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Chemistry Faculty Publications

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Articles 211 - 240 of 1129

Full-Text Articles in Chemistry

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 …


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 …


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 …


Spectroscopy And Formation Of Lanthanum-Hydrocarbon Radicals Formed By Association And Carbon-Carbon Bond Cleavage Of Isoprene, Wenjin Cao, Dilkrushi Hewage, Dong-Sheng Yang May 2018

Spectroscopy And Formation Of Lanthanum-Hydrocarbon Radicals Formed By Association And Carbon-Carbon Bond Cleavage Of Isoprene, Wenjin Cao, Dilkrushi Hewage, Dong-Sheng Yang

Chemistry Faculty Publications

La atom reaction with isoprene is carried out in a laser-vaporization molecular beam source. The reaction yields an adduct as the major product and C—C cleaved and dehydrogenated species as the minor ones. La(C5H8), La(C2H2), and La(C3H4) are characterized with mass-analyzed threshold ionization (MATI) spectroscopy and quantum chemical computations. The MATI spectra of all three species exhibit a strong origin band and several weak vibronic bands corresponding to La-ligand stretch and ligand-based bend excitations. La(C5H8) is a five-membered metallacycle, whereas La(C2H2 …


Biochar From Waste Banana Peels As Growth Promoter For Holy Basil (Ocimum Tenuiflorum) And Chili Pepper (Capsicum Annuum), Regina C. So, N Tan May 2018

Biochar From Waste Banana Peels As Growth Promoter For Holy Basil (Ocimum Tenuiflorum) And Chili Pepper (Capsicum Annuum), Regina C. So, N Tan

Chemistry Faculty Publications

Biochars are porous materials prepared by combustion of biomass under the presence of low oxygen levels. Its application as soil fertilizer has been shown to have positive effects on the plants by increasing the fertility and raising the soil pH, increasing nutrient cycling and moisture holding capacity, improving cation exchange capacity, and reducing the amount of pesticides and nutrients leaching to the surface and ground water (Laird 2008, Speratti 2017). In this study, waste banana peels of the Lakatan variety (Musa x paradisiaca) were pyrolized at temperatures 300, 400, 500 and 700 °C, the resulting basic char were obtained at …


Lipophilic Chemicals From Diesel Exhaust Particles Trigger Calcium Response In Human Endothelial Cells Via Aryl Hydrocarbon Receptor Non-Genomic Signalling, Alena Kubatova, Bendik C. Brinchmann, Eric Le Ferrec, Normand Podechard, Dominique Lagadic-Gossmann, Kenji F. Shoji, Aubin Penna, Klara Kukowski, Jorn A. Holme, Johan Ovrevik May 2018

Lipophilic Chemicals From Diesel Exhaust Particles Trigger Calcium Response In Human Endothelial Cells Via Aryl Hydrocarbon Receptor Non-Genomic Signalling, Alena Kubatova, Bendik C. Brinchmann, Eric Le Ferrec, Normand Podechard, Dominique Lagadic-Gossmann, Kenji F. Shoji, Aubin Penna, Klara Kukowski, Jorn A. Holme, Johan Ovrevik

Chemistry Faculty Publications

Exposure to diesel exhaust particles (DEPs) affects endothelial function and may contribute to the development of atherosclerosis and vasomotor dysfunction. As intracellular calcium concentration [Ca2+]i is considered important in myoendothelial signalling, we explored the effects of extractable organic matter from DEPs (DEP-EOM) on [Ca2+]i and membrane microstructure in endothelial cells. DEP-EOM of increasing polarity was obtained by pressurized sequential extraction of DEPs with n-hexane (n-Hex-EOM), dichloromethane (DCM-EOM), methanol, and water. Chemical analysis revealed that the majority of organic matter was extracted by the n-Hex- and DCM-EOM, with polycyclic aromatic hydrocarbons primarily occurring in n-Hex-EOM. …


Mammalian Cell-Derived Vesicles For The Isolation Of Organelle Specific Transmembrane Proteins To Conduct Single Molecule Studies, Faruk H. Moonschi, Ashley M. Fox-Loe, Xu Fu, Christopher I. Richards May 2018

