Chemistry Commons^™

Reversed Chloroquine Molecules As A Strategy To Overcome Resistance In Malaria, David H. Peyton

Chemistry Faculty Publications and Presentations

This short review tells the story of how Reversed Chloroquine drugs (RCQs) were developed. These are hybrid molecules, made by combining the quinoline nucleus from chloroquine (CQ) with moieties which are designed to inhibit efflux via known transporters in the membrane of the digestive vacuole of the malaria parasite. The resulting RCQ drugs can have potencies exceeding that of CQ, while at the same time having physical chemical characteristics that may make them favorable as partner drugs in combination therapies. The need for such novel antimalarial drugs will continue for the foreseeable future.

Global Variations Of Hdo And Hdo/H2o Ratios In The Upper Troposphere And Lower Stratosphere Derived From Ace-Fts Satellite Measurements, William J. Randel, Elisabeth Moyer, Mijeong Park, Eric Jensen, Peter Bernath

Chemistry & Biochemistry Faculty Publications

High-quality satellite observations of water and deuterated water in the upper troposphere and lower stratosphere (UTLS) from the Atmospheric Chemistry Experiment Fourier transform spectrometer (ACE-FTS) are used to map global climatological behavior. Spatial and temporal variability in these data suggest that convection plays a significant role in setting water vapor isotopic composition in these regions. In many instances, enhancements in HDO/H₂O (i.e., δD) are closely tied to patterns of climatological deep convection and uncorrelated with water vapor, although convection appears to have different isotopic effects in different locations. The ACE-FTS data reveal seasonal variations in the tropics …

Chemiluminescent Reactions Catalyzed By Nanoparticles Of Gold, Silver, And Gold/Silver Alloys, Saqib Ul Abideen

Master's Theses and Doctoral Dissertations

Chemiluminescence (CL) reactions are catalyzed by metals nanoparticles, which display unique catalytic properties due to an increased surface area. The present study describes the catalytic effects of nanoparticles (NP) of silver, gold, and alloys of Au/Ag nanoparticles on the chemiluminescent reaction taking place between luminol and potassium ferricyanide. It was found that silver nanoparticles and alloy nanoparticles enhance the CL process when their sizes remained in the range of 30 nm to 50 nm. The data show that the intensity and rate of chemiluminescence were influenced by the mole fraction of gold and silver in the alloy. Data to this …

Reactivity Of Tri(2-Furyl)Phosphine (Pfu3) With [Mn2(Co)10–N(Ncme)N] (N = 0–2): X-Ray Structure Of Mer-[Mn(Co)3(Η1-C4H3O)(Pfu3)2], Santana Karmaker, Shishir Ghosh, Shariff E. Kabir, Daniel T. Haworth, Sergey V. Lindeman

Chemistry Faculty Research and Publications

In the search for new examples of systems that self-assemble into cyclic metal–organic architectures, the six isomers of X,Y′-bis(di(1H-pyrazolyl)methane)-1,1′-biphenyl, L_XY, and their silver(I) trifluoromethanesulfonate complexes were prepared. Five of the six silver complexes gave crystals suitable for single crystal X-ray diffraction, with only the microcrystalline derivative of 2,3′-bis(di(1H-pyrazolyl)methane)-1,1′-biphenyl, L₂₃, proving to be unsuitable for this analysis. Of the structurally characterized silver(I) complexes, that with L₂₂ showed an unusual trans-spanning chelating coordination mode to silver. At the same time the ligand was also bound to a second silver center …

Responsive Materials Via Diels-Alder Chemistry, Gregory Alan Strange

Master's Theses

The corrosion of infrastructure imposes a significant monetary cost, and at times human cost, upon society. Methods to improve corrosion resistance of materials are described herein which utilize the reversibility of the Diels-Alder reaction to impart thermal responsiveness upon materials. Such stimuli responsiveness can potentially play a role in self healing properties which lead to reduced cracking and thus increased corrosion protection.

