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Size-Based Separation Of Bioparticles Using Planar Nanofluidic Devices, Jie Xuan Sep 2013

Size-Based Separation Of Bioparticles Using Planar Nanofluidic Devices, Jie Xuan

Theses and Dissertations

Nanofluidic devices are structures having at least one dimension in the submicron range, which is of the same order of magnitude as the sizes of biomolecules and bioparticles such as proteins and viruses. As a result, size-selective separations are important applications for nanofluidics. Well-defined micro or nano device structures fabricated via micromachining have greatly reduced sample consumption and enabled separations in a parallel fashion, promising significant speed and resolution advantages over conventional size separation techniques, such as gel electrophoresis and size exclusion chromatography. In collaboration with others, I have developed a size separation method using nanofluidic devices consisting of an …


A Novel Asymmetric Phase-Transfer Catalyzed Approach To The Compounds Ragaglitazar And Kuarsoin A, D. Karl Bedke Sep 2013

A Novel Asymmetric Phase-Transfer Catalyzed Approach To The Compounds Ragaglitazar And Kuarsoin A, D. Karl Bedke

Journal of Undergraduate Research

Asymmetric glycolate alkylation plays a key role in the synthesis of complex biologically active compounds. Such asymmetric transformations have largely to date been accomplished by employing chiral auxiliaries which have shown remarkable success in asymmetric synthesis. However, auxiliaries must also be used in stoichiometric amounts and can become quite expensive. A catalytic approach to asymmetric glycolate alkylations presents an attractive option to the use of auxiliaries. Andrus2,3 et al. have recently developed a methodology utilizing phase-transfer catalyst 1 for alkylation of a novel alkoxyacetophenone substrate 2 that can be readily oxidized to its glycolic ester derivative to provide access to …


Use Of Solid-Phase Extraction To Enrich Protein Biomarkers Of Disease From Blood Serum, Peter F. Mclean, Dr Craig Thulin Sep 2013

Use Of Solid-Phase Extraction To Enrich Protein Biomarkers Of Disease From Blood Serum, Peter F. Mclean, Dr Craig Thulin

Journal of Undergraduate Research

Biomarkers in blood serum are the keys needed for the early detection of several types of cancer, complications of pregnancy, and potentially many other diseases, to allow time for successful treatment. Blood serum is ideal because itp comes in contact with all parts of the body, its sampling is minimally invasive, and it is easily prepared with high reproducibility. There is a problem, however, that prevents the development and wide-scale utilization of this treasure chest of biological information. Pure blood serum is complex and cluttered with high-abundance non-target proteins which makes examination of the low-abundance and low-molecular weight potential biomarkers …


Structural Identification Of The Bioactive Components Of The Samoan Fish Poison Plant Barringtonia Asiatica, Robert A. Burton, Dr. Noel L. Owen Sep 2013

Structural Identification Of The Bioactive Components Of The Samoan Fish Poison Plant Barringtonia Asiatica, Robert A. Burton, Dr. Noel L. Owen

Journal of Undergraduate Research

The seed of the Futu tree, Barringtonia asiatica, has been used by inhabitants of the Pacific islands for many years as a highly toxic fish poison.1 These ethnobotanical studies were responsible for the initiation of this investigation.


Formation, Functionalization, Characterization, And Applications Of A Mixed-Mode, Carbon/Diamond-Based, Core-Shell Phase For High Performance Liquid Chromatography, Landon A. Wiest Sep 2013

Formation, Functionalization, Characterization, And Applications Of A Mixed-Mode, Carbon/Diamond-Based, Core-Shell Phase For High Performance Liquid Chromatography, Landon A. Wiest

Theses and Dissertations

My work has focused on a variety of different types of diamond-based, core-shell particles. These particles are formed with inert cores and poly(allylamine)/nanodiamond shells. Their intended purpose is to form an LC stationary phase that is stable from pH 1 – 14 and at elevated temperatures. At the beginning of my studies, the particles that had been made in the Linford laboratory were pH stable, but irregular and had poor mechanical stability. Since that time, I have worked to improve the particles by using more spherical zirconia and carbon cores, and I have improved their mechanical stability via chemical crosslinking …


