Chemistry Commons^™

Physico-Chemical Regularities Of Chromatographic Retention Of Some Derivatives Of The Isoquinoline Series, I. X. Ruziyev, Sh. N. Jurakulov

Scientific Journal of Samarkand University

The chromatographic retention of the derivatives of pyrimidinone and isoquinolinewas studied under conditions of reversed-phase variant of HPLC. The retention factors were determined for various eluent compositions (CH3CN, CH3OH, and H2O). The relationship between the structure, properties and chromatographic retention of isoquinoline derivatives has been investigated

Excited State Lifetimes Of Sulfur-Substituted Dna And Rna Monomers Probed Using The Femtosecond Fluorescence Up-Conversion Technique, Matthew M. Brister, Carlos E. Crespo-Hernández

Faculty Scholarship

Sulfur-substituted DNA and RNA nucleobase derivatives (a.k.a., thiobases) are an important family of biomolecules. They are used as prodrugs and as chemotherapeutic agents in medical settings, and as photocrosslinker molecules in structural-biology applications. Remarkably, excitation of thiobases with ultraviolet to near-visible light results in the population of long-lived and reactive triplet states on a time scale of hundreds of femtoseconds and with near-unity yields. This efficient nonradiative decay pathway explains the vanishingly small fluorescence yields reported for the thiobases and the scarcity of fluorescence lifetimes in the literature. In this study, we report fluorescence lifetimes for twelve thiobase derivatives, both …

Can Aromaticity Be A Kinetic Trap? Example Of Mechanically Interlocked Aromatic [2-5]Catenanes Built From Cyclo[18]Carbon, Nikita Fedik, Maksim Kulichenko, Dmitriy Steglenko, Alexander I. Boldyrev

Chemistry and Biochemistry Faculty Publications

The unusual stability of cyclo[18]carbon arising from its aromaticity might be used to provide the kinetic trapping needed in the design of interlocked systems. The kinetic barrier separating the interlocked rings and the chemically bonded complex is about 30 kcal mol−1. In addition, the rings can slide freely, which is a promising property for the design of molecular gears and motors.

Molecular Composition And Photochemical Lifetimes Of Brown Carbon Chromophores In Biomass Burning Organic Aerosol, Lauren T. Fleming, Peng Lin, James M. Roberts, Vanessa Selimovic, Robert Yokelson, Julia Laskin, Alexander Laskin, Sergey A. Nizkorodov

Chemistry and Biochemistry Faculty Publications

To better understand the effects of wildfires on air quality and climate, it is important to assess the occurrence of chromophoric compounds in smoke and characterize their optical properties. This study explores the molecular composition of light-absorbing organic aerosol, or brown carbon (BrC), sampled at the Missoula Fire Sciences laboratory as a part of the FIREX Fall 2016 lab intensive. A total of 12 biomass fuels from different plant types were tested, including gymnosperm (coniferous) and angiosperm (flowering) plants and different ecosystem components such as duff, litter, and canopy. Emitted biomass burning organic aerosol (BBOA) particles were collected onto Teflon …

Aromatic Ouroboroi: Heterocycles Involving A Sigma-Donor-Acceptor Bond And 4n+2 Pi-Electrons, Kelling J. Donald, William Tiznado, Rodrigo Baez-Grez, Diego Inostroza

Chemistry Faculty Publications

The aromaticity and dynamics of a set of recently proposed neutral 5- and 6-membered heterocycles that are closed by dative (donor–acceptor) or multi-center s bonds, and have resonance forms with a Hu¨ckel number of p-electrons, are examined. The donors and acceptors in the rings include N, O, and F, and B, Be, and Mg, respectively. The planar geometry of the rings, coupled with evidence from different measures of aromaticity, namely the NICSzz, and NICSpzz components of the conventional nucleus independent chemical shifts (NICS), and ring current strengths (RCS), indicate non-trivial degrees of aromaticity in certain cases, including the cyclic C3B2OH6 …

Aromatic Hydrazide Compounds That Inhibit The Growth Of Mycobacterium Tuberculosis, Ronald Bartzatt, Preeti Sule, Thushara Galbadage, Jeffrey D. Cirillo

Chemistry Faculty Publications

Aims: To demonstrate the efficacy of aromatic hydrazide compounds to inhibit growth of Mycobacterium tuberculosis.

