Chemistry Commons^™

The Influence Of The Sputtering Power On The Structural And Electrochemical Properties Of Tin Oxide Films, Min-Zhen Cai, Jie Song, Ming-Sen Zheng, Qi-Hui Wu, Sun-Tao Wu, Quan-Feng Dong

Journal of Electrochemistry

Tin oxide films were deposited on silicon substrates at room temperature using the radio frequency(RF) magnetron sputtering with different sputtering power.The influence of sputtering power upon the crystal structure,surface morphology and electrochemical properties of tin oxide films were then investigated.The XRD and SEM results illustrate that the phase of tin oxide thin films changed from amorphous to crystalline and the grain size augments with the increase of the sputtering power.The constant current charge and discharge cycle tests imply that the initial irreversible capacity loss of Li/tin oxide batteries increase and which capacity decrease as the sputtering power increases.The sputtering power …

A Quick Charge System For The Agv Automatic Guided Vehicle, Chun-Yuan Pian, Jun-Feng Liu

Journal of Electrochemistry

The quick charge system used for AGV automation guidance vehicle nickel hyarogen driving force battery,witch can test and compute parameter in real time during charging process,judge logically,control the charging process and adopt a depolarization to discharge in order to improve charging efficiency.

Study On The Binding Mode Of In(Bpy)Cl3·H2O With Dna By The Methods Of Electrochemistry, Jun-Wei Wang, Jian-Guo Ren, Bao-Juan Zhou, Xiao-Ling Gao, Yan-Ni Tian

Journal of Electrochemistry

The complex In(bpy)Cl₃·H₂O was synthesized.The binding mode of the complex with DNA was studied by the methods of cyclic voltammetry(CV),differential pulse voltammetry and ac impedance in the buffer Tris-HCl(pH=7.2).A quasi-reversible redox wave for the central Indium ion from the cyclic voltammograms was shown at a PG electrode.It has been found that after the complex acted with DNA,The complex's formal potential negatively shifted from-0.696 V to-0.717 V,the values of the reduction peak current and apparent diffusion coefficient decreased significantly.The results of differential pulse voltammetry were the same as cyclic voltammetry,and the electrochemical reaction resistance values increased from …

Potentiometric Response Of Glucose On Mno2-GoX Carbon Paste Electrode, Cai-Juan Wang, Xiao-Ya Hu

Journal of Electrochemistry

A novel carbon paste electrode(CPE) modified with MnO₂ and glucose oxidase(GO_x), is reported. Different factors, such as the effect of supporting electrolyte, pH of solutions,various paste glues, the amount of MnO₂ and temperature, which may influence the determination of H₂O₂ and glucose were tested to optimize. Based on above, potentiometric determination of glucose was achieved in neutral solution and at 35 ℃, the electrode gave a response of 36.12～34.62 mV/pG lucose between 2.0×10^-5 mol·L-1 and 5.2×10^-3 mol·L^-1 with a detection limit of 3.3×10^-6 mol·L^-1. Moreover, this kind …

Square Wave Stripping Voltammetric Behaviors Of Rutin On Glassy Carbon Electrode And Its Application, Jun Hua, Xiao-Ying He, Fang Liao, Qing-Tao Zhu

Journal of Electrochemistry

The electrochemical behaviors of rutin(Rt) at glassy carbon electrode were studied by square wave stripping voltammeter in the presence of 0.1mol·L^-1HAc-NaAc buffer solution(pH=3.0).The sensitive oxidation peak of rutin was observed and which potential peak is 0.46V(vs.SCE).The experimental parameters,such as pH value,deposition potential and deposition time were investigated and selected.The peak currents were proportional to the concentration of rutin in range of 5.0×10^-8 mol·L^-1~1.0×10^-6mol·L^-1,and the linear regression coefficient equaled 0.99799,the detection limit was 1.1×10-8 mol·L^-1.This method was applied to the determination of rutin content in tablet with satisfactory results.

