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Special Topic 3, Part 2: Pesticides: Herbicides, Vietnam Defoliants, And Dioxin, Gordon Gribble

Chemistry 52, Gordon Gribble lectures on Special Topics

No abstract provided.

Bolstering Cholesteryl Ester Hydrolysis In Liver: A Hepatocyte-Targeting Gene Delivery Strategy For Potential Alleviation Of Atherosclerosis, Hongliang He, Michael G. Lancina Iii, Jing Wang, William J. Korzun, Hu Yang, Shobha Ghosh

Chemistry Publications

Current atherosclerosis treatment strategies primarily focus on limiting further cholesteryl esters (CE) accumulation by reducing endogenous synthesis of cholesterol in the liver. No therapy is currently available to enhance the removal of CE, a crucial step to reduce the burden of the existing disease. Given the central role of hepatic cholesteryl ester hydrolase (CEH) in the intrahepatic hydrolysis of CE and subsequent removal of the resulting free cholesterol (FC), in this work, we applied galactosefunctionalized polyamidoamine (PAMAM) dendrimer generation 5 (Gal-G5) for hepatocyte-specific delivery of CEH expression vector. The data presented herein show the increased specific uptake of Gal-G5/CEH expression …

Palladium Nanoparticles Supported On Ce-Metal–Organic Framework For Efficient Co Oxidation And Low-Temperature Co2 Capture, Andrew Lin, Amr Awad Ibrahim, Pezhman Arab, Hanii M. El-Kaderi, M. Samy El-Shall

Chemistry Publications

In this article, we report the lowest-temperature CO oxidation catalyst supported on metal–organic frameworks (MOFs). We have developed a facile, general, and effective approach based on microwave irradiation for the incorporation of Pd nanoparticle catalyst within Ce-MOF. The resulting Pd/Ce-MOF material is a unique catalyst that is capable of CO oxidation at modest temperatures and also of efficient uptake of the product CO2 gas at low temperatures. The observed catalytic activity of this material toward CO oxidation is significantly higher than those of other reported metal nanoparticles supported on MOFs. The high activity of the Pd/Ce-MOF catalyst is due to …

Roles Of Free Electrons And H2o2 In The Optical Breakdown-Induced Photochemical Reduction Of Aqueous [Aucl4]-, Victoria K. Meader, Mallory G. John, Collin Rodrigues, Katharine M. Tibbetts

Chemistry Publications

Free electrons and H2O2 formed in an optical breakdown plasma are found to directly control the kinetics of [AuCl4]− reduction to form Au nanoparticles (AuNPs) during femtosecond laser-assisted synthesis of AuNPs. The formation rates of both free electrons and H2O2 strongly depend on the energy and duration of the 800 nm laser pulses over the ranges of 10−2400 μJ and 30−1500 fs. By monitoring the conversion of [AuCl4]− to AuNPs using in situ UV−vis spectroscopy during laser irradiation, the first- and second-order rate constants in the autocatalytic rate law, k1 and k2, were extracted and compared to the computed free …

Assessment Of Four Solvents For Extraction And Analysis Of The Chemical Composition Of Sansevieria Extrafoliar Nectar Drops By Gas Chromatography-Mass Spectrometry, Hope L. Juntunen, Patrick Videau, Donna Hazelwood, Michael Gaylor

Research & Publications

In the latter part of the 20th century, much effort was devoted to elucidating the chemical constituents of floral and extrafloral nectar secretions, with the primary aim of understanding their ecological roles, especially in regards to attracting pollinators. But, nearly all these studies focused on determining sugar and amino acid constituents. Only a few studies have reported more comprehensive assessments of the organic chemical constituents of plants, with none of those reporting such efforts for Sansevieria taxa (common houseplants known to purify air by bioaccumulating pollutants). To address this knowledge gap, we evaluated the efficacy of four organic solvents with …

Reply To ‘On The Bonding In Ligand-Protected Gold Clusters’, Wen Wu Xu, Xiao Cheng Zeng, Yi Gao

