Chemistry Commons^™

Atomic Structure And Magnetism Of Ordered And Disordered Al₀.₅Fe₀.₅₋ₓmnₓ Alloys, V. G. Harris, D. J. Fatemi, K. B. Hathaway, Q. Huang, Amitabh Mohan, Gary J. Long

Chemistry Faculty Research & Creative Works

The equiatomic FeAl alloy has been modified by partial substitution of Mn for Fe, and its magnetic and structural properties investigated by neutron diffraction (ND), x-ray absorption fine structure (XAFS) spectroscopy, Mössbauer spectroscopy (MS), and SQUID magnetometry both for the ordered (B2) and disordered states. The unit cell volume is measured to increase linearly with Mn concentration. XAFS measurements indicate local structural displacements occur at the Mn sites in both ordered and disordered states that may act to frustrate long-range magnetic order (LRMO). Although MS and ND show no evidence of LRMO, SQUID magnetometry indicates an induced movement in the …

Synthesis Of A Novel ??-Amino Acid Capable Of Stabilizing A 310-Helix Via Side-Chain Salt-Bridging, Reema K. Thalji

Honors Capstones

No abstract provided.

The Discovery-Oriented Approach To Organic Chemistry 1. Nitration Of Unknown Organic Compounds. An Exercise In 1H Nmr And 13C Nmr Spectroscopy For Sophomore Organic Laboratories, Ram Mohan, Sonia Mcelveen, Kostas Gavardinas, Jean Stamberger

Scholarship

Nitration is one of the most fundamental reactions in organic chemistry. However, the majority of the nitration experiments found in the standard lab textbooks are of the "cookbook" variety and convey none of the excitement associated with discovery in experimental chemistry. We have developed two simple nitration experiments that present the student with a puzzle and are a good exercise in ¹H NMR and ¹³C NMR spectroscopy. ¹³ C NMR spectroscopy is a powerful structure elucidation tool and yet not many examples of the use of ¹³C NMR spectroscopy in organic lab experiments can be found. The …

Gas Sparging And Humic Acid Sorption/Desorption, Masaki Sakakibara

Masters Theses

Partition coefficients (K_DOC) for sorption of PAHs and chlorinated benzenes to dissolved humic acids (HA) were measured using gas-sparging methodology. The resulting K_DOC values were significantly lower than the K_OW-based K_DOC values, which generally appear to provide reliable estimates for K_DOC values. The K_DOC values measured by gas sparging were also strongly influenced by the concentration of HA in solution, as measured by dissolved organic carbon content (DOC). Increasing DOC concentration consistently resulted in decreased K_DOC values for all compounds investigated. Previous studies have claimed that K_DOC values measured using …

Synthesis And Antimalarial Activity Of 11 Dispiro-1,2,4,5-Tetraoxane Analogues Of Wr 148999. 7,8,15,16-Tetraoxadispiro[5.2.5.2]Hexadecanes Substituted At The 1 And 10 Positions With Unsaturated And Polar Functional Groups, Yuxiang Dong, F. Hoffmann-Laroche Ltd., Jacques Chollet, Ronald Kaminsky, James K. Wood, Jonathan L. Vennerstrom

Chemistry Faculty Publications

Eleven novel dispiro-1,2,4,5-tetraoxanes 3 bearing unsaturated and polar functional groups were designed to enhance the oral antimalarial activity of the prototype tetraoxane 2 (WR 148999). With the exception of 3g and 3h, tetraoxanes 3 were available via the peroxidation of corresponding cyclohexanone derivatives in H2SO4/CH3CN. Tetraoxanes 3g and 3h were prepared by hydrolysis of ester tetraoxanes 3e and 3i, respectively. Five of the 11 tetraoxanes were inactive, but six tetraoxanes had IC₅₀ values of 6-26 nM against the K1 and NF54 strains of Plasmodium falciparum compared to corresponding IC₅₀ values of 28 and 39 nM for …

Kinetics Of The Photosubstitution Of Cis-Bis(Benzonitrile)Dichloroplatinum(Ii) In Chloroform, Eric M. Jaryszak, Son L. Phan, Patrick E. Hoggard

Chemistry and Biochemistry

Under 254 nm irradiation cis-[Pt(C6H5CN)2Cl2] is converted to H2PtCl6. Absorption of light by both the metal complex and the solvent contribute to the first step of this process, suggested to form HPt(C6H5CN) Cl3. A linear dependence of the reaction rate on light intensity appears to rule out chlorination by trichloromethyl radicals. However, at higher light intensities a higher order dependence on intensity develops, and under 313 nm irradiation is dominant, and a reaction between trichloromethyl radical and the excited state complex is proposed to account for this.

