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Chemistry Faculty Publications

2018

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Full-Text Articles in Chemistry

The Catalytic Mechanism Of Electron-Bifurcating Electron Transfer Flavoproteins (Etfs) Involves An Intermediary Complex With Nad+, Gerrit J. Schut, Nishya Mohamed-Raseek, Monika Tokmina-Lukaszewska, David W. Mulder, Diep M. N. Nguyen, Gina L. Lipscomb, John Patrick Hoben, Angela Patterson, Carolyn E. Lubner, Paul W. King, John W. Peters, Brian Bothner, Anne-Frances Miller, Michael W. W. Adams Dec 2018

The Catalytic Mechanism Of Electron-Bifurcating Electron Transfer Flavoproteins (Etfs) Involves An Intermediary Complex With Nad+, Gerrit J. Schut, Nishya Mohamed-Raseek, Monika Tokmina-Lukaszewska, David W. Mulder, Diep M. N. Nguyen, Gina L. Lipscomb, John Patrick Hoben, Angela Patterson, Carolyn E. Lubner, Paul W. King, John W. Peters, Brian Bothner, Anne-Frances Miller, Michael W. W. Adams

Chemistry Faculty Publications

Electron bifurcation plays a key role in anaerobic energy metabolism, but it is a relatively new discovery, and only limited mechanistic information is available on the diverse enzymes that employ it. Herein, we focused on the bifurcating electron transfer flavoprotein (ETF) from the hyperthermophilic archaeon Pyrobaculum aerophilum. The EtfABCX enzyme complex couples NADH oxidation to the endergonic reduction of ferredoxin and exergonic reduction of menaquinone. We developed a model for the enzyme structure by using nondenaturing MS, cross-linking, and homology modeling in which EtfA, -B, and -C each contained FAD, whereas EtfX contained two [4Fe-4S] clusters. On the basis …


Mass-Analyzed Threshold Ionization Of Lanthanide Imide Lnnh (Ln = La And Ce) Radicals From N–H Bond Activation Of Ammonia, Yuchen Zhang, Silver Nyambo, Dong-Sheng Yang Dec 2018

Mass-Analyzed Threshold Ionization Of Lanthanide Imide Lnnh (Ln = La And Ce) Radicals From N–H Bond Activation Of Ammonia, Yuchen Zhang, Silver Nyambo, Dong-Sheng Yang

Chemistry Faculty Publications

Ln (Ln = La and Ce) atom reactions with ammonia are carried out in a pulsed laser vaporization supersonic molecular beam source. Lanthanide-containing species are observed with time-of-flight mass spectrometry, and LnNH molecules are characterized by mass-analyzed threshold ionization (MATI) spectroscopy and quantum chemical calculations. The theoretical calculations include density functional theory for both Ln species and a scalar relativity correction, electron correlation, and spin-orbit coupling for the Ce species. The MATI spectrum of LaNH exhibits a single vibronic band system with a strong origin band and two weak vibronic progressions, whereas the spectrum of CeNH displays two band systems …


Canvass: A Crowd-Sourced, Natural-Product Screening Library For Exploring Biological Space, Sara E. Kearney, Gergely ZahoráNszky-KőHalmi, Kyle R. Brimacombe, Mark J. Henderson, Caitlin Lynch, Tongan Zhao, Kanny K. Wan, Zina Itkin, Christopher Dillon, Min Shen, Dorian M. Cheff, Tobie D. Lee, Danielle Bougie, Ken Cheng, Nathan P. Coussens, Dorjbal Dorjsuren, Richard T. Eastman, Ruili Huang, Michael J. Iannotti, Surendra Karavadhi, Carleen Klumpp-Thomas, Jacob S. Roth, Srilatha Sakamuru, Wei Sun, Steven A. Titus, Adam Yasgar, Ya-Qin Zhang, Jinghua Zhao, Rodrigo B. Andrade, M. Kevin Brown, Robert B. Grossman Dec 2018

Canvass: A Crowd-Sourced, Natural-Product Screening Library For Exploring Biological Space, Sara E. Kearney, Gergely ZahoráNszky-KőHalmi, Kyle R. Brimacombe, Mark J. Henderson, Caitlin Lynch, Tongan Zhao, Kanny K. Wan, Zina Itkin, Christopher Dillon, Min Shen, Dorian M. Cheff, Tobie D. Lee, Danielle Bougie, Ken Cheng, Nathan P. Coussens, Dorjbal Dorjsuren, Richard T. Eastman, Ruili Huang, Michael J. Iannotti, Surendra Karavadhi, Carleen Klumpp-Thomas, Jacob S. Roth, Srilatha Sakamuru, Wei Sun, Steven A. Titus, Adam Yasgar, Ya-Qin Zhang, Jinghua Zhao, Rodrigo B. Andrade, M. Kevin Brown, Robert B. Grossman