Xiao Cheng Zeng Publications

In the recent Correspondence, Professor Henrik Grönbeck made several comments on the recently developed grand unified model (GUM), in particular using the ligand-protected gold cluster [Au₂₅(SR)₁₈]¹⁻ as an example. We noted that the latter cluster can be viewed as belonging to a special group of ligand-protected gold clusters that contain one or several icosahedral Au₁₃ motifs. For this group of clusters, a secondary block Au₁₃(8e) has been identified as a more convenient way to describe their structure anatomy and evolution. Another extension of the GUM is the identification of the new elementary …

Improved Characterization And Analysis Strategies For Uv-Lif Bioaerosol Instrumentation: Lab And Field Application, Nicole Justine Savage

Electronic Theses and Dissertations

Atmospheric particles of biological origin, also referred to as bioaerosols or primary biological aerosol particles (PBAP), are important to various human health and environmental systems. There has been a recent steep increase in the frequency of published studies utilizing commercial instrumentation based on ultraviolet laser/light-induced fluorescence (UV-LIF), such as the WIBS (wideband integrated bioaerosol sensor), for bioaerosol detection both outdoors and in the built environment. Significant work over several decades supported the development of these technologies, but efforts to systematically characterize the operation of new commercial sensors has remained lacking. Specifically, there are gaps in the understanding of how different …

Quantification Of Airborne Fungal Spores Comparing Molecular Tracers Via Ion Chromatography And Uv-Lif Methods, Marie Ila Gosselin

Electronic Theses and Dissertations

Fungal spores represent an understudied subcategory of bioaerosols that can impact human health as pathogenic and allergenic particles. Fungal spores also have been shown to act as effective ice nuclei and giant cloud condensation nuclei in some cases. This has implications on the hydrological cycle on local and regional scales by impacting the formation and evolution of clouds and precipitation. The quantification of fungal spores has been limited in the past due to methods that were costly and that suffered from poor time resolution. The most commonly applied methods for airborne fungal spore analysis have traditionally included microscopy and culturing, …

Mechanistic Insights Into The Radical S-Adenosyl L-Methionine Enzyme Mftc, Bulat Khaliullin

Electronic Theses and Dissertations

Mycofactocin is a putative peptide-derived redox cofactor in Mycobacterium family. Its putative biosynthetic pathway is encoded by the operon mftABCDEF. The initial step of this pathway is a posttranslational modification of a peptide precursor MftA, which is catalyzed by MftC enzyme. This modification only occurs in the presence of chaperone MftB. Here, we demonstrate that MftC is a radical S-adenosyl L-methionine (SAM) enzyme and we examine its catalytic mechanism. We show that the modification of MftA requires two equivalents of SAM and is implemented in two steps: (i) the decarboxylation of a C-terminal tyrosine, resulting in formation of an …

A Bioinspired And Biocompatible Ortho-Sulfiliminyl Phenol Synthesis, Feng Xiong, Liang Lu, Tian-Yu Sun, Qian Wu, Dingyuan Yan, Ying Chen, Xinhao Zhang, Wei Wei, Yi Lu, Wei-Yin Sun, Jie Jack Li, Jing Zhao

Chemistry Faculty Publications

Synthetic methods inspired by Nature often offer unique advantages including mild conditions and biocompatibility with aqueous media. Inspired by an ergothioneine biosynthesis protein EgtB, a mononuclear non-haem iron enzyme capable of catalysing the C–S bond formation and sulfoxidation, herein, we discovered a mild and metal-free C–H sulfenylation/intramolecular rearrangement cascade reaction employing an internally oxidizing O–N bond as a directing group. Our strategy accommodates a variety of oxyamines with good site selectivity and intrinsic oxidative properties. Combining an O–N bond with an X–S bond generates a C–S bond and an S¼N bond rapidly. The newly discovered cascade reaction showed excellent chemoselectivity …

Paper-Based Diagnostic Devices, Spencer A. Schultz, Isabelle C. Noxon, Tyler A. Sisley, Andres W. Martinez

Chemistry and Biochemistry

This chapter will provide an overview of existing diagnostic devices made primarily out of paper and then focus on paper-based microfluidic devices, the next generation of paper-based diagnostic devices that promises to extend the use of paper as a material for fabricating diagnostic devices well into the future.

