Physical Sciences and Mathematics Commons^™

Polymorphism And Polyamorphism In Bilayer Water Confined To Slit Nanopore Under High Pressure, Jaeil Bai, Xiao Cheng Zeng

Xiao Cheng Zeng Publications

A distinctive physical property of bulk water is its rich solid-state phase behavior, which includes 15 crystalline (ice I–ice XIV) and at least 3 glassy forms ofwater, namely, low-density amorphous, highdensity amorphous, and very-high-density amorphous (VHDA). Nanoscale confinement adds a new physical variable that can result in a wealth of new quasi-2D phases of ice and amorphous ice. Previous computer simulations have revealed that when water is confined between two flat hydrophobic plates about 7–9 Å apart, numerous bilayer (BL) ices (or polymorphs) can arise [e.g., BL-hexagonal ice (BL-ice I)]. Indeed, growth of the BL-ice I through vapor deposition on …

A Novel Route To Organonitrites By Pd-Catalyzed Cross-Coupling Of Sodium Nitrite And Potassium Organotrifluoroborates, Mohammad Al-Masum, Nabil Saleh, Tasfia Islam

Chemistry Faculty Research

Microwave irradiated palladium-catalyzed cross-coupling reaction of potassium styryltrifluoroborates and sodium nitrite gives the corresponding styryl nitrites in high yields. Potassium aryltrifluoroborates also furnish aryl nitrites under same reaction condition. This unprecedented cross-coupling is an interesting development and has the potential to lead to new nitration protocols.

Facile Molten-Salt Synthesis Of Double Perovskite La2bmno 6 Nanoparticles, Yuanbing Mao

Chemistry Faculty Publications and Presentations

Crystalline double perovskite La2BMnO6 (B = Ni and Co) nanoparticles with an average grain size of ∼64 nm were successfully prepared using a facile, environmentally friendly, scalable molten-salt reaction at 700 °C in air. Their composition and structural and magnetic properties have been characterized.

A Comparison Of Boltzmann And Gibbs Definitions Of Microcanonical Entropy For Small Systems, Randall B. Shirts

Faculty Publications

Two different definitions of entropy, S= klnW, in the microcanonical ensemble have been competing for over 100 years. The Boltzmann/Planck definition is that W is the number of states accessible to the system at its energy E (also called the surface entropy). The Gibbs/Hertz definition is that W is the number of states of the system up to the energy E (also called the volume entropy). These two definitions agree for large systems but differ by terms of order N^-1 for small systems, where N is the number of particles in the system. For three analytical …

Synthesis And Characterization Of Metallocorrole And Metalloporphyrin Complexes For Catalytic Oxidations, Zhibo Yuan

Mahurin Honors College Capstone Experience/Thesis Projects

Macrocyclic ligand-complexed transition metal-oxo intermediates are the active oxidizing species in a variety of important biological and catalytic oxidation reactions. Many transition metal catalysts have been designed to mimic the predominant oxidation catalysts in nature, namely the cytochrome P450 enzymes. Metal porphyrin complexes have been the center of research as catalysts in this context. This study focuses on the synthesis of porphyrin and corrole macrocyclic ligands and the corresponding ruthenium and iron complexes which are fully characterized by UV-vis and NMR spectroscopies.

The catalytic oxidation reactions towards organic sulfides by these metal complexes were also studied. Two ruthenium porphyrin complexes …

The Lyme Disease Spirochete In Tick Species Collected From Warren County, Kentucky, Cheryl C. Onwu

Mahurin Honors College Capstone Experience/Thesis Projects

The overall goal of this present study was to determine the prevalence of the Lyme disease spirochete, Borrelia burgdorferi, in south central Kentucky. A survey of ticks collected from a single location in Warren County, Kentucky was conducted between the months of April and June, 2010. A total of 293 ticks were collected. Three species were identified: 264 (91.7 %) of the ticks were Amblyoma americanum, 18 (6.6%) were Dermacentor variabilis, and 1 (0.35%) was Ixodes scapularis. The ten remaining ticks were immature nymphs and could not be identified. After identifying the species and sex of …