Reversible Diels-Alder chemistry was utilized to manipulate the surface energy of glass substrates. Hydrophobic dieneophiles were prepared and attached to glass slides and capillaries to yield a nonwetting surface. Thermal treatment of the surfaces cleaved the Diels-Alder linkage, …

National Center For Nuclear Security, Veraun Chipman, Amanda Klingensmith, Cathy Snelson

NSTec UNLV Symposium

National Center for Nuclear Security (NCNS) Mission

•Chartered mission is to enhance the Nation’s verification and detection capabilities in support of nuclear arms control and nonproliferation through R&D activities at the NNSS
•Three focus areas
–Treaty Verification Technologies
–Nonproliferation Technologies
–Technical Nuclear Forensics

Progress And Perspective Of Fuel Cell Technology, Ming Hou, Bao-Lian Yi

Journal of Electrochemistry

Fuel cell, a clean and high-efficiency electrochemical power source, has being paid much attention worldwide recent years. In this paper, the progress and perspective of fuel cell technology are elucidated in detail. Fuel cells have been applied in some special fields such as spacecraft, shuttle and submarines. However, in the areas of transportation, stationary station and portable power source, fuel cells are still under demonstration due to the durability and cost problems. The reliability and surrounding survivability of fuel cells should be enhanced in the special application. Meanwhile, the durability and cost of fuel cells are the main issues to …

The Electrocatalytic Study Of Licoo2 In Air Electrode For Lithium-Air, Jun Gao, Wei Wu, Yan-Yan Tian, Yong Yang

Journal of Electrochemistry

The LiCoO₂ has been investigated as a new electrocatalyst for air electrodes using homemade lithium-air battery. The electrochemical performance and structural changes of the LiCoO₂ based composite air electrodes have been studied. The results of CV, XRD and charge-discharge tests show that the composite air electrodes composed of LiCoO₂ can greatly improve the discharge performance of lithium-air batteries. In particular when the composite air electrodes are charged to 4.1 V before further discharging, the obvious catalytic effects of LiCoO₂ are attributed to higher valence state of the Co element in LiCoO₂, esp. at charged …

Preparation And Electrochemical Performance Of Lifepo4/C By Spray Drying Method Assisted With Organic Template, Quan-Bing Liu, Yang-Mei Jiang, Hui-Yu Song, Shi-Jun Liao

Journal of Electrochemistry

In this work, the LiFePO₄/C composites were prepared by the spray drying and carbothermal method, and were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and galvanostatic charge-discharge measurements. The effects of the organic assisted templates on the morphologies and electrochemical properties of the LiFePO₄/C composites were investigated. The results showed that the morphology and microstructure of the composites could be tuned by incorporating with the different templates. The morphology of the composite appeared to be solid microspheres if no organic template was added, while porous microspheres, nest-like …

Synthesis And Electrochemical Performance Of Xlifepo4·Yli3V2(Po4)3 Composites, Ping-Ping Ma, Zhi-Jian Liu, Jian-Hua Xia, Yu Chen, Pu Hu, Zhi-Chao Lu, Ding-Guo Xia

Journal of Electrochemistry

A series of xLiFePO₄·yLi₃V₂(PO₄)₃ composites were systematically synthesized through solid state reactions by variations in the proportions of LiFePO₄ and Li₃V₂(PO₄)₃. The properties of the prepared compounds were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM) and electrochemical measurements. The capacity of 162.7 mAh/g at 0.2 C rate was obtained with the relatively good cycle stability and good conductivity for 0.95LiFePO₄·0.05Li₃V₂(PO₄)₃ due to more uniformed distributed and smaller particle sizes.

Preparation And Characterization Of Mno/Tin Anode For Lithium Ion Batteries, Gao-Jie Xu, Hai-Yan Yang, Peng-Xian Han, Li-Xue Zhang, Ke-Jun Zhang, Chuan-Jian Zhang, Yu-Hua Fan, Cai-Feng Bi, Guang-Lei Cui

Journal of Electrochemistry

Manganese titanate (MnTiO₃) powder was prepared via a sol-gel method using manganese acetate and tetrabutyl titanate as raw materials, and citric acid as a chelating agent. Through high temperature nitridation of MnTiO₃ powder in ammonia, the MnO/TiN composite was obtained. The phase structure, composition and morphology of the composites were characterized by XRD, SEM and EDS. The electrochemical properties of the composite electrodes were studied by performing cyclic voltammetry, galvanostatic charge and discharge, and electrochemical impedance spectroscopy tests. The MnO/TiN electrode delivered specific capacities of 394 mAh·g^-1 and 146 mAh·g^-1 at the current density of …

