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Chemical Reactions (chemical + reaction)
Terms modified by Chemical Reactions Selected AbstractsStudy of Electrochemical Processes with Coupled Homogeneous Chemical Reaction in Differential Pulse Voltammetry at Spherical Electrodes and MicrohemispheresELECTROANALYSIS, Issue 16 2010Eduardo Laborda Abstract Homogeneous chemical reactions coupled to oxidation-reduction processes at electrode surfaces are very common in electrochemistry. In this paper we cope with the application of Differential Pulse Voltammetry at spherical electrodes and microhemispheres for the study of this kind of systems. Analytical expressions are deduced from which the influence of the different experimental variables is examined. Several diagnostic criteria for elucidation of the reaction mechanism from DPV peak parameters are given, as well as working curves for extraction of the kinetic rate constants of the chemical reaction. [source] Selective Patterned Growth of Single-Crystal Ag,TCNQ Nanowires for Devices by Vapor,Solid Chemical Reaction,ADVANCED FUNCTIONAL MATERIALS, Issue 19 2008Kai Xiao Abstract We report the deterministic growth of individual single-crystal organic semiconductor nanowires of silver,tetracyanoquinodimethane (Ag,TCNQ) with high yield (>90%) by a vapor,solid chemical reaction process. Ag,metal films or patterned dots deposited onto substrates serve as chemical reaction centers and are completely consumed during the growth of the individual or multiple nanowires. Selective-area electron diffraction (SAED) revealed that the Ag,TCNQ nanowires grow preferentially along the strong ,,, stacking direction of Ag,TCNQ molecules. The vapor,solid chemical reaction process described here permits the growth of organic nanowires at lower temperatures than chemical vapor deposition (CVD) of inorganic nanowires. The single-crystal Ag,TCNQ nanowires are shown to act as memory switches with high on/off ratios, making them potentially useful in optical storage, ultrahigh-density nanoscale memory, and logic devices. [source] Dual Tuning of Emission Color and Electron Injection Properties Through in-situ Chemical Reaction in a Conjugated Polymer Containing 9,10-PhenanthrenequinoneMACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 23 2009Zhiming Wang Abstract Three new polymers were obtained through an in situ chemical reaction of the matrix conjugated polymer (PPQF) with ortho- amine compounds. By controlling the conjugation degree of diamine compounds, the emission of PPQF was tuned from weak blue to bright blue, green, and orange for PFBQ, PFBP and PFNP, respectively. The photoluminescence efficiencies were also improved in the same tendency, and the LUMO levels were gradually decreased from ,2.76 and ,3.12 to ,3.40,eV, which was beneficial for electron injection and transport in electronic devices. Thus, a dual tuning for the emission color and electron injection properties were realized through an in situ chemical reaction, which is a novel strategy to design and construct new valuable polymers from one reactive matrix polymer. [source] Exothermal Process in Miscible Polylactide/Poly(vinyl phenol) Blends: Mixing Enthalpy or Chemical Reaction?MACROMOLECULAR RAPID COMMUNICATIONS, Issue 23 2006Ester Zuza Abstract Summary: In a previous paper (Macromolecules, 2005, 38, 9221), the enthalpy of mixing in poly(DL -lactide) /poly(vinyl phenol) blends was directly measured by DSC. The first DSC scan for solution/precipitation blends showed phase separation, but miscibility was observed in the second DSC scan. Hence, miscibility was achieved after thermal treatment, an unusual behavior in polymer blend current research. However, the exothermal event observed during the first heating scan could also be the result of a chemical reaction. In this work, a new research study conducted to elucidate the nature of the exothermal heat observed in PDLA/PVPh during the first DSC heating scan. Since the single-phase PDLLA/PVPh blend obtained after thermal treatment can be redissolved and reprecipitated, results obtained in the consecutive DSC scan prove that the process is completely reversible. Furthermore, GPC and 13C NMR results provide evidence that there is no change in the chemical structure of the studied polymers before and after the thermal treatment, which evidences the absence of