Chemistry Commons^™

A Dual-Cell Technique And Its Application In Electrocatalytic Study Of Pt-Ru Metals, Lei Su, Bing-Liang Wu

Journal of Electrochemistry

Two local electrochemical reactive interfaces are established using two strips of Nafion membrane separated each other, which are in contact with different surface regions of the same metal-sheet working electrode. One potentiostatis used to control thepotentialof one electrochemical reactive interface to generate adsorbed surface speciesand the other potentiostatto hold the potential of the second interface as a detector of the intermediate. The adsorbed surface species driven by the difference in surface concentration diffuses alongthe surface of the metal-sheet between both local electrochemical interfaces and can be detected at the second interface when they achieveover there.The surface diffusion coefficient of the …

Electrochemical Reduction Of Nitrobenzene On The Wc Electrode In Acidic Solution, Chun-An Ma, You-Qun Chu, Ying-Hong Zhu, Zhi-Hua Xu

Journal of Electrochemistry

The tungsten carbide (WC) electrode was constructed by using polyterafluoroethylene as binder. The electrochemical behavior of nitrobenzene on the WC electrode in acidic solution was investigated by cyclic voltammetry, linear scan method and chronoamperometry. Experimental results showed that WC electrode had good activity for the electrochemical reduction of nitrobenzene, and the electrode process was controlled by diffusion and electrochemical stepssimultaneously. The apparent active energy of the electrode process is 23.7kJ⋅mol^-1, while the active energy of the electrochemicalstep is 10.91kJ⋅mol^-1.

Preparation And Electrochemical Performance Of New Composite Seperators For Lithium-Ion Batteries, Hu Cheng, Hong-Yan Du, Yong Yang

Journal of Electrochemistry

New composite seperators for lithium ion batteries were prepared by coating PEO mixed with nanosize SiO₂ onto microporous polypropylene(PP) seperators. Highly conductive electrolytes were prepared by soaking them in an electrolyte solution. With these composite separators, the lithium ion cell consisting of Li anode and LiNi_0.8Co_0.2O₂ cathode were assembled. The high initial discharge capacity and good capacity retention were obtained through the cell.

Synthesis Of (S)-3-Phenylpropane-2-Tert-Butoxycarbonylamino-1-Thiol And Its Electrochemical Behavior Self-Assembled On Gold, Ru Sun, Jian-Feng Ge, Mei Wang, Ren-Ao Gu

Journal of Electrochemistry

The synthesis of (S)-3-Phenylpropane-2-tert-butoxycarbonylamino-1-thiol(N-Boc-APT) from L-phenylalanine was reported. L-Phenylalanine was reduced to the corresponding amino alcohol, protection of the amino group using tert-butyl pyrocarbonate gave (S)-2-tert-butoxycarbonylamino-3-phenylpropane-1-ol, which was then O-mesylated and treated with potassium thioacetate in DMF to give 3-phenylpropane-2-tert- butoxycarbonylamino-1-etylmercapto. After the acetyl group was removed with ammonia in alcohol, the desired target molecular was obtained. The structure of intermediate and target molecular was conformed by IR and ¹HNMR. We made N-Boc-APT self-assemble-modificated gold electrode and investigated its electrochemical behavior. The CV results of methylene blue on nano-Au/N-Boc-APT SAM/Au electrode showed that nano-Au could speed this electron transfer …

Effects Of Barium On The Performance Of Secondary Alkaline Zinc Electrode, Yi Zheng, Jian-Ming Wang, Hua Chen, Hai-Bo Shao, Jian-Qing Zhang

Journal of Electrochemistry

The active material of secondary alkaline zinc electrode with barium additives was prepared by a chemical reaction method and characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The electrochemical performance of various pasted Zn electrodes was investigated by cyclic voltammetry, charge/discharge method and electrochemical impedance spectra (EIS) technology. The addition of barium can synthesize a compound barium zincate with the molecular structure of BaZn(OH)₄·xH₂O and improve the discharge performance. The EIS of the various Zn electrodes showed two time constants besides diffusion impedance, including a state variable representing the covering degree of discharge products …