Mammalian Cell-Derived Vesicles For The Isolation Of Organelle Specific Transmembrane Proteins To Conduct Single Molecule Studies, Faruk H. Moonschi, Ashley M. Fox-Loe, Xu Fu, Christopher I. Richards

Chemistry Faculty Publications

Cell-derived vesicles facilitate the isolation of transmembrane proteins in their physiological membrane maintaining their structural and functional integrity. These vesicles can be generated from different cellular organelles producing, housing, or transporting the proteins. Combined with single molecule imaging, isolated organelle specific vesicles can be employed to study the trafficking and assembly of the embedded proteins. Here we present a method for organelle specific single molecule imaging via isolation of ER and plasma membrane vesicles from HEK293T cells by employing OptiPrep gradients and nitrogen cavitation. The isolation was validated through Western blotting, and the isolated vesicles were used to perform single …


Solution Growth And Thermal Treatment Of Crystals Lead To Two New Forms Of 2-((2,6-Dimethylphenyl)Amino)Benzoic Acid, Rong Hu, Yunping Zhoujin, Meng Liu, Mingtao Zhang, Sean Parkin, Panpan Zhou, Jianzhi Wang, Faquan Yu, Sihui Long Apr 2018

Solution Growth And Thermal Treatment Of Crystals Lead To Two New Forms Of 2-((2,6-Dimethylphenyl)Amino)Benzoic Acid, Rong Hu, Yunping Zhoujin, Meng Liu, Mingtao Zhang, Sean Parkin, Panpan Zhou, Jianzhi Wang, Faquan Yu, Sihui Long

Chemistry Faculty Publications

We report the discovery of two new forms (II and III) of a potential non-steroidal anti-inflammatory and thyroid drug, 2-((2,6-dimethylphenyl)amino)benzoic acid (HDMPA) through solution growth and thermal treatment of crystals. Form II has been discovered through crystal growth in a variety of solvents, and characterized by single-crystal X-ray diffraction, powder X-ray diffraction (PXRD), FT-IR, and Raman spectroscopy. Form II converts into form III upon thermal treatment, as indicated by the phase behavior study of form II with differential scanning calorimetry (DSC). Form III has been characterized by IR, Raman and PXRD. Conformational flexibility of the molecule seems to lead to …


Identification Of Significant E0 Strength In The 22+ → 21+ Transitions Of 58,60,62Ni, L. J. Evitts, A. B. Garnsworthy, T. Kibédi, J. Smallcombe, M. W. Reed, B. A. Brown, A. E. Stuchbery, G. J. Lane, T. K. Eriksen, A. Akber, B. Alshahrani, M. De Vries, M. S. M. Gerathy, J. D. Holt, B. Q. Lee, B. P. Mccormick, A. J. Mitchell, M. Moukaddam, Sharmistha Mukhopadhyay, N. Palalani, T. Palazzo, Erin E. Peters, Anthony Paul D. Ramirez, S. R. Stroberg, T. Tornyi, Steven W. Yates Apr 2018

Identification Of Significant E0 Strength In The 22+ → 21+ Transitions Of 58,60,62Ni, L. J. Evitts, A. B. Garnsworthy, T. Kibédi, J. Smallcombe, M. W. Reed, B. A. Brown, A. E. Stuchbery, G. J. Lane, T. K. Eriksen, A. Akber, B. Alshahrani, M. De Vries, M. S. M. Gerathy, J. D. Holt, B. Q. Lee, B. P. Mccormick, A. J. Mitchell, M. Moukaddam, Sharmistha Mukhopadhyay, N. Palalani, T. Palazzo, Erin E. Peters, Anthony Paul D. Ramirez, S. R. Stroberg, T. Tornyi, Steven W. Yates

Chemistry Faculty Publications

The E0 transition strength in the 22+ → 21+ transitions of 58,60,62Ni have been determined for the first time following a series of measurements at the Australian National University (ANU) and the University of Kentucky (UK). The CAESAR Compton-suppressed HPGe array and the Super-e solenoid at ANU were used to measure the δ(E2/M1) mixing ratio and internal conversion coefficient of each transition following inelastic proton scattering. Level half-lives, δ(E2/M1) mixing ratios and γ-ray branching ratios were measured at UK following inelastic neutron scattering. …