Membrane Lipid-Modulated Mechanism Of Action And Non-Cytotoxicity Of Novel Fungicide Aminoglycoside Fg08, Sanjib Shrestha, Michelle Grilley, Marina Y. Fosso, Cheng-Wei Tom Chang, Jon Y. Takemoto Sep 2013

Membrane Lipid-Modulated Mechanism Of Action And Non-Cytotoxicity Of Novel Fungicide Aminoglycoside Fg08, Sanjib Shrestha, Michelle Grilley, Marina Y. Fosso, Cheng-Wei Tom Chang, Jon Y. Takemoto

Chemistry and Biochemistry Faculty Publications

A novel aminoglycoside, FG08, that differs from kanamycin B only by a C8 alkyl chain at the 4″-O position, was previously reported. Unlike kanamycin B, FG08 shows broad-spectrum fungicidal but not anti-bacterial activities. To understand its specificity for fungi, the mechanism of action of FG08 was studied using intact cells of the yeast Saccharomyces cerevisiae and small unilamellar membrane vesicles. With exposure to FG08 (30 µg mL−1), 8-fold more cells were stained with fluorescein isothiocyanate, cells had 4 to 6-fold higher K+ efflux rates, and 18-fold more cells were stained with SYTOX Green in comparison to exposure to kanamycin B …


Laboratory Characterization Of Pm Emissions From Combustion Of Wildland Biomass Fuels, S. Hosseini, S. P. Urbanski, P. Dixit, L. Qi, I. R. Burling, Robert J. Yokelson, T. J. Johnson, M. Shrivastava, H. S. Jung, D. R. Weise, J. W. Miller, D. R. Cocker Iii Sep 2013

Laboratory Characterization Of Pm Emissions From Combustion Of Wildland Biomass Fuels, S. Hosseini, S. P. Urbanski, P. Dixit, L. Qi, I. R. Burling, Robert J. Yokelson, T. J. Johnson, M. Shrivastava, H. S. Jung, D. R. Weise, J. W. Miller, D. R. Cocker Iii

Chemistry and Biochemistry Faculty Publications

[1] Particle emissions from open burning of southwestern (SW) and southeastern (SE) U.S. fuel types during 77 controlled laboratory burns are presented. The fuels include SW vegetation types: ceanothus, chamise/scrub oak, coastal sage scrub, California sagebrush, manzanita, maritime chaparral, masticated mesquite, oak savanna, and oak woodland, as well as SE vegetation types: 1 year, 2 year rough, pocosin, chipped understory, understory hardwood, and pine litter. The SW fuels burned at higher modified combustion efficiency (MCE) than the SE fuels resulting in lower particulate matter mass emission factor. Particle mass distributions for six fuels and particle number emission for all fuels …


A Trojan Horse Approach To Cancer Treatment: A2da And A2noon As Potential Triggered And Targeting Chemotherapeutic Drugs, Jeremy Koontz, Dr. Heidi Vollmer-Snarr Sep 2013

A Trojan Horse Approach To Cancer Treatment: A2da And A2noon As Potential Triggered And Targeting Chemotherapeutic Drugs, Jeremy Koontz, Dr. Heidi Vollmer-Snarr

Journal of Undergraduate Research

Despite the enormous amounts of time and money spent to research effective cures for cancer—the second leading cause of death in the United States —little is known today about how to kill cancer cells without harming normal cells. Current traditional forms of cancer treatment are chemotherapy, radiotherapy, and invasive surgery. However, the challenge with such treatments is they do not discriminate between normal cells and cancerous cells; these therapies struggle to balance toxicity and efficiency. In comparison, photodynamic therapy (PDT) offers a more favorable alternative to traditional methods of cancer treatment. In PDT drugs, called photosensitizers, are activated through specific …


Chimeric Rhinoviruses Displaying Mper Epitopes Elicit Anti-Hiv Neutralizing Responses, Guohua Yi, Mauro Lapelosa, Rachel Bradley, Thomas M. Mariano, Denise Elsasser Dietz, Scott Hughes, Terri Wrin, Chris Petropoulos, Emilio Gallicchio, Ronald M. Levy, Eddy Arnold, Gail Ferstandig Arnold Sep 2013