Reaction Of Halogenated Hydrocarbons With Cysteine And Nucleotides, Brittany S. Morgan

Mahurin Honors College Capstone Experience/Thesis Projects

Our objective is to develop a simple, inexpensive model to better understand the biologically relevant reactions of halogenated hydrocarbons and characterize them by NMR spectroscopy. We currently have a model that mimics the adduct created by the reaction of ethylene dibromide (a known toxin and carcinogen) with cysteine and guanosine 5’-monophosphate. Early attempts led to side products including ethylene oxide and ethylene glycol; however, our most promising method to date reacts cysteine with 2-bromoethanol in sodium methoxide/methanol followed by reaction of the 2-hydroxyethyl adduct with HCl and later with guanosine 5’-monophosphate. By reacting other halogenated hydrocarbons through the same method, …

Interactions Of Aqueous Ag+ With Fulvic Acids: Mechanisms Of Silver Nanoparticle Formation And Investigation Of Stability, Nathaniel F. Adegboyega, Virender K. Sharma, Karolina Siskova, Radek Zboril, Mary Sohn, Brian J. Schultz, Sarbajit Banerjee

Chemistry and Chemical Engineering Faculty Publications

This study investigated the possible natural formation of silver nanoparticles (AgNPs) in Ag+ −fulvic acid (FA) solutions under various environmentally relevant conditions (temperature, pH, and UV light). Increase in temperature (24−90 °C) and pH (6.1−9.0) of Ag+ −Suwannee River fulvic acid (SRFA) solutions accelerated the appearance of the characteristic surface plasmon resonance (SPR) of AgNPs. The rate of AgNP formation via reduction of Ag+ in the presence of different FAs (SRFA, Pahokee Peat fulvic acid, PPFA, Nordic lake fulvic acid, NLFA) and Suwannee River humic acid (SRHA) followed the order NLFA > SRHA > PPFA > SRFA. This order was found to be …

Bf2obn∙Oet2: A Novel Lewis Acid And Its Use In A Regio- And Stereo-Selective Opening Of Trisubstituted Epoxides And Its Application Towards Amphidinolide C, Nicholas A. Morra, Brian Pagenkopf

Chemistry Publications

The generation of a new Lewis acid (BF2OBn·OEt2) has been reported, and its usefulness has been demonstrated in the regio- and stereoselective ring-opening of trisubstituted epoxides. This Lewis acid is one in a series of new Lewis acids generated from BF3·OEt2 that display varying levels of Lewis acidity. When paired with a modified Shi epoxidation protocol, highly functionalized propionate units, such as those found in a wide variety of natural products, can be accessed. In conjunction with a Mukaiyama oxidative cyclization employing our second generation catalyst Co(nmp)2, this procedure ultimately culminated in the shortest and highest yielding route towards the …

Dissolved Organic Matter Composition And Bioavailability Reflect Ecosystem Productivity In The Western Arctic Ocean, Yuan Shen, Cedric Fichot, Ronald Benner

Faculty Publications

Dissolved organic carbon (DOC) and total dissolved amino acids (TDAA) were measured in high (Chukchi Sea) and low (Beaufort Sea) productivity regions of the western Arctic Ocean to investigate the composition and bioavailability of dissolved organic matter (DOM). Concentrations and DOC-normalized yields of TDAA in Chukchi surface waters were relatively high, indicating an accumulation of bioavailable DOM. High concentrations and yields of TDAA were also observed in the upper halocline of slope and basin waters, indicating off-shelf transport of bioavailable DOM from the Chukchi Sea. In contrast, concentrations and yields of TDAA in Beaufort surface waters were relatively low, indicting …

Probing Radical Pathways In Electrophilic Addition Of Halogens: Classical Vs. Bridged Intermediates, Lisa George, Aimable Kalume, Scott Reid