Study Design: To synthesize tuberculostats and test their antibacterial activity in-vitro.

Place and Duration of Study: University of Nebraska, Durham Science Center, 6001 Dodge Street, Omaha NE 68182, and Texas A&M Health Science Center, Department of Microbial Pathogenesis and Immunology, 8447 State Hwy 47, Medical Research and Education Building, Room #3012, Bryan, TX 7780. From March 2019 to October 2019.

Methodology: Hydrazide functional groups were formed by covalently bonding hydrazine onto a carbonyl carbon that is a substituent of a single aromatic …

Resolving The Puzzle Of Single-Atom Silver Dispersion On Nanosized Γ-Al2o3 Surface For High Catalytic Performance, Fei Wang, Jinzhu Ma, Shaohui Xin, Qiang Wang, Jun Xu, Changbin Zhang, Hong He, Xiao Cheng Zeng

Department of Chemistry: Faculty Publications

Ag/γ-Al2O3 is widely used for catalyzing various reactions, and its performance depends on the valence state, morphology and dispersion of Ag species. However, detailed anchoring mechanism of Ag species on γ-Al2O3 remains largely unknown. Herein, we reveal that the terminal hydroxyls on γ-Al2O3 are responsible for anchoring Ag species. The abundant terminal hydroxyls existed on nanosized γ-Al2O3 can lead to single-atom silver dispersion, thereby resulting in markedly enhanced performance than the Ag cluster on microsized γ-Al2O3. Density-functional-theory calculations confirm that Ag atom is mainly anchored by the terminal hydroxyls on (100) surface, forming a staple-like local structure with each Ag …

Dominant Negative Effects By Inactive Spa47 Mutants Inhibit T3ss Function And Shigella Virulence, Jamie L. Burgess, Heather B. Case, R. Alan Burgess, Nicholas E. Dickenson

Chemistry and Biochemistry Faculty Publications

Type three secretion systems (T3SS) are complex nano-machines that evolved to inject bacterial effector proteins directly into the cytoplasm of eukaryotic cells. Many high-priority human pathogens rely on one or more T3SSs to cause disease and evade host immune responses, underscoring the need to better understand the mechanisms through which T3SSs function and their role(s) in supporting pathogen virulence. We recently identified the Shigella protein Spa47 as an oligomerization-activated T3SS ATPase that fuels the T3SS and supports overall Shigella virulence. Here, we provide both in vitro and in vivo characterization of Spa47 oligomerization and activation in the presence and absence …

Production Of The Polysaccharide Curdlan By Agrobacterium Species On Processing Coproducts And Plant Lignocellulosic Hydrolysates, Thomas P. West

Faculty Publications

This review examines the production of the biopolymer curdlan, synthesized by Agrobacterium species(sp.),on processing coproducts and plant ligno cellulosichydrolysates. Curdlanis a-(1 3)-D-glucan that has various food, non-food and biomedical applications. A number of carbon sources support bacterial curdlan production upon depletion of nitrogen in the culture medium. The influence of culture medium pH is critical to the synthesis of curdlan. The biosynthesis of the-(1 3)-D-glucan is likely controlled by a regulatory protein that controls the genes involved in the bacterial production of curdlan. Curdlan overproducer mutant strains have been isolated from Agrobacterium sp. ATCC 31749 and ATCC 31750 by chemical …

A Zinc-Responsive Fluorophore Based On 5’-(P-Hydroxyphenyl)- Pyridylthiazole, Yuichiro Watanabe, Wanna Sungnoi, Andrew O. Sartorio, Matthias Zeller, Alexander Wei