Synthesis And Electrochemical Behavior Of Layered-Structure Limn1-XCrXO2, Jie Xiao, Hui Zhan, Yun-Hong Zhou

Journal of Electrochemistry

The Layered-structure LiMn_1-xCr_xO₂(x=0, 0.15) solid solution has been prepared by the rheological phase method. From the XRD results, undoped LiMnO₂ crystallized almost entirely in the orthorhombic phase while the structure of LiMn_0.85Cr_0.15O₂ belongs to monoclinic phase. TEM investigation shows that the final powder product consists of ultrafine spherical particles which are distributed homogeneously, with the average diameter ranging from 60 to 300nm. The initial discharge capacity of LiMn_0.85Cr_0.15O is much higher than that of undoped LiMnO₂. After 40 cycles, the capacity retention …

Lithium Insertion Into Tio2(B) Nanobelts Synthesized By The "Soft Chemical" Method, Cha-Geng Nie, Zheng-Liang Gong, Lan Sun, Juan Zuo, Yue-Kun Lai, Chang-Jian Lin

Journal of Electrochemistry

TiO₂(B) Nanobelts were synthesized by using the "Soft chemical"method. The products were characterized by means of transmission electron microscope(TEM), X-ray diffraction(XRD), Raman spectrum and energy dispersive spectrum(EDS). Galvanostatic charging and discharging tests showed that lithium-ion intercalation/deintercalation occurred reversibly in the TiO₂(B) nanobelts electrode, and a high capacity (265 mAh·g^-1) can be obtained. The results suggested that TiO₂(B) Nanobelts might be a promising negative electrode material of second Lithium battery.

Fabrication Of Solid Oxide Fuel Cells And Analysis Of Their Structure And Performance, Nai-Tao Yang, Bo Meng, Ru-Jun Yu, Xiao-Yao Tan

Journal of Electrochemistry

An intermediate temperature solid oxide fuel cell (IT-SOFC) was fabricated by co-copressing-sintering methods, and the electrolyte of Ce_0.8Gd_0.2O_1.9 (CGO) and cathode materials of La_0.6Sr_0.4Co_0.2Fe_0.8O_3-α (LSCF) were prepared by sol-gel method. The effect of preparation methods on the microstructure of the prepared fuel cells was analyzed by SEM . It shows that the cells prepared by the co-pressing/co-sintering method possess a dense electrolyte layer and a compact interface between electrolyte and anode but a curved configuration, while those prepared by the colloidal technique have a flat configuration …

Study On The Electrochemical Behaviors Of Prussian Blue Film Using Electrochemical Quartz Crystal Microbalance, Hui Liao, Xia-Qin Wu, Zong-Rang Zhang

Journal of Electrochemistry

Prussian blue (PB) films were electrodeposited on the Pt/QCM electrodes in the solutions with or without Phenanthroline by cyclic voltammetry. The frequencyshift during electrodeposition wasmeasured, and the EQCM behaviors of these two types of PB films in potassium chloridewere also studied. Results show that electrodeposition process of PB film in the solution with phenanthroline wasdifferent from that in the solution without phenanthroline. The PB film modified Pt/QCM electrodeprepared in the solution with phenanthroline shown an excellent electrocatalytic activity for the reduction process of hydrogen peroxide.

Preparation Of Photo-Electrochemical Anticorrosion Tio2 Films By Anodization Method, Peng-Fei Wu, Mou-Cheng Li, Jia-Nian Shen, Mei-Qun Xiao, Dong Liu

Journal of Electrochemistry

Titanium oxide films have photo-electrochemical anticorrosion effect. We investigated the TiO₂ films prepared by anodization method to protect for 45# carbon steel in man-made seawater(3%NaCl). Various parameters, including voltages, electrolytes nature and concentration of electrolyte were examined. The polarization curves and of TiO₂ and coupling photo-current curve between TiO₂ film and 45#  carbon steel were measured.