transesterification reactions. Therefore, it can be concluded that the exothermal heat is the result of a mixing process, and miscibility is a consequence of specific interactions. New structure expected for transesterfication reactions. [source] Soret Diffusion and Non-Ideal Dufour Conduction in Macroporous Catalysts with Exothermic Chemical Reaction at Large Intrapellet Damköhler NumbersTHE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, Issue 3 2007Laurence A. Belfiore Abstract The adiabatic temperature rise in catalytic pellets is predicted from a modified version of the Prater equation. Onsager reciprocal relations for coupled heat and mass transfer are violated in an analysis of thermal diffusion in macroporous catalysts with exothermic chemical reaction when Dufour conduction (i.e., the diffusion-thermo effect) is neglected. In this contribution, Dufour conduction is analyzed for both ideal and non-ideal pseudo-binary gas mixtures that simulate the production of methanol from carbon monoxide and hydrogen. In the diffusion-controlled regime at large intrapellet Damköhler numbers where intermolecular collisions provide the dominant resistance to mass transfer within the catalytic pores, temperatures in the catalytic core could be much greater than predictions based on the original Prater equation when the Prater number exceeds 0.30. The molecular flux of thermal energy includes Fourier's law, the interdiffusional flux, and Dufour conduction. Diffusional mass flux includes Fick's law and the Soret effect. All physicochemical properties of the reactive gas mixture exhibit temperature dependence. There is essentially no difference between maximum intrapellet temperature predictions that include or neglect ideal Dufour conduction when external catalytic surface temperatures range from 300-400 K and thermal diffusion enhances the flux of "smaller" reactants toward the centre of the catalyst. For "large-molecule reactants" that participate in exothermic reactions, thermal diffusion opposes Fick's law and Dufour conduction opposes Fourier's law. Under these conditions, it is demonstrated that core temperatures are overestimated by neglecting both off-diagonal coupling mechanisms (i.e., Soret diffusion and Dufour conduction). Prater numbers greater than unity and unrealistically high gas pressures are required to distinguish between maximum intrapellet temperatures for ideal and real gas simulations, where the latter consider two-body interactions for Lennard-Jones molecules in the virial equation of state. On prédit l'augmentation de la température adiabatique dans les pastilles catalytiques à partir d'une version modifiée de l'équation de Prater. Les relations réciproques d'Onsager pour le transfert de chaleur et de matière couplé sont violées dans une analyse de la diffusion thermique dans les catalyseurs macroporeux avec réaction chimique exothermique lorsque la conduction de Dufour (p.ex., l'effet de thermo-diffusion) est négligée. Dans cet article, on analyse la conduction de Dufour pour des mélanges de gaz pseudo-binaires idéaux et non idéaux qui simulent la production de méthanol à partir d'oxyde de carbone et d'hydrogène. Dans le régime à diffusion contrôlée à grand nombre de Damköhler entre les pastilles pour lesquels les collisions entre les molécules fournit la résistance dominante au transfert de matière à l'intérieur des pores catalytiques, les températures dans le noyau catalytique pourraient être bien plus grandes que les prédictions basées sur l'équation de Prater originale lorsque le nombre de Prater excède 0,30. Le flux moléculaire de l'énergie thermique inclut la loi de Fourier, le flux interdiffusionnel, et la conduction de Dufour. Le flux massique diffusionnel inclut la loi de Fick et l'effet Soret. Toutes les propriétés physicochimiques du mélange de gaz réactif montre une dépendance thermique. Il n'y a essentiellement pas de différence entre les prédictions des températures maximales entre les pastilles qui incluent ou négligent la conduction de Dufour idéale quand les températures de surface catalytiques externes sont comprises entre 300 et 400 K; la diffusion thermique améliore le flux des réactifs «plus petits» vers le centre du catalyseur. Pour les «réactifs composés de grandes molécules» qui participent aux réactions exothermiques, la diffusion thermique s'oppose à la loi de Fick et la conduction de Dufour à la loi de Fourier. Dans ces conditions, il est démontré que les températures de noyau sont surestimées en négligeant les deux mécanismes de couplage hors-diagonales (c.