3d Printable Optomechanical Cage System With Enclosure, Brandon Winters, David Shepler Apr 2018

3d Printable Optomechanical Cage System With Enclosure, Brandon Winters, David Shepler

Chemistry Faculty Publications

The advent of the computer-age in the mid to late 20th century brought the development of sophisticated scientific equipment for myriad chemical analyses. The field of spectroscopy alone has seen significant advances in data collection, processing, and analysis due principally to the incorporation of microprocessors. While it is clear computers have revolutionized the field of instrumental chemical analysis their impact is pervasive through every segment of our lives. From word processing, data management, and Computer Aided Design in our work environments to social media, crowd funding, and digital news at home, technology is everywhere. This work seeks to incorporate the …


Untargeted Bioassay Strategy For Medicinal Plants: In Vitro Antidiabetic Activity And 13c Nmr Profiling Of Extracts From Vitex Negundo L, Fabian M. Dayrit, Myrnille Joy B. Zabala, Lolita G. Lagurin Apr 2018

Untargeted Bioassay Strategy For Medicinal Plants: In Vitro Antidiabetic Activity And 13c Nmr Profiling Of Extracts From Vitex Negundo L, Fabian M. Dayrit, Myrnille Joy B. Zabala, Lolita G. Lagurin

Chemistry Faculty Publications

Bioassay-guided fractionation is the principal method for the identification of active constituents in medicinal plants. By design, this method aims to identify the most active compound in a complex mixture with the objective of discovering novel drug candidates. Described here is a complementary method for the identification of known bioactive compounds in medicinal plants which is untargeted and which takes advantage of the large NMR database of known natural products and availability of statistical software. This untargeted bioassay strategy is demonstrated as a proof of principle in the determination of the antidiabetic compounds in Vitex negundo L. Crude methanol and …


Versatile Sarcosine Biosensing Schemes Utilizing Layer-By-Layer Construction Of Carbon Nanotube-Chitosan Composite Films, Michael J. Pannell, Elizabeth E. Doll, Najwa Labban, Mulugeta B. Wayu, Julie A. Pollack, Michael C. Leopold Apr 2018

Versatile Sarcosine Biosensing Schemes Utilizing Layer-By-Layer Construction Of Carbon Nanotube-Chitosan Composite Films, Michael J. Pannell, Elizabeth E. Doll, Najwa Labban, Mulugeta B. Wayu, Julie A. Pollack, Michael C. Leopold

Chemistry Faculty Publications

Layer-by-layer composite films of carbon nanotubes (CNTs) within a chitosan matrix with sarcosine oxidase enzyme and capped with Nafion have been developed and optimized as a versatile 1st generation amperometric sarcosine biosensing platform that operates successfully both as an isolated sarcosine sensor as well as a functional component within a creatinine sensor. Accurate measurement of sarcosine in urine and creatinine in blood may help with early diagnosis of diseases such as prostate cancer and renal failure, respectively. In this study, each material within the film is systematically optimized toward sarcosine sensitivity, including a critical evaluation of different CNTs effect on …


Synthesis And Catalytic Activity Of (3,4-Diphenylcyclopentadienone)Iron Tricarbonyl Compounds In Transfer Hydrogenations And Dehydrogenations, Timothy W. Funk, Andrew R. Mahoney, Rebecca A. Sponenburg, Kathryn P. Zimmerman, Daniel K. Kim, Emily E. Harrison Mar 2018

Synthesis And Catalytic Activity Of (3,4-Diphenylcyclopentadienone)Iron Tricarbonyl Compounds In Transfer Hydrogenations And Dehydrogenations, Timothy W. Funk, Andrew R. Mahoney, Rebecca A. Sponenburg, Kathryn P. Zimmerman, Daniel K. Kim, Emily E. Harrison