Chimeric Rhinoviruses Displaying Mper Epitopes Elicit Anti-Hiv Neutralizing Responses, Guohua Yi, Mauro Lapelosa, Rachel Bradley, Thomas M. Mariano, Denise Elsasser Dietz, Scott Hughes, Terri Wrin, Chris Petropoulos, Emilio Gallicchio, Ronald M. Levy, Eddy Arnold, Gail Ferstandig Arnold

Publications and Research

Background: The development of an effective AIDS vaccine has been a formidable task, but remains a critical necessity. The well conserved membrane-proximal external region (MPER) of the HIV-1 gp41 glycoprotein is one of the crucial targets for AIDS vaccine development, as it has the necessary attribute of being able to elicit antibodies capable of neutralizing diverse isolates of HIV.

Methodology/Principle Findings: Guided by X-ray crystallography, molecular modeling, combinatorial chemistry, and powerful selection techniques, we designed and produced six combinatorial libraries of chimeric human rhinoviruses (HRV) displaying the MPER epitopes corresponding to mAbs 2F5, 4E10, and/or Z13e1, connected to an immunogenic …


Protein Similarity Networks Reveal Relationships Among Sequence, Structure, And Function Within The Cupin Superfamily, Richard Uberto, Ellen W. Moomaw Sep 2013

Protein Similarity Networks Reveal Relationships Among Sequence, Structure, And Function Within The Cupin Superfamily, Richard Uberto, Ellen W. Moomaw

Faculty Articles

The cupin superfamily is extremely diverse and includes catalytically inactive seed storage proteins, sugar-binding metal-independent epimerases, and metal-dependent enzymes possessing dioxygenase, decarboxylase, and other activities. Although numerous proteins of this superfamily have been structurally characterized, the functions of many of them have not been experimentally determined. We report the first use of protein similarity networks (PSNs) to visualize trends of sequence and structure in order to make functional inferences in this remarkably diverse superfamily. PSNs provide a way to visualize relatedness of structure and sequence among a given set of proteins. Structure- and sequence-based clustering of cupin members reflects functional …


Self-Assembled Dna Origami Templates For The Fabrication Of Electronic Nanostructures, Elisabeth Pound Gates Sep 2013

Self-Assembled Dna Origami Templates For The Fabrication Of Electronic Nanostructures, Elisabeth Pound Gates

Theses and Dissertations

An important goal of nanoscience is the self-assembly of nanoscale building blocks into complex nanostructures. DNA is an important and versatile building block for nanostructures because of its small size, predictable base pairing, and numerous sequence possibilities. I use DNA origami to design and fold DNA into predesigned shapes, to assemble thin, branched DNA nanostructures as templates for nanoscale metal features. Using a PCR-based scaffold strand generation procedure, several wire-like nanostructures with varying scaffold lengths were assembled. In addition, more complex prototype circuit element structures were designed and assembled, demonstrating the utility of this technique in creating complex templates. My …


Lipidomic Analysis Of Metastatic Kidney Cancer, Brendan Coutu, Dr. John Prince Sep 2013

Lipidomic Analysis Of Metastatic Kidney Cancer, Brendan Coutu, Dr. John Prince

Journal of Undergraduate Research

Cancer not only affects individuals and families but has the greatest economic effect worldwide than any other premature cause of death.1 Diverse aspects of cancer biology are under investigation to better understand the mechanism of action of different cancer types, that biomarkers can be identified for early diagnosis, and, most importantly, that a lasting cure can be discovered.32 In the development of cancer, cells undergo a number of phenotypic changes, known as the hallmarks of cancer.2 The hallmarks of cancer are described as sustained proliferative signaling, evading growth suppressors, activating invasion and metastasis, enabling replicative immortality, inducing angiogenesis, and resisting …


Development Of Novel Reaction-Based Fluorescent Probes, Weimin Xuan Sep 2013

Development Of Novel Reaction-Based Fluorescent Probes, Weimin Xuan

Chemistry and Chemical Biology ETDs

Fluorescent probes have been proved to be very valuable tools in chemical and biological applications, and extensive exploration has been made. Recently, reaction-based fluorescent probes became a new design trend and displayed great potential with remarkable implementation to the conventional design method. However, this field is still underdeveloped, and a lot of problems remain to be solved. As part of our groups research interest, my Ph.D. study centered on the development of new reaction-based fluorescent probes. Firstly, our previous research on Hg2+ was continued. In this work, we developed a novel ratiometric fluorescent probe for Hg2+ with impressive …


