Chemistry Commons^™

Development Of A Biosensor For Investigating Membrane Curvature Sorting, Joshua C. Black

Electronic Theses and Dissertations

The physical structure of cellular membranes plays a critical role in lipid and protein sorting. A novel biosensor was developed to probe the influence of curvature on sorting. This biosensor mimics large, two-dimensional membranes in dynamic equilibrium, achieves high spatial resolution between curvature and molecules of interest, and has high sensitivity, enough for single particle detection. The biosensor consists of continuous supported lipid bilayer formed over nanoparticles (40 to 200 nm diameter) deposited on a glass substrate. The nanoparticles determine the extent of curvature. This biosensor is the first to observe large-scale 2-dimensional diffusion of biomolecules on a supported lipid …

Isosteric And Nonisosteric Base Pairs In Rna Motifs: Molecular Dynamics And Bioinformatics Study Of The Sarcin–Ricin Internal Loop, Marek Havrila, Kamila RéBlová, Craig L. Zirbel, Neocles B. Leontis, JiřÍ ŠPoner

Chemistry Faculty Publications

The sarcin-ricin RNA motif (SR motif) is one of the most prominent recurrent RNA building blocks that occurs in many different RNA contexts and folds autonomously, that is, in a context-independent manner. In this study, we combined bioinformatics analysis with explicit-solvent molecular dynamics (MD) simulations to better understand the relation between the RNA sequence and the evolutionary patterns of the SR motif. A SHAPE probing experiment was also performed to confirm the fidelity of the MD simulations. We identified 57 instances of the SR motif in a nonredundant subset of the RNA X-ray structure database and analyzed their base pairing, …

Probing Vibrationally Mediated Ultrafast Excited-State Reaction Dynamics With Multireference (Caspt2) Trajectories, Patrick Z. El-Khoury, Saju Joseph, Igor Schapiro, Samer Gozem, Massimo Olivucci, Alexander N. Tarnovsky

Chemistry Faculty Publications

Excited-state trajectories computed at the complete active space second-order perturbation theory (CASPT2) reveal how vibrational excitation controls the molecular approach to the intersection space that drives the photodissociation of a prototypical halogenated methyl radical, namely CF2I. Translating the Franck-Condon structure along the ground-state CASPT2 vibrational modes in this system followed by propagating the displaced structures in the first excited doublet state simulates specific vibrational excitations and vibrationally mediated dynamics, respectively. Three distinct situations are encountered: the trajectories (i) converge to an energetically flat segment of the intersection space, (ii) locate a segment of the intersection space, and (iii) access a …

Substrate-Dependent Dynamics Of Udp-Galactopyranose Mutase: Implications For Drug Design, Leonardo Boechi, Cesar Augusto F. De Oliveira, Isabel Da Fonseca, Karina Kizjakina, Pablo Sobrado, John J. Tanner, J. Andrew Mccammon

Chemistry Faculty Research & Creative Works

Trypanosoma cruzi is the causative agent of Chagas disease, a neglected tropical disease that represents one of the major health challenges of the Latin American countries. Successful efforts were made during the last few decades to control the transmission of this disease, but there is still no treatment for the 10 million adults in the chronic phase of the disease. In T. cruzi, as well as in other pathogens, the flavoenzyme UDP-galactopyranose mutase (UGM) catalyzes the conversion of UDP-galactopyranose to UDP-galactofuranose, a precursor of the cell surface b-galactofuranose that is involved in the virulence of the pathogen. The fact that …

The Catalytic Behaviour Of Nanoag@Montmorillonite Composite Materials, Martina Karlíková, Libor Kvítek, Robert Prucek, Aleš Panáček, Jan Filip, Jirí Pechoušek, Nathaniel F. Adegboyega

Chemistry and Chemical Engineering Faculty Publications

The preparation of nanoAg@montmorillonite composite materials and their catalytic activity is reported in this article. The nanoAg@montmorillonite composite materials were prepared by the adsorption of silver NPs, with an average size about 30 nm, from their aqueous dispersion onto two types of montmorillonite with different chemical composition. Silver NPs were prepared via modified Tollens process, which involves the reduction of [Ag(NH 3)2]+complex cation by maltose. The amount of silver NPs anchored onto the MMT surfaces was determined by UV-VIS spectroscopy; the decrease in absorbance of the dispersion after the adsorption was monitored. Prepared nanocomposite materials were subsequently characterized by means …