Structural And Kinetic Studies Of A Cisplatin-Modified Dna Icosamer Binding To Hmg1 Domain B*, Elizabeth R. Jamieson, Matthew P. Jacobson, Carmen M. Barnes, Christine S. Chow, Stephen J. Lippard

Chemistry: Faculty Publications

The high mobility group (HMG) domain is a DNA-binding motif found in the non-histone chromosomal proteins, HMG1 and HMG2, and some transcription factors. Experimental evidence has demonstrated that HMG-domain proteins can play a role in sensitizing cells to the anticancer drug cisplatin. Fluorescence resonance energy transfer (FRET) experiments were performed in the present study to investigate structural changes that accompany complex formation between the HMG domain B of HMG1 and a cisplatin-modified, 20-base pair double-stranded DNA probe containing fluorescein and rhodamine tethered at its two ends. The binding affinity of HMG1 domain B for the cisplatin-modified DNA probe was investigated …

Synthesis And Crystal Structure Of Tetrachloro (1,10-Phenanthroline) Platinum (Iv), Robert M. Granger Ii, Jill N. Granger, Kelly Del Campo, Molly B. Becherer, Phillip E. Fanwick

Virginia Journal of Science

We report the crystal structure determination of tetrachloro( l,10-phenan­throline)platinum(IV). X-ray data indicate there is little steric repulsion between the cx.-hydrogens on the phenanthroline ligand and the chloride ligands in the equatorial plane.

Electron Affinities Of The Oxides Of Aluminum, Silicon, Phosphorus, Sulfur, And Chlorine, Nicole R. Brinkmann, Gregory S. Tschumper, Henry F. Schaefer

Chemistry Faculty Research & Creative Works

The adiabatic electron affinities of five second row atoms (Al, Si, P, S, Cl) and their monoxides and dioxides were determined using six different densities functional or hybrid Hartree-Fock/density functional methods. The 15 species selected form a convenient closed set for which reliable experimental electron affinities exist for 13 of the species. Zero-point vibrational energy corrected electron affinities are also reported. Equilibrium geometries and vibrational frequencies were determined with each density functional method. The method based on the Becke exchange functional and the Lee-Yang-Parr correlation (BLYP) functional reproduced the experimental electron affinities most accurately, having an average absolute error of …

Hydrogen Bonding And Cooperative Effects In Mixed Dimers And Trimers Of Methanol And Trifluoromethanol: An Ab Initio Study, Ruben D. Parra, Xiao Cheng Zeng

Xiao Cheng Zeng Publications

Ab initio calculations are used to provide information on the mixed dimers and cyclic trimers of the methanol-trifluoromethanol system. In order to better understand the systems, the monomers and their corresponding dimers and trimers are also investigated. Molecular structures and harmonic frequencies are obtained at the B3LYP/6-311++G(d,p) level. Interaction energies are calculated with the MP2 and B3LYP methods using the 6-311++G(d,p), 6-311++G(2d,2p), and 6-311++G(3d,2p) basis sets for the dimers and heterodimers. The 6-311++G(d,p) basis set was used to calculate the …

Visible And Resonance Raman Spectra Of Low Valent Iron Porphyrins, Chathra De Silva, Kazimierz Czarnecki, Michael D. Ryan

Chemistry Faculty Research and Publications

The resonance Raman spectrum of Fe(TPP)²⁻ was obtained after the three-electron electrochemical reduction of Fe(TPP)(Cl). The coulometric reduction was carried out in the presence of bis(triphenylphosphoanylidine)ammonium chloride in DMF in order to avoid the formation of iron–σ-alkyl complexes. The resonance Raman spectrum of the intermediate oxidation states (Fe(TPP) and Fe(TPP)⁻) were consistent with previous work. The spectrum of the three-electron product, Fe(TPP)²⁻, obtained at 442 nm, was qualitatively similar to the two-electron reduced product, Fe(TPP)⁻, with an intense ν₂ band at 1537 cm⁻¹. The high frequency bands generally decreased in …

Monomer-Dimer Equilibrium Constants Of Rna In The Dimer Initiation Site Of Human Immunodeficiency Virus Type 1, Michael F. Shubsda, Mark P. Mcpike, Jerry Goodisman, James C. Dabrowiak