Effect Of Au At Different States On Electrocatalytic Performance Of Pd Catalyst For Oxidation Of Formic Acid, Xin Wang, Ya-Wen Tang, Tian-Hong Lu

Journal of Electrochemistry

Using liquid-reduction or complex-redution method,four catalysts,i.e,the Au/C,Pd/C,Pd-Au/C-T and Pd-Au/C-H were preparated and which electroanalytic activities and stabilities for the oxidation of formic acid were compares.It was found that the Au/C catalyst has no electrocatalytic activity,and the Pd/C catalyst possesses the good electrocatalytic performance for the oxidation of formic acid.The addition of Au into the Pd/C catalyst can increase the electrocatalytic activity and stability.Especially,the electrocatalytic activity and stability of the Pd-Au/C-T catalyst with the alloy of Pd and Au are better than that of the of the Pd-Au/C-H catalyst,in which,Pd and Au do not form the alloy.The investigation of its reason …

Ab Initio Calculation Of Carbon Clusters. Ii. Relative Stabilities Of Fullerene And Nonfullerene C24, Wei An, Nan Shao, Satya S. Bulusu, Xiao Cheng Zeng

Xiao Cheng Zeng Publications

Chemical stabilities of six low-energy isomers of C₂₄ derived from global-minimum search are investigated. The six isomers include one classical fullerene (isomer 1) whose cage is composed of only five- and six-membered rings (5/6-MRs), three nonclassical fullerene structures whose cages contain at least one four-membered ring (4-MR), one plate, and one monocyclic ring. Chemical and electronic properties of the six C₂₄ isomers are calculated based on a density-functional theory method (hybrid PBE|PBE functional and cc-pVTZ basis set). The properties include the nucleus-independent chemical shifts (NICS), singlet-triplet splitting, electron affinity, ionization potential, and gap between the highest occupied molecular …

Electronic And Magnetic Properties Of Endohedrally Doped Fullerene Mn@C60: A Total Energy Study, Guangping Li, Renat F. Sabirianov, Jing Lu, Xiao Cheng Zeng, Wai-Ning Mei

Xiao Cheng Zeng Publications

We perform total energy calculations on a manganese atom encapsulated inside a C₆₀ cage using density functional theory with the generalized gradient approximation through three optimization schemes and along four paths inside the cage. We find that when Mn is located in the central region, its electronic and magnetic properties are not exactly the same as those of a free Mn atom due to weak coupling between Mn and the cage. As Mn is shifted toward to the edge, the total energy and spin start to change significantly when Mn is situated about one-third of the way between the …

Cobalt Oxide Surface Chemistry: The Interaction Of Coo(1 0 0), Co3O4 (1 1 0), And Co3O4 (1 1 1) With Oxygen And Water, Sarah C. Petitto, Erin M. Marsh, Gregory A. Carson, Marjorie Langell

Marjorie A. Langell Publications

Cobalt oxides comprise two readily accessible cation oxidation states: Co²⁺ and Co³⁺, which are thermodynamically competitive under common ambient conditions, and redox mechanisms connecting the two states are largely responsible for their success in partial oxidation catalysis. In our studies, CoO(1 0 0), Co₃O₄ (1 1 0), and Co₃O₄ (1 1 1) single crystal substrates have been investigated with X-ray photoelectron spectroscopy (XPS), high-resolution electron energy loss spectroscopy (HREELS), and low energy electron diffraction (LEED) for their surface reactivity toward O₂ and H₂O and for their stability under …

4-(4-Chlorophenyl)-5-[1-(4-Chlorophenyl)-2-Methyl-2-Nitropropyl]-1,2,3-Selenadiazole, A. Marx, S. Saravanan, S. Muthusubramanian, V. Manivannan, Nigam Rath

Chemistry & Biochemistry Faculty Works

In the title compound, C18H15Cl2N3O2Se, the selenadiazole ring makes dihedral angles of 49.87 (3) and 55.70 (3)° with the two benzene rings. The dihedral angle between the two benzene rings is 11.90 (5)°. In the crystal structure, intra­molecular C-H...O and C-H...Se inter­actions and inter­molecular C-H...O, C-H...Cl and C-H...N inter­actions are observed.