Effects Of Pd On Catalysis By Au: Co Adsorption, Co Oxidation, And Cyclohexene Hydrogenation By Supported Au And Pd−Au Catalysts, Timothy Ward, L. Delannoy, Ruth Hahn, Shane Kendell, Christopher J. Pursell, C. Louis, Bert D. Chandler

Chemistry Faculty Research

Incorporating small amounts of Pd into supported Au catalysts has been shown to have beneficial effects on selective hydrogenation reactions, particularly 1,3-butadiene hydrogenation and the hydrogenation of nitroaromatics, especially p-chloronitrobenzene. Appropriate Pd incorporation enhances hydrogenation activity while maintaining the desirable high selectivity of supported Au catalysts. To better understand this phenomenon, a series of alumina- and titania-supported Au and dilute Pd–Au catalysts were prepared via urea deposition–precipitation. The catalysts were studied with infrared spectroscopy of CO adsorption, CO oxidation catalysis, and cyclohexene hydrogenation catalysis with the goal of understanding how Pd affects the catalytic properties of Au. CO adsorption …

Cytochrome P450 Family 1 Inhibitors And Structure-Activity Relationships, Jiawang Liu, Jayalakshmi Sridhar, Maryam Foroozesh

Faculty and Staff Publications

With the widespread use of O-alkoxyresorufin dealkylation assays since the 1990s, thousands of inhibitors of cytochrome P450 family 1 enzymes (P450s 1A1, 1A2, and 1B1) have been identified and studied. Generally, planar polycyclic molecules such as polycyclic aromatic hydrocarbons, stilbenoids, and flavonoids are considered to potentially be effective inhibitors of these enzymes, however, the details of the structure-activity relationships and selectivity of these inhibitors are still ambiguous. In this review, we thoroughly discuss the selectivity of many representative P450 family 1 inhibitors reported in the past 20 years through a meta-analysis.

Microbial Natural Products: Molecular Blueprints For Antitumor Drugs, Lesley Ann Giddings, David J. Newman

Chemistry: Faculty Publications

Microbes from two of the three domains of life, the Prokarya, and Eukarya, continue to serve as rich sources of structurally complex chemical scaffolds that have proven to be essential for the development of anticancer therapeutics. This review describes only a handful of exemplary natural products and their derivatives as well as those that have served as elegant blueprints for the development of novel synthetic structures that are either currently in use or in clinical or preclinical trials together with some of their earlier analogs in some cases whose failure to proceed aided in the derivation of later compounds. In …

A Simple Inexpensive Method For The Rapid Testing Of The Photocatalytic Activity Of Self Cleaning Surfaces, Andrew Mills, James Hepburn, David Hazafy, Christopher O'Rourke, Josef Krysa, Michal Baudys, Martin Zlamal, Hana Bartkova, Claire Hill, Kim Winn, Morten Simonsen, Erik Sogaard, Suresh Pillai, Nigel Leyland, Rachel Fagan, Frank Neumann, Christina Lampe, Tobias Graumann

Articles

A rapid semi-quantitative, inexpensive method,using a simple digital scanner and an indicator ink, suitable for use in the laboratory, or in the field, for assessing the photocatalytic activity of commerical photocatalytic self-cleaning materials such as glass, is described. The repeatability of the current method is found to be hight and better than many of the previously reported ISO photocatalyst tests.