Department of Chemistry Faculty Publications

The synthesis and photophysical properties of an ion-sensitive fluorescent compound are described, featuring 5′-(p-hydroxyphenyl)pyridylthiazole (HPPT) as a highly emissive fluorophore. Density functional theory (DFT) calculations indicate that HPPT is capable of intramolecular charge transfer (ICT), with further polarization upon complexation with Zn(II). A 4′-picolyloxy–HPPT derivative was prepared and determined to form a 1 : 1 complex with Zn(NO3)2 in acetonitrile, with a Stokes shift of 137 nm (6323 cm−1) and a 67 nm bathochromic shift in emission relative to the neutral ligand, and a fluorescence quantum yield (ΦPL) of 92%. An X-ray crystal structure of the HPPT–Zn(II) complex confirmed a …

Pine Rosin As A Toxic Cannabis Extract Adulterant, Jiries Meehan-Attrash, Robert Strongin

Chemistry Faculty Publications and Presentations

Pine rosin (colophony) has been identified as a new adulterant in cannabis oil. Its inhalation toxicity poses a significant health concern to users. For example, pine rosin fumes are released during soldering, and have been cited as a causative agent of occupational asthma. Symptoms also include desquamation of bronchial epithelium, which has also been observed in EVALI patients. The sample analyzed herein was acquired from a cannabis industry source, also contains medium chain triglycerides and oleamide, the latter of which is a hypnotic that is commonly found in the synthetic marijuana product Spice, or K2. A combination of NMR and …

Dual-Balance Electrodynamic Trap As A Microanalytical Tool For Identifying Gel Transitions And Viscous Properties Of Levitated Aerosol Particles, David S. Richards, Kristin L. Trobaugh, Josefina Hajek-Herrera, Ryan D. Davis

Chemistry Faculty Research

The formation of gelatinous networks within an aerosol particle significantly alters the physicochemical properties of the aerosol material. Existing techniques for studying gel transitions rely on bulk rheometry, which is limited by contact with the sample, or microrheological techniques such as holographic optical tweezers, which rely on expensive equipment and high-powered lasers that can degrade light-absorbing aerosol. Here, we present a new technique to probe the microrheological characteristics of aerosol particles and explore gel formation under atmospheric conditions in a contactless environment without the need for high-power light sources. In a dual-balance quadrupole electrodynamic balance, levitated droplets of opposite polarity …

Applications Of Triplet-Photosensitizers And Development Of Photochemical Methods, Luke V. Lutkus

Dissertations and Theses

Photochemistry focuses on various aspects of the interaction of light with molecules. This work entails new methodology for fundamental measurements of photochemistry along with novel applications of triplet-photosensitizers. Herein described are two separate methodologies developed for the determination of the quantum yield. A method for the singlet oxygen quantum yield was developed that utilizes the reaction between singlet oxygen and dimethyl sulfoxide (DMSO) to produce dimethyl sulfone. The rate of the reaction is measured by the pressure decrease that results from the consumption of oxygen from the headspace of a sealed system. It was found that the rate of pressure …

Author Correction: Closing The Nuclear Fuel Cycle With A Simplified Minor Actinide Lanthanide Separation Process (Alsep) And Additive Manufacturing, Artem V. Gelis, Peter Kozak, Andrew T. Breshears, M. Alex Brown, Cari Launiere, Emily L. Campbell, Gabriel B. Hall, Tatiana G. Levitskaia, Vanessa E. Holfeltz, Gregg J. Lumetta

Chemistry and Biochemistry Faculty Research

No abstract provided.

Methods Of Making And Using Lignin Derivatives, Mark Alan Helle, Chin Li Cheung

Department of Chemistry: Faculty Publications

Materials and methods for preparing reactive lignin and for preparing a bio-based adhesive are described herein.