Antimicrobial Activity And Mechanistic Study For The Poly(Phenylene Ethynylene) (Ppe)-Based Cationic Conjugated Polyelectrolytes And Oligo-Phenylene Ethynylenes, Ying Wang Sep 2013

Antimicrobial Activity And Mechanistic Study For The Poly(Phenylene Ethynylene) (Ppe)-Based Cationic Conjugated Polyelectrolytes And Oligo-Phenylene Ethynylenes, Ying Wang

Chemistry and Chemical Biology ETDs

My dissertation work focuses on recent progress made in elucidating the intermolecular interactions between a novel class of synthetic phenylene ethynylene (PPE)-based conjugated polyelectrolyte polymers (CPEs) and oligomers (OPEs) and multiscale cellular targets that give rise to their remarkable broad spectrum biocidal activity. We studied the interactions and self-assembly behaviors of the CPEs and OPEs with a set of vital biomolecules, including lipids, proteins and nucleic acids, that reveal the potential pathways by which the synthetic biocidal agents could exert toxicity. Then, we explored the antimicrobial effects and mechanisms of the CPEs and OPEs on multiple clinically relevant pathogens, with …


Translational Control Of Poly(A)-Binding Protein Expression, Eliott Spencer, Dr. Roger Kaspar Sep 2013

Translational Control Of Poly(A)-Binding Protein Expression, Eliott Spencer, Dr. Roger Kaspar

Journal of Undergraduate Research

Poly(A)-binding protein or PABP is found in high concentrations in all eukaryotic cells. Cell biologists have speculated for a long time that PABP plays an important role in stabilizing the fragile MRNA molecule so that it can be more effectively translated into its final gene product. PABP does this by binding to the Poly(A) tail at the 3′ end of the MRNA. 1,2


A Novel Mglur5 Antagonist, Mfz 10-7, Inhibits Cocaine-Taking And Cocaine-Seeking Behavior In Rats, Thomas Keck, Mu-Fa Zou, Gui-Hua Bi, Hai-Ying Zhang, Xiao-Fei Wang, Hong-Ju Yang, Ratika Srivastava, Elliott L. Gardner, Zheng-Xiong Xi, Amy Hauck Newman Sep 2013

A Novel Mglur5 Antagonist, Mfz 10-7, Inhibits Cocaine-Taking And Cocaine-Seeking Behavior In Rats, Thomas Keck, Mu-Fa Zou, Gui-Hua Bi, Hai-Ying Zhang, Xiao-Fei Wang, Hong-Ju Yang, Ratika Srivastava, Elliott L. Gardner, Zheng-Xiong Xi, Amy Hauck Newman

College of Science & Mathematics Departmental Research

Pre-clinical studies suggest that negative allosteric modulators (NAMs) of the metabotropic glutamate receptor subtype 5 (mGluR5), including 2-methyl-6-(phenylethynyl)pyridine (MPEP), 3-[(2-methyl-1,3-thiazol-4-yl)ethynyl]pyridine (MTEP) and fenobam are highly effective in attenuating drug-taking and drug-seeking behaviors. However, both MPEP and MTEP have no translational potential for use in humans because of their off-target effects and short half-lives. Here, we report that 3-fluoro-5-[(6-methylpyridin-2-yl)ethynyl]benzonitrile (MFZ 10-7), a novel mGluR5 NAM, is more potent and selective than MPEP, MTEP and fenobam in both in vitro binding and functional assays. Similar to MTEP, intraperitoneal administration of MFZ 10-7 inhibited intravenous cocaine self-administration, cocaine-induced reinstatement of drug-seeking behavior and …