Chemistry Faculty Publications

Natural products and their derivatives continue to be wellsprings of nascent therapeutic potential. However, many laboratories have limited resources for biological evaluation, leaving their previously isolated or synthesized compounds largely or completely untested. To address this issue, the Canvass library of natural products was assembled, in collaboration with academic and industry researchers, for quantitative high-throughput screening (qHTS) across a diverse set of cell-based and biochemical assays. Characterization of the library in terms of physicochemical properties, structural diversity, and similarity to compounds in publicly available libraries indicates that the Canvass library contains many structural elements in common with approved drugs. The …


A Simple And Robust Approach To Reducing Contact Resistance In Organic Transistors, Zachary A. Lamport, Katrina J. Barth, Hyunsu Lee, Eliot Gann, Sebastian Engmann, Hu Chen, Martin Guthold, Iain Mcculloch, John E. Anthony, Lee J. Richter, Dean M. Delongchamp, Oana D. Jurchescu Dec 2018

A Simple And Robust Approach To Reducing Contact Resistance In Organic Transistors, Zachary A. Lamport, Katrina J. Barth, Hyunsu Lee, Eliot Gann, Sebastian Engmann, Hu Chen, Martin Guthold, Iain Mcculloch, John E. Anthony, Lee J. Richter, Dean M. Delongchamp, Oana D. Jurchescu

Chemistry Faculty Publications

Efficient injection of charge carriers from the contacts into the semiconductor layer is crucial for achieving high-performance organic devices. The potential drop necessary to accomplish this process yields a resistance associated with the contacts, namely the contact resistance. A large contact resistance can limit the operation of devices and even lead to inaccuracies in the extraction of the device parameters. Here, we demonstrate a simple and efficient strategy for reducing the contact resistance in organic thin-film transistors by more than an order of magnitude by creating high work function domains at the surface of the injecting electrodes to promote channels …


Data On Spectrum-Based Fluorescence Resonance Energy Transfer Measurement Of E. Coli Multidrug Transporter Acrb, Yuguang Cai, Thomas E. Wilkop, Yinan Wei Dec 2018

Data On Spectrum-Based Fluorescence Resonance Energy Transfer Measurement Of E. Coli Multidrug Transporter Acrb, Yuguang Cai, Thomas E. Wilkop, Yinan Wei

Chemistry Faculty Publications

This paper presented the dataset of correction parameters used in the determination of the energy transfer efficiencies from the spectrum-based fluorescence resonance energy transfer (FRET) measurement in a trimeric membrane protein AcrB. The cyan fluorescent protein (CFP) and yellow fluorescent protein (YPet) were used as the donor and acceptor, respectively. Two AcrB fusion proteins were constructed, AcrB-CFP and AcrB-YPet. The proteins were co-expressed in Escherichia coli cells, and energy transfer efficiency were determined in live cells. To obtain reliable energy transfer data, a complete set of correction parameters need to be first determined to accommodate for factors such as background …


Synthesis And Characterization Of Cobalt(Ii) N,N′‑Diphenylazodioxide Complexes, Kylin A. Emhoff, Lakshmi Balaraman, Sydney R. Simpson, Michael L. Stromyer, Haitham F. Kalil, James R. Beemiller, Philipp Sikatzki, Teya S. Eshelman, Ahmed M.H. Salem, Michael A. Debord, Matthew J. Panzer, Wiley J. Youngs, W. Christropher Boyd Nov 2018

Synthesis And Characterization Of Cobalt(Ii) N,N′‑Diphenylazodioxide Complexes, Kylin A. Emhoff, Lakshmi Balaraman, Sydney R. Simpson, Michael L. Stromyer, Haitham F. Kalil, James R. Beemiller, Philipp Sikatzki, Teya S. Eshelman, Ahmed M.H. Salem, Michael A. Debord, Matthew J. Panzer, Wiley J. Youngs, W. Christropher Boyd

Chemistry Faculty Publications

Removal of chloride from CoCl2 with TlPF6 in acetonitrile, followed by addition of excess nitrosobenzene, yielded the eight-coordinate cobalt(II) complex salt [Co{Ph(O)NN(O)- Ph}4](PF6)2, shown by single-crystal X-ray analysis to have a distorted tetragonal geometry. The analogous treatment of the bipyridyl complex Co(bpy)Cl2 yielded the mixed-ligand cobalt(II) complex salt [Co(bpy){Ph(O)NN(O)Ph}2](PF6)2, whose singlecrystal X-ray structure displays a trigonal prismatic geometry, similar to that of the iron(II) cation in the previously known complex salt [Fe{Ph(O)NN(O)Ph}3](FeCl4)2. The use of TlPF6 to generate …