Chapter Contents:

• 2.1 Introduction
• 2.2 Current paper-based diagnostic devices
• 2.2.1 Dipstick devices
• 2.2.2 Lateral-flow devices
• 2.2.2.1 Vertical-flow devices
• 2.2.3 Paper-based arrays
• 2.3 Paper-based microfluidic devices
• 2.3.1 Fabrication of paper-based microfluidic devices
• 2.3.2 Applications of paper-based microfluidic devices
• 2.4 Conclusions
• References

Enantioselective Γ-Borylation Of Unsaturated Amides And Stereoretentive Suzuki–Miyaura Cross-Coupling, Gia L. Hoang, James M. Takacs

James M. Takacs Publications

The rhodium-catalyzed, directed catalytic asymmetric hydroboration of γ,δ-unsaturated amides affords a direct route to chiral acyclic secondary γ-borylated carbonyl derivatives in high enantiomeric purity. In contrast to a similar β-borylated amide derivative, the γ-borylated amide undergoes Suzuki–Miyaura cross-coupling with stereoretention. The utility of the boronic ester products is further illustrated by other stereospecific C–B bond transformations leading to γ-amino acid derivatives, 1,4-amino alcohols, and 5-substituted-γ-lactone and γ-lactam ring systems.

Includes Supplementary Materials.

Chemical Applications In Techniques Of Emerging Significance: Nanoparticle Transformation In Mitochondria And Relative Tautomer Populations In Cellular Automata, Gregory Arland Bowers

Browse all Theses and Dissertations

Two techniques of emerging importance were used to study different biochemical phenomena: the fate of silver nanoparticles in Vero 76 African green monkey kidney cell mitochondria, and the effect of pH on tautomer ratios using cellular automata. In the first area of research Vero 76 Africa green monkey kidney cells were incubated with silver nanoparticles (AgNP) and ionic silver (Ag+). After 24 hours the cell mitochondria were harvested, then processed with CPE-TFF and ICP-OES. The initial AgNP incubation formed 52.9% ± 15.5% AgNP and 29.9% ± 4.0% Ag+, while the ionic silver incubation formed 9.5% ± 0.9% AgNP and 60.6% …

Mesopore Etching Under Supercritical Conditions – A Shortcut To Hierarchically Porous Silica Monoliths, Martin Von Der Lehr, Kristof Hormann, Alexandra Höltzel, Lauren S. White, Arved E. Reising, Massimo F. Bertino, Bernd M. Smarsly, Ulrich Tallarek

Chemistry Publications

Hierarchically porous silica monoliths are obtained in the two-step Nakanishi process, where formation of a macro microporous silica gel is followed by widening micropores to mesopores through surface etching. The latter step is carried out through hydrothermal treatment of the gel in alkaline solution and necessitates a lengthy solvent exchange of the aqueous pore fluid before the ripened gel can be dried and calcined into a mechanically stable macro mesoporous monolith. We show that using an ethanol water (95.6/4.4, v/v) azeotrope as supercritical fluid for mesopore etching eliminates the solvent exchange, ripening, and drying steps of the classic route and …

Mechanochemical Synthesis Of Fuels From Sustainable Sources Utilizing Solid Catalysts, Jacob Todd

Electronic Theses and Dissertations

Mechanochemistry requires less solvents which results in less waste generation. The question becomes can we apply mechanochemistry to current chemical reactions and reduce the generation of waste. This process can be simple or can be very extensive resulting in the generation of large amounts of waste and very little product. A significant advantage of mechanochemistry is the reduced need for solvents that would be common place for reactions. Mechanochemistry transfers energy to reagents via impacts from milling media. Energy can be transferred to the reagents no matter their state-of-matter. Much of the current studies in mechanochemistry today are done using …

