Chemistry Commons^™

An Electrochemical Cell For The Efficient Turn Around Of Wafer Working Electrodes, Nicholas Wozniak, Alyssa Frey, Lucas Osterbur, Timothy Boman, Jennifer R. Hampton

Faculty Publications

We present a new design for an electrochemical cell for use with wafer working electrodes. The key feature of the design is the use of half turn thumb screws to form a liquid-tight seal between an o-ring and the sample surface. The assembly or disassembly of the cell requires a half turn of each thumb screw, which facilitates the quick turn around of wafer samples. The electrochemical performance of the cell is demonstrated by cyclic voltammetry and double step chronoamperometry measurements of the ferricyanide/ferrocyanide couple.

Organization, Structure, And Assembly Of Alpha-Carboxysomes Determined By Electron Cryotomography Of Intact Cells, Cristina V. Iancu, Dylan M. Morris, Zhicheng Dou, Sabine Heinhorst, Gordon C. Cannon, Grant J. Jensen

Faculty Publications

Carboxysomes are polyhedral inclusion bodies that play a key role in autotrophic metabolism in many bacteria. Using electron cryotomography, we examined carboxysomes in their native states within intact cells of three chemolithoautotrophic bacteria. We found that carboxysomes generally cluster into distinct groups within the cytoplasm, often in the immediate vicinity of polyphosphate granules, and a regular lattice of density frequently connects granules to nearby carboxysomes. Small granular bodies were also seen within carboxysomes. These observations suggest a functional relationship between carboxysomes and polyphosphate granules. Carboxysomes exhibited greater size, shape, and compositional variability in cells than in purified preparations. Finally, we …

Tetraaquabis(3-Fluoropyridine-4-Carboxylato-Κn)Zinc(Ii) Dihydrate, Jonetha Fleming, Jennifer Kelley, Leroy Peterson Jr., Mark D. Smith, Hans-Conrad Zur Loye

Faculty Publications

In the title compound, [Zn(C₆H₃FNO₂)₂(H₂O)₄]·2H₂O, the Zn^II atom is octahedrally coordinated in a ZnO₄N₂ environment by two 3-fluoropyridine-4-carboxylate (3-fpy4-cbx) ligands and four water molecules. The [Zn(3-fpy4-cbx)₂(H₂O)₄] molecules form a three-dimensional network through strong O-HO and weak O-HF hydrogen bonds between 3-fpy4-cbx and water molecules. The crystal used for data collection was a twin, with the twin law corresponding to a 180° rotation about the real-space [001] axis. The major twin fraction refined to 0.795 (1).

Carboxysomal Carbonic Anhydrases: Structure And Role In Microbial Co2 Fixation, Gordon C. Cannon, Sabine Heinhorst, Cheryl A. Kerfeld

Faculty Publications

Cyanobacteria and some chemoautotrophic bacteria are able to grow in environments with limiting CO₂ concentrations by employing a CO₂-concentrating mechanism (CCM) that allows them to accumulate inorganic carbon in their cytoplasm to concentrations several orders of magnitude higher than that on the outside. The final step of this process takes place in polyhedral protein microcompartments known as carboxysomes, which contain the majority of the CO₂-fixing enzyme, RubisCO. The efficiency of CO₂ fixation by the sequestered RubisCO is enhanced by co-localization with a specialized carbonic anhydrase that catalyzes dehydration of the …

Effects Of Metal Compounds With Distinct Physicochemical Properties On Iron Homeostasis And Antibacterial Activity In The Lungs: Chromium And Vanadium, Mitchell D. Cohen, Maureen Sisco, Colleen Prophete, Kotaro Yoshida, Lung-Chi Chen, Judith T. Zelikoff, Jason Smee, Alvin A. Holder, Jacqueline Stormhuerner, Debbie C. Crans, Andrew J. Ghio

