Chemistry Commons^™

Synthesis Of Limn2O4-ΔClΔ Cathode Material By Like-Sol-Gel Methode, Zhao-Yong Chen, Yi He, Xing-Quan Liu, Zhi-Jie Li, Zuo-Long Yu

Journal of Electrochemistry

LiMn₂O_4-δCl_δ was synthesized by like sol gel methode, with calculated LiOH·H₂O, Mn(No₃)₂⋅6H₂O and LiCl·H₂O, and made electrochemical test with these compounds as positive materials. Result demostrated that LiMn₂O_4-δCl_δ cathode material has exellent stability and nearly no capacity loss after reaching stability.

Raman Spectroelectrochemical Study On Bioactive Molecules, Xiao-Wei Cao, Hai-Feng Yang, Zhe Su Meng Xiao Yun Wang, Xia-Qin Wu, Zong-Rang Zhang

Journal of Electrochemistry

Electron-transfer reaction is known to be one of the key reactions for generating biological functions. Mechanism revelation at a molecular level of such kind reactions is to be very helpful for us to understand life essence. In fact, surface enhanced Raman scattering (SERS) is one of the most powerful tools for the study on metal-electrolyte and metal-vacuum interfaces since 1970's. Moreover, Raman spectroscopic study in enzymology has provided attractive results during last twenty-five years.

In Situ Raman Spectroelectrochemical Characterization Of The Prussian Blue/Platinum Modified Electrode, Xiao-Wei Cao, Rong Wang, Gui-Hua Wang, Zong-Rang Zhang

Journal of Electrochemistry

Prussian Blue is known to be deposited electrochemically on the electrode surface, producing a dense redox active layer. Since the Prussian Blue modified electrode was first reported by Neff in 1978, different in situ spectroelectrochemical techniques have been widely used to investigate its electrochemical mechanism. But no research work related to the in situ Raman spectroscopic studies on it has been reported. In this paper we try to characterize the nature of thin Prussian Blue films on platinum substrates with in situ Raman spectroelectrochemical technique.

Adsorption Behavior Of Co At The Ultrathin Rh And Pt Film Electrodes, Yong Xie, Xiao-Qin Li, Bin Ren, Zhong-Qun Tian

Journal of Electrochemistry

Pt group metals have been widely used in catalysis such as hydrogenation of organic compounds and the oxidation of carbon monoxide. The information about CO adsorption on the Pt group surfaces and the influence of other surface species, such as hydrogen and CO₂ will be greatly helpful to elucidate the adsorption behavior of CO on Pt group metal surfaces and get a deeper understanding of catalytic mechanisms of Pt group metals. Surface enhanced Raman spectroscopy (SERS) has been becoming an increasingly important means to characterize the electrochemical metal solution interface over the past two decades. Our laboratory has successfully …

Adsorption And Oxidation Of Ethanol On Nm-Pt/Gc Electrode Ii. Eqcm And In-Situ Ftir Spectroscopic Studies In Acid Media, Guo-Liang Chen, Sheng-Pei Chen, Zhi-You Zhou, Chun-Hua Zhen, Shi-Gang Sun

Journal of Electrochemistry

The adsorption and oxidation of ethanol on nm Pt/GC electrode in acid solutions containing 0.1 mol·L ^-1 H₂SO₄ +0.1 mol·L ^-1 CH₃CH₂OH was investigated by using cyclic voltammetry, EQCM and in situ FTIR spectroscopy. The experimental results demonstrated that the oxidation of CH₃CH₂OH is closely relaed to solution acidity and oxygen species on electrode surface; CH₃CH₂OH was oxidized on nm Pt/GC electrode in acidic media via a dual path reaction mechanism, i.e . CH₃CH₂OH may be oxidized into CO₂ through …

The Photoelectrochemistry Of Tio2-Polyaniline Composite Film, Huai-Guo Huang, Zhi-Xin Zheng, Jin Luo, Hong-Ping Zhang, Ling-Ling Wu, Zhong-Hua Lin

Journal of Electrochemistry

A TiO₂ and polyaniline (PANI) composite film was obtained by electrochemical methods. The SEM image of the composite film showed that the PANI film is almost completely covered with TiO₂ efficiency. The spectra of photocurrent for the TiO₂-PANI composite film were different from these of TiO₂ film photosensitized by PANI. The bandgap energy of TiO₂ film on partially oxidized PANI film was determined as 3.0 eV by the threshold energy of photocurrent band for TiO₂. The spectra of photocurrent for partially oxidized PANI film electrode suggested that it has the characteristics of …