Synergisms Of Electric Or Electromagnetic Fields And Photodynamic Effects Induce Apoptosis And Necrosis Of Cancer Cells, Radeva Maria, Lambrera Maya, Angelova Plamena, Traitcheva Nelly, Berg Hermann

Journal of Electrochemistry

Weak pulsating sinusoidal electromagnetic fields (PEMF) have been applied to change membrane permeation and induction of apoptosis (necrosis). In the case of suspension of human cancer cells U-937 and K-562 inside of Helmholtz-coils the amplitude of PEMF B=10 and at 39mT (at 50 Hz) was combined gradually with the cytotoxic agent actinomycin-C on one hand with its novel photodynamic activity on the other.

Nucleation And Crystal Growth Of Pt Electrodeposition On Poly Crystal Au Microdisc Electrode, Zhi-Yong Tao, Pei-Fang Liu

Journal of Electrochemistry

Based on the Fleischmann's model of nucleation and crystal growth for electrodeposition combined with the Barradas-Bosco's adsorption-nucleation model for electrochemical phase formation, the chronoamperometry was well fitted for Pt deposition on polycrystalline Au micro disc electrodes (30 μm in diameter) in different H₂PtCl₆ concentrations at different over-potentials. The initial stage of Pt deposition in dilute H₂PtCl₆ could be interpreted by the model of H₂PtCl₆ adsorption combined with instantaneous nucleation and two-dimensional cylindrical growth. The rate constant of the two-dimensional growth increased linearly with overpotential. Then the deposit grew layer by layer …

Solid State Synthesis And Electrocatalysis Of Pt/Moo3 For The Oxidation Of Methanol, Qing Wang, Yi-Ming Zhou, Yang Shao, Yi-Gang Ji, Juan Xu, Ya-Wen Tang, Tian-Hong Lu, Tao Shen

Journal of Electrochemistry

The electrocatalyst, Pt/MoO₃ synthesized by solid state reaction, was used for the oxidation of methanol in direct methanol fuel cells. The X-Ray diffraction and cyclic voltammetry were employed to investigate the performance of the material. It was shown that the typical diffraction peaks for Pt appeared in XRD. And a good electrocatalysis for methanol oxidation was observed. The peak potential of the methanol oxidation appeared at ca. 0.63V(vs.SCE) and the peak current density for the oxidation was 78.1 mA⋅cm^-2.

Preliminary Study Of Speek Membranes For Direct Methanol Fuel Cells Application, Su-Zhen Ren, Zhen-Xing Liang, Xin-Sheng Zhao, Qin Xing, Gong-Quan Sun, Xue-Feng Yang

Journal of Electrochemistry

This paper describes the methanol permeability characterization of SPEEK membranes and their feasibility for DMFC application. The SPEEK membranes showed a significant lower methanol permeation than Nafion 115 determined from voltammetric methods. An increase in open circuit voltage was found in the performance of SPEEK membranes in DMFC. The power density of the cell using SPEEK membrane was considerably poorer than that of Nafion 115. If modified properly, the SPEEK membranes can be chosen for DMFC application based on this study.

Study On An Intermediate Temperature Planar Solid Oxide Fuel Cell, Shao-Rong Wang, Wen-Xia Chen, Ting-Lian Wen, Jia-Di Cao, Zhi-Yi Lv, Da-Qian Wang

Journal of Electrochemistry

Tape cast method was applied to prepare green sheets of Ni/YSZ anode supported YSZ thin film. After isostatic pressure treatment and cosintering, the YSZ film on the Ni/YSZ anode was gas-tight dense, and 15~30 μm thick. The area of the composite film was over 100 cm². A Ce_0.8Sm_0.2O_1.9 (CSO) interlayer was sintered on to the YSZ electrolyte film to protect La_0.6Sr_0.4CoO₃ (LSCO) cathode from reaction with YSZ at high temperatures. The LSCO cathode layer was screen printed onto the CSO interlayer and sintered at 1200 ℃ for 3 …