Chemistry - All Scholarship

The genome of the human immunodeficiency virus (HIV) exists as a dimer of two identical RNA molecules hydrogen bonded to each other near their 5' ends. The dimer, known to be important for viral infectivity, is formed by two monomers interacting through a stem-loop structure called the dimer initiation site (DIS). An initially formed intermediate, the "kissing" dimer, is unstable and rearranges to the stable, duplex form. In this report we use nondenaturing polyacrylamide gel electrophoresis to measure the monomer-dimer equilibrium constant of three RNA sequences, 41-, 27-, and 19-mers, located in the DIS of the MAL isolate of HIV-1. …

Novel Carbon-Carbon Bond Oxidative Cleavage Of Hexabenzyl-Hexaazaisowurtzitane By N-Buono And (Nh4)2ce(No3)6, Xiao-Pei Guan, Hong Yan, Jian-Guang Sun, Yong-Zhong Yu

Publications and Research

Treatment of 2,4,6,8,10,12-hexabenzyl-2,4,6,8,10,12-hexaazatetracyclo-[5.5.0.05,9.03,11]dodecane with n-butyl nitrite or ammonium cerium nitrate results in novel C(1)-C(7) oxidative cleavage to give 1,3,4,5,7,8-hexabenzyl-cis-cisoid-cis-hexahydro-1H,5H-diimidazolinium[4,5-b:4′,5′-e]pyrazine dinitrate.

Activated Carbon Produced From Agricultural Residues, Daniel W. Armstrong, V. J. Flanigan, William Joseph James, Jui-Lung Li, Kimber L. Rundlett

Chemistry Faculty Research & Creative Works

A process for producing activated carbon from agricultural residues by heating the residues to a temperature in the range of about 250° C. to about 550° C. to volatilize organic compounds in the residues and to carbonize the residues and further heating to activate the carbonized residues. Activated carbon produced from agricultural residues.

Monte Carlo Study Of The Capacitance Of The Double Layer In A Model Molten Salt, Douglas Henderson, Dezso Boda, Kwong-Yu Chan

Faculty Publications

Monte Carlo simulations are reported for charged hard spheres at high density near a charged wall. This system is a simple model for a molten salt double layer. Unfortunately, the reduced temperatures that correspond to experiment are very small. This results in a large Boltzmann factor. As a result, we are unable to obtain meaningful results for such low values and report results only for moderately low values of the reduced temperature. Even so, our results should be a useful benchmark. Further, we are able to give a qualitative answer to an interesting question. We find that at low temperatures …

Bulletin 4357 - Fertilisers For Pastures On Sandy Soils Of The Swan Coastal Plain, K. W. Angell

Bulletins 4000 -

When newly cleared for agriculture, the sandy soils of the Swan Coastal Plain were acutely deficient in phosphorus (P), nitrogen (N), and the trace elements copper ( Cu) and zinc (Zn) and sometimes molybdenum (Mo). Phosphorus deficiency was overcome by applying single superphosphate. Trace element deficiencies were overcome by adding Cu, Zn and Mo to superphosphate during manufacture, allowing P, Cu, Zn and Mo to be applied to the pasture in the one operation.

It was subsequently found that low sulphur (S) and potassium (K) were limiting production and persistence of subterranean clover-based pastures on the sandy soils of the …

Infrared Cavity Ringdown Spectroscopy Of Methanol Clusters: Single Donor Hydrogen Bonding, R. A. Provencal, J. B. Paul, K. Roth, C. Chapo, R. N. Casaes, R. J. Saykally, G. S. Tschumper, H. F. Schaefer

Chemistry Faculty Research & Creative Works

Infrared cavity ringdown laser absorption spectroscopy has been used to study the O-H stretching vibrations of jet-cooled methanol clusters in direct absorption. Rovibrational bands for (CH₃OH)₂, (CH₃OH)₃, and (CH₃OH)₄ have been measured. Both bonded and free O-H stretches were measured for the dimer, indicating that its structure is linear. Five bands were assigned to the methanol trimer, indicating the presence of a second cyclic isomer in the molecular beam. A detailed study of the free O-H stretching region shows that methanol clusters larger than dimer must exist in cyclic …

Molecular Dynamics Study Of A Phase-Separating Fluid Mixture Under Shear Flow, Ryoichi Yamamoto, Xiao Cheng Zeng

Xiao Cheng Zeng Publications

Molecular dynamics simulation is carried out to study domain structures and rheological properties of a two-dimensional phase-separating binary fluid mixture under shear flow. In the early stage of the phase separation, anisotropic composition fluctuations appear immediately after the quench. As the domain grows, the anisotropy in the composition fluctuations increases. The quenched system eventually reaches a dynamical steady state, in which anisotropic domain structures are preserved. In the steady state, the shortest characteristic length scale R⊥ of domains decreases with increasing shear rate γ̇ as R⊥∼γ̇^-1/3. Stringlike domain structures are observed in the strong shear regime, …