Chemistry Faculty Research and Publications

We examine radical mediated pathways in electrophilic addition to the simplest alkene, ethylene, where the structure of the radical intermediate has been extensively debated. Starting from the π-complex with a dihalogen, C₂H₄⋯I₂, isolated in an inert matrix, we initiate reaction by photolytically cleaving the I₂ bond. We succeed in trapping and spectroscopically interrogating the symmetrically bridged radical complex, which calculations confirm is the global minimum on the C₂H₅I Potential Energy Surface (PES). Consistent with the participation of a bridged intermediate, radical addition preferentially but not exclusively yields the anti …

Judging A Book By Its Cover: Using Lectin Microarrays To Identify How Glycosylation Is Regulated, John F. Rakus

Chemistry Faculty Research

Glycosylation involves the post-translational addition of carbohydrates to protein molecules and is an intricate and indispensable biochemical process. Study of this complicated network of interactions is hindered by the lack of a coding template analogous to the genetic code, and by the vast structural complexity inherent to carbohydrate polymers. We use lectins (non-enzymatic carbohydrate-binding proteins of non-immunological origin) as microarray probes to identify carbohydrate features expressed on cellular surfaces. Specifically, we utilized lectin microarray technology to investigate the differences in carbohydrates expressed by the cell lines of the Nation Cancer Institute’s NCI-60 panel. Our investigation identified tissue-specific expression differences in …

G-Ruption: The Third International Meeting On G-Quadruplex And G-Assembly, Liliya A. Yatsunyk, T. M. Bryan, F. B. Johnson

Chemistry & Biochemistry Faculty Works

A three and a half day conference focusing on nucleic acid structures called G-quadruplexes (G4s) and other guanine-based assemblies was held in Sorrento. Italy (June 28-July 1, 2011) and featured 35 invited talks and over 89 posters. The G-quadruplex field continues to expand at an explosive rate with the emergence of new connections to biology, chemistry, physics, and nanotechnology. Following the trend established by the previous two international G4 meetings, the conference touched upon all these areas and facilitated productive exchanges of ideas between researchers from all over the world.

Host Guest Complexes Of Pentiptycene Receptors Display Edge-To-Face Interaction, Lorenzo Mosca, Petr Koutník, Vincent M. Lynch, Grigory V. Zyryanov, Nina A. Esipenko, Pavel Anzenbacher Jr.

Chemistry Faculty Publications

The pentiptycene receptors form edge-to-face complexes with a variety of aromatic guests including nitroaromatics. X-ray diffractometry revealed that compounds 1, 2, and 3 form host-guest assemblies with a thienyl fragment (from a neightboring molecule of 1), benzene and nitrobenzene, respectively. X-ray studies of the three crystal structures reported here strongly suggest the edge-to-face to be a predominant binding mode between the aromatic guests and electron-rich faces of the pentiptycene aromatic cavity.

Supramolecular Sensor For Cancer-Associated Nitrosamines, Tsuyoshi Minami, Nina A. Esipenko, Ben Zhang, Maria E. Kozelkova, Lyle Isaacs, Ryuhei Nishiyabu, Yuji Kubo, Pavel Anzenbacher Jr.

Chemistry Faculty Publications

A supramolecular assay based on two fluorescent cucurbit[n]uril probes enables the recognition and quantification of nitrosamines, including cancer-associated nitrosamines, compounds that are difficult to recognize. The cross-reactive sensor leverages weak interactions and competition among the probe, metal, and guest, yielding high information density in the signal output (variance) and enabling the recognition of structurally similar guests.