Catalytic Effect Of Cl- On Electrodeposition Of Binary Zinc Alloys With Iron Group Metals, Ren-He Yin, Zheng-Hua Fang, Wei-Min Cao, A.Za Karia, Rong-Ming Zhou

Journal of Electrochemistry

Zinc iron group metal alloys were deposited under coulostatic (10C⋅cm^-2) at 40 ℃ chloride baths. The deposited alloys were quantitatively analyzed by Atomic Absorption Spectrometry. The current efficiency, percent content and partial polarization curves were obtained by the results. The morphology of the deposits was observed by means of Scanning Electron Microscopy(SEM). We observe that the electrodeposition of zinc iron group metal alloys is one of the best known examples of anomalous codeposition. We found the catalytic effect of Cl^- on the electrodeposition behavior of iron group metal. Overpotential of iron group metal droped abruptly at high …

Dansylation Of Hydroxyl And Carboxylic Acid Functional Groups, Ronald Bartzatt

Chemistry Faculty Publications

Fluorescent labeling of primary and secondary amines using dansyl chloride has been widely used in the past. Its application provides an extremely sensitive means to detect amine functional groups to amounts of less than 1 mg of material. This work describes a method for the dansylation of hydroxyl (–OH) and carboxylic acid (–COOH) functional groups. This technique is demonstrated with ethanol, gamma hydroxy butyric acid (GHB), benzoic acid, and p-chloroaniline. Sensitivity of detection for all compounds are microgram or microliter. For the compounds ethanol and GHB which are liquids at room temperature, as little as 1 ml quantity can be …

Calculation Of 13C Chemical Shifts In Rna Nucleosides: Structure-13C Chemical Shift Relationships, Paolo Rossi, Gerard S. Harbison

Gerard S. Harbison Publications

Isotropic ¹³C chemical shifts of the ribose sugar in model RNA nucleosides are calculated using SCF and DFT-GIAO ab initio methods for different combinations of ribose sugar pucker, exocyclic torsion angle, and glycosidic torsion angle. Idealized conformations were obtained using structures that were fully optimized by ab initio DFT methods starting with averaged parameters from a collection of crystallographic data. Solid-state coordinates of accurate crystal or neutron diffraction structures were also examined directly without optimization. The resulting ¹³C chemical shifts for the two sets of calculations are then compared. The GIAO-DFT method overestimates the shifts by an average …

Ice Nucleation In Sulfuric Acid And Ammonium Sulfate Particles, Anthony J. Prenni, Matthew E. Wise, Sarah D. Brooks, Margaret A. Tolbert

CUP Faculty Research

Cirrus clouds are composed of ice particles and are expected to form in the upper troposphere when highly dilute sulfate aerosols cool and become supersaturated with respect to ice. In the laboratory we have used Fourier transform infrared spectroscopy to monitor ice nucleation from sulfate particles for relevant compositions of sulfuric acid/water and ammonium sulfate/water aerosols. Measured freezing temperatures are presented as a function of aerosol composition, and results are compared to existing aerosol data. We find that sulfuric acid solution aerosol exhibits greater supercooling than ammonium sulfate solution aerosol of similar weight percent. Ice saturation ratios based on these …

Solubilizing Single Walled Carbon Nanotubes By Direct Reaction With Amines And Alkylaryl Amines, Robert C. Haddon, Jian Chen

Chemistry Faculty Patents

Naked single-walled nanotube carbon metals and semiconductors are dissolved in organic solutions by direct functionalization with amines or alkylaryl amines having an uninterrupted carbon chain of at least 5 and more preferably 9 carbon atoms in length.