Faculty Publications

In situ reactions of metal ions or their compounds are important mechanisms by which particles alter lung immune responses. The authors hypothesized that major determinants of the immunomodulatory effect of any metal include its redox behavior/properties, oxidation state, and/or solubility, and that the toxicities arising from differences in physicochemical parameters are manifest, in part, via differential shifts in lung iron (Fe) homeostasis. To test the hypotheses, immunomodulatory potentials for both pentavalent vanadium (V(V); as soluble metavanadate or insoluble vanadium pentoxide) and hexavalent chromium (Cr(VI); as soluble sodium chromate or insoluble calcium chromate) were quantified in rats after inhalation (5 h/day …

Poly[[(Μ-2,2'-Bipyrimidine-Κ4N1,N1':N3,N3')(Μ-Sulfato-Κ2O:O')Zinc(Ii)] Monohydrate], Aaron Oxendine, Jennifer Kelley, Leroy Peterson Jr., Mark D. Smith, Hans-Conrad Zur Loye

Faculty Publications

In the title compound, {[Zn(SO₄)(C₈H₆N₄)]·H₂O}_n, the Zn^II atom is in a distorted octahedral environment. The Zn^II atoms are bridged by both 2,2'-bipyrimidine and sulfate ligands, thus forming a three-dimensional polymeric metal-organic solid that contains uncoordinated water molecules in the interstitial space. O-HO hydrogen bonding consolidates the crystal structure.

A Dielectric Affinity Microbiosensor, Xian Huang, Siqi Li, Jerome S. Schultz, Qian Wang, Qiao Lin

Faculty Publications

We present an affinity biosensing approach that exploits changes in dielectric properties of a polymer due to its specific, reversible binding with an analyte. The approach is demonstrated using a microsensor comprising a pair of thin-film capacitive electrodes sandwiching a solution of poly(acrylamide-ran-3-acrylamidophenylboronic acid), a synthetic polymer with specific affinity to glucose. Binding with glucose induces changes in the permittivity of the polymer, which can be measured capacitively for specific glucose detection, as confirmed by experimental results at physiologically relevant concentrations. The dielectric affinity biosensing approach holds the potential for practical applications such as long-term continuous glucose monitoring.

Construction, Figures Of Merit And Testing Of A Single-Cell Fluorescence Excitation Spectroscopy System, Laura S. Hill, Tammi L. Richardson, Louisa T.M. Profeta, Timothy J. Shaw, Christopher J. Hintz, Benjamin S. Twining, Evelyn Lawrenz, Micheal L. Myrick

Faculty Publications

Characterization of phytoplankton community composition is critical to understanding the ecology and biogeochemistry of the oceans. One approach to taxonomic characterization takes advantage of differing pigmentation between algal taxa and thus differences in fluorescence excitation spectra. Analyses of bulk water samples, however, may be confounded by interference from chromophoric dissolved organic matter or suspended particulate matter. Here, we describe an instrument that uses a laser trap based on a Nikon TE2000-U microscope to position individual phytoplankton cells for confocal fluorescence excitation spectroscopy, thus avoiding interference from the surrounding medium. Quantitative measurements of optical power give data in the form of …

Quantum Trajectory Dynamics In Imaginary Time With The Momentum-Dependent Quantum Potential, Sophya Garashchuk

Faculty Publications

The quantum trajectory dynamics is extended to the wave function evolution in imaginary time. For a nodeless wave function a simple exponential form leads to the classical-like equations of motion of trajectories, representing the wave function, in the presence of the momentum-dependent quantum potential in addition to the external potential. For a Gaussian wave function this quantum potential is a time-dependent constant, generating zero quantum force yet contributing to the total energy. For anharmonic potentials the momentum-dependent quantum potential is cheaply estimated from the global Least-squares Fit to the trajectory momenta in the Taylor basis. Wave functions with nodes are …

Mechanistic And Computational Studies Of Oxidatively-Induced Aryl-Cf3 Bond Formation At Palladium, J. Brannon Gary