à-d. la diffusion de Soret et la conduction de Dufour). Des nombres de Prater plus grands que l'unité et des pressions de gaz élevées peu réalistes sont nécessaires pour distinguer les températures maximales entre les pastilles entre les simulations de gaz idéales et réelles, en considérant pour ces dernières les interactions à deux corps pour les molécules de Lennard-Jones dans l'équation d'état du viriel. [source] ChemInform Abstract: Room-Temperature Deposition of Defect-Free Magnetic Film by Chemical Reaction from an Aqueous Solution.CHEMINFORM, Issue 18 2001Masanobu Izaki Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] On the Chemical Reaction of Matter with AntimatterCHEMPHYSCHEM, Issue 8 2007Evandro Lodi Rizzini Prof. Abstract A chemical reaction between the building block antiatomic nucleus, the antiproton (p, or in chemical notation), and the hydrogen molecular ion () has been observed by the ATHENA collaboration at CERN. The charged pair interact via the long-range Coulomb force in the environment of a Penning trap which is purpose-built to observe antiproton interactions. The net result of the very low energy collision of the pair is the creation of an antiproton,proton bound state, known as protonium (Pn), together with the liberation of a hydrogen atom. The Pn is formed in a highly excited, metastable, state with a lifetime against annihilation of around 1 ,s. Effects are observed related to the temperature of the prior to the interaction, and this is discussed herein. [source] Titanium Containing ,-MnO2 (TM) Hollow Spheres: One-Step Synthesis and Catalytic Activities in Li/Air Batteries and Oxidative Chemical ReactionsADVANCED FUNCTIONAL MATERIALS, Issue 19 2010Lei Jin Abstract Titanium containing ,-MnO2 octahedral molecular sieves having hollow sphere structures are successfully prepared for the first time using a one-step synthesis method. Titanium cations are used as structure-directing agents in the synthesis process. The assembly of the hollow spheres is carried out at the beginning of the process. Various techniques including XRD, N2 adsorption, SEM, EDX, RAMAN, TEM, XPS, and TGA are employed for the materials characterization. Ti is incorporated into the MnO2 framework in isolated sites, and TiO2 phases (anatase and rutile) are not observed. When introduced in medium-sized lithium-air batteries, the materials give very high specific capacity (up to 2.3 A h g,1). These materials are also catalytically tested in the oxidation of toluene with molecular oxygen at atmospheric pressure, showing significant oxidative catalytic activities in this difficult chemical reaction. [source] Molecular Orbitals and Organic Chemical Reactions.ANGEWANDTE CHEMIE, Issue 17 2010Student Edition. John Wiley & Sons, Hoboken 2009. 376,S., Broschur, 42.90,,.,ISBN 978-0470746592 [source] Evaluation of the Chemical Reactions from Two Electrogenerated Species in Picoliter Volumes by Scanning Electrochemical MicroscopyCHEMPHYSCHEM, Issue 13 2010Qian Wang Abstract The volume created by the positioning of two scanning electrochemical microscope (SECM) probes (tip and substrate) at a micrometric distance defines a "picoliter beaker" where homogeneous electron-transfer reactions are studied. The SECM is used to concurrently electrogenerate in situ two reactive species and to evaluate the possibility of detecting their reactivity. Two reaction cases are studied: the first, called the "reversible case", occurs when the electrochemically generated species at the substrate electrode can also react at the tip to yield the same product as the reaction in the gap. The second case, named the "irreversible case", occurs when the electrochemically generated species at the substrate are not able to react at the tip. Digital simulations are performed and compared to experimental studies. These show that an unusual compensation between collection and feedback effects render the analysis inapplicable in the "reversible case". The "irreversible case" is shown experimentally. [source] The Synthesis and Reactivity of Group 4 Zwitterionic Complexes of the Type Mt+CH2AlCl3,: One-Component Stereoselective Polymerization and Oligomerization