Effect Of Carrier-Gas Pressure On Barrier To Nucleation: Monte Carlo Simulation Of Water/Nitrogen System, K.J. Oh, Xiao Cheng Zeng

Xiao Cheng Zeng Publications

Carrier gases are used in most nucleation experiments for releasing the latent heat generated during vapor condensation. In the analysis of experimental data it is often assumed that the carrier gas is inert and would not participate in the nucleation process of the target gas. Several recent nucleation experiments show that the influence of carrier gases to nucleation rate is not negligible under certain conditions. To gain more insight into the carrier-gas effect, we carry out Monte Carlo simulation to compute the free energy of formation of water clusters in the presence of a nitrogen carrier gas. At fixed temperature …

Synthons And Design In Metal Phosphates And Oxalates With Open Architectures, Chintamani Nagesa Ramachandra Rao, Srinivasan R. Natarajan, Amitava Choudhury, Sharma Neeraj, Ramamurthy Vaidhyanathana

Chemistry Faculty Research & Creative Works

We briefly describe the structures of open-framework metal phosphates with different dimensionalities, such as the one-dimensional linear-chain and ladder structures, two-dimensional layer structures and three-dimensional structures with channels. We demonstrate the role of the zero-dimensional four-membered ring monomer and of the one-dimensional ladder structure as the starting building units or synthons involved in the formation of the complex architectures. Thus, we show how the one-dimensional ladder structure transforms to two- and three-dimensional structures under mild conditions. The two-dimensional layer structures also transform to three-dimensional structures, while the zero-dimensional monomer transforms to layered and three-dimensional structures under ordinary reaction conditions. These …

Rayleigh And Raman Scattering, David W. Ball

Chemistry Faculty Publications

Details the molecular aspect of Raman spectroscopy. Overview on the molecular absorption process; Information on Rayleigh scattering; Effects of the Raman scattering.

Simulations Of Ice And Liquid Water Over A Range Of Temperatures Using The Fluctuating Charge Model, Steven W. Rick

Chemistry Faculty Publications

The temperature dependence of the thermodynamic and dynamical properties of liquid water using the polarizable fluctuating charge (FQ) model is presented. The properties of ice Ih, both for a perfect lattice with no thermal disorder and at a temperature of 273 K, are also presented. In contrast to nonpolarizable models, the FQ model has a density maximum of water near 277 K. For ice, the model has a dipole moment of the perfect lattice of 3.05 Debye, in good agreement with a recent induction model calculation. The simulations at 273 K and the correct density find that thermal motion decreases …

Effects Of External Electric Field On The Interfacial Properties Of Weakly Dipolar Fluid, V. B. Warshavsky, T. V. Bykov, Xiao Cheng Zeng

Xiao Cheng Zeng Publications

In the framework of modified mean-field density-functional theory, effects of a uniform electric field on the interfacial properties of a model dipolar fluid are studied. Both density and orientational order-parameter profiles of the planar vapor-liquid interface are obtained as a function of the field strength. For the dipolar fluids with reduced dipole moment μ₀^*0^*E*/T*!1) can shift the surface tension by few percent. We also find that the electric field actually reduces the thermodynamical surface tension but enhances the mechanical surface tension at the equimolar dividing surface. To detect these field effects on …

Adsorption And Decomposition Of Nickelocene On Ag(100): A High-Resolution Electron Energy Loss Spectroscopy And Temperature Programmed Desorption Study, D. L. Pugmire, C. M. Woodbridge, N. M. Boag, Marjorie Langell

Marjorie A. Langell Publications

Nickelocene adsorption and decomposition on the Ag(100) surface were studied with temperature programmed desorption and high resolution electron energy loss spectroscopy. At monolayer coverages on the relatively inert Ag(100) surface at 175 K, nickelocene physisorbs molecularly, with its molecular axis perpendicular to the surface plane. Nickelocene begins decomposing to adsorbed cyclopentadienyl and nickel at 225 K. Molecular desorption is only observed from multilayer material, at 210 K, or from the first monolayer if adjacent surface sites for decomposition are not available. The cyclopentadienyl decomposes through disproportionation to cyclopentadiene, which desorbs, and adsorbed nickel and carbon fragments on the Ag(100) surface …

Probing The Relative Timing Of Hydrogen Abstraction Steps In The Flavocytochrome B2 Reaction With Primary And Solvent Deuterium Isotope Effects And Mutant Enzymes, P. Sobrado, S. C. Daubner, P. F. Fitzpatrick

Chemistry Faculty Research & Creative Works

Flavocytochrome b2 catalyzes the oxidation of lactate to pyruvate. Primary deuterium and solvent kinetic isotope effects have been used to determine the relative timing of cleavage of the lactate O - H and C - H bonds by the wild-type enzyme, a mutant protein lacking the heme domain, and the D282N enzyme. The DVmax and D(V/Klactate) values are both 3.0 with the wild-type enzyme at pH 7.5 and 25 °C, increasing to about 3.6 with the flavin domain and increasing further to about 4.5 with the D282N enzyme. Under these conditions, the D20Vmax values are 1.38, 1.18, and 0.98 for …

Process For Immobilizing Waste Using Bagasse (Us Patent 6174275), Michael A. Janusa

Faculty Publications

No abstract provided.