Designing Tools For Studying The Dynamic Glycome, John F. Rakus

Chemistry Faculty Research

Glycosylation involves the post-translational addition of carbohydrates to protein molecules and is an intricate and indispensable biochemical process. Study of this complicated network of interactions is hindered by the lack of a coding template analogous to the genetic code, and by the vast structural complexity inherent to carbohydrate polymers. We use lectins (non-enzymatic carbohydrate-binding proteins of non-immunological origin) as microarray probes to identify carbohydrate features expressed on cellular surfaces. Specifically, we utilized lectin microarray technology to investigate the differences in carbohydrates expressed by the cell lines of the Nation Cancer Institute’s NCI-60 panel. Our investigation identified tissue-specific expression differences in …

On Metal Synthesis Of Some Substituted Rhenium And Manganese Complexes, Jaron Michael Thomas

Masters Theses & Specialist Projects

Heterocyclic organic and organometallic compounds (i.e. polypyrrole), and their derivatives, have been of great interest for conductive polymers due to their novel properties and environmental stability as compared to their non-aromatic analogs (i.e. polyacetylene). Our current interest focus upon the potential role of metal ligand bound pyridazines as the next generation of electronic devices that utilize the metal ligands bound to organics as the semiconducting material. Pyridazine is a 6-membered aromatic ring with two adjacent nitrogen atoms. These are promising candidates for a variety of materials and commercial applications; but they are difficult to get a metal ligand to fuse …

Investigations Of Inter- And Intramolecular C-O Bond Forming Reactions Of Peroxide Electrophiles, Benjamin W. Puffer

Department of Chemistry: Dissertations, Theses, and Student Research

A common reaction to yield ethers relies on an alkoxide nucleophile and a carbon electrophile (Williamson ether formation). Ethers can also be formed by reactions with carbon nucleophiles and oxygen electrophiles by way of the peroxide functional group. We screened a number of carbon nucleophiles suitable for attack on dialkyl peroxides to form new C-O bonds. Also a novel approach using a peroxyketal electrophile is shown to increase the efficiency of this intermolecular reaction. This method of C-O bond formation can also be implemented intramolecularly, not seen before in the literature, to yield cyclic ethers. This approach requires the generation …

Phosphorus Transport And Distribution In Kentucky Soils Prepared Using Various Biochar Types, Anvesh Reddy

Masters Theses & Specialist Projects

Conserving the environment is an issue that is gaining popularity day by day. Phosphorus transfer from agricultural soils is an important environmental issue that is being closely observed as the transport of phosphorous to water bodies is adversely affecting water quality due to accelerated eutrophication. It is important to establish phosphorous models that accurately account for soil test phosphorous. Standard models like SWAT (Soil and Water Assessment Tool) and EPIC (Environmental Policy Integrated Climate) were designed for serving this purpose. They are now used as the basis for developing new models that can more accurately account for the phosphorus transport, …

The Use Of Rhenium (Vii) Oxide As A Catalyst For The Substution Of Hemiacetals, Michael W. Richardson

Department of Chemistry: Dissertations, Theses, and Student Research

Rhenium (VII) oxides have proven to be mild and versatile catalysts in organic chemistry. They have previously been utilized to catalyze the transposition of allylic aclohols, Prins reaction, and reductive amination to name a few examples. This thesis reports the application of Re(VII) oxide in the substitution of hemi-acetals with a wide array of nucleophiles including oxo-, thio-, and peroxy-nucleophiles. These reactions proceed efficiently with rapid reaction times and high yields.

Adviser: Patrick H. Dussault

Hygroscopic Growth And Ccn Activity Of Hulis From Different Environments, Thomas B. Kristensen, Heike Wex, Bettina Nekat, Jacob K. Nøjgaard, Dominik Van Pinxteren, Douglas H. Lowenthal, Lynn Mazzoleni, Katrin Dieckmann, Christian Bender Koch, Thomas F. Mentel, Hartmut Herrmann, A. Gannet Hallar

Department of Chemistry Publications

[1] Humic-like substances (HULIS) constitute a significant fraction of aerosol particles in different environments. Studies of the role of HULIS in hygroscopic growth and cloud condensation nuclei (CCN) activity of aerosol particles are scarce, and results differ significantly. In this work the hygroscopic growth and CCN activity of water extracts (WE) and HULIS extracted from particulate matter (PM) collected at a polluted urban site (Copenhagen, Denmark), a rural site (Melpitz, Germany) and the remote site Storm Peak Laboratory (Colorado, USA) were investigated. Measurements of inorganic ions, elemental carbon, organic carbon and water soluble organic carbon (WSOC) within the PM confirmed …