Decreasing Phosphatidylcholine On The Surface Of The Lipid Droplet Correlates With Altered Protein Binding And Steatosis, Laura Listenberger, Elizabeth Townsend, Cassandra Rickertsen, Anastasia Hains, Elizabeth Brown, Emily G. Inwards, Angela K. Stoeckman Nov 2018

Decreasing Phosphatidylcholine On The Surface Of The Lipid Droplet Correlates With Altered Protein Binding And Steatosis, Laura Listenberger, Elizabeth Townsend, Cassandra Rickertsen, Anastasia Hains, Elizabeth Brown, Emily G. Inwards, Angela K. Stoeckman

Chemistry Faculty Publications

Alcoholic fatty liver disease (AFLD) is characterized by an abnormal accumulation of lipid droplets (LDs) in the liver. Here, we explore the composition of hepatic LDs in a rat model of AFLD. Five to seven weeks of alcohol consumption led to significant increases in hepatic triglyceride mass, along with increases in LD number and size. Additionally, hepatic LDs from rats with early alcoholic liver injury show a decreased ratio of surface phosphatidylcholine (PC) to phosphatidylethanolamine (PE). This occurred in parallel with an increase in the LD association of perilipin 2, a prominent LD protein. To determine if changes to the …


Intranasal Rapamycin Ameliorates Alzheimer-Like Cognitive Decline In A Mouse Model Of Down Syndrome, Antonella Tramutola, Chiara Lanzillotta, Eugenio Barone, Andrea Arena, Ilaria Zuliani, Luciana Mosca, Carla Blarzino, D. Allan Butterfield, Marzia Perluigi, Fabio Di Domenico Nov 2018

Intranasal Rapamycin Ameliorates Alzheimer-Like Cognitive Decline In A Mouse Model Of Down Syndrome, Antonella Tramutola, Chiara Lanzillotta, Eugenio Barone, Andrea Arena, Ilaria Zuliani, Luciana Mosca, Carla Blarzino, D. Allan Butterfield, Marzia Perluigi, Fabio Di Domenico

Chemistry Faculty Publications

Background: Down syndrome (DS) individuals, by the age of 40s, are at increased risk to develop Alzheimer-like dementia, with deposition in brain of senile plaques and neurofibrillary tangles. Our laboratory recently demonstrated the disturbance of PI3K/AKT/mTOR axis in DS brain, prior and after the development of Alzheimer Disease (AD). The aberrant modulation of the mTOR signalling in DS and AD age-related cognitive decline affects crucial neuronal pathways, including insulin signaling and autophagy, involved in pathology onset and progression. Within this context, the therapeutic use of mTOR-inhibitors may prevent/attenuate the neurodegenerative phenomena. By our work we aimed to rescue mTOR signalling …


Crystal Structure Of The 13-(E)-(2-Aminobenzylidene)-Parthenolide, Shobanbabu Bommagani, Narsihma R. Penthala, Sean Parkin, Peter A. Crooks Nov 2018

Crystal Structure Of The 13-(E)-(2-Aminobenzylidene)-Parthenolide, Shobanbabu Bommagani, Narsihma R. Penthala, Sean Parkin, Peter A. Crooks

Chemistry Faculty Publications

The title compound, C21H25NO3 [systematic name: (1aR,4E,7aS,8E,10aS,10bR)-8-(2-amino­benzyl­idene)-1a,5-dimethyl-2,3,6,7,7a,8,10a,10b-octa­hydro­oxireno[2′,3′:9,10]cyclo­deca­[1,2-b]furan-9(1aH)-one], was synthesized by the reaction of parthenolide [systematic name (1aR,7aS,10aS,10bS,E)-1a,5-dimethyl-8-methyl­ene-2,3,6,7,7a,8,10a,10b-octa­hydro­oxireno[2′,3′:9,10]cyclo­deca­[1,2-b]furan-9(1aH)-one] with 2-iodo­aniline via Heck reaction conditions. The mol­ecule is composed of fused ten-, five- (lactone), and three-membered (epoxide) rings. The lactone ring shows a flattened envelope-type conformation (r.m.s. deviation from planarity = 0.0477 Å), and bears a 2-amino­benzyl­idene substituent that is disordered over two conformations [occupancy …


Magnetic Ordering In A Vanadium-Organic Coordination Polymer Using A Pyrrolo[2,3-D:5,4-D']Bis(Thiazole)-Based Ligand, Yulia A. Getmanenko, Christopher S. Mullins, Vladimir N. Nesterov, Stephanie Lake, Chad Risko, Ezekiel Johnston-Halperin Oct 2018

Magnetic Ordering In A Vanadium-Organic Coordination Polymer Using A Pyrrolo[2,3-D:5,4-D']Bis(Thiazole)-Based Ligand, Yulia A. Getmanenko, Christopher S. Mullins, Vladimir N. Nesterov, Stephanie Lake, Chad Risko, Ezekiel Johnston-Halperin