Chemistry Faculty Publications

Four (3,4-diphenylcyclopentadienone)iron tricarbonyl compounds were synthesized, and their activities in transfer hydrogenations of carbonyl compounds and transfer dehydrogenations of alcohols were explored and compared to those of the well-established [2,5-(SiMe3)2-3,4-(CH2)4(η4-C4C═O)]Fe(CO)3 (3). A new compound, [2,5-bis(3,5-dimethylphenyl)-3,4-diphenylcyclopentadienone]iron tricarbonyl (7), was the most active catalyst in both transfer hydrogenations and dehydrogenations, and compound 3 was the least active catalyst in transfer hydrogenations. Evidence was found for product inhibition of both 3 and 7 in a transfer dehydrogenation reaction, with the activity of 3 being more heavily affected. A monomeric iron hydride derived from 7 was spectroscopically observed during a …


Dynamics Of Singlet Fission And Electron Injection In Self-Assembled Acene Monolayers On Titanium Dioxide, Natalie A. Pace, Dylan H. Arias, Devin B. Granger, Steven Christensen, John E. Anthony, Justin C. Johnson Mar 2018

Dynamics Of Singlet Fission And Electron Injection In Self-Assembled Acene Monolayers On Titanium Dioxide, Natalie A. Pace, Dylan H. Arias, Devin B. Granger, Steven Christensen, John E. Anthony, Justin C. Johnson

Chemistry Faculty Publications

We employ a combination of linear spectroscopy, electrochemistry, and transient absorption spectroscopy to characterize the interplay between electron transfer and singlet fission dynamics in polyacene-based dyes attached to nanostructured TiO2. For triisopropyl silylethynyl (TIPS)-pentacene, we find that the singlet fission time constant increases to 6.5 ps on a nanostructured TiO2 surface relative to a thin film time constant of 150 fs, and that triplets do not dissociate after they are formed. In contrast, TIPS-tetracene singlets quickly dissociate in 2 ps at the molecule/TiO2 interface, and this dissociation outcompetes the relatively slow singlet fission process. The addition …


Polymers Course For Small Colleges And Universities, Joseph Furgal Mar 2018

Polymers Course For Small Colleges And Universities, Joseph Furgal

Chemistry Faculty Publications

This article describes the course design and teaching methodology for a polymer chemistry and applications lecture class specifically aimed at small college and university instruction. This intermediate course for advanced undergraduates and masters level graduate students focuses on teaching the basics of polymer history, synthesis and characterization with connections to the core chemistry curriculum in a small class size environment and without a textbook. Furthermore, an extensive overview of the applications of polymeric materials gives students a connection to real life applications. The course includes polymer case studies, informational lessons on real world objects made of polymers, and demonstrations. Student …


Structure And Magnetic Properties Of A 1d Alternating Cu(Ii) Monomer―Paddlewheel Chain, Vanessa Machado, Mark M. Turnbull, Louise N. Dawe Feb 2018

Structure And Magnetic Properties Of A 1d Alternating Cu(Ii) Monomer―Paddlewheel Chain, Vanessa Machado, Mark M. Turnbull, Louise N. Dawe

Chemistry Faculty Publications

One-dimensional metal–organic coordination polymers make up a class of compounds with potential towards the development of practical, new magnetic materials. Herein, a rare example of an ABBABB coupled linear chain comprised of alternating dicopper(II) tetraacetate units bridged to copper(II) acetate monomer units via axial η212 coordinated acetate is reported. Examination of the structure, determined by small molecule X-ray crystallography, shows that each Cu(II) ion is in a dx2–y2 magnetic ground state. Magnetic susceptibility and magnetization data were collected and, consistent with the structural interpretation, demonstrate that the Cu(II) dimer (paddlewheel) exhibits …


Preventing Crossover In Redox Flow Batteries Through Active Material Oligomerization, Susan A. Odom Feb 2018

Preventing Crossover In Redox Flow Batteries Through Active Material Oligomerization, Susan A. Odom

Chemistry Faculty Publications

No abstract provided.