Faculty Publications

This article describes the rational design of 1st generation systems for oxidatively-induced Aryl– CF3 bond-forming reductive elimination from PdII. Treatment of (dtbpy)PdII(Aryl)(CF3) (dtbpy = di-tert-butylbipyridine) with NFTPT (N-fluoro-1,3,5-trimethylpyridium triflate) afforded the isolable PdIV intermediate (dtbpy)PdIV(Aryl)(CF3)(F)(OTf). Thermolysis of this complex at 80 °C resulted in Aryl–CF3 bond-formation. Detailed experimental and computational mechanistic studies have been conducted to gain insights into the key reductive elimination step. Reductive elimination from this PdIV species proceeds via pre-equilibrium dissociation of TfO− followed by Aryl–CF3 coupling. DFT calculations reveal that the transition state for Aryl–CF3 bond formation involves the CF3 acting as an electrophile with the …

Platinum And Palladium Complexes Containing Cationic Ligands As Catalysts For Arene Hid Exchange And Oxidation., J. Brannon Gary

Faculty Publications

The direct functionalization of CH bonds has frequently been deemed a “Holy Grail” of organometallic chemistry.[1] A seminal example of this transformation was the demonstration by Shilov and co-workers that platinum(II) salts catalyze the direct oxidation of alkanes into their corresponding alcohols and alkyl halides.[2] Subsequent work in this area has focused on surveying diverse ligands for these reactions in an effort to enhance reactivity and selectivity, slow catalyst decomposition, and replace platinum(IV)-based oxidants with more cost-effective alternatives.[3–5] In a key development, chemists at Catalytica identified [bpymPtCl2] (bpym = bipyrimidine) as a pre-catalyst for the oxidation of CH4 into CH3OSO3H …

Transition-Metal Ion Exchange Using Poly(Ethylene Glycol) Oligomers As Solvents, Gina M. Canfield, Michael Bizimis, Susan E. Latturner

Faculty Publications

Poly(ethylene glycol) oligomers have been found to be effective as alternative solvents for the ion exchange of Mn2þ , Fe2 þ , and Co2þ into hydrated and dehydrated Zeolite X (Na80Al80Si112- O384 3 nH2O). When attempted in aqueous solutions, the exchange of these cations quickly leads to destruction of the zeolite structure within 1-2 exchange cycles. However, in PEG oligomer solvents, the structure can be maintained and exchanges of 48% (Co2þ ), 80% (Mn2þ ), and 91% (Fe2þ ) are observed after one cycle under hydrated conditions. When rigorous steps are taken to remove all water from the zeolite before …

Dynamic Path Bifurcation For The Beckmann Reaction: Observation And Implication, H. Yamataka, M. Sato, H. Hasegawa, Salai Cheettu Ammal

Faculty Publications

The reaction of oximes to amides, known as the Beckmann rearrangement, may undergo fragmentation to form carbocations + nitriles instead of amides when the cations have reasonable stability. The reactions of oxime derivatives of 1-substituted-phenyl-2-propanones and 3-substituted-phenyl-2-butanones in aqueous solvents gave both rearrangement and fragmentation products, the ratio of which was dependent on substituents. Transition state (TS) optimizations and intrinsic reaction coordinate (IRC) calculations for the reaction of 1-phenyl-2-propanone oximes showed that there is a single TS for each substituted compound. The IRC path from the TS either led to a rearrangement product or a fragmentation product depending on the …

Selective Complexation And Reactivity Of Metallic Nitride And Oxometallic Fullerenes With Lewis Acids And Use As An Effective Purification Method, Steven Stevenson, Mary A. Mackey, Jane E. Pickens, Melissa A. Stuart, Bridget S. Confait, J. Paige Phillips

Faculty Publications

Metallic nitride fullerenes (MNFs) and oxometallic fullerenes (OMFs) react quickly with an array of Lewis acids. Empty-cage fullerenes are largely unreactive under conditions used in this study. The reactivity order is Sc₄O₂@I_h-C₈₀ > Sc₃N@C₇₈ > Sc₃N@C₆₈ > Sc₃N@D_5h-C₈₀ > Sc₃N@I_h-C₈₀. Manipulations of Lewis acids, molar ratios, and kinetic differences within the family of OMF and MNF metallofullerenes are demonstrated in a selective precipitation scheme, which can be used either alone for purifying Sc₃N@I_{h …}