Chemistry Faculty Publications

Here we present the synthesis and characterization of a hybrid vanadium-organic coordination polymer with robust magnetic order, a Curie temperature TC of ∼110 K, a coercive field of ∼5 Oe at 5 K, and a maximum mass magnetization of about half that of the benchmark ferrimagnetic vanadium(tetracyanoethylene)~2 (V·(TCNE)~2). This material was prepared using a new tetracyano-substituted quinoidal organic small molecule 7 based on a tricyclic heterocycle 4-hexyl-4H-pyrrolo[2,3-d:5,4-d′]bis(thiazole) (C6-PBTz). Single crystal X-ray diffraction of the 2,6-diiodo derivative of the parent C6-PBTz, showed a disordered hexyl chain and …


Photocatalytic Activity: Experimental Features To Report In Heterogeneous Photocatalysis, Md. Ariful Hoque, Marcelo I. Guzman Oct 2018

Photocatalytic Activity: Experimental Features To Report In Heterogeneous Photocatalysis, Md. Ariful Hoque, Marcelo I. Guzman

Chemistry Faculty Publications

Heterogeneous photocatalysis is a prominent area of research with major applications in solar energy conversion, air pollution mitigation, and removal of contaminants from water. A large number of scientific papers related to the photocatalysis field and its environmental applications are published in different journals specializing in materials and nanomaterials. However, many problems exist in the conception of papers by authors unfamiliar with standard characterization methods of photocatalysts as well as with the procedures needed to determine photocatalytic activities based on the determination of “apparent quantum efficiencies” within a wavelength interval or “apparent quantum yields” in the case of using monochromatic …


The Aromatization Of Propene Via Nano-Size Hzsm-5, Wayne Seames, Swapnil Fegade, Inna Sakodynskaya, Darrin Muggli, Brian Tande, Alena Kubatova, Evguenii Kozliak Oct 2018

The Aromatization Of Propene Via Nano-Size Hzsm-5, Wayne Seames, Swapnil Fegade, Inna Sakodynskaya, Darrin Muggli, Brian Tande, Alena Kubatova, Evguenii Kozliak

Chemistry Faculty Publications

Zeolite (ZSM) catalysts are known to convert small-size alkenes, e.g., propene, into aromatic hydrocarbons, specifically benzene, toluene and xylenes (BTX), with both high efficiency and specificity. The efficiency of conventional and hierarchical nano-size ZSM-5 for propene aromatization was compared in this study using a Design of Experiments (DOE) approach combined with detailed product analysis. Contrary to our expectations, the former showed a significantly greater BTX yield than the latter. Analysis of the obtained data by DOE and additional experiments with soybean oil cracking using both catalyst types indicated that a reason for the observed reduced activity of nano-scale zeolites may …


Synthesis And Evaluation Of Protein-Phenylboronic Acid Conjugates As Lectin Mimetics, Joshua Whited, Czharena Kay Rama, Xue-Long Sun Oct 2018

Synthesis And Evaluation Of Protein-Phenylboronic Acid Conjugates As Lectin Mimetics, Joshua Whited, Czharena Kay Rama, Xue-Long Sun

Chemistry Faculty Publications

Glycan-binding molecules, such as lectins, are very important tools for characterizing, imaging, or targeting glycans and are often involved in either physiological or pathological processes. However, their availability is far less compared to the diversity of native glycans. Therefore, development of lectin mimetics with desired specificity and affinity is in high demand. Boronic acid reacts with 1,2- and 1,3-diols of saccharides in aqueous media through reversible boronate ester formation and are regarded as synthetic lectin mimetics. In this study, bovine serum albumin (BSA)-phenylboronic acid (PBA) conjugates were synthesized in a density-controlled manner by targeting both aspartic and glutamic acids to …


How To Fold And Protect Mitochondrial Ribosomal Rna With Fewer Guanines, Maryam Hosseini, Poorna Roy, Marie Sissler, Craig L. Zirbel, Eric Westhof, Neocles B. Leontis Sep 2018

How To Fold And Protect Mitochondrial Ribosomal Rna With Fewer Guanines, Maryam Hosseini, Poorna Roy, Marie Sissler, Craig L. Zirbel, Eric Westhof, Neocles B. Leontis

Chemistry Faculty Publications

Mammalian mitochondrial ribosomes evolved from bacterial ribosomes by reduction of ribosomal RNAs, increase of ribosomal protein content, and loss of guanine nucleotides. Guanine is the base most sensitive to oxidative damage. By systematically comparing high-quality, small ribosomal subunit RNA sequence alignments and solved 3D ribosome structures from mammalian mitochondria and bacteria, we deduce rules for folding a complex RNA with the remaining guanines shielded from solvent. Almost all conserved guanines in both bacterial and mammalian mitochondrial ribosomal RNA form guaninespecific, local or long-range, RNA–RNA or RNA– protein interactions. Many solvent-exposed guanines conserved in bacteria are replaced in mammalian mitochondria by …