Enhancement Of Dielectric Properties With The Addition Of Bromine And Dopamine Modified Barium Titanate Particles To Silicone Rubber, Liang Jiang, David Kennedy, Stephen Jerrams, Tony Betts

Articles

Dual-coated barium titanate (BT) particles were prepared using dopamine (DP) in conjunction with bromine (Br) in order to enhance the dielectric constant of silicone rubber (SR) composites containing evenly distributed BT particles. The results showed that both DP and Br were deposited on the BT particles. The dielectric constant of the SR/BT composite was significantly increased from 3.6 to 4.7 at 1 kHz with the addition of BT modified with dopamine (DP–BT). Moreover, the dielectric constant further rose to 4.9 at 1 kHz when the DP–BT particle was grafted with bromine (Br–DP–BT).

Development Of Magnetorheological Elastomers (Mres) For Strength And Fatigue Resistance, J. Mcintyre, Stephen Jerrams

Books/Book Chapters

Natural rubber (NR)-based magnetorheological elastomers (MREs) exhibiting a reasonable switching effect were fabricated and tested. They were strong enough for use in automotive applications but still needed protection against ageing. Ethylene–propylene–diene rubber (EPDM) is a cost-effective material that is frequently used in the automotive industry because of its advantageous range of properties. With these applications in mind, it was a logical progression to the development of EPDM-based MREs. Unlike strain-crystallising NR, EPDM requires reinforcement to render its tensile and fatigue strength suitable for use in most applications. While small amounts of carbon black were sufficient for the NR-based MREs, a …

Relative Properties And Relative Potency Of Various Hydrazide Compounds That Inhibit Growth Of Mycobacterium Tuberculosis, Ronald Bartzatt

Chemistry Faculty Publications

The molecular properties of compounds expressing growth inhibition of Mycobacterium tuberculosis are determined and examined for underlying relationships by pattern recognition methods. Pattern recognition methods such as hierarchical cluster analysis will show relationships between compounds. Descriptive statistical analysis of molecular properties reveal commonality among bacteriostatic compounds. Outliers within any category of descriptor is identified by Grubb’s test. Potency of growth inhibition measured as MIC (minimum inhibitory concentration) after in vitro evaluation will be compared and analyzed. Structure moieties and their effect on activity is identified. All compounds analyzed showed substantial growth inhibition of Mycobacterium tuberculosis, having MIC values ranging from …

Phthalate And Non-Phthalate Plasticizers In Indoor Dust From Childcare Facilities, Salons, And Homes Across The Usa, Bikram Subedi, Kenneth D. Sullivan, Birendra Dhungana

Faculty & Staff Research and Creative Activity

The quality of indoor environment has received considerable attention owing to the declining outdoor human activities and the associated public health issues. The prolonged exposure of children in childcare facilities or the occupational exposure of adults to indoor environmental triggers can be a culprit of the pathophysiology of several commonly observed idiopathic syndromes. In this study, concentrations of potentially toxic plasticizers (phthalates as well as non-phthalates) were investigated in 28 dust samples collected from three different indoor environments across the USA. The mean concentrations of non-phthalate plasticizers [acetyl tri-n-butyl citrate (ATBC), di-(2-ethylhexyl) adipate (DEHA), and diisobutyl adipate (DIBA)] were found …

Mass Loading And Removal Of Pharmaceuticals And Personal Care Products Including Psychoactives, Antihypertensives, And Antibiotics In Two Sewage Treatment Plants In Southern India, Bikram Subedi, Keshava Balakrishna, Derrick Ian Joshua, Kurunthachalam Kannan