Modeling, Simulation, And Experiments Of Coating Growth On Nanofibers, C. B. Clemons, P. Hamrick, J. Heminger, K. L. Kreider, G. W. Young, A. Buldum, Edward A. Evans, G. Zhang

Chemical, Biomolecular, and Corrosion Engineering Faculty Research

This work is a comparison of modeling and simulation results with experiments for an integrated experimental/modeling investigation of a procedure to coat nanofibers and core-clad nanostructures with thin film materials using plasma enhanced physical vapor deposition. In the experimental effort, electrospun polymer nanofibers are coated with metallic materials under different operating conditions to observe changes in the coating morphology. The modeling effort focuses on linking simple models at the reactor level, nanofiber level and atomic level to form a comprehensive model. The comprehensive model leads to the definition of an evolution equation for the coating free surface around an isolated …

Quenching Of Highly Vibrationally Excited Pyrimidine By Collisions With Co4, Jeremy A. Johnson, Andrew M. Duffin, Brian J. Hom, Karl E. Jackson, Eric T. Sevy

Faculty Publications

Relaxation of highly vibrationally excited pyrimidine (C4N2H4) by collisions with carbon dioxide has been investigated using diode laser transient absorption spectroscopy. Vibrationally hot pyrimidine (E'=40,635 cm^-1) was prepared by 248-nm excimer laser excitation, followed by rapid radiationless relaxation to the ground electronic state. The nascent rotational population distribution (J=58–80) of the 0000 ground state of CO2 resulting from collisions with hot pyrimidine was probed at short times following the excimer laser pulse. Doppler spectroscopy was used to measure the CO2 recoil velocity distribution for J=58–80 of the 0000 state. Rate constants and probabilities for collisions populating these CO2 rotational states …

Ozone Exposure In A Mouse Model Induces Airway Hyperreactivity That Requires The Presence Of Natural Killer T Cells And Il-17, Paul B. Savage, Muriel Pichavant, Sho Goya, Everett H. Meyer, Richard A. Johnston, Hye Y. Kim, Ponpan Matangkasombut, Ming Zhu, Yoichiro Iwakura, Rosemarie H. Dekruyff, Stephanie A. Shore, Dale T. Umetsu

Faculty Publications

Exposure to ozone, which is a major component of air pollution, induces a form of asthma that occurs in the absence of adaptive immunity. Although ozone-induced asthma is characterized by airway neutrophilia, and not eosinophilia, it is nevertheless associated with airway hyperreactivity (AHR), which is a cardinal feature of asthma. Because AHR induced by allergens requires the presence of natural killer T (NKT) cells, we asked whether ozone-induced AHR had similar requirements. We found that repeated exposure of wild-type (WT) mice to ozone induced severe AHR associated with an increase in airway NKT cells, neutrophils, and macrophages. Surprisingly, NKT cell-deficient …

The Decomposition Of Yba₂Cu₃O₇₋Δ Doped Into Ba₂Yruo₆, H. A. Blackstead, William B. Yelon, M. Kornecki, M. P. Smylie, P. J. Mcginn, Jinbo Yang, Qingsheng Cai, William Joseph James

Physics Faculty Research & Creative Works

One of the persistent criticisms of claims for observation of superconductivity in Ba2YRu1−uCuuO6 (O6) is that the diamagnetism is actually due to the decomposition of the material into YBa2Cu3O7−delta and other phases. We report a series of experiments in which YBa2Cu3O7−delta is doped into Ba2YRuO6 and carried through a series of sintering steps which were followed by magnetization, neutron diffraction, and scanning electron microscopy/microprobe measurements. It was found that the dopant YBa2Cu3O7−delta decomposed and failed to reform with cooling. It is concluded that the O6 phase is the stable high-temperature phase. The Cu released from the Y123 decomposition doped the …

Colossal Positive Magnetoresistance In A Doped Nearly Magnetic Semiconductor, Rongwei Hu, Karin Jessica Thomas, Yong Jae Lee, Thomas J. Vogt, Eun Sang Choi, Vesna F. Mitrovic, Raphäel P. Hermann, Fernande Grandjean, Paul C. Canfield, Jong Woo Kim, Alan I. Goldman, Cedomir Petrovic

Chemistry Faculty Research & Creative Works

We report on a positive colossal magnetoresistance (MR) induced by metallization of FeSb₂, a nearly magnetic or “Kondo” semiconductor with 3d ions. We discuss the contribution of orbital MR and quantum interference to the enhanced magnetic field response of electrical resistivity.

