Organic Chemistry Commons^™

Reactivity Of Acyclic (Pentadienyl)Iron(1+) Cations: Synthetic Studies Directed Toward The Frondosins, Do W. Lee, Rajesh K. Pandey, Sergey V. Lindeman, William A. Donaldson

Chemistry Faculty Research and Publications

A short, 4-step route to the scaffold of frondosin A and B is reported. The [1-methoxycarbonyl-5-(2′,5′-dimethoxyphenyl)pentadienyl]Fe(CO)₃⁺ cation was prepared in two steps from (methyl 6-oxo-2,4-hexadienoate)Fe(CO)₃. Reaction of this cation with isopropenyl Grignard or cyclohexenyllithium reagents affords (2-alkenyl-5-aryl-1-methoxycarbonyl-3-pentene-1,5-diyl)Fe(CO)₃ along with other addition products. Oxidative decomplexation of these (pentenediyl)iron complexes, utilizing CuCl₂, affords 6-aryl-3-methoxycarbonyl-1,4-cycloheptadienes via the presumed intermediacy of a cis-divinylcyclopropane.

6-[(4-Hydroxyphenyl)Diazenyl]- 1,10-Phenanthrolin-1-Ium Chloride Monohydrate, Akram Hazeen, Yan Zhang, Minchong Mao, Kraig A. Wheeler, Mark E. Mcguire

Faculty Research and Creative Activity

In the cation of the title molecular salt, C18H13N4O+_Cl__H2O, the dihedral angle between the mean planes of the 1,10- phenanthroline system and the phenol ring is 14.40 (19)_. The crystal packing is stabilized by O—H_ _ _O hydrogen bonds, weak N—H_ _ _Cl and O—H_ _ _Cl intermolecular interactions and _—_ stacking interactions [centroid–centroid distance = 3.6944 (13) and 3.9702 (12) [A °]

Synthesis Of N-Acyl-N,O-Acetals From N-Aryl Amides And Acetals In The Presence Of Tmsotf, C. Wade Downey, Alan S. Fleisher, James T. Rague, Chelsea L. Safran, Megan E. Venable, Robert D. Pike

Chemistry Faculty Publications

Secondary amides undergo in situ silyl imidate formation mediated by TMSOTf and an amine base, followed by addition to acetal acceptors to provide N-acyl-N,O-acetals in good yields. An analogous, high-yielding reaction is observed with 2-mercaptothiazoline as the silyl imidate precursor. Competing reduction of the acetal to the corresponding methyl ether via transfer hydrogenation can be circumvented by the replacement of i-Pr₂NEt with 2,6-lutidine under otherwise identical reaction conditions.

An Integrated Systems Approach To Deconstructing Glycosylation, L. K. Mahal, John F. Rakus, Kanoelani Pilobello, P. Agrawal

Chemistry Faculty Research

Glycosylation involves the post-translational addition of carbohydrates to protein molecules and is an intricate and indispensable biochemical process. Study of this complicated network of interactions is hindered by the lack of a coding template analogous to the genetic code, and by the vast structural complexity inherent to carbohydrate polymers. We use lectins (non-enzymatic carbohydrate-binding proteins of non-immunological origin) as microarray probes to identify carbohydrate features expressed on cellular surfaces. Specifically, we utilized lectin microarray technology to investigate the differences in carbohydrates expressed by the cell lines of the Nation Cancer Institute’s NCI-60 panel. Our investigation identified tissue-specific expression differences in …

Synthesis And Structure Of A Substituted Pyridazine, Kiranmai Byrichetti

Masters Theses & Specialist Projects

Pyridazines are heterocyclic compounds with an N-N bond in their ring structure. Heterocyclic aromatic compounds are of great interest as a result of their novel properties and commercial applications. Our current research is focused on the potential role of pyridazines in next generation electronic devices that utilize organics as the semiconducting material. The synthesis of 5, 6-fused ring pyridazines beginning from fulvenes (Scheme 1) is described herein. These fused heterocycles will serve as synthetic models and building blocks for potential organic or organometallic conducting polymers.

Our goal was to modify the route of Snyder et al. previously reported for the …

Regiospecific Synthesis Of Ortho Substituted Phenols, Ravindra Kotha Balasainath

Masters Theses & Specialist Projects

Phenol is highly reactive toward electrophilic aromatic substitution. By this general approach, many groups can be appended to the ring, via halogenation, acylation, sulfonation, and other processes. Phenol contains the hydroxyl group (–OH), which is a strongly activating ortho/para directing group in aromatic electrophilic substitution (AES). AES gives a mixture of ortho-and para isomers, which must be separated.