Effect Of Molecular Side Groups And Local Nanoenvironment On Photodegradation And Its Reversibility, Nicole Quist, Mark Li, Ryan Tollefsen, Michael Haley, John Anthony, Oksana Ostroverkhova Feb 2018

Effect Of Molecular Side Groups And Local Nanoenvironment On Photodegradation And Its Reversibility, Nicole Quist, Mark Li, Ryan Tollefsen, Michael Haley, John Anthony, Oksana Ostroverkhova

Chemistry Faculty Publications

Degradation of organic semiconductors in the presence of oxygen is one of the bottlenecks preventing their wide-spread use in optoelectronic devices. The first step towards such degradation in functionalized pentacene (Pn) derivatives is formation of endoperoxide (EPO), which can either revert back to the parent molecule or proceed to molecule decomposition. We present the study of reversibility of EPO formation through probing the photophysical properties of functionalized fluorinated pentacene (Pn-R-F8) derivatives. Experiments are done in solutions and in films both at the single molecule level and in the bulk. In solutions, degradation of optical absorption and its partial recovery after …


Distinct Properties Underlie Flavin-Based Electron Bifurcation In A Novel Electron Transfer Flavoprotein Fixab From Rhodopseudomonas Palustris, H. Diessel Duan, Carolyn E. Lubner, Monika Tokmina-Lukaszewska, George H. Gauss, Brian Bothner, Paul W. King, John W. Peters, Anne-Frances Miller Feb 2018

Distinct Properties Underlie Flavin-Based Electron Bifurcation In A Novel Electron Transfer Flavoprotein Fixab From Rhodopseudomonas Palustris, H. Diessel Duan, Carolyn E. Lubner, Monika Tokmina-Lukaszewska, George H. Gauss, Brian Bothner, Paul W. King, John W. Peters, Anne-Frances Miller

Chemistry Faculty Publications

A newly recognized third fundamental mechanism of energy conservation in biology, electron bifurcation, uses free energy from exergonic redox reactions to drive endergonic redox reactions. Flavin-based electron bifurcation furnishes low-potential electrons to demanding chemical reactions, such as reduction of dinitrogen to ammonia. We employed the heterodimeric flavoenzyme FixAB from the diazotrophic bacterium Rhodopseudomonas palustris to elucidate unique properties that underpin flavin-based electron bifurcation. FixAB is distinguished from canonical electron transfer flavoproteins (ETFs) by a second FAD that replaces the AMP of canonical ETF. We exploited near-UV–visible CD spectroscopy to resolve signals from the different flavin sites in FixAB and to …


Undergraduate Research In Petrology Approached Through Computer Modeling Of Fabric Evolution In Igneous Rocks, Michael C. Leopold, M. J. Bonder, C. W. Holyoke, T. G.M. Krohn, R. V. Amenta Feb 2018

Undergraduate Research In Petrology Approached Through Computer Modeling Of Fabric Evolution In Igneous Rocks, Michael C. Leopold, M. J. Bonder, C. W. Holyoke, T. G.M. Krohn, R. V. Amenta

Chemistry Faculty Publications

Undergraduate research is an important part of the curriculum in many geology departments but, in recent years, it has become more difficult to attract students into projects dealing with solid-earth studies due to the limited employment prospects in these areas compared to those in environmental geology. This report describes how petrologic research can be made more attractive to students by an approach using C programming to model crystal growth and fabric development in poly crystalline solids. This topic has broad appeal to students in the other sciences as well as geology, and the computer skills learned have wide practical utility …


Lanthanum-Mediated Dehydrogenation Of Butenes: Spectroscopy And Formation Of La(C4H6) Isomers, Wenjin Cao, Dilkrushi Hewage, Dong-Sheng Yang Jan 2018

Lanthanum-Mediated Dehydrogenation Of Butenes: Spectroscopy And Formation Of La(C4H6) Isomers, Wenjin Cao, Dilkrushi Hewage, Dong-Sheng Yang