Formation Free Energy Of Clusters In Vapor-Liquid Nucleation: A Monte Carlo Simulation Study, K.J. Oh, Xiao Cheng Zeng

Xiao Cheng Zeng Publications

The formation free energy of clusters in a supersaturated vapor is obtained by a constrained Monte Carlo technique. A key feature of this approach is to set an upper limit to the size of cluster. This maximum cluster size serves essentially as an extra thermodynamic variable that constrains the system. As a result, clusters larger than the critical cluster of nucleation in the supersaturated vapor can no longer grow beyond the limiting size. Like changing the overall density of the system, changing the maximum cluster size also results in a different supersaturation and thereby a different formation free energy. However, …

Tga/Ftir Studies On The Thermal Degradation Of Some Polymeric Sulfonic And Phosphonic Acids And Their Sodium Salts, David D. Jiang, Qiang Yao, Michael A. Mckinney, Charles Wilkie

Chemistry Faculty Research and Publications

The thermal degradation of poly(vinyl sulfonic acid) and its sodium salt, poly(4-styrenesulfonic acid) and its sodium salt, and poly(vinylphosphonic acid) was studied by a combination of techniques, including TGA/FTIR, to identify the volatile products which were evolved during the degradation as well as analysis of the residues which were obtained in order to propose a mechanism for the degradation. The motivation for the work was to attempt to identify new monomers which could be graft copolymerized onto a polymer in order to improve the thermal stability of that polymer.

Study Of Localized Corrosion Of Metals By Using The Electrochemical Techniques With Spatial Resolution, Chang-Jian Lin, Xiang-Dong Zhuo, Zu-De Feng, Rong-Gui Du, Zhao-Wu Tian

Journal of Electrochemistry

The electrochemical inhomogeneities at interface of metal/solution play an important and often controlling role in localized corrosion of metals. The traditional electrochemical techniques involving potential, current density or ac impedance measurements over bulk specimens can only provide average and general information of the interface. Thus, the development of in situ imaging techniques is essential for further characterizing electrochemical inhomogeneities at the metal/solution interface of localized corrosion system. The electrochemical techniques with spatial resolution,including scanning single micro electrode, scanning double micro electrodse and scanning micro chemical probes are reviewed. The effects of electrochemical inhomogeneities on the corrosion behavior, and the mechanism …

Electrochemical Surface Characterization Of Titanium Alloy(Ti-6al-4v), Jian-Zhong Chen, Qing-Liang Gao, Zhong-Yi Wang, Wen-Jing Xue

Journal of Electrochemistry

With its low density and high strength ratio, titanium alloy(Ti₆Al₄V) has become one of the most important materials both in the fields of aerospace and biomedical assays. Recently, titanium alloy was used as the implantation materials in human body because of its biocompatibility. The elecrochemical impedance techniques were then used to investigate the corrosion behavior of this material in hydrochloride and sulfuric acid solutions. A comparison between impedance spectra and anodic polarization over the correlated range of applied voltage confirms that AC impedance data can be used as a powerful tool for surface characterization of titanium …

Some Effects Of Co On The Electrochromic Properties Of NioXHY Film, Xiao-Yan Cao, Wen-Hu Zhang, Hua-Tang Yuan, Wan-Lin Zhang, Yin-Nong Lin, Zuoxiang Zhou, Yunshi Zhang

Journal of Electrochemistry

Some effects of Co addition upon the electrochromic characteristics of a nic-kel hydroxide film were studied. The films were electrodeposited on both polished Ni plate and conductive ITO glass. The electrochemical behaviors were investigated using the film on Ni plate by linear potential sweep, a.c. impedance, and anodic polarization curves for OER(oxygen evolution reaction). It was found that Co can lower the working voltage and raise the oxygen overpotential, but has little effect on the reaction kinetics. It was also found that the Co can improve the optical properties of the electrochromic film.

Kinetic Study Of Electrooxidation Of Benzene, Xin-Sheng Zhang, Ping Ding, Ying-Chun Dai, Wei-Kang Yuan

Journal of Electrochemistry

A reaction kinetic study for electrochemical oxidation of benzene was performed on a PbO₂ rotating disk electrode in 1 mol/L H₂SO₄ aqueous solution. The reaction orders, the activation energies and transfer coefficient were measured, and the kinetic expression was obtained.

