolyl isomerase activity (PPlase) activity. Because rapamycin (RAP) similarly binds to FKBP-12, although it acts in a manner different from FK-506, by inhibiting T cell responses to lymphokines, such an interaction with FKBP-12 …

34th Rocky Mountain Conference On Applied Spectroscopy

Rocky Mountain Conference on Magnetic Resonance

Program and registration information for the 34th annual meeting of the Rocky Mountain Conference on Applied Spectroscopy, co-sponsored by the Colorado Section of the American Chemical Society and the Rocky Mountain Section of the Society for Applied Spectroscopy. Held in Denver, Colorado, August 2-6, 1992.

Dispiro- 1,2,4,5-Tetraoxanes: A New Class Of Antimalarial Peroxides, Jonathan L. Vennerstrom, Hong-Ning Fu, Walter Reed Army Institute Of Research, Arba L. Ager Jr., James K. Wood

Chemistry Faculty Publications

Dispiro-l,2,4,5tetraoxanes2 -4 were synthesized as potential peroxide a n t h a l a* d drugs. They had curative activity against Plasmodium berghei in vivo at single doses of 320 and 640 mg/kg which confirms earlier unpublished data Moreover, artemisinin (1) and 4 had equivalent ED”s against P. berghei in vivo in the multiple-dose Thompson tat; neither showed any evidence of acute toxicity at total doses of more than 12 g/kg. Dispiro-l,2,4,5-tetraoxane 4 had IC₅₀’s comparable to those of 1 against Plasmodium falciparum clones in vitro. These results confirm the potential of dispiro-l,2,4,5-tetraoxanes as a new class of …

Nmr Analysis Of Sulfur Compounds In Petroleum, Kanning Wu

Masters Theses & Specialist Projects

The speciation and quantification of organic sulfur forms in fossil fuel is an area of research. This thesis describes an NMR method which offers potential for identifying and possibly quantifying both nonvolatile and volatile sulfur forms in fossil fuels. The method is based on the methylation of sulfur compounds to form methyl sulfonium salts:

RSR + Ch₃I --> (R₂S+-Ch₃)I^~

We propose to apply this chemistry to the analysis of sulfur functions in fossil fuels. The sulfur functions are methylated using ¹³C-enriched methyl iodide. The products are then analyzed by ¹³C NMR …

Quantitative Footprinting Analysis Of The Chromomycin A 3 - D N A Interaction, Allison Stankus, Jerry Goodisman, James C. Dabrowiak

Chemistry - All Scholarship

Chromomycin A3 (CHR) binding to the duplex d(CAAGTCTGGCCATCAGTC)- d(GACTGATGGCCAGACTTG) has been studied using quantitative footprinting methods. Previous NMR studies indicated CHR binds as a dimer in the minor groove. Analysis of autoradiographic spot intensities derived from DNase I cleavage of the 18-mer in the presence of various amounts of CHR revealed that the drug binds as a dimer to the sequence 5’-TGGCCA-3’, 3’-ACCGGT-5’ in the 18-mer with a binding constant of (2.7 f 1.4) X lo7 M-l. Footprinting and fluorescence data indicate that the dimerization constant for the drug in solution is -lo5 M-l. Since it has been suggested that …

Three-Dimensional Solution Structure Of Human Interleukin-4 By Multidimensional Heteronuclear Magnetic Resonance Spectroscopy, Robert Powers, Daniel S. Garrett, Carl J. March, Eric A. Frieden, Angela M. Gronenborn, G. Marius Clore

Department of Chemistry: Faculty Publications

The three-dimensional solution structure of recombinant human interleukin-4, a protein of 133 residues and 15.4 kilodaltons that plays a key role in the immune and inflammatory systems, has been solved by multidimensional heteronuclear magnetic resonance spectroscopy. The structure is dominated by a left-handed four-helix bundle with an unusual topology comprising two overhand connections. The linker elements between the helices are formed by either long loops, small helical turns, or short strands. The overall topology is remarkably similar to that of growth hormone and granulocyte-macrophage colony stimulating factor, despite the absence of any sequence homology, and substantial differences in the relative …