Catalysts for Olefins and AcetylenesEUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 15 2004John J. Eisch Abstract A reinvestigation of the interaction of TiCl4 with 2 equiv. of Me3Al in toluene between ,78 °C and 25 °C over 24 h has now established that the ultimate black product obtained is an associated zwitterion of the type [Ti+,CH2,AlCl3,]n, supported by multinuclear NMR spectroscopy and mass spectrometric and gasometric analyses of the gases evolved (CH4, H2) upon its protolysis. Chemical reactions of the zwitterion have corroborated specific aspects of its proposed structure: 1) its methylene character, by its transformation of benzophenone into 1,1-diphenylethylene; 2) its divalent titanium content, by the substantial reductive dimerization of benzophenone to tetraphenylethylene, and 3) its Lewis acidic Ti center, by its catalytic isomerization of trans -stilbene oxide to 1,1-diphenylacetaldehyde. Similar individual reactions of ZrCl4 or HfCl4 with Me3Al have led to the analogous zwitterions [Zr+,CH2,AlCl3,]n and [Hf+,CH2,AlCl3,]n, respectively. These zwitterions of Ti, Zr and Hf have been proven to be capable of the cyclotrimerization and/or polymerization of acetylenes with varying facility, as evidenced by their catalytic action on 1-hexyne, phenylacetylene, di- n -butylacetylene, and diphenylacetylene. Furthermore, all three zwitterions were able to polymerize ethylene, without any added cocatalyst, with an activity following the order Zr > Ti > Hf. The Ti and Zr zwitterions effected the stereoselective polymerization of propylene to yield 50% of isotactic polymer, and all three catalysts induced the polymerization of 1-hexene to yield 85% (Zr, Hf) or 100% (Ti) of isotactic polymer. These oligomerizations and stereoselective polymerizations of acetylenes and olefins can be rationalized through a model for the active site resembling a three-membered metallacyclopropa(e)nium ion intermediate formed from the attack of the Group 4 metal zwitterion on the unsaturated hydrocarbon. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004) [source] Chemical reactions in the gas phase and in condensed matter: From wavefunctions to density operatorsINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 13 2009David A. Micha Abstract This contribution generalizes the treatment of chemical reactions in the gas phase based on the reaction channel decomposition of the wavefunction, by introducing a similar channel decomposition of the statistical density operator valid also for condensed phases such as liquid solutions and solid surfaces. Coupled equations for the channel components of the density operator are derived and a brief presentation is given of their partial Wigner transform, which leads to a general treatment for coupling quantum and classical variables. This provides a general approach for reactions involving electronically excited states in many-atom systems. It is pointed out that reactions involving coupled quantal and classical variables can be correctly described provided (a) initial conditions for trajectories are generated from quantal distributions and (b) the bundle of trajectories for the whole initial classical phase space is propagated coupled to the quantal elements of the density matrix and used in the calculation of reaction flux averages. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2009 [source] Symbolic methods for invariant manifolds in chemical kineticsINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 1 2006Simon J. Fraser Abstract Chemical reactions show a separation of time scales in transient decay due to the stiffness of the ordinary differential equations (ODEs) that describe their evolution. This evolution can be represented as motion in the phase space spanned by the concentration variables of the chemical reaction. Transient decay corresponds to a collapse of the "compressible fluid" representing the continuum of possible dynamical states of the system. Collapse occurs sequentially through a hierarchy of nested, attracting, slow invariant manifolds (SIMs), i.e., sets that map into themselves under the action of the phase flow, eventually reaching the asymptotic attractor of the system. Using a symbolic manipulative language, explicit formulas for the SIMs can be found by iterating functional equations obtained from the system's ODEs. Iteration converges geometrically fast to a SIM at large concentrations and, if necessary, can be stabilized at small concentrations. Three different chemical models are examined in order to show how finding the SIM for a model depends on its underlying dynamics. For every model the iterative method provides a global SIM formula; however, formal series expansions for the SIM diverge in some models. Repelling SIMs can be also found by iterative methods because of the invariance of trajectory geometry under time reversal. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2006 [source] Flowers and Leaves of Tropaeolum majus L. as Rich Sources of LuteinJOURNAL OF FOOD SCIENCE, Issue 9 2005P.Y. Niizu ABSTRACT: As increasing evidence supports the role of lutein and zeaxanthin in reducing the risk of cataract and macular degeneration, food sources of these carotenoids are being sought. In the present study, the lutein content of the edible flowers and leaves of Tropaeolum majus L. was determined by high-performance liquid chromatography-photodiode array detector (HPLC-PDAD), complemented by HPLC-mass spectrometry (MS) for identification. Chemical reactions were also used as identifying parameters. The yellow and brownish orange flowers had 450 ± 60 ,g/g and 350 ± 50 ,g/g lutein, respectively. Violaxanthin, antheraxanthin, zeaxanthin, zeinoxanthin, ,-cryptoxanthin, ,-carotene, and ,-carotene were also detected at very low levels. The leaves had 136 ± 18 ,g/g lutein, 69 ± 7 ,g/g ,-carotene, 74 ± 23 ,g/g violaxanthin, and 48 ± 13 ,g/g neoxanthin. Lutein was partly esterified in the flowers and unesterified in the leaves. The flowers of T. majus are therefore excellent food sources of lutein and the leaves good sources of both lutein and the provitamin A ,-carotene. [source] Poly(vinyl chloride) on the way from the 19th century to the 21st centuryJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 3 2004D. Braun Abstract Despite all the technical and economic problems and the public discussions on the environmental dangers and hazards of chlorine chemistry, poly(vinyl chloride) (PVC) is the second most produced plastic (with a worldwide capacity of about 31 million tons), placing after polyolefins and before styrene polymers. Presently, PVC production worldwide is growing at a rate of more than 4% per year. The application of PVC was first described in a patent in 1913, but only after 1930 did a sustained interest in PVC arise in several industrial laboratories. The most remarkable milestones in PVC history and their importance to the development of macromolecular chemistry are briefly described, and some present PVC research and industrial applications, with respect to polymerization, stabilization, bulk property modification, and chemical and material recycling of PVC waste, are discussed. Some actual selected topics include the emulsion polymerization of vinyl chloride with polymeric surfactants and controlled free-radical polymerization with nitroxyls, whereas ionic and metal organic initiators have not found any technical applications. Chemical reactions offer many possibilities for the modification of PVC, but they have been not used on a technical scale yet. Much work has been done on stabilization with nontoxic or metal-free systems. The bulk properties of PVC can be influenced by impact modification through the addition of graft copolymers or by blending with other polymers. Also presented are some problems and recent developments in PVC recycling. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 578,586, 2004 [source] Effects of Electrode Protrusion Length, Pre-Existing Bubbles, Solution Conductivity and Temperature, on Liquid Phase Pulsed Electrical DischargePLASMA PROCESSES AND POLYMERS, Issue 11 2009Kai-Yuan Shih Abstract The effects of high voltage electrode needle protrusion length and the presence of low density pre-existing bubbles on liquid phase pulsed electrical discharge were investigated. Liquid phase pulsed corona discharge was operated with two different protrusion length needle electrodes (short , 2,mm and long , 20,mm) with different bulk solution conductivities (5,µS,·,cm,1 and 150,µS,·,cm,1) at room temperature (25,°C) and near boiling (95,°C). Chemical reactions formed in the discharge were also investigated by measuring the generation rates of hydrogen (H2), oxygen (O2) and hydrogen peroxide (H2O2). [source] Dynamic study of cerebral bioenergetics and brain function using in vivo multinuclear MRS approachesCONCEPTS IN MAGNETIC RESONANCE, Issue 2 2005Wei Chen Abstract One of the greatest merits of nuclear magnetic resonance (NMR) methodology used in biomedical research and clinical settings is its capability of measuring various physiological parameters in vivo. Besides MR imaging (MRI), which has been routinely applied to obtain vital information in living organs at normal and diseased states, in vivo MR spectroscopy (MRS) provides an invaluable tool for determining metabolites, chemical reaction rates, bioenergetics, and their dynamic changes in the human and animals noninvasively. These MRS capabilities are further enhanced at high/ultrahigh magnetic fields because of significant gain in NMR detection sensitivity and improvement in the spectral resolution. Recent progress has shown that in vivo MRS holds great promise in many biomedical research areas,in particular, brain research. This article provides a broad review of (i) in vivo multinuclear MRS approaches, (ii) advanced MRS methodologies, and (iii) MRS applications for determining cerebral metabolism as well as bioenergetics at resting brain state and their dynamic changes in response to brain activation. © 2005 Wiley Periodicals, Inc. Concepts Magn Reson Part A 27A: 84-121, 2005 [source] Crystal structures and isotope effect on Na5H3(SeO4)4·2H2O and Na5D3(SeO4)4·2D2O crystalsCRYSTAL RESEARCH AND TECHNOLOGY, Issue 8 2010T. Fukami Abstract Differential scanning calorimetry (DSC) and X-ray diffraction measurements have been performed on pentasodium trihydrogen tetraselenate dihydrate Na5H3(SeO4)4·2H2O and deuterated Na5D3(SeO4)4·2D2O crystals. Any distinct anomaly around 428 K in the DSC curves for both crystals is suggested to be caused by a chemical reaction of thermal decomposition with hydrolysis at high temperature. The space group symmetry (triclinic P) and the structure parameters are determined at room temperature. The hydrogen atom in the centrosymmetric O-H(D)-O hydrogen bond of both crystals is found to be equally distributed at two equivalent sites in the bond. The expansions of two O-H-O hydrogen bonds by the substitution of deuterium are observed to be 0.016(6) and 0.011(4) Å. The geometric isotope effect on hydrogen bonds is confirmed to be existed in Na5H3(SeO4)4·2H2O. (© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source] Study of Electrochemical Processes with Coupled Homogeneous Chemical Reaction in Differential Pulse Voltammetry at Spherical Electrodes and MicrohemispheresELECTROANALYSIS, Issue 16 2010Eduardo Laborda Abstract Homogeneous chemical reactions coupled to oxidation-reduction processes at electrode surfaces are very common in electrochemistry. In this paper we cope with the application of Differential Pulse Voltammetry at spherical electrodes and microhemispheres for the study of this kind of systems. Analytical expressions are deduced from which the influence of the different experimental variables is examined. Several diagnostic criteria for elucidation of the reaction mechanism from DPV peak parameters are given, as well as working curves for extraction of the kinetic rate constants of the chemical reaction. [source] Simultaneous Determination of Quinoline and Pyridine Compounds in Gasoline and Diesel by Differential Pulse VoltammetryELECTROANALYSIS, Issue 6 2007Leonardo Abstract The presence of trace basic organonitrogen compounds such as quinoline and pyridine in derivative petroleum fuels plays an important role in maintaining the engines of vehicles. However, these substances can contaminate the environment and so must be controlled because most of them are potentially carcinogenic and mutagenic. For these reasons, a reliable and sensitive method was developed for the determination of basic nitrogen compounds in fuel samples such as gasoline and diesel. This method utilizes preconcentration on an ion,exchange resin (Amberlyte IR,120,H) followed by differential pulse voltammetry (DPV) on a glassy carbon electrode. The electrochemical behavior of quinoline and pyridine as studied by cyclic voltammetry (CV) suggests that their reduction occurs via a reversible electron transfer followed by an irreversible chemical reaction. Very well resolved diffusion-controlled voltammetric peaks were obtained in