Temperature Effects On The Electron-Transfer Reactions Of Fe(Cn)63-/4- And Cytochrome C, Jing Tang, Lin Du, Xiao-Jian Xiao, Ning Zhang

Journal of Electrochemistry

Cyclic voltammetric and chronoamperometric techniques were employed to study the temperature effects on the electrochemical reaction of Fe(CN)₆^3-/4- by self-made thermostatic water bath electrochemical cell. The diffusion coefficient D and the formal heterogeneous electron-transfer rate constant k0 were calculated at different temperatures from 25 °C to 75 °C. In the Fe(CN)₆^3-/4- system, the DO values of Fe(CN)₆^3- were directly proportional to temperature, while DR of Fe(CN)₆^4- inversely proportional to temperature. The values of k^₀ decreased with the increase of temperature due possibly to the electrode passivation resulted from the decomposition of …

Electrochemical Fabrication Of The Ordered Polyaniline Nanowires Array, Yan-Xin Gao, Li-Chao Sun, Su-Yuan Xie, Kang Shi

Journal of Electrochemistry

The effects of electrochemical fabrication methods in different aniline concentrations on the morphologies of polyaniline, which was polymerized on the aligned-multi-walled carbon nanotubes electrode in H₂SO₄ or HClO₄ electrolyte solution, were investigated. It was demonstrated that the polyaniline nanowires would not be prepared by cyclic voltammotry, whereas the nanowires could be obtained by the potentiostatic method without forming the ordered array. Only when the aniline concentration in HClO₄ solution was high enough, the ordered polyaniline nanowires array could be fabricated by the constant current method.

Electrochemical Characterization Of (Phmgcl)2-Alcl3/Mixed Ether Electrolytes, Fei-Fei Wang, Yong-Sheng Guo, Jun Yang, Li-Yan-Na Nu, Jiu-Lin Wang

Journal of Electrochemistry

The (PhMgCl)₂-AlCl₃ salts were prepared and the electrochemical properties of (PhMgCl)₂-AlCl₃ electrolytes containing dimethoxyethane(DME)+THF, Diglyme(DG)+THF and Tetraglyme(TG)+THF solvents with different proportions on various metal electrodes were studied. Compared with (PhMgCl)₂-AlCl₃/THF, the (PhMgCl)₂-AlCl₃/DG+THF(3:2) solvents showed high ionic conductivity of 1.605×10^-3 S·cm^-1, good reversible Mg deposition behavior and anodic anti-oxidation performance with an electrochemical window wider than 2.8 V. In addition, the DG+THF mixed solvent could greatly lower the saturated vapor pressure by reducing from 23.46 kPa to 9.41 kPa, which suppresses volatilization of the …

Preparation And Hydrogen Evolution Properties Of Ni/Ag2O/Ruo2-Pt Cathodes, Shu Huang, Xue-Ming Li, Wu-Lin Li, Wen Wang

Journal of Electrochemistry

The Ni/Ag₂O/RuO₂-Pt composite cathode was prepared by sol-gel method using RuCl₃ and H₂PtCl₆ as raw materials. The effects of heat treatment conditions and AgNO₃ concentrations on hydrogen evolution properties were investigated. The morphology and composition of Ni/Ag₂O/RuO₂-Pt composite cathode have been characterized by XRD, XPS and SEM-EDS. It is demonstrated that the surface structure of Ni/Ag₂O/RuO₂-Pt composite cathode is more compact, with fewer cracks and larger surface roughness than pure nickel. At the conditions of 0.3 A·cm^-2, 90 ^oC, and …

Electrocatalytic Study Of Pseudomonas Aeruginosa Bte-1 Strain, Ping Zhou, En-Ren Zhang, Li Zhou, Guo-Wang Diao, Jun-Le Niu