Nitroxide-Functionalized Graphene Oxide From Graphite Oxide, Yazmin I. Avila-Vega, Cesar C. Leyva-Porras, Marcela Mireles, Manuel Quevedo-Lopez, Javier Macossay-Torres, Jose Bonilla-Cruz

School of Integrative Biological & Chemical Sciences (Formerly Dept. of Chemistry)

A facile method for preparing functionalized graphene oxide single layers with nitroxide groups is reported herein. Highly oxidized graphite oxide (GO=90.6%) was obtained, slightly modifying an improved Hummer’s method. Oxoammonium salts (OS) were investigated to introduce nitroxide groups to GO, resulting in a one-step functionalization and exfoliation. The mechanisms of functionalization/exfoliation are proposed, where the oxidation of aromatic alcohols to ketone groups, and the formation of alkoxyamine species are suggested. Two kinds of functionalized graphene oxide layers (GOFT1 and GOFT2) were obtained by controlling the amount of OS added. GOFT1 and GOFT2 exhibited a high interlayer spacing (d0001 = 1.12nm), …

Mri Characterization Of Radiation Necrosis In An Animal Model: Time To Onset, Progression, And Therapeutic Response, Xiaoyu Jiang

All Theses and Dissertations (ETDs)

Radiation necrosis is a severe, but late occurring type of injury to normal tissue, within and surrounding a radiation treatment field, which can lead to significant complications for neurooncology patients. Radiation necrosis is difficult to distinguish from recurrent tumor by either neurologic examination or clinical imaging protocols. Concerns for the development of radiation necrosis often limit therapeutic radiation doses. Current treatment options for radiation necrosis are limited. The development of solutions to these clinical challenges has been hampered by an appropriate animal model of radiation necrosis.

With a novel mouse model of radiation necrosis developed in our lab employing a …

Synthesis Of Environmentally-Friendly Polyurethane Dispersions Based On Soybean Oil- Derived Polyols And Their Applications In Advanced Water-Based And Uv-Cure Coatings, Senthikumar Rengasamy

Master's Theses and Doctoral Dissertations

Polyurethane dispersions (PUD) have established themselves as most versatile polymeric binder in coating, adhesive, sealant, and elastomer industries. Like any other polymers, PUDs also have certain limitations, such as hydrolytic stability, water resistance, and oil resistance. In order to develop these properties, two different polyol families were synthesized. The first polyol can be used in ambient curable systems, and the second can be utilized in ultraviolet radiation cure coatings. For ambient curable systems polyether chemistry based soy-polyol was developed from epoxidized soy fatty acid methyl ester (ESFAME). The cationic ring opening of oxirane oxygen groups from ESFAME resulted in polyol …

Laser Vaporization Methods For The Synthesis Of Metal And Semiconductor Nanoparticles; Graphene, Doped Graphene And Nanoparticles Supported On Graphene, Parichehr Afshani

Theses and Dissertations

The major objective of the research described in this dissertation is the development of new laser vaporization methods for the synthesis of metal and semiconductor nanoparticles, graphene, B- and N-doped graphene, and metal and semiconductor nanoparticles supported on graphene. These methods include the Laser Vaporization Controlled Condensation (LVCC) approach, which has been used in this work for the synthesis of: (1) gold nanoparticles supported on ceria and zirconia nanoparticles for the low temperature oxidation of carbon monoxide, and (2) graphene, boron- and nitrogen-doped graphene, hydrogen-terminated graphene (HTG), metal nanoparticles supported on graphene, and graphene quantum dots. The gold nanoparticles supported …

On Molecular Origin Of Mass-Independent Fractionation Of Oxygen Isotopes In The Ozone Forming Recombination Reaction, Mikhail V. Ivanov, Dmitri Babikov

Chemistry Faculty Research and Publications

Theoretical treatment of ozone forming reaction is developed within the framework of mixed quantum/classical dynamics. Formation and stabilization steps of the energy transfer mechanism are both studied, which allows simultaneous capture of the delta zero-point energy effect and η-effect and identification of the molecular level origin of mass-independent isotope fractionation. The central role belongs to scattering resonances; dependence of their lifetimes on rotational excitation, asymmetry; and connection of their vibrational wave functions to two different reaction channels. Calculations, performed within the dimensionally reduced model of ozone, are in semiquantitative agreement with experiment.