Lack Of P53 Affects The Expression Of Several Brain Mitochondrial Proteins: Insights From Proteomics Into Important Pathways Regulated By P53, Ada Fiorini, Rukhsana Sultana, Eugenio Barone, Giovanna Cenini, Marzia Perluigi, Cesare Mancuso, Jian Cai, Jon B. Klein, Daret K. St. Clair, D. Allan Butterfield

Chemistry Faculty Publications

The tumor suppressor protein p53 has been described "as the guardian of the genome" for its crucial role in regulating the transcription of numerous genes responsible for cells cycle arrest, senescence, or apoptosis in response to various stress signals. Although p53 promotes longevity by decreasing the risk of cancer through activation of apoptosis or cellular senescence, several findings suggest that an increase of its activity may have deleterious effects leading to selected aspects of the aging phenotype and neurodegenerative diseases. There is the link between p53 and oxidative stress, the latter a crucial factor that contributes to neurodegenerative processes like …

A Cucurbit[8]Uril Sponge, Vijayakumar Ramalingam, Sharon K. Kwee, Lisa M. Ryno, Adam R. Urbach

Chemistry Faculty Research

This paper describes a convenient approach to quantitative removal of the synthetic host cucurbit[8]uril (Q8) from aqueous mixtures using a sepharose resin coated in memantine groups to selectively sequester Q8 in the presence of competing hosts and guests. The “Q8 sponge” can separate Q8 from Q6 and reverse the Q8-mediated dimerization of peptides.

Proposed Coherent Trapping Of A Population Of Electrons In A C60 Molecule Induced By Laser Excitation, Thomas George, G.P. Zhang

Chemistry & Biochemistry Faculty Works

This Letter demonstrates the possibility of generating coherent population trapping in C60. Similar to a three-level Λ system, C60 has a forbidden transition between the highest occupied molecular orbital (HOMO) (|a⟩) and the lowest unoccupied molecular orbital (LUMO) (|c⟩), but a dipole-allowed transition between HOMO and LUMO+1 (|b⟩) and between |b⟩ and |c⟩. We employ two cw laser fields, one coupling and one probe. The strong coupling field is switched on first to resonantly excite the transition between |b⟩ and |c⟩. After a delay, the probe is switched on; the coherent interaction between the coupling and probe fields traps the …

A Peculiarly Cerebroid Convex Zygo-Dodecahedron Is An Axiomatically Balanced “House Of Blues”: The Circle Of Fifths To The Circle Of Willis To Cadherin Cadenzas, David A. Becker

Department of Chemistry and Biochemistry

A bilaterally symmetrical convex dodecahedron consisting of twelve quadrilateral faces is derived from the icosahedron via a process akin to Fuller’s Jitterbug Transformation. The unusual zygomorphic dodecahedron so obtained is shown to harbor a bilaterally symmetrical jazz/blues harmonic code on its twelve faces that is related to such fundamental music theoretical constructs as the Circle of Fifths and Euler’s tonnetz. Curiously, the patterning within the aforementioned zygo-dodecahedron is discernibly similar to that observed in a ventral view of the human brain. Moreover, this same pattern is arguably evident during development of the embryonic pharynx. A possible role for the featured …

Effects Of Heterogeneity In Small Π-Type Dimers: Homogeneous And Mixed Dimers Of Diacetylene And Cyanogen, Kari L. Copeland, Gregory S. Tschumper