Journal of Electrochemistry

The aim of the present study is to investigate the electrocatalytic activity of electricity-producing Pseudomonas aeruginosa BTE-1 strain under anaerobic conditions. Pseudomonas aeruginosa BTE-1 was inoculated into anaerobic three-electrode electrochemical cells, and the electrocatalytic activity was measured at poised potentials. HPLC and cyclic voltammetry were used to detect potential electron mediators in solutions. Experimental results showed that no detectable pyocyanine was excreted by P. aeruginosa BTE-1 strain in the anaerobic electrochemcial cells, and P. aeruginosa BTE-1 exhibited direct electrocatalytic activity through the formation of biofilm on the electrode surface which was induced by the electron transfer from the cells of …

Cycle Lifetime Investigation Of Nickel Electrode Prepared By Electrochemical Impregnation For Applications In Aerospace Nickel Hydrogen Cells, Hai-Chang Zhang, Li-Xin Tan, Cheng Guo, Wen-Cheng Ming, Xue-Ying Ren

Journal of Electrochemistry

In this paper, the effects of overcharge, charge-discharge C rate and pore size on cycle lifetime of 4.5’ electrochemical impregnated nickel electrode were investigated. In the case of the electrode was overcharged to 170% of nominal capacity, the initial capacity of the electrode could be maintained 2.7 Ah up to 150 cycles without deterioration and a discharge capacity of 1.7 Ah (remaining 63% of 2.7 Ah) could be delivered after 300 cycles. Without overcharge, more than 300 charge-discharge cycles could be realized without loss of capacity and a discharge capacity of electrode could be maintained about 76% of initial capacity …

Electrochemical Behavior Of Imidacloprid, Jie-Qiong Wang, Wang Zhang, Ming Chen, Guo-Wang Diao

Journal of Electrochemistry

The electrochemical behavior of imidacloprid（IDP）on glassy carbon electrode has been investigated by cyclic voltammetry. The result shows that the electrochemical reduction of IDP is irreversible and controlled by diffusion. At 25 ℃, the numbers of the electrons transferred of IDP in the electrochemical reaction are four. The diffusion coefficient of IDP is 2.44×10⁶ cm²·s^-1 and the diffusion activation energy is calculated to be 9.33 kJ·mol^-1.

Ag Nanoparticles Self-Assembled Films On Iron Surface And Their Inhibition Properties, Zhe Zhang, Ming-Zi Jia, Le Ruan

Journal of Electrochemistry

The Ag nanoparticles were prepared in aqueous solutions through a chemical reduction method and transferred from water phase to toluene phase with the protection of 1-dodecanethiol (DDT). The polished iron electrode was immersed in the DDT-protected metal nanoparticles toluene solutions to form DDT/Ag nanoparticles self-assembled mixed films. Electrochemical methods such as electrochemical impedance spectroscopy and polarization curve measurement were used to study the inhibition properties of the self-assembled films in the 0.5 mol·L^-1 H₂SO₄ solution. The appearance of elements such as S and Ag from the XPS data identified the presences of DDT and Ag nanoparticles.

Dissolved Oxygen Seawater Battery With Electrochemical Capacitance, Hai-Bo Xu, Yong-Hong Lu, Wei Zhang, Yan-Ting Yu, Chuan-Wei Yan, Ya-Ping Sun, Lian Zhong, Jian-Guo Liu, Yi Zheng, Bing Han, Yong-Liang Wang

Journal of Electrochemistry

A new concept of seawater battery with electrochemical capacitance (SWB-EC) has been proposed using carbon fibre brush (CFB) as the cathode material, and three testing prototypes have been made accordingly. The discharge performances of the CFB before- and after-oxidation and Mg alloy sacrifice anode were studied by cyclic voltammetry and constant current discharge tests under steady state conditions. Results show that the oxidized CFB exhibits the pseudo-capacitive characteristic and its activity of oxygen reduction reaction (ORR) in stirred seawater highly increases, comparing with the non-oxidized CFB. The open circuit potential of Mg alloy sacrifice anode is -1.74 V, having the …

Simultaneous Determinations Of Ascorbic Acid, Dopamine And Uric Acid At Ca/Gc Electrode, Ying Zhang, Wang Ren, Min-Jiao Li