Rfx2 Is A Candidate Downstream Amplifier Of A-Myb Regulation In Mouse Spermatogenesis, Gary C. Horvath, Malathi K. Kistler, Wilson Stephen Kistler

Faculty Publications

Background: Mammalian spermatogenesis involves formation of haploid cells from the male germline and then a complex morphological transformation to generate motile sperm. Focusing on meiotic prophase, some tissue-specific transcription factors are known (A-MYB) or suspected (RFX2) to play important roles in modulating gene expression in pachytene spermatocytes. The current work was initiated to identify both downstream and upstream regulatory connections for Rfx2.

Results: Searches of pachytene up-regulated genes identified high affinity RFX binding sites (X boxes) in promoter regions of several new genes: Adam5, Pdcl2, and Spag6. We confirmed a strong promoter-region X-box for Alf, a germ cell-specific variant of …

Wavepacket Approach To The Cumulative Reaction Probability Within The Flux Operator Formalism, Sophya Garashchuk, Tijo Vazhappilly

Faculty Publications

Expressions for the singular flux operator eigenfunctions and eigenvalues are given in terms of the Dirac δ-function representable as a localized Gaussian wavepacket. This functional form enables computation of the cumulative reaction probability N(E) from the wavepacket time-correlation functions. The Gaussian based form of the flux eigenfunctions, which is not tied to a finite basis of a quantum-mechanical calculation, is particularly useful for approximate calculation of N(E) with the trajectory based wavepacket propagation techniques. Numerical illustration is given for the Eckart barrier using the conventional quantum-mechanical propagation and the quantum trajectory dynamics with the approximate quantum potential. N(E) converges with …

Succination Of Thiol Groups In Adipose Tissue Proteins In Diabetes: Succination Inhibits Polymerization And Secretion Of Adiponectin, Norma Frizzell, Mathur Rajesh, Matthew J. Jepson, Ryoji Nagai, James A. Carson, Suzanne R. Thorpe, John W. Baynes

Faculty Publications

S-(2-Succinyl)cysteine (2SC) is formed by reaction of the Krebs cycle intermediate fumarate with cysteine residues in protein, a process termed succination of protein. Both fumarate and succination of proteins are increased in adipocytes cultured in high glucose medium (Nagai, R., Brock, J. W., Blatnik, M., Baatz, J. E., Bethard, J., Walla, M. D., Thorpe, S. R., Baynes, J. W., and Frizzell, N. (2007) J. Biol. Chem. 282, 34219-34228). We show here that succination of protein is also increased in epididymal, mesenteric, and subcutaneous adipose tissue of diabetic (db/db) mice and that adiponectin is a major target for succination in both …

Identification And Structural Analysis Of A Novel Carboxysome Shell Protein With Implications For Metabolite Transport, Michael G. Klein, Peter Zwart, Sarah C. Bag By, Fei Cai, Sallie W. Chisolm, Sabine Heinhorst, Gordon C. Cannon, Cheryl A. Kerfeld

Faculty Publications

Bacterial microcompartments (BMCs) are polyhedral bodies, composed entirely of proteins, that function as organelles in bacteria; they promote subcellular processes by encapsulating and co-localizing targeted enzymes with their substrates. The best-characterized BMC is the carboxysome, a central part of the carbon-concentrating mechanism that greatly enhances carbon fixation in cyanobacteria and some chemoautotrophs. Here we report the first structural insights into the carboxysome of Prochlorococcus, the numerically dominant cyanobacterium in the world's oligotrophic oceans. Bioinformatic methods, substantiated by analysis of gene expression data, were used to identify a new carboxysome shell component, CsoS1D, in the genome of Prochlorococcus strain MED4; …

A Spectral Time-Domain Method For Computational Electrodynamics, James V. Lambers