An Overview Of Dynamic Heterogeneous Oxidations In The Troposphere, Elizabeth A. Pillar-Little, Marcelo I. Guzman Sep 2018

An Overview Of Dynamic Heterogeneous Oxidations In The Troposphere, Elizabeth A. Pillar-Little, Marcelo I. Guzman

Chemistry Faculty Publications

Due to the adverse effect of atmospheric aerosols on public health and their ability to affect climate, extensive research has been undertaken in recent decades to understand their sources and sinks, as well as to study their physical and chemical properties. Atmospheric aerosols are important players in the Earth’s radiative budget, affecting incoming and outgoing solar radiation through absorption and scattering by direct and indirect means. While the cooling properties of pure inorganic aerosols are relatively well understood, the impact of organic aerosols on the radiative budget is unclear. Additionally, organic aerosols are transformed through chemical reactions during atmospheric transport. …


Gold-Catalyzed Conversion Of Lignin To Low Molecular Weight Aromatics, Yang Song, Justin K. Mobley, Ali Hussain Motagamwala, Mark Isaacs, James E. Dumesic, John Ralph, Adam F. Lee, Karen Wilson, Mark Crocker Sep 2018

Gold-Catalyzed Conversion Of Lignin To Low Molecular Weight Aromatics, Yang Song, Justin K. Mobley, Ali Hussain Motagamwala, Mark Isaacs, James E. Dumesic, John Ralph, Adam F. Lee, Karen Wilson, Mark Crocker

Chemistry Faculty Publications

A heterogeneous catalyst system, employing Au nanoparticles (NPs) and Li–Al (1 : 2) layered double hydroxide (LDH) as support, showed excellent activity in aerobic oxidation of the benzylic alcohol group in β-O-4 linked lignin model dimers to the corresponding carbonyl products using molecular oxygen under atmospheric pressure. The synergistic effect between Au NPs and the basic Li–Al LDH support induces further reaction of the oxidized model compounds, facilitating facile cleavage of the β-O-4 linkage. Extension to oxidation of γ-valerolactone (GVL) extracted lignin and kraft lignin using Au/Li–Al LDH under similar conditions produced a range of aromatic monomers in high yield. …


Sintering-Induced Nucleation And Growth Of Noble Metal Nanoparticles For Plasmonic Resonance Ceramic Color, Nathan Dinh, Michael C. Leopold, Ryan Coppage Aug 2018

Sintering-Induced Nucleation And Growth Of Noble Metal Nanoparticles For Plasmonic Resonance Ceramic Color, Nathan Dinh, Michael C. Leopold, Ryan Coppage

Chemistry Faculty Publications

This study demonstrates the formation of nanoparticles (NPs) from metal salts within ceramic glazes, such that the use of this colorant technology is more accessible to artisans, employs less metal content, is less environmentally harmful, and allows for the use of traditional kilns. Gold NPs have been demonstrated to possess a specific, low material loading use as a ceramic glaze colorant via plasmon resonance. Pre-synthesized gold NPs that are added to ceramic glazes have been found to significantly change in size after firing in both reductive and oxidative atmospheres, but still maintain some size relationships and color properties. Unfortunately, it …


Enhanced Acidity Of Acetic And Pyruvic Acids On The Surface Of Water, Alexis J. Eugene, Elizabeth A. Pillar, Agustín J. Colussi, Marcelo I. Guzman Aug 2018

Enhanced Acidity Of Acetic And Pyruvic Acids On The Surface Of Water, Alexis J. Eugene, Elizabeth A. Pillar, Agustín J. Colussi, Marcelo I. Guzman

Chemistry Faculty Publications

Understanding the acid–base behavior of carboxylic acids on aqueous interfaces is a fundamental issue in nature. Surface processes involving carboxylic acids such as acetic and pyruvic acids play roles in (1) the transport of nutrients through cell membranes, (2) the cycling of metabolites relevant to the origin of life, and (3) the photooxidative processing of biogenic and anthropogenic emissions in aerosols and atmospheric waters. Here, we report that 50% of gaseous acetic acid and pyruvic acid molecules transfer a proton to the surface of water at pH 2.8 and 1.8 units lower than their respective acidity constants pKa …


Manganese Oxide/Hemin-Functionalized Graphene As A Platform For Peroxynitrite Sensing, Haitham F. Kalil, Shaimaa Maher, Tiyash Bose, Mekki Bayachou Aug 2018

Manganese Oxide/Hemin-Functionalized Graphene As A Platform For Peroxynitrite Sensing, Haitham F. Kalil, Shaimaa Maher, Tiyash Bose, Mekki Bayachou