Faculty & Staff Research and Creative Activity

Environmental contamination by pharmaceuticals and personal care products (PPCPs) is barely studied in India despite being one of the largest global producers and consumers of pharmaceuticals. In this study, 29 pharmaceuticals and six metabolites were determined in sewage treatment plants (STPs) in Udupi (STP_U: population served ~150,000) and Mangalore (STP_M: population served ~450,000); the measured mean concentrations ranged from 12 to 61,000 ng/L and 5.0 to 31,000 ng/L, respectively. Atorvastatin (the most prescribed antihypercholesterolemic in India), mefenamic acid, and paraxanthine were found for the first time in wastewater in India at the mean concentrations of 395 …

Deciphering Of Interactions Between Platinated Dna And Hmgb1 By Hydrogen/Deuterium Exchange Mass Spectrometry, Yuanyuan Wang, Zhifeng Du, Wei Zheng, Kui Wu, Decheng Xu, Qun Luo, Yao Zhao, Juanjuan Han, Yangzhong Liu, Fuyi Wang

Chemistry Publications

A high mobility group box 1 (HMGB1) protein has been reported to recognize both 1,2-intrastrand crosslinked DNA by cisplatin (1,2-cis-Pt-DNA) and monofunctional platinated DNA using trans-[PtCl2(NH3)(thiazole)] (1-trans-PtTz-DNA). However, the molecular basis of recognition between the trans-PtTz-DNA and HMGB1 remains unclear. In the present work, we described a hydrogen/deuterium exchange mass spectrometry (HDX-MS) method in combination with docking simulation to decipher the interactions of platinated DNA with domain A of HMGB1. The global deuterium uptake results indicated that 1-trans-PtTz-DNA bound to HMGB1a slightly tighter than the 1,2-cis-Pt-DNA. The local deuterium uptake …

Fluorogenic Protein Labeling Using A Genetically Encoded Unstrained Alkene, Xin Shang, X. Song, C. Faller, R. Lai, H. Li, R. Cerny, Wei Niu, Jiantao Guo

Department of Chemistry: Faculty Publications

We developed a new fluorogenic bioorthogonal reaction that is based on the inverse electron-demand Diels–Alder reaction between styrene (an unstrained alkene) and a simple tetrazine. The reaction forms a new fluorophore with no literature precedent. We have identified an aminoacyl-tRNA synthetase/tRNA pair for the efficient and site-specific incorporation of a styrene-containing amino acid into proteins in response to amber nonsense codon. Fluorogenic labeling of purified proteins and intact proteins in live cells were demonstrated. The fluorogenicity of the styrene–tetrazine reaction can be potentially applied to the study of protein folding and function under physiological conditions with low background fluorescence interference.

Validation Of A Membrane Touch Biosensor For The Qualitative Detection Of Igg Class Antibodies To Herpes Simplex Virus Type 2, Tony Loughman, Baljit Singh, Brian Seddon, Philip Noone, Padmanabhan Santhosh

Articles

A novel type of biosensor was assessed for application to the qualitative determination of circulating antibodies to herpes simplex virus type 2 (HSV-2). The device utilises a high activity HSV-2 type specific gG2 antigen for antibody capture and commercially available ELISA reagents. The study compares the diagnostic performance of a prototype HSV-2 biochip to well-established in vitro tests routinely applied in clinical procedures. A panel of human serum samples (n = 60) previously characterised for HSV-2 serological status using the DiaSorin LIAISON® HSV-2 chemiluminescent immunoassay were assayed on the HSV-2 biochip and the Focus Diagnostics HerpeSelect® 2 ELISA IgG kit …

Wilhelm Ostwald, Kori K. Johnson

Natural Sciences Student Research Presentations

This poster for the Natural Sciences Poster Session at Parkland College features chemist Wilhelm Ostwald who discovered the law of dilution in 1988, which is the application of the law of mass action to weak electrolytes in solution. He also developed a process of catalytic oxidation of ammonia to nitric acid and introduced the word "mole".