Chemistry Faculty Publications

La atom reactions with 1-butene, 2-butene, and isobutene are carried out in a laser-vaporization molecular beam source. The three reactions yield the same La-hydrocarbon products from the dehydrogenation and carbon-carbon bond cleavage and coupling of the butenes. The dehydrogenated species La(C4H6) is the major product, which is characterized with mass-analyzed threshold ionization (MATI) spectroscopy and quantum chemical computations. The MATI spectrum of La(C4H6) produced from the La+1-butene reaction exhibits two band systems, whereas the MATI spectra produced from the La+2-butene and isobutene reactions display only a single band system. Each of these …


Informing Efforts To Develop Nitroreductase For Amine Production, Anne-Frances Miller, Jonathan T. Park, Kyle L. Ferguson, Warintra Pitsawong, Andreas S. Bommarius Jan 2018

Informing Efforts To Develop Nitroreductase For Amine Production, Anne-Frances Miller, Jonathan T. Park, Kyle L. Ferguson, Warintra Pitsawong, Andreas S. Bommarius

Chemistry Faculty Publications

Nitroreductases (NRs) hold promise for converting nitroaromatics to aromatic amines. Nitroaromatic reduction rate increases with Hammett substituent constant for NRs from two different subgroups, confirming substrate identity as a key determinant of reactivity. Amine yields were low, but compounds yielding amines tend to have a large π system and electron withdrawing substituents. Therefore, we also assessed the prospects of varying the enzyme. Several different subgroups of NRs include members able to produce aromatic amines. Comparison of four NR subgroups shows that they provide contrasting substrate binding cavities with distinct constraints on substrate position relative to the flavin. The unique architecture …


A Galactomannoglucan Derived From Agaricus Brasiliensis: Purification, Characterization And Macrophage Activation Via Mapk And Ikappab/Nfkappab Pathways, Yanqing Zhang, Danting Liu, Leilei Fang, Xiaotong Zhao, Aimin Zhou, Junbo Xie Jan 2018

A Galactomannoglucan Derived From Agaricus Brasiliensis: Purification, Characterization And Macrophage Activation Via Mapk And Ikappab/Nfkappab Pathways, Yanqing Zhang, Danting Liu, Leilei Fang, Xiaotong Zhao, Aimin Zhou, Junbo Xie

Chemistry Faculty Publications

In this study, a novel galactomannoglucan named as TJ2 was isolated from Agaricus brasiliensis with microwave extraction, macroporous resin, ion exchange resin and high resolution gel chromatography. TJ2 is composed of glucose, mannose and galactose in the ratio 99.2:0.2:0.6. Infrared spectra (IR), methylation analysis and nuclear magnetic resonance spectra indicated that TJ2 mainly contained a b-(1?3) – linked glucopyranosyl backbone. Interestingly, TJ2 significantly promoted RAW264.7 cell proliferation, and was able to activate the cells to engulf E. coli. In addition, TJ2 induced the expression of Interleukin 1b (IL-1b), Interleukin 6 (IL-6), tumor necrosis factor a (TNF-a) and cyclooxygenase-2 (Cox-2) in …


Sphingomyelin And Gm1 Influence Huntingtin Binding To, Disruption Of, And Aggregation On Lipid Membranes, Maxmore Chaibva, Xiang Gao, Pranav Jain, Warren A. Campbell, Shelli L. Frey, Justin Legleiter Jan 2018

Sphingomyelin And Gm1 Influence Huntingtin Binding To, Disruption Of, And Aggregation On Lipid Membranes, Maxmore Chaibva, Xiang Gao, Pranav Jain, Warren A. Campbell, Shelli L. Frey, Justin Legleiter

Chemistry Faculty Publications

Huntington disease (HD) is an inherited neurodegenerative disease caused by the expansion beyond a critical threshold of a polyglutamine (polyQ) tract near the N-terminus of the huntingtin (htt) protein. Expanded polyQ promotes the formation of a variety of oligomeric and fibrillar aggregates of htt that accumulate into the hallmark proteinaceous inclusion bodies associated with HD. htt is also highly associated with numerous cellular and subcellular membranes that contain a variety of lipids. As lipid homeostasis and metabolism abnormalities are observed in HD patients, we investigated how varying both the sphingomyelin (SM) and ganglioside (GM1) contents modifies the interactions between htt …