Design Of Stable Di And Tetraradical Nitroxides As Magnetic Resonance Imaging Agents, Radha V. Iyer

Theses

Several nitroxides have been prepared in the Biotechnology Laboratory at NJIT to study their image enhancement capability. These nitroxides contain different moieties within one molecule and their paramagnetism is found to be initially increasing proportionally to the number of their radical centers. It is found that the addition of nitroxides at very close distances causes interference and a reduction of intensity due to the interaction of the two paramagnetic centers with each other. Thus MRI contrast agents are not improved by simple addition of nitroxide centers to a given molecule and drug designers must pay special attention to intramolecular spacing. …

The Removal Hcl From Hot Gases With Calcium Compounds, Qian Lao

Theses

The use of CaCO₃, Ca(OH)₂, and CaO as adsorbents for removal of HCl from hot gas streams is investigated through a series of experiments. The experiments are conducted to evaluate the influence of key parameters such as temperature, (500 K to 1000 K), particle size, (0.037 mm to 3.36 mm), pressure drop of the packed bed, (0.1 cm H₂O to 25.5 cm H₂O), and concentration of CCl in the feed gas, (1,550 ppm to 20,000 ppm), on HCl adsorption. The results of these experiments show that all three of the calcium compound …

Evidence For Helical Structures In Poly(1-Olefin Sulfones) By Transmission Electron Microscopy, George C. Ruben, W H. Stockmayer

Dartmouth Scholarship

Transmission electron microscope images were obtained of fractions of poly(1-tetradecene sulfone) and poly(cyclohexene sulfone) cast from very dilute solutions (0.007%, wt/vol) and rapidly freeze-dried on a mica surface. The samples were then vertically platinum-carbon (Pt-C) replicated with 9 +/- 0.3-A Pt-C and held together with 128 A of electron-transparent evaporated carbon. The Pt-C coating enlarges the molecular chain diameters by approximately 5 A, so that a single polysulfone chain has an apparent diameter of 9-12 A in the transmission electron microscope. Poly(1-tetradecene sulfone) forms short helical regions that show irregular helical turns of pitch 7-18 A, two to eight turns …

Photochemistry Of Nitrous Acid And Nitrite Ion, Jane A. Johnson '92

Honors Projects

A study of the solution phase photochemistry of the nitrous acid/nitrite ion system in both water and non-aqueous solvents has been undertaken. Photolysis at 366nm of the aqueous system is known to form hydroxyl radical and nitric oxide. The relative contributions of the molecular and ionic forms to the photochemical production of radicals is unknown. Scavenging reactions of the hydroxyl radicals in aqueous and nonaqueous solution are used to determine the relative production of OH. formed by photolysis of HONO and N02-. Molecular nitrous acid is isolated from its conjugate base by extraction into benzene from water. The thermal decomposition …

Analysis Of Carbon Across The Cenomanian-Turonian Boundary, Andrew J. Carr '92

Honors Projects

Following the work of Wolbach et al., who studied reduced carbon across the 65 Ma-old Cretaceous-Tertiary extinction boundary, a study was conducted to analyze reduced carbon across the 92 Ma-old Cenomanian-Turonian (C-T) extinction horizon, in the hope that evidence could be gathered which might support a particular mechanism for these extinction events. Currently two sample sites are being analyzed for reduced carbon content at the C-T boundary: Red Wash, New Mexico and Chispa Summit, Texas. Both sample sites are from the Western Interior Basin of North America. During the time of the extinctions 92 million years ago, the basin was …

Isolation Of Protein Synthesis Initiation Factors Using Volvox Carteri: A Clue To The Translational Control Of Cytodifferentiation, Claudia Hackethal

Honors Theses

Volvox carteri, a multicellular green algae, possesses two distinct cell types--the gonidia and somatic cells. This simple germ-soma dichotomy is ideal for the study of the control of cytodifferentiation. The control of cytodifferentiation in this organism has been identified as a posttranscriptional mechanism, which suggests translation. Initiation factors have been shown to play an important role in controlling translation in many other developmental systems. Therefore, study of the initiation factors in Volvox may shed light on a translational control mechanism. In order to study any modifications of these factors, they must be isolated, possibly by following an adapted wheat germ …