Pitting Corrosion Of Ni-Based Alloy In Thiosulfate-Ion Containing Chloride Solutions, Yung-Fa Lee, Ting-Yu Wang, Wen-Ta Tsai

Journal of Electrochemistry

The effect of thiosulfate ion on the pitting corrosion behavior of Ni-Based Alloy 690 in chloride solution was investigated. In plain sodium thiosulfate solution, Alloy 690 was immune to pitting corrosion. However, the addition of low concentration of sodium thiosulfate can enhance the initiation of pitting corrosion of Alloy 690. Nevertheless, inhibition of pitting corrosion was observed at high concentration of addition.

Effect Of Stress On Electrochemical Behaviour Of Various Thermal History Zones And Different Phase Structures On The Weldment For Low Alloy Steel, Yin-Shun Wu, De-Yu Liu, Bei Cao, Feng-Li Wang, Zhi Fang, Lin Zhang, Zheng-Rong Zhang, Hai Yang

Journal of Electrochemistry

The electrochemical behaviour of various thermal history zones on the weldment for steel 16Mn and also of the ferrite, pearlite in various zones was measured by use of a self-developed measuring technique for investigating the electrochemicl behaviour of single and mixed phase structures in metal materials. Especially the effect of stress on this electrochemical behaviour was investigated. The results showed that by comparison with non-stress condition, the free corrosion potential of the various thermal history zones and of the ferrite, pearlite under stress condition was shifted in negative direction, correspondingly their free corrosion current density was increased, the free corrosion …

Structural And Electrochemical Studies On Todorokite/Vernadite As Cathodes For Rechargeable Lithium Ion Batteries, Wei Chu, De-Yao Liu, Jin-Kua You, Yong Yang, Zu-Geng Lin

Journal of Electrochemistry

XRD, TEM, ICP, low scan-rate CV and charge/discharge tests were carried out for the studies on the structural and electrochemical behavior of a prepared 3 V manganese oxide cathode for rechargeable lithium ion batteries.XRD analysis revealed that the cathode sample is mainly composed of tunneled Todorokite and layered Vernadite. TEM investigation confirmed that the morphology of the sample is a laminated construction with approximate 10nm layer space. The reversibility of Li⁺ removal/intercalation and structural stability of this sample framework to lithium insertion are good in CV and charge/discharge tests. The discharge capacities were found to be about 129mAh/g obtained …

Studies Of Electrochemical Characteristics Of Pasted Nickel Hydroxide Electrode With Surface Deposited Cobalt, Xian-You Wang, Yun-Shi Zhang, Jie Yan, Zheng Zhu, Hua-Tang Yuan, De-Ying Song

Journal of Electrochemistry

The surface of the spherical nickel hydroxide particles used as an active material in pasted nickel electrodes is surface-deposited with cobalt. This paper investigated the effects of the amount of cobalt deposit on the characteristics of nickel hydroxide electrode. The performances of the electrode, such as discharge capacity, utilization of active material and reversibility of Ni(OH)₂/NiOOH redox reaction, were studied by comparing the charging/discharging curves and cyclic voltammograms. The mechanism of action of cobalt deposits has been described in terms of the electrochemical impedance spectroscopy of nickel hydroxide electrode.

Study On Ionic Conductivity Of A Novel Solid State Electrolyte, Ying-Xin Zhao, Chang-Yan Liu

Journal of Electrochemistry

Various novel predominantly lithium-ion-conducting solid state electrolytes were described, which had high conductivity at room temperature. It comprised low-melting-point eutectic lithium salts in which a small amount of an single ion polyeletrolyte poly(lithium acrylate) was dissolved to rubberize them. The effects of the eutectic and polymer features upon the ionic conductivity were discussed.

Electrohydrodimerization Of Fumarodinitrile On Liquid Gallium Electrode, He Wei, Huang Ying, Sheng-Tao Zhang

Journal of Electrochemistry

Electrohydrodimerization (EHD) of fumarodinitrile on liquid gallium electrode can take place not only in hydrotropic solution of tetraethylammonium p-toluenesulphonate (TEA-PTS), but also in aqueous solution containing low concentration of strong surfactants, such as TritonX-100. In solution without organic surfactant, FDN yields a single two-electron reduction wave corresponding to the formation of a saturated monomer called as butanedinitrile. If some TEA-PTS or TritonX-100 is added into the solution, the original two-electron wave is splitted into two continuous single-electron reduction wave and corresponding EHD of fumarodinitrile is obtained.