This disclosure generally relates to methods of making and using reactive lignin. This disclosure also generally relates to methods of making and using bio-based adhesives. Lignin is the second most abundant natural polymer behind cellulose, yet lignin has very little commercial value despite years of research. Lignin is one of the major components of the cell wall in wood and other plant based materials such as hemp or crop wastes. It is produced in enormous quantities each year, primarily as a by-product in the …

Analyses Of The Oncogenic Brafd594g Variant Reveal A Kinase-Independent Function Of Braf In Activating Mapk Signaling, Nicholas J. Cope, Borna Novak, Zhiwei Liu, Amber Y. Gunderwala, Matthew Connolly, Zhihong Wang

College of Science & Mathematics Departmental Research

Class 3 mutations in B-Raf proto-oncogene, Ser/Thr kinase (BRAF), that result in kinase-impaired or kinase-dead BRAF have the highest mutation frequency in BRAF gene in lung adenocarcinoma. Several studies have reported that kinase-dead BRAF variants amplify mitogen-activated protein kinase (MAPK) signaling by dimerizing with and activating WT C-Raf proto-oncogene, Ser/Thr kinase (CRAF). However, the structural and functional principles underlying their activation remain elusive. Herein, using cell biology and various biochemical approaches, we established that variant BRAFD594G, a kinase-dead representative of class 3 mutation-derived BRAF variants, has a higher dimerization potential as compared with WT BRAF. Molecular dynamics simulations uncovered that …

In Situ Monitoring Of Catalytic Molecular Transformations On Noble Metal Nanocatalysts Using Surface-Enhanced Raman Spectroscopy, Hui Wang, Qingfeng Zhang, Esteban Villarreal, Hao Jing, Kexun Chen

Journal of the South Carolina Academy of Science

Noble metal nanoparticles have long been of tremendous interest in the nanophotonics and nanocatalysis communities owing to their intriguing size- and shape-dependent plasmonic and catalytic properties. The combination of tunable plasmon resonances with superior catalytic activities on the same noble metal nanoparticle, however, has long been challenging because the research on nanoplasmonics and nanocatalysis deals with nanoparticles in two drastically different size regimes. While tunable plasmon resonances are a unique feature of metallic nanoparticles in the sub-wavelength size regime, heterogeneous catalysis requires the use of substrate-supported sub-5 nm nanoparticulate catalysts. In this mini-review article, we share with the readers several …

A Possible Unaccounted Source Of Atmospheric Sulfate Formation: Amine-Promoted Hydrolysis And Non-Radical Oxidation Of Sulfur Dioxide, Shixian Wang, Xiao Cheng Zeng, Hui Li, Joseph S. Francisco

Xiao Cheng Zeng Publications

Numerous field and laboratory studies have shown that amines, especially dimethylamine (DMA), are crucial to atmospheric particulate nucleation. However, the molecular mechanism by which amines lead to atmospheric particulate formation is still not fully understood. Herein, we show that DMA molecules can also promote the conversion of atmospheric SO₂ to sulfate. Based on ab initio simulations, we find that in the presence of DMA, the originally endothermic and kinetically unfavourable hydrolysis reaction between gaseous SO₂ and water vapour can become both exothermic and kinetically favourable. The resulting product, bisulfite NH₂(CH₃)₂⁺ ∙ HSO …

Analysis Of Organochlorine Pesticides Levels In Irrigation Water From Various Water Sources Across Egypt, Omar Tarek Khairy

Theses and Dissertations

Organochlorine pesticides are extensively used in agriculture to cope with the world’s increasing population and demands for nutrition. This class of pesticides poses a serious risk to human health upon chronic exposure to elevated levels. Determination of organochlorine pesticides levels in water has been extensively covered in literature in Egypt and other parts of the world. The need for up-to date data and statistical information regarding the levels of organochlorine pesticides in water is ever increasing. These compounds, although a lot have been prohibited from use decades ago, can still be detected in trace levels in water due to their …

Redox Polymers Incorporating Pendant 6-Oxoverdazyl And Nitronyl Nitroxide Radicals, Michael Anghel, Francois Magnan, Sara D. Catingan, Matthew A. Mccready, Elaheh Aawani, Victor Wong, Deepa Singh, Giovanni Fanchini, Joe Gilroy

Chemistry Publications

Polymers comprised of redox-active organic radicals have emerged as promising materials for use in a variety of organic electronics, including fast-charging batteries. Despite these advances, relatively little attention has been focused on the diversification of the families of radicals that are commonly incorporated into polymer frameworks, with most radical polymers being comprised of nitroxide radicals. Here, we report two new examples prepared via ring-opening methathesis polymerization containing 6-oxoverdazyl and nitronyl nitroxide radicals appended to their backbones. The polymerization reaction and optoelectronic properties were explored in detail, revealing high radical content and redox activity that may be advantageous for their use …