dimethylformamide (DMF) with tetrabutylammonium tetrafluoroborate (TBAF4 0.1,mol L,1) for quinoline (,1.95,V) and pyridine (,2.52,V) vs. Ag|AgCl|KClsat reference electrode. The proposed DPV method displayed a good linear response from 0.10 to 300,mg L,1 and a limit of detection (LOD) of 5.05 and 0.25,,g L,1 for quinoline and pyridine, respectively. Using the method of standard additions, the simultaneous determination of quinoline and pyridine in gasoline samples yielded 25.0±0.3 and 33.0±0.7,mg L,1 and in diesel samples yielded 80.3±0.2 and 131±0.4,mg L,1, respectively. Spike recoveries were 94.4±0.3% and 101±0.5% for quinoline and pyridine, respectively, in the fuel determinations. This proposed method was also compared with UV-vis spectrophotometric measurements. Results obtained for the two methods agreed well based on F and t student's tests. [source] Electrolyte Effects on Charge Transport Behavior of [Os(bpy)2(PVP)10Cl]Cl and [Ru(bpy)2(PVP)10Cl]Cl Redox Polymers in Ultra-Thin Films of PolyionsELECTROANALYSIS, Issue 18 2005Bingquan Wang Abstract Metallopolymer films have important applications in electrochemical catalysis. The alternate electrostatic layer-by-layer method was used to assemble films of [Ru(bpy)2(PVP)10Cl]Cl (denoted as ClRu-PVP) and [Os(bpy)2(PVP)10Cl]Cl (ClOs-PVP) metallopolymers onto pyrolytic graphite electrodes. Film thickness estimated by quartz crystal microbalance was 6,8,nm. The effects of pH, electrolyte species and concentration on the electrochemical properties of these electroactive polymers were studied using cyclic voltammetry (CV). Behavior in various electrolytes was compared. Also the mass changes within the ultra-thin film during redox of Os2+/3+ were characterized by in situ electrochemical quartz crystal microbalance (EQCM). The results indicate rapid reversible electron transfer, and show that both ClRu-PVP and ClOs-PVP have compact surface structures while ClOs-PVP is a little denser than ClRu-PVP. Although hydrogen ions do not participate in the chemical reaction of either film, the movement of Na+ cation and water accompanies the redox process of ClOs-PVP films. [source] Spectroelectrochemical and Voltammetric Studies of L -DOPAELECTROANALYSIS, Issue 2 2003Xiaoqiang Liu Abstract The electrooxidation of L -dopa at GC electrode was studied by in situ UV-vis spectroelectrochemistry (SEC) and cyclic voltammetry. The mechanism of electrooxidation and some reaction parameters were obtained. The results showed that the whole electrooxidation reaction of L -dopa at glassy carbon (GC) electrode was an irreversible electrochemical process followed by a chemical reaction in neutral solution (EC mechanism). The spectroelectrochemical data were treated by the double logarithm method together with nonlinear regression, from which the formal potential E0=228,mV, the apparent electron-transfer number of the electrooxidation reaction ,n=0.376 (R=0.99, SD=0.26), the standard electrochemical rate constant k0=(3.93±0.12)×10,4,cm s,1 (SD=1.02×10,2), and the formation equilibrium constant of the following chemical reaction kc=(5.38±0.34)×10,1,s,1 (SD=1.02×10,2) were also obtained. [source] Errata: Microfluidic droplet trapping array as nanoliter reactors for gas-liquid chemical reactionELECTROPHORESIS, Issue 8 2010Qingquan Zhang No abstract is available for this article. [source] Removal of the , -Case Layer from Precision-Cast Cellular TiAl6Nb7 to be Used for Biomedical Applications,ADVANCED ENGINEERING MATERIALS, Issue 8 2009Teodolito Guillén The present work deals with the chemical removal of the ,-case layer formed during precision casting of cellular TiAl6Nb7 sponges for biomedical applications. The major part of the brittle ,-case layer can be attributed to chemical reaction between titanium and the investment mold components. To improve the ductility of the cell struts by eliminating the brittle surface, a pickling-vibration treatment was developed by which the ,-case layer is chemically removed. [source] Titanium Containing ,-MnO2 (TM) Hollow Spheres: One-Step Synthesis and Catalytic Activities in Li/Air Batteries and Oxidative Chemical ReactionsADVANCED FUNCTIONAL MATERIALS, Issue 19 2010Lei Jin Abstract Titanium containing ,-MnO2 octahedral molecular sieves having hollow sphere structures are successfully prepared for the first time using a one-step synthesis method. Titanium cations