Chemistry Faculty Publications

Peroxynitrite (ONOO−, PON) is a powerful oxidizing agent generated in vivo by the diffusion-limited reaction of nitric oxide (NO) and superoxide (O2˙) radicals. Under oxidative stress, cumulated peroxynitrite levels are associated with chronic inflammatory disorders and other pathophysiological conditions. The accurate detection of peroxynitrite in biological systems is important, not only to understand the genesis and development of diseases, but also to explore and design potential therapeutics. Herein, a manganese oxide/hemin-modified graphene interface is explored as a platform for peroxynitrite amperometric detection. Hemin-functionalized reduced graphene oxide was further modified with manganese oxide nanoparticles to provide a …


Oxidation Of Benzylic Alcohols And Lignin Model Compounds With Layered Double Hydroxide Catalysts, Justin K. Mobley, John A. Jennings, Tonya Morgan, Axel Kiefer, Mark Crocker Jul 2018

Oxidation Of Benzylic Alcohols And Lignin Model Compounds With Layered Double Hydroxide Catalysts, Justin K. Mobley, John A. Jennings, Tonya Morgan, Axel Kiefer, Mark Crocker

Chemistry Faculty Publications

Alcohol oxidation to carbonyl compounds is one of the most commonly used reactions in synthetic chemistry. Herein, we report the use of base metal layered double hydroxide (LDH) catalysts for the oxidation of benzylic alcohols in polar solvents. These catalysts are ideal reagents for alcohol oxidations due to their ease of synthesis, tunability, and ease of separation from the reaction medium. LDHs synthesized in this study were fully characterized by means of X-ray diffraction, NH3-temperature programmed desorption (TPD), pulsed CO2 chemisorption, N2 physisorption, electron microscopy, and elemental analysis. LDHs were found to effectively oxidize benzylic alcohols …


Spectroscopy And Formation Of Lanthanum-Hydrocarbon Radicals Formed By C—H And C—C Bond Activation Of 1-Pentene And 2-Pentene, Wenjin Cao, Yuchen Zhang, Silver Nyambo, Dong-Sheng Yang Jul 2018

Spectroscopy And Formation Of Lanthanum-Hydrocarbon Radicals Formed By C—H And C—C Bond Activation Of 1-Pentene And 2-Pentene, Wenjin Cao, Yuchen Zhang, Silver Nyambo, Dong-Sheng Yang

Chemistry Faculty Publications

La atom reactions with 1-pentene and 2-pentene are carried out in a laser-vaporization molecular beam source. The two reactions yield the same metal-hydrocarbon products from the dehydrogenation and carbon–carbon bond cleavage of the pentene molecules. The dehydrogenated species La(C5H8) is the major product, whereas the carbon–carbon bond cleaved species La(C2H2) and La(C3H4) are the minor ones. La(C10H18) is also observed and is presumably formed by La(C5H8) addition to a second pentene molecule. La(C5H8) and La(C2 …


Doxorubicin-Induced Elevated Oxidative Stress And Neurochemical Alterations In Brain And Cognitive Decline: Protection By Mesna And Insights Into Mechanisms Of Chemotherapy-Induced Cognitive Impairment ("Chemobrain"), Jeriel T. R. Keeney, Xiaojia Ren, Govind Warrier, Teresa Noel, David K. Powell, Jennifer M. Brelsfoard, Rukhsana Sultana, Kathryn E. Saatman, Daret K. St. Clair, D. Allan Butterfield Jul 2018

Doxorubicin-Induced Elevated Oxidative Stress And Neurochemical Alterations In Brain And Cognitive Decline: Protection By Mesna And Insights Into Mechanisms Of Chemotherapy-Induced Cognitive Impairment ("Chemobrain"), Jeriel T. R. Keeney, Xiaojia Ren, Govind Warrier, Teresa Noel, David K. Powell, Jennifer M. Brelsfoard, Rukhsana Sultana, Kathryn E. Saatman, Daret K. St. Clair, D. Allan Butterfield

Chemistry Faculty Publications

Chemotherapy-induced cognitive impairment (CICI) is now widely recognized as a real and too common complication of cancer chemotherapy experienced by an ever-growing number of cancer survivors. Previously, we reported that doxorubicin (Dox), a prototypical reactive oxygen species (ROS)-producing anti-cancer drug, results in oxidation of plasma proteins, including apolipoprotein A-I (ApoA-I) leading to tumor necrosis factor-alpha (TNF-α)-mediated oxidative stress in plasma and brain. We also reported that co-administration of the antioxidant drug, 2-mercaptoethane sulfonate sodium (MESNA), prevents Dox-induced protein oxidation and subsequent TNF-α elevation in plasma. In this study, we measured oxidative stress in both brain and plasma of Dox-treated mice …