The strong directing ability of phenol can also result in multiple substitutions on the aromatic ring which could be a major concern in the regiospecific synthesis of phenols. AES and Directed ortho--Metalation (DoM) are the only ways to directly substitute …

High Yield Synthesis Of Positron Emission Tomography Ligands For Metabotropic Glutamate Receptor Imaging, Saraanne E. Hitchcock

Department of Chemistry: Dissertations, Theses, and Student Research

Positron Emission Tomography (PET) is a powerful and non-invasive imaging technique used for human and animal organ imaging. Currently, the market for PET is project to reach $5.4 billion per year by 2015.5 This research focuses on the direct incorporation of [18F]-fluoride into PET ligands. The widespread use of PET imaging is currently frustrated, in part, by the lack of efficient fluorination chemistry.

Glutamate, one of the 20 most abundant naturally occurring amino acids, serves as a neurotransmitter in the central nervous system. Glutamate functions in this capacity by binding to ionotropic and metabotropic receptors. Metabotropic receptors are Gcoupled proteins …

Conjugated Polymers And Inter-Chromophore Interactions: Synthesis, Photophysical Characterization And Application, Anshuman Mangalum

All Dissertations

Ever since the discovery of conducting polymers (CPs)in the late 1970s, organic conjugated materials and polymers is one of the most popular and fascinating research area among the scientists due to the remarkably unique properties and broad range of applications of (CPs), notably organic photovoltaic (OPVs), organic or polymer based light emitting devices (OLEDs / PLEDs), field effect transistors (FETs), nonlinear optical (NLO) devices and sensor for biologically relevant analytes, metal ions and anions. Optical properties of these materials depend on intra / interchromophoric interaction, geometry and relative orientation in space. Detailed study of such materials can also help us …

Zirconium Mediated One-Pot Synthesis Of Γ-Amino Acids From Carbon Dioxide, Diego A. Pedroza ^, Shizue Mito *

COURI Symposium Abstracts, Summer 2011

No abstract provided.

Fullerene-Based Organized Self-Assembled Photoactive Layer, Marcelo A. Yates ^, Danisha M. Rivera, Luis Echegoyen *

COURI Symposium Abstracts, Summer 2011

No abstract provided.

Endohedral Derivatives For Bulk Heterojunction Organic Photovoltaic Devices, Gustavo Hernandez^, Michael D. Irwin*

COURI Symposium Abstracts, Summer 2011

No abstract provided.

Octaethyl-Nickel-Porphyrin Functionalized Silica For Fullerene Separation, Adriana Rodríguez^, Danisha M. Rivera, Luis Echegoyen*

COURI Symposium Abstracts, Summer 2011

No abstract provided.

Synthesis Of The Precursors For A New Covalent Organic Framework With Triangular Shaped Pores, Fernando J. Correa ^, Venkata P. Neti, Luis A. Echegoyen *

COURI Symposium Abstracts, Summer 2011

No abstract provided.

A Systems Approach To Understanding The Role Of Glycans In Cancer, John F. Rakus, Kaneolani T. Pilobello, Laura K. Mahal

Chemistry Faculty Research

Glycosylation involves the post-translational addition of carbohydrates to protein molecules and is an intricate and indispensable biochemical process. Study of this complicated network of interactions is hindered by the lack of a coding template analogous to the genetic code, and by the vast structural complexity inherent to carbohydrate polymers. We use lectins (non-enzymatic carbohydrate-binding proteins of non-immunological origin) as microarray probes to identify carbohydrate features expressed on cellular surfaces. Specifically, we utilized lectin microarray technology to investigate the differences in carbohydrates expressed by the cell lines of the Nation Cancer Institute’s NCI-60 panel. Our investigation identified tissue-specific expression differences in …

Application Of Raman Spectroscopy To Lubricants, Lubricated Surfaces And Lubrication Phenomena, David W. Johnson

Chemistry Faculty Publications

Recent advances in lasers and detector technologies and the development of low-cost instruments and fiber-optic probes have brought about an explosion in the lubrication systems being studied by Raman spectroscopy. This article provides examples of the use of Raman spectroscopy in the study of lubrication phenomena, including the characterization of liquid lubricants, lubricant additives, and solid lubricants; the study of vapor-phase lubrication; and the use of coated nanoparticles as lubricants.