Tectorna: Modular Assembly Units For The Construction Of Rna Nano-Objects, Neocles B. Leontis, Luc Jaeger, Eric Westhof

Chemistry Faculty Publications

Structural information on complex biological RNA molecules can be exploited to design tectoRNAs or artificial modular RNA units that can self-assemble through tertiary interactions thereby forming nanoscale RNA objects. The selective interactions of hairpin tetraloops with their receptors can be used to mediate tectoRNA assembly. Here we report on the modulation of the specificity and the strength of tectoRNA assembly tin the nanomolar to micromolar range) by variation of the length of the RNA subunits, the nature of their interacting motifs and the degree of flexibility of linker regions incorporated into the molecules. The association is also dependent on the …

Semiclassical Application Of The Mo”Ller Operators In Reactive Scattering, Sophya Garashchuk, John C. Light

Faculty Publications

Mo\ller operators in the formulation of reaction probabilities in terms of wave packet correlation functions allow us to define the wave packets in the interaction region rather than in the asymptotic region of the potential surface. We combine Mo\ller operators with the semiclassical propagator of Herman and Kluk. This does not involve further approximations and can be used with any initial value representation (IVR) semiclassical propagator. Time propagation in asymptotic regions of the potential due to Mo\ller operators reduces the oscillations of the propagator integrand and improves convergence of the results with respect to the number of trajectories. The effectiveness …

High-Performance Liquid Chromatographic And Capillary Electrophoretic Enantioseparation Of Plant Growth Regulators And Related Indole Compounds Using Macrocyclic Antibiotics As Chiral Selectors, F. Hui, K. H. Ekborg-Ott, Daniel W. Armstrong

Chemistry Faculty Research & Creative Works

Enantioseparation of plant growth regulators, such as 3-(3-indolyl)-butyric acid, abscisic acid and structurally related molecules including a variety of substituted tryptophan compounds, has been achieved by HPLC and/or CE. The covalently bonded macrocyclic antibiotics, teicoplanin, ristocetin A and vancomycin, were used as chiral stationary phases (CSPs) in HPLC. Most of the racemates were baseline resolved in the reversed-phase mode (EtOH-H2O) using the teicoplanin CSP. The chiral recognition mechanism is discussed in regard to the structure of the analytes. In CE, the three aforementioned macrocyclic antibiotics were used as chiral additives in a phosphate run buffer. The effect of pH and …

Fabricating And Imaging Carbon-Fiber Immobilized Enzyme Ultramicroelectrodes With Scanning Electrochemical Microscopy, David O. Wipf, Fuyun Ge, Robert C. Tenent

Publications

The scanning electrochemical microscope (SECM) is used to image the activity of enzymes immobilized on the surfaces of disk-shaped carbon-fiber electrodes. SECM was used to map the concentration of enzymatically produced hydroquinone or hydrogen peroxide at the surface of a 33-mm diameter disk-shaped carbon-fiber electrode modified by an immobilized glucose-oxidase layer. Sub-monolayer coverage of the enzyme at the electrode surface could be detected with micrometer resolution. The SECM was also employed as a surface modification tool to produce microscopic regions of enzyme activity by using a variety of methods. One method is a gold-masking process in which microscopic gold patterns …

Atomically Resolved Single-Walled Carbon Nanotube Intramolecular Junctions, Min Ouyang, Jin-Lin Huang, Chin Li Cheung, Charles M. Lieber

Barry Chin Li Cheung Publications

Intramolecular junctions in single-walled carbon nanotubes are potentially ideal structures for building robust, molecular-scale electronics but have only been studied theoretically at the atomic level. Scanning tunneling microscopy was used to determine the atomic structure and electronic properties of such junctions in single-walled nanotube samples. Metal-semiconductor junctions are found to exhibit an electronically sharp interface without localized junction states, whereas a more diffuse interface and low-energy states are found in metal-metal junctions. Tight-binding calculations for models based on observed atomic structures show good agreement with spectroscopy and provide insight into the topological defects forming intramolecular junctions. These studies have important …