Myeloperoxidase, Paraoxonase-1, And Hdl Form A Functional Ternary Complex, Ying Huang, Zhiping Wu, Meliana Riwanto, Shengqiang Gao, Bruce S. Levison, Xiaodong Gu, Xiaoming Fu, Matthew A. Wagner, Christian Besler, Gary Gerstenecker, Renliang Zhang, Xin Min Li, Anthony J. Didonato, Valentin Gogonea, W.H. Wilson Tang, Jonathan D. Smith, Edward F. Plow, Paul L. Fox, Diana M. Shih, Aldons J. Lusis, Edward A. Fisher, Joseph A. Didonato, Ulf Landmesser, Stanley L. Hazen Sep 2013

Myeloperoxidase, Paraoxonase-1, And Hdl Form A Functional Ternary Complex, Ying Huang, Zhiping Wu, Meliana Riwanto, Shengqiang Gao, Bruce S. Levison, Xiaodong Gu, Xiaoming Fu, Matthew A. Wagner, Christian Besler, Gary Gerstenecker, Renliang Zhang, Xin Min Li, Anthony J. Didonato, Valentin Gogonea, W.H. Wilson Tang, Jonathan D. Smith, Edward F. Plow, Paul L. Fox, Diana M. Shih, Aldons J. Lusis, Edward A. Fisher, Joseph A. Didonato, Ulf Landmesser, Stanley L. Hazen

Chemistry Faculty Publications

Myeloperoxidase (MPO) and paraoxonase 1 (PON1) are high-density lipoprotein–associated (HDL-associated) proteins mechanistically linked to inflammation, oxidant stress, and atherosclerosis. MPO is a source of ROS during inflammation and can oxidize apolipoprotein A1 (APOA1) of HDL, impairing its atheroprotective functions. In contrast, PON1 fosters systemic antioxidant effects and promotes some of the atheroprotective properties attributed to HDL. Here, we demonstrate that MPO, PON1, and HDL bind to one another, forming a ternary complex, wherein PON1 partially inhibits MPO activity, while MPO inactivates PON1. MPO oxidizes PON1 on tyrosine 71 (Tyr71), a modified residue found in human atheroma that is critical for …


Cloning And Characterization Of Ef-Tu And Ef-Ts From Pseudomonas Aeruginosa, Stephanie O. Palmer, Edna Y. Rangel, Alberto E. Montalvo, Alexis T. Tran, Kate C. Ferguson, James M. Bullard Sep 2013

Cloning And Characterization Of Ef-Tu And Ef-Ts From Pseudomonas Aeruginosa, Stephanie O. Palmer, Edna Y. Rangel, Alberto E. Montalvo, Alexis T. Tran, Kate C. Ferguson, James M. Bullard

School of Integrative Biological & Chemical Sciences (Formerly Dept. of Chemistry)

We have cloned genes encoding elongation factors We have cloned genes encoding elongation factors EF-Tu and EF-Ts from Pseudomonas aeruginosa and expressed and purified the proteins to greater than 95% homogeneity. Sequence analysis indicated that P. aeruginosa EF-Tu and EF-Ts are 84% and 55% identical to E. coli counterparts, respectively. P. aeruginosa EF-Tu was active when assayed in GDP exchange assays. Kinetic parameters for the interaction of EF-Tu with GDP in the absence of EF-Ts were observed to be = 33 μM, = 0.003 s−1, and the specificity constant was  s−1 μM−1. In the presence of EF-Ts, these values were …


Hypothesis Driven Single Nucleotide Polymorphism Search (Hydn-Snp-S), Rebecca J. Swett, Angela Elias, Jeffrey A. Miller, Gregory E. Dyson, G. AndréS Cisneros Sep 2013

Hypothesis Driven Single Nucleotide Polymorphism Search (Hydn-Snp-S), Rebecca J. Swett, Angela Elias, Jeffrey A. Miller, Gregory E. Dyson, G. AndréS Cisneros

Chemistry Faculty Research Publications

The advent of complete-genome genotyping across phenotype cohorts has provided a rich source of information for bioinformaticians. However the search for SNPs from this data is generally performed on a study-by-study case without any specific hypothesis of the location for SNPs that are predictive for the phenotype. We have designed a method whereby very large SNP lists (several gigabytes in size), combining several genotyping studies at once, can be sorted and traced back to their ultimate consequence in protein structure. Given a working hypothesis, researchers are able to easily search whole genome genotyping data for SNPs that link genetic locations …