The Nature, Origin And Preservation Of Amide Organic Nitrogen In Organic Matter, Georgina Anne Mckee

Chemistry & Biochemistry Theses & Dissertations

Past studies have found much of nonliving sedimentary/aqueous nitrogen-containing organic matter (NCOM) is composed of amides, assumed to be peptides/proteins. Their lability calls into question their survival, and several hypotheses have been suggested to explain this. Using Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) and nuclear magnetic resonance (NMR) spectroscopy I investigated the molecular amide composition in sedimentary/aqueous systems while reassessing their preservation and formation routes.

Development of a suitable methodology is essential for successful NCOM study due to electrospray ionisation source requirements: sediment samples need to be rendered into solution. Based on NMR and FT-ICR-MS analysis, I determined …

Insights Into Chemical Structure Changes Of Kerogen From Bituminous Coal In Response To Dike Intrusions Investigated By Advanced Solid-State 13C Nmr, Yuan Li

Chemistry & Biochemistry Theses & Dissertations

Variations in the chemical structures of kerogens From highly volatile bituminous coal located near two igneous dike intrusions in the Illinois Basin were examined in detail by advanced solid-state ¹³C nuclear magnetic resonance (NMR) spectroscopy. Spectral-editing techniques were used to identify specific functional groups. Direct polarization was used to quantify different functional groups. ¹H-¹³C two- dimensional heteronuclear NMR was used to examine connectivities and proximities, and ¹H-¹³C long-range recoupled dipolar dephasing was used to estimate aromatic cluster sizes. With decreasing distance to dike contacts and increasing thermal maturity (vitrinite reflectance R₀ from …

Development Of Two-Dimensional Gel Electrophoresis Procedures For Analysis Of Cupriavidus Necator H16 Subcellular Proteomes, Smita Joshi

Morehead State Theses and Dissertations

A thesis presented to the faculty of the College of Science and Technology at Morehead State University in partial fulfillment of the requirements for the Degree of Master of Science by Smita Joshi on June 17, 2011.

Part A: The Use Of Nonionic Associative Polymers For The Thickening And Emulsifying Of Personal Care Products/ Part B: The Synthesis Of A Manganese Sod Mimetic For Reactive Coatings, Mallory Lynn Mcmahon

Master's Theses

Part A

The use of nonionic associative thickeners was proposed for personal care applications.  Various limitations of current rheology modifiers used in personal care were discussed.  Nonionic associative polymers were examined as both thickeners and emulsifiers.  The structure/property relationship for nonionic polymers and their ability to thicken and emulsify were fully examined.  Results showed an increase in thickening efficiency for nonionic associative polymers with higher log(P) (partition coefficient) values.  This was due to the formation of smaller aggregates and increased bridging between aggregates.  The connection between oil polarity, log(P) of the associative polymer, and emulsion stability showed no relationship however; …

The Preparation Of Functional Surfaces, Philip Thomas Dirlam

Master's Theses

Diels-Alder chemistry was utilized to manipulate the surface energy of glass substrates in reversible manner. Glass slides and capillaries were functionalized with hydrophobic dieneophiles resulting in a  non-wetting surface.  A retro Diels-Alder reaction facilitated by the thermal treatment of the surface’s function to cleave the hydrophobic dieneophile and resulted in the fabrication of a hydrophilic surface. Contact angle (CA) measurements were used as preliminary measurements for monitoring the changes in surface energy exhibited during the initial hydrophobic state (CA - 70±3°), after attachment of the dieneophile creating  a hydrophobic state (CA - 101±9°) followed by reestablishment of the hydrophilic state …

Characterization Of Esterase Activity From The Bacteria, Francisella Tularensis, The Causative Agent Of Tularemia, Leigh Anna Weston

Undergraduate Honors Thesis Collection

Francisella tularensis is the bacteria responsible for causing the disease tularemia and is listed as one of the top three-biowarfare agents. Among the proteins essential to the virulence and infectivity of F.tularensis are multiple esterases, which are enzymes that break down various ester, thioester, and amide bonds. In this project, the catalytic activity, substrate speci fi city, and structure of a putative esterase from F.tularensis was studied. Latent fluorophores based on the molecule, fluorescein, were unmasked by the enzymatic activity of the esterase and the increase in fluorescence was measured over time to determine how well the e tcrase recognized …

Chiral Recognition Study Of A Bimolecular Process In Amino Acid Chiral Ionic Liquids, Laurel Millikan Heckman

Undergraduate Honors Thesis Collection

In this study, chiral ionic liquid (CIL) solvents were prepared and tested for their chiral discrimination ability by probing with luminescence quenching. The CIL's were also tested for their impurities, viscosity and density. These experiments will help to determine the ability of CIL's to act as solvents in asymmetric catalysis. The chiral ionic liquids in this study were composed of amino acid methyl ester cations and bis(trifluoromethane) sulfonimide or bistri flimide anions (i.e. I-alanine methyl ester bistriflimid e, d-alanine methyl ester bistr iflim ide and I-leuci ne methyl ester bistriflimde). Circularly polarized luminescence (CPL) and its quenching in the chiral …