Cross Photoreaction Of Glyoxylic And Pyruvic Acids In Model Aqueous Aerosol, Sha-Sha Xia, Alexis J. Eugene, Marcelo I. Guzman Jul 2018

Cross Photoreaction Of Glyoxylic And Pyruvic Acids In Model Aqueous Aerosol, Sha-Sha Xia, Alexis J. Eugene, Marcelo I. Guzman

Chemistry Faculty Publications

Aerosols of variable composition, size, and shape are associated with public health concerns as well as with light-particle interactions that play a role in the energy balance of the atmosphere. Photochemical reactions of 2-oxocarboxylic acids in the aqueous phase are now known to contribute to the total secondary organic aerosol (SOA) budget. This work explores the cross reaction of glyoxylic acid (GA) and pyruvic acid (PA) in water, the two most abundant 2-oxocarboxylic acids in the atmosphere, under solar irradiation and dark thermal aging steps. During irradiation, PA and GA are excited and initiate proton-coupled electron transfer or hydrogen abstraction …


Laser-Induced Fluorescence Detection Of The Elusive Sicf Free Radical, Gretchen Rothschopf, Tony C. Smith, Dennis J. Clouthier Jul 2018

Laser-Induced Fluorescence Detection Of The Elusive Sicf Free Radical, Gretchen Rothschopf, Tony C. Smith, Dennis J. Clouthier

Chemistry Faculty Publications

The SiCF free radical has been spectroscopically identified for the first time. The radical was produced in an electric discharge jet using CF3Si(CH3)3 or CF3SiH3 vapor in high pressure argon as the precursor. The laser-induced fluorescence spectrum of the à 2Σ+ 2Π band system in the 610 − 550 nm region was recorded and the 2Π3/2 spin component of the 0—0 band was studied at high resolution. Rotational analysis gave the B values for the combining states, and by fixing the CF bond lengths at …


Hydrophilic Interaction Liquid Chromatography-Electrospray Ionization Mass Spectrometry For Therapeutic Drug Monitoring Of Metformin And Rosuvastatin In Human Plasma, Nikolaos Antonopoulos, Giorgos Machairas, George Migias, Ariadni Vonaparti, Vasiliki Brakoulia, Constantinos Pistos, Dimitra Gennimata, Irene Panderi Jun 2018

Hydrophilic Interaction Liquid Chromatography-Electrospray Ionization Mass Spectrometry For Therapeutic Drug Monitoring Of Metformin And Rosuvastatin In Human Plasma, Nikolaos Antonopoulos, Giorgos Machairas, George Migias, Ariadni Vonaparti, Vasiliki Brakoulia, Constantinos Pistos, Dimitra Gennimata, Irene Panderi

Chemistry Faculty Publications

In this work a hydrophilic interaction liquid chromatography/positive ion electrospray mass spectrometric assay (HILIC/ESI-MS) has been developed and fully validated for the quantitation of metformin and rosuvastatin in human plasma. Sample preparation involved the use of 100 µL of human plasma, following protein precipitation and filtration. Metformin, rosuvastatin and 4-[2-(propylamino) ethyl] indoline 2 one hydrochloride (internal standard) were separated by using an X-Bridge-HILIC BEH analytical column (150.0 × 2.1 mm i.d., particle size 3.5 µm) with isocratic elution. A mobile phase consisting of 12% (v/v) 15 mM ammonium formate water solution in acetonitrile was used for the separation and pumped …


N-Glycosylation In The Protease Domain Of Trypsin-Like Serine Proteases Mediates Calnexin-Assisted Protein Folding, Hao Wang, Shuo Li, Juejin Wang, Shenghan Chen, Xue-Long Sun, Qingyu Wu Jun 2018

N-Glycosylation In The Protease Domain Of Trypsin-Like Serine Proteases Mediates Calnexin-Assisted Protein Folding, Hao Wang, Shuo Li, Juejin Wang, Shenghan Chen, Xue-Long Sun, Qingyu Wu

Chemistry Faculty Publications

Trypsin-like serine proteases are essential in physiological processes. Studies have shown that N-glycans are important for serine protease expression and secretion, but the underlying mechanisms are poorly understood. Here, we report a common mechanism of N-glycosylation in the protease domains of corin, enteropeptidase and prothrombin in calnexin-mediated glycoprotein folding and extracellular expression. This mechanism, which is independent of calreticulin and operates in a domain-autonomous manner, involves two steps: direct calnexin binding to target proteins and subsequent calnexin binding to monoglucosylated N-glycans. Elimination of N-glycosylation sites in the protease domains of corin, enteropeptidase and prothrombin inhibits corin and enteropeptidase cell surface …