Shared Mycobacterium Avium Genotypes Observed Among Unlinked Clinical And Environmental Isolates, M. Ashworth Dirac, Kris M. Weigel, Mitchell A. Yakrus, Annie L. Becker, Hui-Ling Chen, Gina Fridley, Arthur Sikora, Cate Speake, Elizabeth D. Hilborn, Stacy Pfaller, Gerard A. Cangelosi Sep 2013

Shared Mycobacterium Avium Genotypes Observed Among Unlinked Clinical And Environmental Isolates, M. Ashworth Dirac, Kris M. Weigel, Mitchell A. Yakrus, Annie L. Becker, Hui-Ling Chen, Gina Fridley, Arthur Sikora, Cate Speake, Elizabeth D. Hilborn, Stacy Pfaller, Gerard A. Cangelosi

Chemistry and Physics Faculty Articles

Our understanding of the sources of Mycobacterium avium infection is partially based on genotypic matching of pathogen isolates from cases and environmental sources. These approaches assume that genotypic identity is rare in isolates from unlinked cases or sources. To test this assumption, a high-resolution PCR-based genotyping approach, large-sequence polymorphism (LSP)-mycobacterial interspersed repetitive unit–variable-number tandem repeat (MIRU-VNTR), was selected and used to analyze clinical and environmental isolates of M. avium from geographically diverse sources. Among 127 clinical isolates from seven locations in North America, South America, and Europe, 42 genotypes were observed. Among 12 of these genotypes, matches were seen in …


Toward An Understanding Of The Retinal Chromophore In Rhodopsin Mimics, Mark M. Huntress, Samer Gozem, Konstantin R. Malley, Askat E. Jailaubekov, Chrysoula Vasileiou, Mikas Vengris, James H. Geiger, Babak Borhan, Igor Schapiro, Delmar S. Larsen, Massimo Olivucci Sep 2013

Toward An Understanding Of The Retinal Chromophore In Rhodopsin Mimics, Mark M. Huntress, Samer Gozem, Konstantin R. Malley, Askat E. Jailaubekov, Chrysoula Vasileiou, Mikas Vengris, James H. Geiger, Babak Borhan, Igor Schapiro, Delmar S. Larsen, Massimo Olivucci

Chemistry Faculty Publications

Recently, a rhodopsin protein mimic was constructed by combining mutants of the cellular retinoic acid binding protein II (CRABPII) with an all-trans retinal chromophore. Here, we present a combine computational quantum mechanics/molecular mechanics (QM/MM) and experimental ultrafast kinetic study of CRABPII. We employ the QM/MM models to study the absorption (lambda(a)(max)), fluorescence (lambda(f)(max)), and reactivity of a CRABPII triple mutant incorporating the all-trans protonated chromophore (PSB-KLE-CRABPII). We also study the spectroscopy of the same mutant incorporating the unprotonated chromophore and of another double mutant incorporating the neutral unbound retinal molecule held inside the pocket. Finally, for PSB-KLE-CRABPII, stationary fluorescence spectroscopy …


Thermodynamic Characterization Of Five Key Kinetic Parameters That Define Neuronal Nitric Oxide Synthase Catalysis, Mohammad Mahfuzul Haque, Jesus Tejero, Mekki Bayachou, Zhi-Qiang Wang, Mohammed Fadlalla, Dennis J. Stuehr Sep 2013

Thermodynamic Characterization Of Five Key Kinetic Parameters That Define Neuronal Nitric Oxide Synthase Catalysis, Mohammad Mahfuzul Haque, Jesus Tejero, Mekki Bayachou, Zhi-Qiang Wang, Mohammed Fadlalla, Dennis J. Stuehr

Chemistry Faculty Publications

NO synthase (NOS) enzymes convert L-arginine to NO in two sequential reactions whose rates (kcat1 and kcat2) are both limited by the rate of ferric heme reduction (kr). An enzyme ferric heme –NO complex forms as an immediate product complex and then undergoes either dissociation (at a rate that we denote as kd) to release NO in a productive manner, or reduction (kr) to form a ferrous heme –NO complex that must react with O2 (at a rate that we denote as kox) in a NO dioxygenase reaction that regenerates the ferric enzyme. The interplay of these five kinetic parameters …