Synthesis Of Pani/Nihcf Nanocomposite Particles And Eqcm Measurement Of Ion Exchange Properties In Solutions Containing Cd2+, Yu-Jiao Yang, Xiao-Gang Hao, Xu-Li Ma, Zhong-De Wang, Zhong-Lin Zhang, Nian-Chen Han

Journal of Electrochemistry

The PANI/NiHCF nanocomposite particles were synthesized on the CNTs-modified Pt substrate by one-step co-polymerization using cyclic voltammetry. Electrochemical quartz crystal microbalance (EQCM) technique was adopted to investigate the polymerization process of the nanocomposite particles and the mechanism of ion exchange in aqueous solution containing Cd²⁺． The morphology and structure of the as-prepared composite particles were characterized by scanning electron microscope (SEM), transmission electron microscope (TEM), and Fourier transform infrared spectroscopy (FT-IR). Combined with cyclic voltammetry (CV) and energy dispersive spectroscopy (EDS), the electrochemical behavior and the mechanism of ion exchange were also investigated in electrolytes of Cd^{2+ …}

Anaerobic Biotransformation Of Environmental Pollutants Stimulated By Electric Field: Electron-Transfer Mechanisms And Application Examples, Chun-Hua Feng, Dao-Hai Xie, Yun-Meng Pang, Tao Han, Chao-Hai Wei

Journal of Electrochemistry

The ability of some microorganisms to accept electrons from an electrode for the reduction of terminal electron acceptors in anaerobic environments has attracted growing interest on the electric field-stimulated biological reduction technology, which may open new possibility for the sustainable wastewater treatment and bioremediation in the field of environmental engineering. Here, we reviewed the extracellular electron transfer mechanism which is thought to play a key role in determining the feasibility and efficiency for the anaerobic biotransformation of environmental pollutants. Possible mechanisms that may be involved in bioelectrochemical reactors (BERs) with biocathodes include indirect electron transfer via hydrogen generated from water …

Electrochemically Switched Separation Of Yttrium Ion Using Electroactive Nickel Hexacyanoferrate Thin Films In Rare Earth Metal Solution, Hao Zhang, Xiao-Gang Hao, Zhong-De Wang, Zhong-Lin Zhang, Xu-Li Ma, Yi-Bing Li, Shi-Bin Liu

Journal of Electrochemistry

Electroactive nickel hexacyanoferrate (NiHCF) thin films were synthesized by cathodic deposition and investigated as electrochemically switched ion exchange (ESIX) materials for the separation of Y³⁺ from aqueous solutions. In 0.1 mol·L^-1 Y(NO₃)₃ solution, cyclic voltammetry (CV) combined with electrochemical quartz crystal microbalance (EQCM) technique was used to investigate the electroactivity, reversibility of the film electrodes and the mechanism of ion exchange. The electrochemical behavior of NiHCF film electrodes was also compared with that in Sr(NO₃)₂ solutions. The ion selectivity of the film was investigated in 0.1 mol·L^-1 solutions containing [Y(NO_{3 …}

A Comparative Study In Pretreatments Of Acid Chemical Wastewater By Electrochemical Oxidation And Ozonation, Han-Shui Liu, Su Yu, Shao-Ping Tong, Chun-An Ma

Journal of Electrochemistry

Under the condition of keeping certain acidity, the pretreatment efficiency of an acid chemical wastewater (pH 0.85) by electrochemical oxidation was compared with that by ozonation. The results showed that the electrochemical oxidation pretreatment could obtain a better result than the ozonation at pH 0.85. After the addition of 2 g·L^-1 NaCl and with the electrochemical oxidation pretreatment at 30 mA·cm^-2, the removal rate of chemical oxygen demand (CODCr) reached 43.4%, and the value of biochemical oxygen demand/chemical oxygen demand (BOD₅/COD_Cr) also increased from 0.034 to 0.14 in 20 minutes, indicating significantly improvement …

Electrocatalytic Properties Of The Keggin-Type Co(Ii)-Substituted Heteropolyanion Pw11O39Co(Ii)(H2O)5-, Bin Wang, Chong-Tai Wang, Ying-Jie Hua, Jin-Yuan Liu, Liang-Fei Zheng

Journal of Electrochemistry

The electrochemical properties of the Keggin-type Co(II)-substituted heteropolyanion PW₁₁O₃₉Co(II)(H₂O)^5- (PW₁₁Co), as well as the electrocatalytic properties of PW₁₁Co towards the anodic oxidations of H₂O₂ and CH₃OH were studied using the electrochemical methods such as cyclic voltammetry and AC impedance spectroscopy in this paper. An electrocatalytic mechanism of PW₁₁Co as an anodic medium was also proposed. It was found that PW₁₁Co showed a pair of pseudo-reversible redox peaks at the potentials of 1.367 V/1.266 V, corresponding to the redox responses of …