Dirubidium Digallium Oxide Bis(Orthoborate), Robert W. Smith, Chunhua Hu, Christopher D. Despain

Chemistry Faculty Publications

The title compound, Rb2Ga2O(BO3)2, is part of the homologous series A2Ga2O(BO3)2 (A = Na, K, Rb and Cs). The structure contains pairs of gallium-centered tetrahedra connected through a shared oxygen vertex. Orthoborate triangles connect the basal vertices of the tetrahedra, forming a three-dimensional network with voids occupied by rubidium ions.

C–N Bond Rotation And E–Z Isomerism In Some N-Benzyl-N-Methylcarbamoyl Chlorides: A Dft Study, Michael Horwath, Vladimir Benin

Chemistry Faculty Publications

The current report presents the first theoretical study of the restricted CN bond rotation in carbamoyl chlorides. Several N-benzyl-N-methylcarbamoyl chlorides were investigated, with varying pattern of substitution in the aromatic ring. Optimizations and frequency calculations were conducted employing DFT at the B3LYP/6-31+G(d) level of theory. Each of the studied structures exhibits a pair of rotamers (s-Z and s-E), generated upon rotation around the C(O)N bond. The s-E isomer is the global minimum in every case, but the preference for it is usually less than 1 kcal/mol. Two possible transition state structures were identified …

Discrete Sums For The Rapid Determination Of Exponential Decay Constants, Michael A. Everest, Dean B. Atkinson

Chemistry Faculty Publications and Presentations

Several computational methods are presented for the rapid extraction of decay time constants from discrete exponential data. Two methods are found to be comparably fast and highly accurate. They are corrected successive integration and a method involving the Fourier transform (FT) of the data and the application of an expression that does not assume continuous data. FT methods in the literature are found to introduce significant systematic error owing to the assumption that data are continuous. Corrected successive integration methods in the literature are correct, but we offer a more direct way of applying them which we call linear regression …

Evaluation Of Cs/Sr Waste Form For Long Term Storage And Disposal, Gary Cerefice

Waste Forms Campaign (TRP)

The goal of this project is to examine the potential long term performance of the proposed aluminosilicate waste/storage form for the isolation and eventual direct disposal of the cesium and strontium separated from recycled nuclear fuel. In the first phase of this work, researchers will investigate the sintering procedure to prepare the drum-like aluminosilicate waste/storage form from the as-received aluminosilicate powder, and then examine the basic physical properties, phase structure and microstructure of the sintered aluminosilicate with /without mixing solution with several ppm Cs/Sr. In the second phase, researchers will evaluate the interaction of the proposed waste form with structural …

Structure And Thermochemistry Of Disulfide-Oxygen Species, Shyamala Pravin Pillai

Theses

Sulfur compounds are known to form aerosols that can counteract the greenhouse effect, and recent studies suggest that aerosols can also contribute to global warming; sulfur species are also known as major contributors to acid rain. Both of these atmospheric chemistry interactions involve SO₂, which is formed by oxidation of sulfur hydrocarbons and H₂S. This study describes the structure, internal rotor potentials, bond energies and determines thermochemical properties (Δ_fH°, S° and Cp(T)) on the S-S bridge system in the sulfur bridged molecules CH₃SSOH, CH₃SS(=O)H, HSSOH, HSS(=O)H and CH₃SSOCH …

A Dynamic Bayesian Network Approach To Protein Secondary Structure Prediction, Xin-Qiu Joe Yao, Huaigiu Zhu, Zhen-Su She

Chemistry Faculty Publications

Background

Protein secondary structure prediction method based on probabilistic models such as hidden Markov model (HMM) appeals to many because it provides meaningful information relevant to sequence-structure relationship. However, at present, the prediction accuracy of pure HMM-type methods is much lower than that of machine learning-based methods such as neural networks (NN) or support vector machines (SVM).