Chemistry Faculty Research & Creative Works

The homo- and heterogeneous dimers of diacetylene (H-C≡C-C≡C-H) and cyanogen (N≡C-C≡N) were studied using ab initio electronic structure computations to probe the effects of heterogeneity on noncovalent interactions between systems with delocalized π electron networks. Full geometry optimizations and harmonic vibrational frequencies were performed using the robust coupled-cluster with single and double and perturbative triple excitations (CCSD(T)) method with the triple-ζ plus 2 sets of polarization functions TZ2P(f,d)++ basis set. Seven basic configurations were examined for each dimer (cross, stacked, parallel-slipped, parallel-tipped, linear, T-shaped and Y-shaped), but only four stationary points were identified on the potential energy surfaces (PESs) of …

Flexural Rigidity Measurements Of Biopolymers Using Gliding Assays, Douglas S. Martin, Lu Yu, Brian L. Van Hoozen Jr.

Chemistry and Physics Faculty Articles

Microtubules are cytoskeletal polymers which play a role in cell division, cell mechanics, and intracellular transport. Each of these functions requires microtubules that are stiff and straight enough to span a significant fraction of the cell diameter. As a result, the microtubule persistence length, a measure of stiffness, has been actively studied for the past two decades. Nonetheless, open questions remain: short microtubules are 10-50 times less stiff than long microtubules, and even long microtubules have measured persistence lengths which vary by an order of magnitude.

Here, we present a method to measure microtubule persistence length. The method is based …

Capturing Fleeting Intermediates In A Catalytic C-H Amination Reaction Cycle, Richard H. Perry, Thomas J. Cahill Iii, Jennifer L. Roizen, Justin Du Bois, Richard N. Zare

Chemistry and Physics Faculty Articles

We have applied an ambient ionization technique, desorption electrospray ionization MS, to identify transient reactive species of an archetypal C–H amination reaction catalyzed by a dirhodium tetracarboxylate complex. Using this analytical method, we have detected previously proposed short-lived reaction intermediates, including two nitrenoid complexes that differ in oxidation state. Our findings suggest that an Rh-nitrene oxidant can react with hydrocarbon substrates through a hydrogen atom abstraction pathway and raise the intriguing possibility that two catalytic C–H amination pathways may be operative in a typical bulk solution reaction. As highlighted by these results, desorption electrospray ionization MS should have broad applicability …

New Multidetector Solution Could Lead To Safer Alternatives To Faulty Silicone Breast Implants, Judit D. Puskas, Geof Wyatt

Chemical, Biomolecular, and Corrosion Engineering Faculty Research

The article discusses the effort of the University of Akron's Department of Chemical and Biomolecular Engineering to pursue research which aims to reduce or eliminate capsular contracture associated with breast implants. It notes that the new multidetector nanotechnology developed by researchers can be better alternative to silicone gel-filled breast implants. It mentions that the new technology can also help in early diagnosis and imaging of breast cancer.

Spectral Data For "Reactivity Of Acyclic (Pentadienyl)Iron(1+) Cations: Synthetic Studies Directed Toward The Frondosins", Do W. Lee, Rajesh K. Pandey, Sergey V. Lindeman, William A. Donaldson

Natural Products Synthesis via Organoiron Methodology

Spectral data created in the course of the research project. Supports specific findings in "Reactivity of acyclic (pentadienyl)iron(1+) cations: Synthetic studies directed toward the frondosins".

A short, 4-step route to the scaffold of frondosin A and B is reported. The [1-methoxycarbonyl-5-(2′,5′-dimethoxyphenyl)pentadienyl]Fe(CO)₃⁺ cation was prepared in two steps from (methyl 6-oxo-2,4-hexadienoate)Fe(CO)₃. Reaction of this cation with isopropenyl Grignard or cyclohexenyllithium reagents affords (2-alkenyl-5-aryl-1-methoxycarbonyl-3-pentene-1,5-diyl)Fe(CO)₃ along with other addition products. Oxidative decomplexation of these (pentenediyl)iron complexes, utilizing CuCl₂, affords 6-aryl-3-methoxycarbonyl-1,4-cycloheptadienes via the presumed intermediacy of a cis-divinylcyclopropane.