Journal of Electrochemistry

The citric acid modified glassy carbon electrode (CA/GC) was constructed by potentiostatic technique and used for simultaneous determinations of ascorbic acid (AA), dopamine (DA) and uric acid (UA) by cyclic voltammetry (CV) and differential pulse voltammetry (DPV). The CA/GC electrode exhibits excellent electrocatalytic activity towards AA, DA and UA. The oxidation peaks are well separated with the potential differences between AA and DA, DA and UA, and AA and UA being 170, 130 and 300 mV, respectively, which is large enough to determine AA, DA and UA simultaneously. The catalytic peak currents obtained were linearly dependent on the concentrations of …

Detection Of Radioactive Isotopes From The Fukushima Daiichi Nuclear Power Plant In The Kittitas Valley Of Washington State, Randle Affholter, Michael Braunstein, Cesar Mendoza, Anne Johansen

Student Published Works

Following the Fukushima Daiichi nuclear power plant disaster in March, 2011, various radioactive isotopes were emitted from the plant [Ewing, 2011]. We hypothesized that emissions would bind to particulate matter, which then could be dispersed by wind currents and deposited across the planet. We analyzed an aerosol sample collected with a high volume cascade impactor in the Kittitas Valley of Washington state. NaI(Tl) gamma spectrometry revealed the presence of the isotopes ¹³²Te and ¹³¹I, consistent with the type of nuclear accident at Fukushima Daiichi.

Halocarbocyclization Entry Into The Oxabicyclo[4.3.1]Decyl Exomethylene-Δ-Lactone Cores Of Linearifolin And Zaluzanin A - Exploiting Combinatorial Catalysis, Sandeep K. Ginotra, Jacob A. Friest, David B. Berkowitz

David Berkowitz Publications

A streamlined entry into the sesquiterpene lactones (SQL) cores of linearifolin and zaluzanin A is described. Stereochemistry is controlled through transformations uncovered by ISES (In-Situ- Enzymatic-Screening). Absolute stereochemistry derives from kinetic resolution of 5- benzyloxypentene-1,2-oxide, utilizing a β-pinene-derived-Co(III)-salen. Relative stereochemistry (1,3-cis-fusion)is set via formal halometalation/carbocyclization, mediated by [Rh(O₂CC₃F₇)₂]₂/ LiBr. Subsequent ring-closing metathesis (RCM-Grubbs II) yields the title exomethylene-δ- lactone SQL-cores. In complementary fashion, RCM with Grubbs-I catalyst provides the oxabicyclo[3.3.1]nonyl-core of xerophilusin R and zinagrandinolide.

Dimensionality Selection In A Molecule-Based Magnet, Paul A. Goddard, Jamie L. Manson, John Singleton, Isabel Franke, Tom Lancaster, Andrew J. Steele, Stephen J. Blundell, Christopher Baines, Francis L. Pratt, Ross D. Mcdonald, Oscar E. Ayala-Valenzuela, Jordan F. Corbey, Heather I. Southerland, Pinaki Sengupta, John A. Schlueter

Chemistry and Biochemistry Faculty Publications

Gaining control of the building blocks of magnetic materials and thereby achieving particular characteristics will make possible the design and growth of bespoke magnetic devices. While progress in the synthesis of molecular materials, and especially coordination polymers, represents a significant step towards this goal, the ability to tune the magnetic interactions within a particular framework remains in its infancy. Here we demonstrate a chemical method which achieves dimensionality selection via preferential inhibition of the magnetic exchange in an S = 1/2 antiferromagnet along one crystal direction, switching the system from being quasi-two-to quasi-one-dimensional while effectively maintaining the nearest-neighbor coupling strength.

Additions And Corrections. Critical Perspective: Named Reactions Discovered And Developed By Women, Julie A. Olsen, Kevin M. Shea

Chemistry: Faculty Publications

New Information on Reactions not Described Previously

Professor Gerald Dyker informed us about another reaction unambiguously named for a woman. The Catellani reaction is named for Professor Marta Catellani from the University of Parma in Italy. Catellani earned her PhD at the University of Parma in 1971 and is currently a full professor and director of the Department of Organic and Industrial Chemistry.