An Investigation Of Photocatalytic Degradation Reactions Of Pollutants By Combination Of (Photo)Electrochemical Measurements, Wen-Hua Leng, Hong-Qiao Zhu

Journal of Electrochemistry

Semiconductor photocatalysis plays a critical role in the environment protection and future energy development. (Photo)electrochemical measurements are powerful tools for studying the kinetics and mechanism of photocatalytic reactions, since photo-carriers, as reactants of photocatalytic reactions, are involved in the interfacial transfer and recombination of semiconductor/electrolyte interface. This review describes the part of our recent results regarding aqueous photocatalytic decontamination obtained by these methods, and the focus of future work in this field is suggested.

Preparation Of Benzoquinone From Phenol By Electrooxidation, Dong-Fang Niu, Cheng-Kai Yu, Xin-Sheng Zhang

Journal of Electrochemistry

The benzoquinone was prepared from phenol by electrooxidation in an H-type cell with cation exchange membrane, in which lead plates were used both as an anode and a cathode, while H₂SO₄ was used as a supporting electrolyte. The effects of current density, concentration of sulphuric acid, concentrations of benzoquinone in electrolyte and extractant on the yields and efficiencies of electrolysis were investigated. Under the optimized conditions of current density being 4 A·dm^-2, concentration of sulphuric acid 1 mol·L^-1, passed charge 3.2 A·h, the yield and current efficiency of benzoquinone could reach 68% and …

Continuous Electroextraction And Concentration Technology, Qiong Ren, Wen Liao, Zu-Cheng Wu

Journal of Electrochemistry

Electrodeionization process combined electrodialysis with ion exchange provides a method to produce pure water and ultrapure water due to the ions accumulated in the resin instantaneously to reduce the system resistance. Meanwhile, large numbers of hydrogen ions and hydroxyl ions are dissociated by water hydrolysis, thus, the ion exchange resins are in-situ regenerated electrochemically. This technology has been utilized to retrieve useful ions which are enriched in the concentrated compartment from a dilute solution. This hybrid process is consequently developed as a new type of extraction and concentration technology and has been gradually employed in the recoveries of heavy metals, …

Experimental Design Methodology Applied To The Oxidation Of Quinolines In Aqueous Medium By Electro-Fenton Process, Souhaila Trabelsi Souissi, Nihal Oturan, Nizar Bellakhal, Mehmet A. Oturan

Journal of Electrochemistry

The degradation behavior of 8-hydroxyquinoleine sulfate (8-HQS), a model molecule of quinolines, was studied in an aqueous medium by electro-Fenton process using a carbon felt cathode and a platinum anode. The great oxidation ability of this process is due to a large production of hydroxyl radical (OH) by electrochemically induced Fenton’s reagent (H₂O₂, Fe²⁺). Hydroxyl radicals are very powerful oxidizing agents which react on organics up to complete mineralization. A factorial experimental design was used for determining the operating parameters on the degradation of 8-HQS in an aqueous medium. The results showed that the …

Generation And Formal Analysis Of Algorithmic Fractals In Hyperspaces, Minglei Xu, Dr. Robert P. Burton

Journal of Undergraduate Research

n-D fractals, where n> 4, have long been under scrutiny for their mathematical properties and artistic values. Multi-dimensional space filling curves, for instance, are a focus for contemporary topologists. Notable works in this area include the uses of quaternions, commutative hyper-complex calculus, and, most recently, doubling processes. However, all these discoveries have been limited to algebraic fractals such as the Mandelbrot set and the Julia sets. Algorithmic fractals are equally interesting since they serve as bridges connecting chaos theory to well studied formal language theory.1 2-D and 3-D algorithmic fractals are conventionally generated and analyzed using L-systems and iterated function …

Basic Principles And Applications Of Secm In Metal Corrosion, Fa-He Cao, Yan Xia, Wen-Juan Liu, Lin-Rong Chang, Jian-Qing Zhang

Journal of Electrochemistry

Scanning electrochemical microscopy (SECM) is chemical microscopy with higher spatial resolution. After 24 years of development, SECM has been widely applied in mapping and kinetics study of heterogeneous electron transfer in localized processes at solid-liquid or liquid-liquid interfaces. The fundamentals and recent advances of SECM in corrosion applications are described, including SECM mapping and kinetics on localized corrosion of metal or coating. Research work of SECM in corrosion by our group is also introduced. Future applications of SECM in corrosion are highlighted.