The Effect Of Ferrous Sulphate On The Electroless Depositionof Co-Fe-P Alloys, Sen-Lin Wang, Qing-Hua Li

Journal of Electrochemistry

Electroless deposition of Co-P alloy and Co-Fe-P alloy from an alkaline bath, containing sodium hypophosphite as a reducer, boric acid as a buffer agent and sodium citrate as a complexing agent, was investigated respectively. The effects of process parameters, such as pH of solution and metallic salt mole ratio of CoSO₄/FeSO₄, on the plating rate were examined. It was found that the presence of ferrous sulfate in the bath has an inhibitory effect on the alloy deposition. As a consequence, the plating rate of Co-Fe-P is lower than that of Co-P. The electrochemical polarization measurements have …

Studies On The Electrochemical Behavior Of Copper Paratolysulfate And Its Complexes, Ji-Guo Song, Pei-Kang Shen

Journal of Electrochemistry

Copper (II) paratolysulfate has been synthesized and characterized by thermo-gravimetric (TG) measurements and differential scanning calorimetric (DSC) analysis. This salt can easily lose all crystal water and the dehydrated salt does not deliquesce in the air. It is found for the first time that the complex of Cu(p-OTs)₂/ethanolamine(1∶1) can catalyze the oxidation of 1,1′-bi-2-naphthol in DMSO and DMF, while the process is difficult to perform in H₂O and CH₃OH. The electrochemical behaviors of both Cu(p-OTs)₂ and its complexes with ethanolamine have been studied on platinum electrode in DMSO, DMF, CH₃OH and …

The Fad-Shielding Residue Phe1395 Regulates Neuronal Nitric-Oxide Synthase Catalysis By Controlling Nadp+ Affinity And A Conformational Equilibrium Within The Flavoprotein Domain, David Konas, Keng Zhu, Manisha Sharma, Kulwant S. Aulak, Gary W. Brudvig, Dennis J. Stuehr

Department of Chemistry and Biochemistry Faculty Scholarship and Creative Works

Phe1395 stacks parallel to the FAD isoalloxazine ring in neuronal nitric-oxide synthase (nNOS) and is representative of conserved aromatic amino acids found in structurally related flavoproteins. This laboratory previously showed that Phe1395 was required to obtain the electron transfer properties and calmodulin (CaM) response normally observed in wild-type nNOS. Here we characterized the F1395S mutant of the nNOS flavoprotein domain (nNOSr) regarding its physical properties, NADP+ binding characteristics, flavin reduction kinetics, steady-state and pre-steady-state cytochrome c reduction kinetics, and ability to shield its FMN cofactor in response to CaM or NADP(H) binding. F1395S nNOSr bound NADP+ with 65% more of …

Franck-Condon Effects In Collision-Induced Electronic Energy Transfer: I2(E;V=1,2)+He,Ar, Pooja P. Chandra , '03, Thomas Alex Stephenson

Chemistry & Biochemistry Faculty Works

Collisions of I-2 in the E electronic state with rare gas atoms result in electronic energy transfer to the D, beta, and D-' ion-pair electronic states. Rate constants for each of these channels have been measured when I-2 is initially prepared in the J=55, v=1 and 2 levels in the E state. The rate constants and effective hard sphere collision cross sections confirm the trends observed when v=0 in the E state is initially prepared: He collisions favor population of the D state, while Ar collisions favor population of the beta state. Final state vibrational level distributions are determined by …

Synthesis, Relaxometric And Photophysical Properties Of A New Ph-Responsive Mri Contrast Agent: The Effect Of Other Ligating Groups On Dissociation Of A P-Nitrophenolic Pendant Arm, Mark Woods, Garry Kiefer, Simon G. Bott, Aminta Castillo-Muzquiz, Carrie Eshelbrenner, Lydie Michaudet, Kenneth Mcmillan, Siva D.K. Mudigunda, Doug Ogrin, Gyula Tircso, Shanrong Zhang, Piyu Zhao, A. Dean Sherry