Faculty Publications

We present a new approach to the numerical solution of Maxwell’s equations in the case of spatially‐varying electric permittivity and/or magnetic permeability, based on Krylov subspace spectral (KSS) methods. KSS methods for scalar equations compute each Fourier coefficient of the solution using techniques developed by Gene Golub and Gérard Meurant for approximating elements of functions of matrices by Gaussian quadrature in the spectral, rather than physical, domain. We show how they can be generalized to coupled systems of equations, such as Maxwell’s equations, by choosing appropriate basis functions that, while induced by this coupling, still allow efficient and robust computation …

Interface Slippage Study Between Polyamide 12 And Ethylene Butene Copolymer Melt In Capillary Extrusion, Jinhai Yang, James L. White

Faculty Publications

Extrusion of a polyamide 12 (PA12) material through a capillary die coated with an ethylene butene copolymer (EBM) was studied. The EBM coated die significantly increased the flow rates of the PA12 melt compared to a clean die at the same extrusion pressure. Introducing a maleic anhydride grafted ethylene-octene copolymer (EOM-g-MAH) into the EBM suppressed the effect. This behavior seems only explained by significant interface slippage between PA12 and EBM melts, which could be eliminated by introducing covalent chemical bonds across the interface. A mathematical analysis was carried out to calculate the interface slippage. The shear stress where slippage began …

Cardiac And Renal Function Are Progressively Impaired With Aging In Zucker Diabetic Fatty Type Ii Diabetic Rats, John W. Baynes, David B. Murray

Faculty Publications

This study investigated the temporal relationship between cardiomyopathy and renal pathology in the type II diabetic Zucker diabetic fatty (ZDF) rat. We hypothesized that changes in renal function will precede the development of cardiac dysfunction in the ZDF rat. Animals (10 weeks old) were divided into four experimental groups: Lean Control (fa/?) LC(n = 7), untreated ZDF rats (n = 7) sacrificed at 16 weeks of age, and LC (n = 7) untreated ZDF rats (n = 9) sacrificed at 36 weeks of age. LV structural/functional parameters were assessed via Millar conductance catheter. Renal function was evaluated via markers of …

Ionic Selectivity In L-Type Calcium Channels By Electrostatics And Hard-Core Repulsion, Dezso Boda, Douglas Henderson, Monika Valisko, Bob Eisenberg, Dirk Gillespie

Faculty Publications

A physical model of selective "ion binding" in the L-type calcium channel is constructed, and consequences of the model are compared with experimental data. This reduced model treats only ions and the carboxylate oxygens of the EEEE locus explicitly and restricts interactions to hard-core repulsion and ion–ion and ion–dielectric electrostatic forces. The structural atoms provide a flexible environment for passing cations, thus resulting in a self-organized induced-fit model of the selectivity filter. Experimental conditions involving binary mixtures of alkali and/or alkaline earth metal ions are computed using equilibrium Monte Carlo simulations in the grand canonical ensemble. The model pore rejects …

Structure–Mutagenicity Relationships And Energies Of 1-, And 2-Nitrotriphenylenes [Abstract], Kefa Karimu Onchoke

Faculty Publications

No abstract provided.

Controlled Assembly Of Rodlike Viruses With Polymers, Tao Li, Laying Wu, Nisaraporn Suthiwangcharoen, Michael A. Bruckman, Dayton Cash, Joan S. Hudson, Soumitra Ghoshroy, Qian Wang

Faculty Publications

A practical method to assemble rodlike tobacco mosaic virus and bacteriophage M13 with polymers was developed, which afforded a 3D core–shell composite with morphological control.