Results

In this paper, we report a new method of probabilistic nature for protein secondary structure prediction, based on dynamic Bayesian networks (DBN). The new method models the PSI-BLAST profile of a protein sequence using a multivariate Gaussian distribution, and simultaneously takes into …

Strictosidine Synthase: Mechanism Of A Pictet-Spengler Catalyzing Enzyme, Justin J. Maresh, Lesley Ann Giddings, Anne Friedrich, Elke A. Loris, Santosh Panjikar, Bernhardt L. Trout, Joachim Stöckigt, Baron Peters, Sarah E. O'Connor

Chemistry: Faculty Publications

The Pictet-Spengler reaction, which yields either a β-carboline or a tetrahydroquinoline product from an aromatic amine and an aldehyde, is widely utilized in plant alkaloid biosynthesis. Here we deconvolute the role that the biosynthetic enzyme strictosidine synthase plays in catalyzing the stereoselective synthesis of a β-carboline product. Notably, the rate-controlling step of the enzyme mechanism, as identified by the appearance of a primary kinetic isotope effect (KIE), is the rearomatization of a positively charged intermediate. The KIE of a nonenzymatic Pictet-Spengler reaction indicates that rearomatization is also rate-controlling in solution, suggesting that the enzyme does not significantly change the mechanism …

New Extracellular Resistance Mechanism For Cisplatin, Corey R. Centerwall, Deborah J. Kerwood, Jerry Goodisman, Bonnie B. Toms, James C. Dabrowiak

Chemistry - All Scholarship

The HSQC NMR spectrum of ¹⁵N-cisplatin in cell growth media shows resonances corresponding to the monocarbonato complex, cis-[Pt(NH₃)₂(CO₃)Cl]^-, 4, and the dicarbonato complex, cis-[Pt(NH₃)₂(CO₃)₂]^-2, 5, in addition to cisplatin itself, cis-[Pt(NH₃)₂Cl₂], 1. The presence of Jurkat cells reduces the amount of detectable carbonato species by (2.8 ± 0.7) fmol per cell and has little effect on species 1. Jurkat cells made resistant to cisplatin reduce the amount of detectable carbonato species by (7.9 ± 5.6) …

Electrical, Structural, And Chemical Properties Of Semiconducting Metal Oxide Nanofiber Yarns, A. F. Lotus, E. T. Bender, E. A. Evans, R. D. Ramsier, D. H. Reneker, George G. Chase

Chemical, Biomolecular, and Corrosion Engineering Faculty Research

The electrical, structural, and chemical properties of twisted yarns of metal-oxide nanofibers, fabricated using a modified electrospinning technique, are investigated in this report. In particular, synthesized zinc oxide and nickel oxide yarns having diameters in the range of 4-40 mu m and lengths up to 10 cm were characterized, whose constituent nanofibers had average diameters of 60-100 nm. These yarns have one macroscopic dimension for handling while retaining some of the properties of nanofibers. (C) 2008 American Institute of Physics.

Preparation And Characterization Of 3 Nm Magnetic Niau Nanoparticles, Bethany J. Auten, B. P. Hahn, G. Vijayaraghavan, K. J. Stevenson, Bert D. Chandler

Chemistry Faculty Research

Using PAMAM dendrimers as nanoparticle templates, a synthetic route to prepare 3 nm magnetic NiAu nanoparticles was developed. Aqueous solutions of hydroxyl-terminated generation 5 PAMAM dendrimers in 25 mM NaClO₄ were shown to bind aqueous Ni^II. Coreduction of Ni^II and Au^III salts yielded bimetallic dendrimer stabilized nanoparticles, which were extracted into toluene with decanethiol. Characterization of the resulting monolayer protected clusters (MPCs) with transmission electron microscopy and UV–visible, atomic absorption, and X-ray photoelectron spectroscopies suggested that the MPCs had substantial surface enrichment in Au. Superconducting quantum interference device (SQUID) measurements at 5 K show the …

Critically Evaluated Thermochemical Properties Of Polycyclic Aromatic Hydrocarbons, María Roux, Manuel Temprado, James Chickos, Yatsuhisa Nagano

Chemistry & Biochemistry Faculty Works

No abstract provided.