Development Of Hplc-Ec Methodology & Its Use In The Determination Of The Daily Pattern Of Brain Octopamine Levels In Leucophaea Maderae, Maya Siddiqui

Masters Theses & Specialist Projects

A solid phase extraction technique was developed to aid in removing interfering substances from the cockroach brain extract. Quantitative analysis of octopamine was subsequently achieved by HPLC with amperometric electrochemical detection. The procedure affords 80 to 100 percent recovery of octopamine. The presence of octopamine in brain extract was confirmed by GC-MS.

The daily pattern of brain octopamine levels in cockroach Leucophaea maderae was investigated using the HPLC-EC assay procedure. It was concluded that the concentration of brain octopamine in the cockroach L. maderae does not exhibit daily rhythm.

Mobilization Of Iron Enhances The Iron-Dependent Biochemical Reactivity Of Asbestos In Vitro And Contributes To The Cytotoxicity Of Asbestos In Cultured Cells, Loren Glen Lund

All Graduate Theses and Dissertations, Spring 1920 to Summer 2023

Asbestos related research began approximately 60 years ago, yet, the mechanism(s) by which asbestos exerts its biological effects is not well understood. The hypothesis upon which this dissertation is based is that mobilization of iron from asbestos enhances the iron-dependent biochemical reactivity of asbestos in vitro and contributes to asbestos-dependent cytotoxicity. The specific aims for this hypothesis were, 1) to determine whether iron was responsible for the biochemical reactivity of asbestos in vitro and asbestos-induced cytotoxicity in cultured cells, and 2) to determine whether mobilization of iron from asbestos enhanced the reactions catalyzed by asbestos in vitro and contributes to …

Thermal Properties Of Some Lipid Components Of Cell Membranes, Lihua Wei

Masters Theses & Specialist Projects

Phospholipids are the major structural components of the lipid portion of biological membranes. The study of the thermal properties of these phospholipid provides a systematic understanding of the relationships between the chemical structures and functional properties of phospholipid molecules in artificial and biological membranes. This study examined the thermal behavior of phospholipids in the solid state using DSC and TG coupled with FITR. The phospholipids were found to have phase transitions below the melting point. Egg-yolk lecithin had four transitions below its melting point; sphingomyelin had two phase transitions below its melting point. Phosphatidylethanolamine and phosphatidylserine had complex phase transitions. …

Biodegradation Of Crude Oil By Marine Higher Fungi, Brian J. Dyer

Biological Sciences Theses & Dissertations

Four experiments were performed to determine the ability of marine higher fungi to grow in and degrade crude oil. Eight species, previously determined to be hydrocarbonoclastic, were grown in artificial sea water medium (ASM) and southern Louisiana crude oil. The dry mycelial weights were measured and consumption of crude oil was measured gravimetrically. The two species with the best growth, Corollospora maritima and Zalerion maritimum, were grown in ASM containing crude oil spiked with three known hydrocarbons. To this was added glucose (0.15%) and incubated 49 days to test for possible cometabolism of hydrocarbons. Hydrocarbons remaining in the growth …

Development Of A System For Survey Of Radon Concentration Of The Dayton Area Using A Liquid Scintillation Counter And Analysis Of The Data, Taewon Kim

Theses and Dissertations

A system to do a large scale survey was developed. The data obtained from the survey was analyzed using a database. The database incorporated an equation for converting cpm into radon concentration pCi/ℓ). The equation of conversion, protocol for measuring radon concentration, survey form, and a database program were modified (from previous theses) or developed for this thesis. The elution time constant, adsorption time constant, and calibration factor were calculated for equation of conversion. Two surveys were during the course of the thesis. On the first survey, the arithmetic average radon concentration with standard error of the mean was 2.9 …

I. Removal Of Chromium From A Highly Contaminated Soil/Slag Matrix By Soil Washing At Low Ph, Ii. Removal Of Chromium From Impregnated Clay Matrices By Soil Washing At Low Ph, Erez Gotlieb

Theses

Section I. Chromium is a major soil contaminant of industrial sites in New Jersey, as well as in many of the Superfund sites throughout the United States. Removal of chromium by soil/slag washing with low pH sulfuric acid solutions is described. The extraction parameters are acid concentration, contact time, temperature, solvent/soil ratio, and acid type. The effect of two-stage extraction is discussed.