Isotopes And Horses, Evyjo M. Compton

Natural Sciences Student Research Presentations

This presentation for the Natural Sciences Poster Session at Parkland College defines isotopes and summarizes an experiment conducted on a modern horse to examine the seasonal shifts of trace elements by measuring the oxygen and carbon isotopes in tooth enamel.

Synthesis Of Discrete Transition Metal (Ni, Fe, Co, Mn) Phosphide Nanoparticles: Compositional Effect On Catalytic And Magnetic Properties, Da Li

Wayne State University Dissertations

This dissertation research is focused on the synthesis, characterization of binary and ternary transition metal (Ni, Co, Fe, Mn) phosphide nanomaterials and their catalytic and magnetic properties.

A phase-control strategy enabling the arrested-precipitation synthesis of nanoparticles of Ni5P4 and NiP2 is presented. The composition and purity of the product can be tuned by changing key synthetic levers, including the metal precursor, the oleylamine (OAm) and Trioctylphosphine (TOP) concentrations, temperature, time and the presence or absence of a moderate temperature soak step to facilitate formation of Ni and/or Ni-P amorphous nanoparticle intermediates.

New CoxFe2-xP nanoparticles (0 ≤ x ≤ 2), Co2-xMnxP …

Identification Of Selective Anti-Trypanosome Agents From Compound Library Lopac, Cody M. Orahoske, Myah S. Marbury

Undergraduate Research Posters 2017

Sleeping sickness disease (human African trypanosomiasis) is still a major health threat to a large number of people in 36 countries of sub-Saharan Africa. Currently, the estimated infection cases in these areas are between 300,000 and 500,000. Trypanosoma brucei gambiense and Trypanosoma brucei rhodesiense are the pathogens of sleeping sickness in humans. These parasites live and proliferate mainly in the blood and tissue fluids of the infected mammals and are transmitted by tsetse flies (Glossina spp.). The disease starts from a bite by an infected tsetse fly and goes through an initial stage, where trypanosomes multiply in the bloodstream and …

Rnase L Mediates The Insulin Signalling Pathway, Oroshay Kaiwan, Danting Liu

Undergraduate Research Posters 2017

Diabetes is characterized by hyperglycemia mainly due to defect in insulin secretion and/or action. Regulation of glucose transport and use by insulin is central to the maintenance of whole-body glucose homeostasis. One of the potential mechanisms associated with insulin sensitivity is the activation of insulin receptor (IR) and subsequently transduces the signal through phosphorylation of insulin receptor substrate1 (IRS1) and activation of the PI-3K/Akt pathway. RNase L, an interferon (IFN)-inducible enzyme, plays an important role in IFN functions against viral infection and cell proliferation. However, a direct link between RNase L and insulin sensitivity has yet to be clearly established. …

P1: Using Modified Dean Flow Designs To Increase Mixing Performance, Joshua Clark

Undergraduate Research Posters 2017

We are using numerical solutions for the Navier-Stokes equations and the concentration - diffusion equation to model fluid flow and reactant distribution in serpentine type channels for micromixers/microreactors development. These mixers exploit centripetal forces on the fluid to induce cross-sectional fluid mixing, aka Dean flows. Various modifications are used to increase the mixing character of these crosssectional flows. We found that the performance of these mixers exceeds that of unmodified channels and we currently assess their performance relative to other state of the art methodologies used to induce mixing on the microscale.

P2: Implementation Of Groove Based Designs For Engineering Fluid Flow In Micromixers, Tahir Butt

Undergraduate Research Posters 2017

Mixing on microscale is important for the development of miniaturized chemical reactors that use small quantities of reactants and allow better control over the reaction conditions and products. Nevertheless, achieving rapid mixing in this type of micro-reactors is challenging due to the lack of turbulence and slow diffusion on the microscale. In this work we implement micromixers designs based on surface groove/ridge patterns targeted at inducing cross-sectional flows that both extend the interface between the different reactants, as well as induce chaotic advection. We discuss the fabrication of these structures using soft-lithography in PDMS employing a mold and their optical …