Chemistry Faculty Publications and Presentations

Two gadolinium(III) chelates, GdNP-DO3A (1-methlyene-(p-NitroPhenol)-1,4,7,10-tetraazacycloDOdecane-4,7,10-triAcetate) and GdNP-DO3AM (1-methlyene(p-NitroPhenol)-1,4,7,10-tetraazacycloDOdecane-4,7,10-triacetAMide), containing a single nitrophenolic pendant arm plus either three acetate or three amide pendant arms were synthesized and characterized. The properties of the gadolinium, terbium, and dysprosium complexes of these ligands were examined as a function of pH. The extent and mechanism of the changes in water relaxivity with pH of each gadolinium complex was found to differ substantially for the two complexes. The water relaxivity of Gd(NP-DO3A) increases from 4.1 …

Carbon-Carbon Bond Formation Via O-Lithiointermediates, Julia Raymer

Masters Theses & Specialist Projects

The process of C-C bond formation via Directed ort/zo-Metalation (DoM) consists of two separate steps. Utilizing fractional equivalents of TMEDA in hydrocarbon solvents at 60°C, o-lithiation of anisole and dimethylaniline can be effected in >95% yields. The first step in the DoM process involves preparation of solid samples of these o-lithiointermediates. Completing the sequence, the second step concerns formation of a new arene-derivative bond at the reactive site. For this thesis the arene-derivative bond formed is to carbon. Various carbon electrophiles have been studied using different solvent systems, and results reveal a possible disconnect between the reaction conditions for the …

Examination Of Technologies For Student-Generated Work In A Peer-Led, Peer-Review Instructional Environment, Brian P. Coppola, Alan L. Kiste

Chemistry and Biochemistry

There is a growing literature demonstrating the effectiveness of using computer environments to assist students’ in visualizing science and mathematics concepts. However, with many of these computerized learning environments, students do not have the option of manipulating the environment. Instead, they are presented with pre-made visualizations. Enabling students to display their understanding through multiple representational forms is more interesting. In our peer-led, peer-review environment, students generate a complex, literature-based, multimedia text on which their final examination is based. However, there are great time and personnel costs in this design. Collaborating with SRI Inc., we are addressing these demands via the …

Eliminating Absorbing Interference Using The H-Point Standard Addition Method: Case Of Griess Assay In The Presence Of Interferent Heme Enzymes Such As Nos, Perera N. Indika, Mekki Bayachou

Chemistry Faculty Publications

Standard calibration methods used to determine trace analytes usually yield significant deviations from the actual analyte value in the presence of interferents in the assay media. These deviations become of particular concern when the concentration of the analyte is low, and when the results are used to draw mechanistic or kinetic conclusions, for instance in enzyme structure-function studies. In these circumstances, the H-point standard addition method (HPSAM) provides superior precision and accuracy. This method is developed here for the case of the spectrophotometric Griess assay used to determine nitrite in various enzymology investigations, such as nitrite determination in studies of …

Inside Unlv, Cate Weeks, Carol C. Harter, Diane Russell, Holly Ivy De Vore

Inside UNLV

No abstract provided.

46th Rocky Mountain Conference On Analytical Chemistry

Rocky Mountain Conference on Magnetic Resonance

Final program, abstracts, and information about the 46th annual meeting of the Rocky Mountain Conference on Analytical Chemistry, co-endorsed by the Colorado Section of the American Chemical Society and the Rocky Mountain Section of the Society for Applied Spectroscopy. Held in Denver, Colorado, August 1-5, 2004.