Soil/slag washing with sulfuric acid concentrations of 2% weight:volume (units are g/ml. This concentration is approximately equal to 0.4 N) at 75:1 v:w solvent/soil ratios yielded chromium extraction efficiencies of 95%, but 50% of the soil matrix was …

Partial Characterization Of The Major Lipooligosaccharide From A Strain Of Haemophilus Ducreyi, The Causative Agent Of Chancroid, A Genital Ulcer Disease, William Melaugh, Nancy J. Phillips, A A. Campagnari, R Karalus, B W. Gibson

Chemistry Faculty Publications

The first preliminary structure of a surface lipooligosaccharide from Haemophilus ducreyi has been determined. The major oligosaccharide was released by mild acid hydrolysis and analyzed by liquid secondary ion and tandem mass spectrometry. The mass spectral data combined with composition and methylation analysis yielded the most probable structure; Gal1----4GlcNAc1----3Gal1----4Hep1----6Glc1----( Hep1----2Hep1----)3,4Hep1---- KDO, where the reducing terminal 3-deoxy-D-manno-octulosonic acid (or KDO) exists in an anhydro form. This anhydro species results from the elimination of a phosphate from C-4 of KDO during mild acid hydrolysis. The core heptose trisaccharide consists of L-glycero-D-manno-heptose, but analysis of the peracetylated sugars indicated that the 1,4-linked heptose …

Characterization And Implementation Of A Continuos Flow Trace Metal Preconcentration System For Inductively Couples Plasma Atomic Emission Spectrometry, Robert N. Sibley

Senior Scholar Papers

A continuous flow pre-concentration system for analysis of trace metals in natural waters was characterized and used to determine the copper(II) and lead(II) concentrations in seawater from Penobscot Bay, Maine. Pre-concentrated samples were analyzed by inductively coupled plasma atomic emission spectrometry (ICP-AES). System characterization involved elucidation of the thermodynamic complexation constants, KCu(II) and KPb(II), for Cu(II) and Pb(II) with the pre-concentration column chromatographic material. This was done in aqueous media of known pH and ionic strength. The column contained 8-hydroxyquinoline immobilized on Toyopearl HW-75 fractogel chromatographic resin. The buffer system used for metal binding experiments was an equimolar mixture of …

Calculation Of Barriers To Proton Transfer Using Multiconfiguration Self‐Consistent‐Field Methods. I. Effects Of Localization, K. Luth, Steve Scheiner

Chemistry and Biochemistry Faculty Publications

The usefulness of multiconfiguration self‐consistent‐field (MCSCF) calculations in computing correlated proton transfer potentials is investigated for the systems HF₂⁻, H₇N₂⁺, H₃O₂⁻, and H₅O₂⁺. In deciding whether to include particular molecular orbitals, it is important to consider the balance of electron density between the donor and acceptor groups and the interactions that are incorporated in the orbitals. Only orbitals which have the proper symmetry to interact with the transferring hydrogen need be included in the MCSCF active space. Reasonable transfer barriers are obtained …

Lithium Transport, Mg2+ Competition, And Phospholipid Composition In Human Erythrocytes: A Multinuclear Magnetic Resonance Study, Aida Abraha

Dissertations

No abstract provided.

Spin Label Studies Of Radical Reduction In Normal And Sickle Erythrocyte Membranes Associated With Antioxidants, Yin Zhang

Dissertations

No abstract provided.

Multinuclear Magnetic Resonance Study Of Chlorine And Cesium Ion Distribution In Human Erythrocyte Suspensions, Lisa Wittenkeller

Dissertations

No abstract provided.