Computational Study Of The Cyclization Of 5-Hexenyl, 3-Oxa-5-Hexenyl And 4-Oxa-5-Hexenyl Radicals, Albert Matlin, Matthew C. Leyden Sep 2013

Computational Study Of The Cyclization Of 5-Hexenyl, 3-Oxa-5-Hexenyl And 4-Oxa-5-Hexenyl Radicals, Albert Matlin, Matthew C. Leyden

Faculty & Staff Scholarship

The intramolecular cyclization of 5-hexenyl radicals continues to be an important synthetic method for the construction of five-membered rings. The synthetic utility arises from the high degree of regioselectivity to give predominantly cyclopentyl products in high yield under mild conditions. Recently we reported product cyclization studies on 4-oxa perturbed 5-hexenyl radical. In this paper we report our results from a computational study (UB3LYP and UCCSD(T)) of the cyclization of a series of 5-hexenyl and 3- and 4-oxa-5-hexenyl radicals. Three highly conserved cyclization transitions states (exo-chair, exo-boat and endo-chair) were located for 10 acyclic radicals. Activation en-ergies …


Preparation Of Cyclohexenones From Acyclic (Pentadienyl)Iron(1+) Cations: Synthesis Of Carvone Metabolites And Synthetic Studies Directed Toward Dihydrotachysterols, Charles Felix Manful Sep 2013

Preparation Of Cyclohexenones From Acyclic (Pentadienyl)Iron(1+) Cations: Synthesis Of Carvone Metabolites And Synthetic Studies Directed Toward Dihydrotachysterols, Charles Felix Manful

Dissertations (1934 -)

ABSTRACT

PREPARATION OF CYCLOHEXENONES FROM ACYCLIC (PENTADIENYL)IRON(1+) CATIONS: SYNTHESIS OF CARVONE METABOLITES AND SYNTHETIC STUDIES DIRECTED TOWARD DIHYDROTACHYSTEROLS

Charles Felix Manful, BSc.

Marquette University, 2013

Six-membered carbocycles are abundant in natural products. This structural feature is present in terpenes, secosteroids, antibiotics, and even imbedded in the polycyclic framework of complex alkaloids. A wide variety of methodologies have been utilized for the preparation of six-membered carbocycles including Robinson annulation, Diels-Alder cycloaddition, Dieckmann condensation, ring closing metathesis, photochemical carbonylation of alkenylcyclopropanes, addition of soft nucleophiles to acyclic (ç5-pentadienyl)iron cations, etc.

Acyclic (ç5-pentadienyl)iron(+1) cations were first prepared about 50 years ago. The reactivity …


Supramolecular Polysaccharide Composite Materials: Green And Recyclable Synthesis, Characterization, Analytical And Biomedical Applications, Simon Duri Sep 2013

Supramolecular Polysaccharide Composite Materials: Green And Recyclable Synthesis, Characterization, Analytical And Biomedical Applications, Simon Duri

Dissertations (1934 -)

A simple novel recyclable synthetic method was successfully developed for the synthesis of polysaccharide composite materials. The method involves the use of 1-butyl-3-methylimidazolium chloride [BMIm+Cl-], a simple ionic liquid, as the sole solvent. Naturally abundant and renewable materials such as cellulose (CEL) and chitosan (CS) were used for the preparation of the composite materials. CEL is the most abundant compound on earth, while CS is a product of deacetylation of chitin, which is the second most abundant material on earth. [BMIm+Cl-] is relatively non toxic, non volatile and stable over a wide range of temperature eliminating one of the major …


Intramolecular Hydrogen Bonding In CuIi Complexes With 2,6-Pyridinedicarboxamide Ligands: Synthesis, Structural Characterization, And Physical Properties, Denan Wang, Sergey V. Lindeman, Adam T. Fiedler Sep 2013

Intramolecular Hydrogen Bonding In CuIi Complexes With 2,6-Pyridinedicarboxamide Ligands: Synthesis, Structural Characterization, And Physical Properties, Denan Wang, Sergey V. Lindeman, Adam T. Fiedler