Transient Ru-Methyl Formate Intermediates Generated With Bifunctional Transfer Hydrogenation Catalysts, Richard H. Perry, Kristen R. Brownell, Konstantin Chingin, Thomas J. Cahill Iii, Robert M. Waymouth, Richard N. Zare

Chemistry and Physics Faculty Articles

Desorption electrospray ionization (DESI) coupled to high-resolution Orbitrap mass spectrometry (MS) was used to study the reactivity of a (β-amino alcohol)(arene)RuCl transfer hydrogenation catalytic precursor in methanol (CH₃OH). By placing [(p-cymene)RuCl₂]₂ on a surface and spraying a solution of β-amino alcohol in methanol, two unique transient intermediates having lifetimes in the submillisecond to millisecond range were detected. These intermediates were identified as Ru (II) and Ru (IV) complexes incorporating methyl formate (HCOOCH₃). The Ru (IV) intermediate is not observed when the DESI spray solution is sparged with Ar gas, indicating that …

Hierarchical Templates And Their Application To Multimodal Porous Materials Fabrication, Bo Zhao

Theses and Dissertations

Hierarchical materials offer great promise for high-performance sensors and catalysis carriers. Well-defined hierarchically porous materials are promising candidates for a wide range of applications relating to biosensors, separations, drug delivery, surface-enhanced Raman scattering (SERS), etc. Research on synthetic methodologies is expanding. However, fabrication of hierarchical porous structures with tunable pore dimension and shape, controllable pore distribution and interconnectivity is still a challenging task in materials science. One of the main tasks of this work is to establish a facile and reliable approach of making well-defined hierarchically porous materials. Then, based on those multimodal porous structures, different functions and applications can …

Van Der Waals Density Functional Study Of Co2 Binding In Zeolitic Imidazolate Frameworks, Keith G. Ray, David Olmsted, Ning He, Yao Houndonougbo, Brian B. Laird, Mark Asta

Chemistry and Biochemistry Faculty Publications

The van der Waals density functional (vdW-DF) formalism is employed in a study of the binding energetics for CO2 in a set of five zeolitic imidazolate framework (ZIF) compounds. The ZIF structures investigated share the same RHO-type zeolite topology and metal atoms, but feature imidazolate linkers with different chemical functionalization. Three distinct binding sites are identified, for which the binding energies are found to show different dependencies on the functionalization of the linker molecules. The origin of the variations in the binding energies across the ZIF compounds is discussed through analyses of the binding geometries and charge-density distributions. A comparison …

Dynamics Of The Solvent Exchange Reaction Of Weakly Bound Organic Solvents To Group 6 Transition Metal Carbonyls And The Molybdenum Hexacarbonyl Mediated Pauson-Khand Reaction, Richard J. Gates

Theses and Dissertations

Many organometallic reactions are solvent-dependent, suggesting solvent molecules interact with reaction intermediates. Studies of the solvent exchange reaction of group 6 transition metal carbonyls with moderately binding ligands have provided insight into these interactions, however, studies of the mechanism for this reaction with weakly binding ligands have not been performed. Experiments were conducted on the nanosecond time scale in methylcyclohexane over the temperature range of 4 to 44 °C using Step Scan FTIR (SS FTIR) spectroscopy with weakly binding ligands benzene and mesitylene. Upon photolysis of the metal hexacarbonyls, the kinetically favored product (M(CO)5(solv)), decays following pseudo-first-order kinetics to the …

Tackling Teaching: Understanding Commonalities Among Chemistry, Mathematics, And Physics Classroom Practices., Samuel Pazicni, Karen A. Marrongelle, Warren Christensen

Chemistry

Abstract:

Education research in chemistry, mathematics, and physics tends to focus on issues inherent to the discipline, most notably content. At this time, little literature evidence exists that documents fruitful collaborations between education specialists across the STEM disciplines. This work seeks to unite the disciplines by investigating a common task: teaching. This study explores how discipline-specific practices influence the common act of reformed teaching pedagogy with a focus on the use of inquiry. We seek to identify commonalities among classroom teaching practices in these disciplines and contribute to the development of analytical tools to study STEM teaching.