Thermodynamic Investigation Of The Si7 And Si8 Clusters By Knudsen Cell Mass Spectrometry, Giovanni Meloni, Karl A. Gingerich

Chemistry Faculty Publications

The Knudsen cell mass spectrometric method has been employed to measure the partial pressures of the Si[sub 7] and Si[sub 8] clusters under equilibrium conditions above liquid silicon, contained in a boron nitride liner inside a graphite Knudsen cell. Gaussian 2 (G2) theory and B3LYP density functional method were employed to determine the geometry, the vibrational frequencies, and the binding energy of the Si[sub 8] cluster. From the all-gas analyzed equilibria the following atomization enthalpies, Δ[sub a]H[sub 0][sup o](Si[sub n]), and enthalpies of formation, Δ[sub f]H[sub 298.15][sup o](Si[sub n]), in kJ mol-1, have been obtained: Si[sub 7], 2381±36 and …

Structure And Thermodynamic Stability Of The Osc And Osc2 Molecules By Theoretical Calculations And By Knudsen Cell Mass Spectrometry, Giovanni Meloni, L M. Thomson, Karl A. Gingerich

Chemistry Faculty Publications

Knudsen cell mass spectrometric equilibrium measurements together with theoretical computations have been employed to gain structural and thermodynamic information of the OsC and OsC[sub 2] molecules. Several levels of theory have been applied to determine the structures, molecular parameters, and physico-chemical properties of OsC(g) and OsC[sub 2](g), and their singly charged ions. Complete active space self-consistent field (CASSCF) calculations were performed on the apparent [sup 3]Σ[sup -] ground state and first [sup 3]Δ excited state of OsC. From the analyzed gaseous equilibria and the thermal functions calculated from the computed molecular parameters, the following atomization enthalpies, Δ[sub a]H[sub 0][sup o](OsC,g) …

Solidification/Stabilization Of Lead With The Aid Of Bagasse As An Additive To Portland Cement, Michael A. Janusa

Faculty Posters

No abstract provided.

Cooperativity Of Dna Object Self-Assembly, Ava Caudill Dykes

Theses, Dissertations and Capstones

In this study, the temperature dependence of self-assembling DNA structures was investigated. Specially designed two-dimensional DNA nanoarrays offer not only structural stability not normally associated with DNA, but also provide several possible sites of interaction, referred to as free ends, which can be easily exploited through conventional Watson-Crick base pairing. The ability to synthesize two-dimensional DNA nanoarrays was corroborated by confirming the presence of the nanoarrays by AFM imaging in air. The physical characteristics of two-dimensional DNA nanoarrays were also studied. DNA nanoarray synthesis occurs via a self-assembly process based on Watson-Crick base pairing. This self-assembly occurs through an annealing …

Report Of The State Nuclear Safety Advisor Submitted To The Governor And 120th Legislature As Of January 15, 2001, Paula M. Craighead

Maine Collection

Report of the State Nuclear Safety Advisor submitted to the Governor and 120th Legislature As of January 15, 2001

Paula M. Craighead, State Nuclear Safety Advisor, Executive Department, Maine State Planning Office, Augusta, Maine, 2001.

Contents: Introduction and Executive Summary / I. Maine Yankee Decommissioning / II. Portsmouth Naval Shipyard (PNS) / III. Low-Level Radioactive Waste (LLRW) / IV. High Level Radioactive Waste / V. Transport Routes and Safety Response / VI. Shipments / VII. Status of Federal and State Legal and Administrative Proceedings / References and Resources / Glossary

Fluoroalcohols As Nucleating Agents In Supersaturated Vapors: Efficient Clustering With Water In The Vapor Phase, V. Abdalsayed, Y. Ibrahim, M. Rusyniak, M. Rabeony, M. S. El-Shall

Chemistry Publications

Fluoroalcohols in small concentrations in the vapor phase display striking enhancing effects on homogeneous nucleation of supersaturated aliphatic alcohols, and on the formation of water clusters by supersonic expansion. The enhanced nucleationeffects are attributed to the surfactant properties of fluoroalcohols, which lower the surface tension of the growing droplets, and therefore lower the barrier to nucleation.