Chemistry Faculty Research and Publications

The significance of second-sphere interactions in synthetic catalysts and metalloenzyme active sites has encouraged the development of ligand frameworks capable of supporting intramolecular hydrogen-bonding networks. With this approach in mind, we prepared a series of 2,6-pyridinedicarboxamide ligands (H2LX) that feature outer-sphere heterocyclic groups (pyridine, pyrimidine, or quinoline rings). Reaction with CuCl2 yields complexes with the general formula [CuCl2(LX{H}2)] (1X), in which the pincer ligands coordinate to the CuII center in a tridentate fashion through the central pyridine and two amidato nitrogen atoms. The LX …


Advanced Treatment Of Dyeing Wastewater For Reuse By Electrochemical Oxidation, Fei-Xiang Chen, Chu-Yin Yang, Ming-Ming Zhou, Jia-De Wang Aug 2013

Advanced Treatment Of Dyeing Wastewater For Reuse By Electrochemical Oxidation, Fei-Xiang Chen, Chu-Yin Yang, Ming-Ming Zhou, Jia-De Wang

Journal of Electrochemistry

In response to the characteristics of dye wastewater, the electrochemical oxidation of effluents from the biochemical process of dyeing wastewater was studied in the electrochemical reactor using PbO2/Ti electrode as the anode and stainless steel plate as the cathode. The results revealed that the electrochemical oxidation could simultaneously remove the Chemical Oxygen Demand (COD), ammonia and chromaticity. At the residence time of 60 min and current density of 10 mA·cm-2, the COD, ammonia, chromaticity, concentration of chloride ion and pH values could meet the water standards for “the reuse of urban recycling water-water quality standard for …


Electrochemically Switched Ion Exchange Properties Of Pani-Snp Composite Films In Wastewater Containing Ni2+ And Cd2+, Yan-Ting Feng, Jun-Qiang Xiao, Xiao-Gang Hao, Xu-Li Ma, Zhong-De Wang, Nian-Chen Han Aug 2013

Electrochemically Switched Ion Exchange Properties Of Pani-Snp Composite Films In Wastewater Containing Ni2+ And Cd2+, Yan-Ting Feng, Jun-Qiang Xiao, Xiao-Gang Hao, Xu-Li Ma, Zhong-De Wang, Nian-Chen Han

Journal of Electrochemistry

Electroactive PANI-SnP composite films were prepared by drop-coating method on Pt electrodes and investigated as electrochemically switched ion exchange (ESIX) materials for the separation of Cd2+ from aqueous solutions. The composition and morphology of the composite film were characterized by Fourier transform infrared spectrometer (FTIR) and scanning electron microscope (SEM). In solutions containing 0.1 mol·L-1 Ni(NO3)2 and Cd(NO3)2, cyclic voltammetry (CV) and electrochemical quartz crystal microbalance (EQCM) were used to investigate the electrochemical behavior and ion-exchange mechanism of PANI-SnP composite film. The elementary composition of PANI-SnP composite films in both oxidation …


Pitfalls With The Use Of Enhancement Ratios Or Normalized Excess Mixing Ratios Measured In Plumes To Characterize Pollution Sources And Aging, Robert J. Yokelson, Meinrat O. Andreae, S. K. Akagi Aug 2013

Pitfalls With The Use Of Enhancement Ratios Or Normalized Excess Mixing Ratios Measured In Plumes To Characterize Pollution Sources And Aging, Robert J. Yokelson, Meinrat O. Andreae, S. K. Akagi

Chemistry and Biochemistry Faculty Publications

Normalized excess mixing ratios (NEMRs), also known as enhancement ratios, are a common way to characterize plumes of pollution in atmospheric research. As single-source pollutant plumes disperse in the atmosphere, they are diluted by mixing with the adjacent background air. Changes in the composition of this background air can cause large changes to the NEMR that is subsequently measured by remote-sensing, airborne, or ground-based instruments. This scenario is common when boundary layer plumes enter the free troposphere and could also impact long-range transport or plumes near the top of the troposphere. We provide a context for these issues and an …


Book Review, Zong-Rang Zhang Aug 2013

Book Review, Zong-Rang Zhang

Journal of Electrochemistry

No abstract provided.