Capillary Liquid Chromatography Using Micro Size Particles, Yanqiao Xiang

Theses and Dissertations

High speed and/or high efficiency separations can be realized using small particles (~ 1 µm) in liquid chromatography (LC). However, due to the large pressure drop caused by small particles, conventional LC pumping systems cannot satisfy the pressure requirements needed to drive the mobile phase through the column. Use of ultrahigh pressure, elevated temperature, or both can overcome these pressure limitations and allow the use of very small particles for high speed and/or high efficiency separations.

In this dissertation, the use of ultrahigh pressures with and without elevated temperatures in capillary LC is described. Very fast separations of various samples …

The Catalytic Role Of Glutamate 151 In The Leucine Aminopeptidase From Aeromonas Proteolytica, Krzysztof P. Bzymek, Richard C. Holz

Chemistry Faculty Research and Publications

Glutamate 151 has been proposed to act as the general acid/base during the peptide hydrolysis reaction catalyzed by the co-catalytic metallohydrolase from Aeromonas proteolytica (AAP). However, to date, no direct evidence has been reported for the role of Glu-151 during catalytic turnover by AAP. In order to elucidate the catalytic role of Glu-151, altered AAP enzymes have been prepared in which Glu-151 has been substituted with a glutamine, an alanine, and an aspartate. The Michaelis constant (K_m) does not change upon substitution to aspartate or glutamine, but the rate of the reaction changes drastically in the following …

Collision-Induced Non-Adiabatic Transitions Between The Ion-Pair States Of Molecular Iodine: A Challenge For Experiment And Theory, T. V. Tscherbul, A. A. Buchachenko, M. E. Akopyan, S. A. Poretsky, A. M. Pravilov, Thomas Alex Stephenson

Chemistry & Biochemistry Faculty Works

The ion-pair states of molecular iodine provide a unique system for studying the efficiency, selectivity, and mechanisms of collision-induced non-adiabatic transitions. Non-adiabatic transitions between the first-tier ion-pair states in collisions with molecular partners and rare gases are analyzed and discussed. The qualitative features of the rate constants and product state distributions under single collision conditions are summarized and interpreted in terms of appropriate theoretical approaches. Two mechanisms for the non-adiabatic transitions are clearly identified. The first, operative for collisions involving molecular partners possessing permanent or transition electrostatic moments, is highly selective. It connects the initially prepared level in the E …

Environment-Induced Degradation And Crack-Growth Studies Of Candidate Target Materials: Annual Progress Report (May 2003 – May 2004), Ajit K. Roy

Transmutation Sciences Materials (TRP)

As indicated in the original proposal, the primary objective of this task was to evaluate the effect of hydrogen on environment-assisted cracking of candidate target structural materials for applications in spallation-neutron-target (SNT) systems such as accelerator production of tritium (APT) and accelerator transmutation of waste (ATW). The materials selected for evaluation and characterization were martensitic stainless steels including Alloy EP 823, HT-9, and Type 422 stainless steel. The susceptibility to stress corrosion cracking (SCC) of these materials were evaluated in neutral and acidic aqueous environments using smooth and notched tensile specimens under constant-load (CL) and slow-strain-rate (SSR) conditions. Further, the …

Probabilistic Disease Classification Of Expression-Dependent Proteomic Data From Mass Spectrometry Of Human Serum, Ryan H. Lilien, Hany Farid, Bruce R. Donald

Dartmouth Scholarship

We have developed an algorithm called Q5 for probabilistic classification of healthy vs. disease whole serum samples using mass spectrometry. The algorithm employs Principal Components Analysis (PCA) followed by Linear Discriminant Analysis (LDA) on whole spectrum Surface-Enhanced Laser Desorption/Ionization Time of Flight (SELDI-TOF) Mass Spectrometry (MS) data, and is demonstrated on four real datasets from complete, complex SELDI spectra of human blood serum.

Q5 is a closed-form, exact solution to the problem of classification of complete mass spectra of a complex protein mixture. Q5 employs a novel probabilistic classification algorithm built upon a dimension-reduced linear discriminant analysis. Our solution is …