Mammaglobin As A Potential Molecular Target For Breast Cancer Drug Delivery, Lian Zuo, Ly Li, Qian Wang, Timothy P. Fleming, Shaojin You

Faculty Publications

Background Mammaglobin (MAM) has been used as a specific molecular marker for breast cancer diagnosis. Recently, several groups of researchers proposed a number of therapeutic strategies targeting this molecule. Some of the strategies are based upon an essential but not demonstrated hypothesis - mammaglobin is associated with the surface of breast cancer cells, which strongly disputes the therapeutic strategies. Results We conducted a computer-based predictive analysis and identified a small fragment at the N-end of MAM as a potential transmembrane domain. We provided several evidences to demonstrate the presence of the membrane-associated MAM. We isolated the membrane protein components from …

Tobacco Mosaic Virus Templated Synthesis Of One Dimensional Inorganic–Polymer Hybrid Fibres, Jianhua Rong, Fiona Oberbeck, Xinnan Wang, Xiaodong Li, Jerry Oxsher, Zhongwei Niu, Qian Wang

Faculty Publications

Inorganic–polymer hybrid nanofibres were prepared by using a rod-like tobacco mosaic virus (TMV) as a template. With tetraethylorthosilicate (TEOS) as a precursor, long silica-coated TMVfibres were formed via a head-to-tail assembly, which showed a substantial increase of the elastic modulus. Furthermore, homogenous titania–TMV hybrid fibres could be prepared using polyaniline-coated TMV fibres as a template, which were used to form a composite film that was able to sense liquefied petroleum gases.

Tetraquabis(5-Fluorosaccharinato)Nickel(Ii), Larnelle Peterson, Jennifer Kelley, Leroy Peterson Jr., Mark D. Smith, Hans-Conrad Zur Loye

Faculty Publications

In the centrosymmetric title complex, [Ni(C₇H₃FNO₃S)₂(H₂O)₄], the Ni^II atom exhibits a slightly distorted trans-NiN₂O₄ octahedral coordination. The nitrogen donors are provided by two 5-fluorosaccharinate ligands and the oxygen donors are provided by four water molecules. The crystal structure features O-HO and bifurcated O-H(F,O) hydrogen bonds, the latter involving the F atom of the 5-fluorosaccharinate ligand.

Diaquabis(5-Fluoro-2-Hydroxybenzoato-Κo1)Zinc(Ii), Diana Rishmawi, Jennifer Kelley, Mark D. Smith, Leroy Peterson, Hans-Conrad Zur Loye

Faculty Publications

The title compound, [Zn(C₇H₄FO₃)₂(H₂O)₂], is a monomeric Zn^II complex. The Zn^II atom, which lies on a twofold rotation axis, is situated in a distorted tetrahedral environment composed of two monodentate carboxlyate O atoms and two water O atoms. O-HO hydrogen bonds link these units, forming sheets that are stacked along the c axis.

Singlet Oxygen Delivery Through The Porous Cap Of A Hollow-Core Fiber Optic Device, Matibur Zamadar, David Aebisher, Alexander Greer

Faculty Publications

The development of the first photosensitizer/fiber optic device is reported. An oxygen-flowing, fiber-capped configuration is used for the application of heterogeneous, spatially confined singlet oxygen delivery in aqueous media. This is a unique device, unlike other heterogeneous photosensitizers, in which local concentrations of singlet oxygen can be delivered via introduction and withdrawal of the fiber tip.

Halothiobacillus Neapolitanus Carboxysomes Sequester Heterologous And Chimeric Rubisco Species, Balaraj B. Menon, Zhicheng Dou, Sabine Heinhorst, Jessup M. Shively, Gordon C. Cannon

Faculty Publications

Background: The carboxysome is a bacterial microcompartment that consists of a polyhedral protein shell filled with ribulose 1,5-bisphosphate carboxylase/oxygenase (RubisCO), the enzyme that catalyzes the first step of CO(2) fixation via the Calvin-Benson-Bassham cycle. Methodology/Principal Findings: To analyze the role of RubisCO in carboxysome biogenesis in vivo we have created a series of Halothiobacillus neapolitanus RubisCO mutants. We identified the large subunit of the enzyme as an important determinant for its sequestration into alpha-carboxysomes and found that the carboxysomes of H. neapolitanus readily incorporate chimeric and heterologous RubisCO species. Intriguingly, a mutant lacking carboxysomal RubisCO assembles empty carboxysome shells of …