Nanoscale Colocalization Of Fluorogenic Probes Reveals The Role Of Oxygen Vacancies In The Photocatalytic Activity Of Tungsten Oxide Nanowires, Meikun Shen, Tianben Ding, Steven T. Hartman, Fudong Wang, Christina Krucylak, Zheyu Wang, Che Tan, Bo Yin, Rohan Mishra, Matthew D. Lew, Bryce Sadtler

Electrical & Systems Engineering Publications and Presentations

Defect engineering is a strategy that has been widely used to design active semiconductor photocatalysts. However, understanding the role of defects, such as oxygen vacancies, in controlling photocatalytic activity remains a challenge. Here, we report the use of chemically triggered fluorogenic probes to study the spatial distribution of active regions in individual tungsten oxide nanowires using super-resolution fluorescence microscopy. The nanowires show significant heterogeneity along their lengths for the photocatalytic generation of hydroxyl radicals. Through quantitative, coordinate-based colocalization of multiple probe molecules activated by the same nanowires, we demonstrate that the nanoscale regions most active for the photocatalytic generation of …

Diverse N-Substituted Azole-Containing Amino Acids As Building Blocks For Cyclopeptides, Somayeh Motevalli, Michelle T. Nguyen, Jiacheng Tan, Amelia A. Fuller

Chemistry and Biochemistry

The preparation of 16 oxazole- or thiazole-containing amino esters bearing a wide array of N-substitution is reported. These were accessed in 40–92% yield via an AgClO4-promoted substitution reaction between a primary amine and a chloromethyl-functionalized thiazole or oxazole. These new synthetic building blocks will be useful for the preparation of new cyclopeptide analogues bearing heterocyclic backbone modifications. Four macrocyclic N-substituted oligoamides that include thiazole or oxazole heterocycles were obtained, following cyclooligomerization reactions of azole-modified N-substituted amino acids.

Air/Sea Transfer Of Highly Soluble Gases Over Coastal Waters, J. G. Porter, Warren J. De Bruyn, S. D. Miller, E. S. Saltzman

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

The deposition of soluble trace gases to the sea surface is not well studied due to a lack of flux measurements over the ocean. Here we report simultaneous air/sea eddy covariance flux measurements of water vapor, sulfur dioxide (SO₂), and momentum from a coastal North Atlantic pier. Gas transfer velocities were on average about 20% lower for SO₂ than for H₂O. This difference is attributed to the difference in molecular diffusivity between the two molecules (D _{SO 2}/D _{H 2O} = 0.5), in reasonable agreement with bulk parameterizations in air/sea gas …

Anoxic Conditions Maintained High Phosphorus Sorption In Humid Tropical Forest Soils, Yang Lin, Avner Gross, Christine S. O'Connell, Whendee L. Silver

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

The strong phosphorus (P) sorption capacity of iron (Fe) and aluminum (Al) minerals in highly weathered, acidic soils of humid tropical forests is generally assumed to be an important driver of P limitation to plants and microbial activity in these ecosystems. Humid tropical forest soils often experience fluctuating redox conditions that reduce Fe and raise pH. It is commonly thought that Fe reduction generally decreases the capacity and strength of P sorption. Here we examined the effects of 14 d oxic and anoxic incubations on soil P sorption dynamics in humid tropical forest soils from Puerto Rico. Contrary to the …

Granulins Modulate Liquid-Liquid Phase Separation And Aggregation Of Prion-Like C-Terminal Domain Of The Neurodegeneration-Associated Protein Tdp-43, Anukool A. Bhopatkar, Vladimir N. Uversky, Vijay Rangachari