Applications Of Spectroscopic Ellipsometry In Corrosion Investigation, Ling-Jie Li, Yu-Ling He, Jing-Lei Lei, Sheng Tao Zhang

Journal of Electrochemistry

As a highly-sensitive and non-destructive in situ technique, spectroscopic ellipsometry has been widely applied in corrosion investigation to acquire the dynamic information of the “electrode-medium” interface during corrosion. This paper lays out some representative demonstrations in several established optical models used to interpret data obtained with spectroscopic ellipsometry in corrosion investigation. In addition, the latest trends in development of this technique are analyzed.

An Investigation Of Thin Films Formed On Zinc By Spectroscopic Ellipsometry, Juan Zuo, Ying Chen, Chang-Jian Lin, Andreas Erbe

Journal of Electrochemistry

The formation of natural oxide films on polycrystalline zinc surface, the growth of natural oxide films in different atmospheres, as well as the electrochemical process of metal zinc in alkaline carbonate solution, studied recently by using spectroscopic ellipsometry in our group, are introduced. The objective of this paper is to outline that the optical, electrical properties, the change and growth kinetics of zinc metal oxide film on the surface can be investigated by in-situ and ex-situ ellipsometry, which makes significant sense to evaluate the overall performance of zinc oxide layer.

Corrosion Behavior Of A High Strength Low Alloy Steel Under Hydrostatic Pressure In Deep Ocean, Hai-Jing Sun, Li Liu, Ying Li

Journal of Electrochemistry

The corrosion behavior of a high strength low alloy steel (HSLA steel) in 3.5% NaCl solution under hydrostatic pressure (HP) in deep ocean has been investigated by performing weight loss measurement, obtaining potentiodynamic polarization curve and emplying electrochemical impedance spectroscopy (EIS) using the set up for simulation of deep sea environment in laboratory. The results were compared with that at atmospheric pressure and the influence of HP was emphatically discussed. The results revealed identical corrosion mechanism for HSLA steel at 3.5 × 10⁶ Pa and 1 × 10⁵ Pa. Howevere, the development of such a corrosion process was …

Corrosion Resistance Of Low Pressure Cold Sprayed Al Coating On Q235 Steel In Seawater, Xiang-Bo Li, Li-Kun Xu, Shan-Guang Qiu, Jia Wang, Guo-Sheng Huang, Cai-Chang Dong

Journal of Electrochemistry

Taking aluminium (Al) powder mixed with 10% (by volume) of Al₂O₃ powder as raw materials, the Al coating was prepared on the Q235 carbon steel substrate using a portable low pressure cold spraying equipment. Through the measurements of the corrosion potential and potentiodynamic polarization, the electrochemical corrosion behavior of the low pressure cold sprayed Al coating in seawater was studied in comparison with those of the Al coatings deposited with high pressure cold spray and thermal spray processes. At the same time, the surface and cross-section morphologies of these coatings were observed with scanning electron microscope. The …

Corrosion Behavior Of Zinc Covered With Thin Electrolyte Layers Under External Electric Field, Xu-Jie Yuan, Jun-Xi Zhang, Shi-Ming Zhang, Tian Tan, Qi-Meng Chen

Journal of Electrochemistry

The corrosion behavior of zinc covered with thin electrolyte layers (TELs) under an application of external electric field was investigated by performing corrosion potential and cathodic polarization current measurements. The results showed that the Ecorr and ic values first increased and then decreased with the increase of electrolyte layer thickness. Pure zinc exhibited the maximum corrosion potential as the TELs increased to 400 μm under the controls of cathodic process and corrosion products. The application of external electric field resulted in either a negative shift in corrosion potential of zinc or an increase of cathodic current. The effect of external …