Oxidation Of N-Doped Multiwalled Carbon Nanotubes And Formation Of Discontinuous Spiraled Carbon Nanoribbons, Aman Preet Kaur, Mark S. Meier, Rodney Andrews, Dali Qian Jun 2018

Oxidation Of N-Doped Multiwalled Carbon Nanotubes And Formation Of Discontinuous Spiraled Carbon Nanoribbons, Aman Preet Kaur, Mark S. Meier, Rodney Andrews, Dali Qian

Chemistry Faculty Publications

The effects of five commonly used wet chemical oxidations were studied for the extent of oxidation of graphitized nitrogen-doped multiwalled carbon nanotubes (N-MWCNTs). KMnO4/ H2SO4 was the most potent oxidant, as it produced the highest fraction of oxygen-containing functional groups. Electron microscopy studies showed that the treatment of annealed N-MWCNTs (G-N-MWCNTs) with H2SO4/HNO3 and H2SO4/KMnO4 mixtures leads to interesting spiraled ribbon textures. A structural model, involving the stacking of coiled subunits to form a discontinuous carbon nanoribbon rather than a continuous ribbon is proposed to …


A Multi-Size Study Of Gold Nanoparticle Degradation And Reformation In Ceramic Glazes, Nathan Nl. Dinh, Luke T. Dipasquale, Michael C. Leopold, Ryan H. Coppage Jun 2018

A Multi-Size Study Of Gold Nanoparticle Degradation And Reformation In Ceramic Glazes, Nathan Nl. Dinh, Luke T. Dipasquale, Michael C. Leopold, Ryan H. Coppage

Chemistry Faculty Publications

Most traditional ceramic glazes employ high amounts of transition metal colorants that are toxic to the environment and can cause health issues in humans through surface leaching. Gold nanoparticles (Au-NPs) have been found to be environmentally friendly and non-toxic alternative metal colorant in ceramic glazes. The plasmon band observed with Au-NPs can result in vibrant solutions by manipulating NP size, shape, and concentration; however, the effects of traditional firing in both reductive and oxidative kilns on Au-NPs are poorly understood. Aside from ancient art processes whose mechanisms have not been fully explored, the use of Au-NPs as suspended ceramic glaze …


Absolute Configuration Of 2,2',3,3',6-Pentachlorinatedbiphenyl (Pcb 84) Atropisomers, Xueshu Li, Sean R. Parkin, Hans-Joachim Lehmler Jun 2018

Absolute Configuration Of 2,2',3,3',6-Pentachlorinatedbiphenyl (Pcb 84) Atropisomers, Xueshu Li, Sean R. Parkin, Hans-Joachim Lehmler

Chemistry Faculty Publications

Nineteen polychlorinated biphenyl (PCB) congeners, such as 2,2′,3,3′,6-pentachlorobiphenyl (PCB 84), display axial chirality because they form stable rotational isomers, or atropisomers, that are non-superimposable mirror images of each other. Although chiral PCBs undergo atropselective biotransformation and atropselectively alter biological processes, the absolute structure of only a few PCB atropisomers has been determined experimentally. To help close this knowledge gap, pure PCB 84 atropisomers were obtained by semi-preparative liquid chromatography with two serially connected Nucleodex β-PM columns. The absolute configuration of both atropisomers was determined by X-ray single-crystal diffraction. The PCB 84 atropisomer eluting first and second on the Nucleodex β-PM …


Striking The Right Balance Of Intermolecular Coupling For High-Efficiency Singlet Fission, Ryan D. Pensack, Andrew J. Tilley, Christopher Grieco, Geoffrey E. Purdum, Evgeny E. Ostroumov, Devin B. Granger, Daniel G. Oblinsky, Jacob C. Dean, Grayson S. Doucette, John B. Asbury, Yueh-Lin Loo, Dwight S. Seferos, John E. Anthony, Gregory D. Scholes Jun 2018

Striking The Right Balance Of Intermolecular Coupling For High-Efficiency Singlet Fission, Ryan D. Pensack, Andrew J. Tilley, Christopher Grieco, Geoffrey E. Purdum, Evgeny E. Ostroumov, Devin B. Granger, Daniel G. Oblinsky, Jacob C. Dean, Grayson S. Doucette, John B. Asbury, Yueh-Lin Loo, Dwight S. Seferos, John E. Anthony, Gregory D. Scholes

Chemistry Faculty Publications

Singlet fission is a process that splits collective excitations, or excitons, into two with unity efficiency. This exciton splitting process, unique to molecular photophysics, has the potential to considerably improve the efficiency of optoelectronic devices through more efficient light harvesting. While the first step of singlet fission has been characterized in great detail, subsequent steps critical to achieving overall highly-efficient singlet-to-triplet conversion are only just beginning to become well understood. One of the most elementary suggestions, which has yet to be tested, is that an appropriately balanced coupling is necessary to ensure overall highly efficient singlet fission; that is, the …