Monolayer-Protected Nanoparticle Film Assemblies As Platforms For Controlling Interfacial And Adsorption Properties In Protein Monolayer Electrochemistry, Andrew F. Loftus, Katelyn P. Reighard, Susanna A. Kapourales, Michael C. Leopold

Chemistry Faculty Publications

Assembled films of nonaqueous nanoparticles, known as monolayer-protected clusters (MPCs), are investigated as adsorption platforms in protein monolayer electrochemistry (PME), a strategy for studying the electron transfer (ET) of redox proteins. Modified electrodes featuring MPC films assembled with various linking methods, including both electrostatic and covalent mechanisms, are employed to immobilize cytochrome c (cyt c) for electrochemical analysis. The background signal (non-Faradaic current) of these systems is directly related to the structure and composition of the MPC films, including nanoparticle core size, protecting ligand properties, as well as the linking mechanism utilized during assembly. Dithiol-linked films of Au225(C6)75 are …

Probing The Electronic And Structural Properties Of Doped Aluminum Clusters: Mal12- (M=Li, Cu, And Au), R. Pal, Li-Feng Cui, Satya S. Bulusu, Hua-Jin Zhai, Lai-Sheng Wang, Xiao Cheng Zeng

Xiao Cheng Zeng Publications

Photoelectron spectroscopy (PES) is combined with theoretical calculations to investigate the electronic and atomic structures of three doped aluminum clusters, MAl₁₂^- (M=Li, Cu, and Au). Well-resolved PES spectra have been obtained at two detachment photon energies, 266 nm (4.661 eV) and 193 nm (6.424 eV). Basin-hopping global optimization method in combination with density-functional theory calculations has been used for the structural searches. Good agreement between the measured PES spectra and theoretical simulations helps to identify the global minimum structures. It is found that LiAl₁₂^- (C_5v) can be viewed as replacing a surface Al …

Modulation Of Water Exchange In Europium(Iii) Dota–Tetraamide Complexes Via Electronic Substituent Effects, S. James Ratnakar, Mark Woods, Angelo J.M. Lubag, Zoltan Kovacs, A. Dean Sherry

Chemistry Faculty Publications and Presentations

The chemical exchange saturation transfer (CEST) efficiency for a series Eu³⁺-based tetraamide complexes bearing p-substituents on a single coordinating pendant arm is highly sensitive to water exchange rates. The CEST effect increases in the order Me < MeO < F ∼ CO₂^tBu < CN ≪ H. These results show that CEST contrast can be modulated by changes in electron density at a single ligating atom, and this forms the basis of creating imaging agents that respond to chemical oxidation and reduction.

Magnetic Properties Of La 0.6 Sr 0.4 Mno 3 Thin Films On Srtio 3 And Buffered Si Substrates With Varying Thickness, A. K. Pradhan, D. Hunter, T. Williams, B. Lasley-Hunter, R. Bah, H. Mustafa, R. Rakhimov, J. Zhang, D. J. Sellmyer, E. E. Carpenter, D. R. Sahu, J. -L. Huang

Chemistry Publications

La0.60Sr0.40MnO3 (LSMO) thin films of varying thickness from 12 to 55 nm were deposited using the pulsed-laser deposition technique onto single-crystalline SrTiO3 (STO) and STO-buffered Si substrates. The Tc of LSMO filmsgrown on STO-buffered Si substrates decreases faster than films directly grown on STO with decreasing film thickness. The LSMO/STO film with thickness of 55 nm shows Tc at about 360 K, which is close to the bulk value, whereas TcLSMO film on STO-buffered Si film of similar thickness is reduced to 320 K. This difference is attributed to the strain and interfacial disorders in LSMO film on STO/Si. The …