Faculty Publications

Tar DNA binding protein 43 (TDP-43) has emerged as a key player in many neurodegenerative pathologies including frontotemporal lobar degeneration (FTLD) and amyotrophic lateral sclerosis (ALS). Hallmarks of both FTLD and ALS are the toxic cytoplasmic inclusions of the prion-like C-terminal fragments of TDP-43 (TDP-43 CTD), formed upon proteolytic cleavage of full-length TDP-43 in the nucleus and subsequent transport to the cytoplasm. Both full-length TDP-43 and its CTD are also known to form stress granules (SGs) by coacervating with RNA in the cytoplasm during stress and may be involved in these pathologies. Furthermore, mutations in PGRN gene, leading to haploinsufficiency …

Enhancing Protein Electrospray Charge States By Multivalent Metal Ions: Mechanistic Insights From Md Simulations And Mass Spectrometry Experiments., Leanne M Martin, Lars Konermann

Chemistry Publications

The structure and reactivity of electrosprayed protein ions is governed by their net charge. Native proteins in non-denaturing aqueous solutions produce low charge states. More highly charged ions are formed when electrospraying proteins that are unfolded and/or exposed to organic supercharging agents. Numerous studies have explored the electrospray process under these various conditions. One phenomenon that has received surprisingly little attention is the charge enhancement caused by multivalent metal ions such as La³⁺ when electrospraying proteins out of non-denaturing solutions. Here, we conducted mass spectrometry and ion mobility spectrometry experiments, in combination with molecular dynamics (MD) simulations, to uncover …

Correlation Between Ocean Acidification And Zooplankton In The South Pacific Gyre, Samuel Noonan, Rachel Scudder

DU Undergraduate Research Journal Archive

The South Pacific Gyre is a naturally occurring carbon sink, meaning that it absorbs atmospheric carbon dioxide by dissolving it into the moving surface water. The dissolution of CO2 level will dictate the water’s acidic levels a larger the concentration of dissolved CO2 is known to increase the salt water’s acidity. A great amount of the ocean’s biomass is composed of calcifying organisms, which produce tests or shells made from calcium carbonate CaCO3.The goal of our project is to determine if there is a correlation between the water acidity across various locations, as we sailed through the South Pacific gyre …

Controlling The Morphology Of Copper-Silica Nanocomposites From Laser Ablation In Liquid, Mallory John, Katharine M. Tibbetts

Chemistry Publications

No abstract provided.

Dissociation Of Singly And Multiply Charged Nitromethane Cations: Femtosecond Laser Mass Spectrometry And Theoretical Modeling, G. L. Gutsev, S. L. Mcpherson, Hugo A. López Peña, Derrick Ampadu Boateng, L. G. Gutsev, B. R. Ramachandran, Katharine M. Tibbetts

Chemistry Publications

Dissociation pathways of singly- and multiply charged gas-phase nitromethane cations were investigated with strong-field laser photoionization mass spectrometry and density functional theory computations. There are multiple isomers of the singly charged nitromethane radical cation, several of which can be accessed by rearrangement of the parent CH3–NO2 structure with low energy barriers. While direct cleavage of the C–N bond from the parent nitromethane cation produces NO2+ and CH3+, rearrangement prior to dissociation accounts for fragmentation products including NO+, CH2OH+, and CH2NO+. Extensive Coulomb explosion in fragment ions observed at high laser intensity indicates that rapid dissociation of multiply charged nitromethane cations …

Investigation Of Coherent Charge Transfer In Transition Metal Dichalcogenide Heterostructures With Multiresonant Coherent Multidimensional Spectroscopy, Darien J. Morrow

Link Foundation Energy Fellowship Reports

Photovoltaic solar cells convert sunlight into electricity by using material heterojunctions to facilitate separation of photo-excited charges in order to generate a current. Understanding and optimizing the efficiency of charge separation at the quantum mechanical level defines the future of the solar energy landscape and its impact on society. In the past decade, new charge separation mechanisms have been researched in heterostructures of layered 2D materials which facilitate ultrafast charge transfer and separation (see Figure 1a).[1, 2] Theoreticians have studied the mechanism of ultrafast transfer in these 2D materials and predict ultrafast transfer occurs by electrons collectively flowing back-and-forth between …