Development Of A Green Method For Amide Synthesis, Megan Ruth Darragh

Undergraduate Honors Thesis Collection

The aim of this work was to determine the scope and limitations of using microwave technology, solvent-free conditions and green chemistry-applicable solid supports for amide synthesis. We hypothesize that the method developed by Comerford et al [12] may be applicable to other solid support systems already in use (silica, fly ash, and alumina), and that combined with the use of microwave technology, green and efficient synthesis of varied amides and other dehydration reaction products may be possible. These methods should show application to undergraduate, organic chemistry laboratories as well as large-scale production laboratories.

Towards The Synthesis Of Alpha-Aminogalactosylceramides, Shaun C. Christian

Master's Theses

No abstract provided.

Approach To Arsenic And Selenium Removal From Fly Ash By Oxalate And Estimation Of Calcium Effects On Both Elements, Ying Wen

Masters Theses & Specialist Projects

An approach to arsenic and selenium removal from fly ash is studied. This research includes a comparison of the leaching ability of ammonium oxalate, ammonium citrate, ammonium nitrate and EDTA to extract arsenic and selenium; use of common agricultural waste as a source of oxalate anion to remove arsenic and selenium from fly ash and estimation of additional calcium effects on arsenic and selenium leaching behaviors.
This research shows that extraction strength order is EDTA > ammonium oxalate > ammonium citrate > ammonium nitrate > water, achieving arsenic extraction efficiencies of 94.18%, 84.17%, 4.50%, 2.89% and 0.18%, respectively; achieving selenium extraction efficiencies of 96.14%, …

Exploring The Potential For B12-Based Oral Vaccine Delivery; Cubilin Mediated Uptake Of B12-Conjugate Systems Greater Than 160 Kda, Teresa Soldner

Renée Crown University Honors Thesis Projects - All

This project aimed to create a novel oral tetanus vaccine by exploiting the B₁₂ uptake pathway. While many linkers were attempted, the only successful complex was created using CDT coupling. After synthesis, purification (with some difficulty), and characterization, tests were done in vitro and in vivo. These supported the conclusion that while the complex was being successfully taken up by the cell, the complex was not created a strong enough immune response for a positive titer. On a second note, simply the uptake of B₁₂-TT is remarkable because it is the largest molecule that has been …

Adsorbents With Chemically Bonded Saccharide Surfaces: Synthesis And Application For Stereoisomer Separation And The Synthesis Of Chiral Porous Silicas Using Templates Chiral Surfactant, Edwin Vega

Seton Hall University Dissertations and Theses (ETDs)

.

Self-Assembling Organic Semiconductors With Tunable Electronic Properties Based On Novel Asymmetric Phenazine And Bisphenazine, Kyoungmi Jang

UNLV Theses, Dissertations, Professional Papers, and Capstones

Current demands in the area of organic semiconductors focus on both electronic and self-assembling properties. Particularly, one-dimensionally grown nanostructures of small organic semiconductors have drawn much attention for nanodevice fabrication. Self-assembly through various intermolecular interactions has been widely used to produce one-dimensionally grown nanostructures which can be induced by various methods such as rapid solution dispersion, a phase transfer method, vapor annealing, crystallization, and organogelation in conjunction with proper molecular design. Controlling the morphology of the nanostructures plays an important role in achieving desirable properties in optoelectronic device applications. While significant advancements have been made in developing molecular architectures for …

Targeting A-Form Nucleic Acids: A Neomycin Based Approach, Nicholas Shaw

All Dissertations

This manuscript reflects our most recent advancements in the recognition of nucleic acids. Chapter one focuses on previously established methods in nucleic acid recognition. Nucleic acid targeting by small molecules affords a unique way to potentially inhibit biological functions, which is different from targeting enzyme and protein bio-macromolecules. We seek to further develop an aminoglycoside approach to targeting nucleic acids. Since aminoglycosides were first introduced, over 60 years ago, as treatment for tuberculosis, natural product discovery and demands for therapeutically more effective aminoglycosides, with lowered toxicity, have dominated the landscape of aminoglycoside research. More recently, our group has established neomycin …

Scope And Mechanistic Studies Of The Palladium On Carbon Catalyzed Suzuki Cross Coupling Reaction, Carl Leblond

Seton Hall University Dissertations and Theses (ETDs)

No abstract provided.