are used as structure-directing agents in the synthesis process. The assembly of the hollow spheres is carried out at the beginning of the process. Various techniques including XRD, N2 adsorption, SEM, EDX, RAMAN, TEM, XPS, and TGA are employed for the materials characterization. Ti is incorporated into the MnO2 framework in isolated sites, and TiO2 phases (anatase and rutile) are not observed. When introduced in medium-sized lithium-air batteries, the materials give very high specific capacity (up to 2.3 A h g,1). These materials are also catalytically tested in the oxidation of toluene with molecular oxygen at atmospheric pressure, showing significant oxidative catalytic activities in this difficult chemical reaction. [source] Preliminary study of the crack healing and strength recovery of Al2O3 -matrix compositesFATIGUE & FRACTURE OF ENGINEERING MATERIALS AND STRUCTURES, Issue 2 2004L. JUN ABSTRACT This study focused on the crack-healing behaviour of three commercial Al2O3,ceramic-matrix composites: TiCP/Al2O3, ZrO2/Al2O3 and SiCW/Al2O3. Vickers indentation was used to introduce surface flaws with different loads of 49, 98 and 196 N. Then the cracked specimens were annealed in air for 1 h at 1000, 1200 and 1400 °C. The annealing treatment was also conducted at 1200 °C in vacuum for 1 h. Results showed that the annealing treatments increased the indentation strength, but the extent of the increase was different. When annealed in air, the main crack-healing mechanism of TiCP/Al2O3 and SiCW/Al2O3 composites was chemical reaction. When annealed in vacuum, stress relaxation caused much less strength recovery. The main crack-healing mechanism of ZrO2/Al2O3 was the existence of low melting eutectic and the rearrangement of grains caused by ZrO2(m), ZrO2(t) transformation in the crack-opening process zone. The effects of annealing temperature, atmosphere and indentation load on the degree of strength recovery were all related to the crack-healing mechanisms. [source] The loose coupling mechanism in molecular machines of living cellsGENES TO CELLS, Issue 1 2000Fumio Oosawa Living cells have molecular machines for free energy conversion, for example, sliding machines in muscle and other cells, flagellar motors in bacteria, and various ion pumps in cell membranes. They are constructed from protein molecules and work in the nm (nanometer), pN (piconewton) and ms (millisecond) ranges, without inertia. In 1980s, a question was raised of whether the input,output or influx,efflux coupling in these molecular machines is tight or loose, and an idea of loose coupling was proposed. Recently, the long-distance multistep sliding of a single myosin head on an actin filament, coupled with the hydrolysis of one ATP molecule, was observed by Yanagida's group using highly developed techniques of optical microscopy and micromanipulation. This gave direct evidence for the loose coupling between the chemical reaction and the mechanical event in the sliding machine. In this review, I will briefly describe a historical overview of the input,output problem in the molecular machines of living cells. [source] Pigment Synthesis: PY181 Pigment Microspheres of Nanoplates Synthesized via Polymer-Induced Liquid Precursors (Adv. Funct.ADVANCED FUNCTIONAL MATERIALS, Issue 13 2009Mater. A polymer-induced liquid precursor is used for a pigment yellow 181 crystal formed by chemical reaction in mixed solvents of water and isopropanol by direct azo coupling under the directing influence of a designed copolymer additive. This leads to a pigment with novel complex morphology and unusal properties, as shown by Cölfen et al. on page 2095. [source] PY181 Pigment Microspheres of Nanoplates Synthesized via Polymer-Induced Liquid PrecursorsADVANCED FUNCTIONAL MATERIALS, Issue 13 2009Yurong Ma Abstract Organic pigments are important crystalline substances, and their properties and applications rely on size and shape control. Pigment Yellow 181 (PY181) is an industrial azo pigment that is light and weatherfast and suitable for high temperature processing. One disadvantage is its needle-like shape in the default , -phase, which makes the pigment difficult to process in industry, e.g., in polymer melts, where a spherical structure would be ideal. Here, we show for the first time, that polymer-induced liquid precursor structures can be formed even in association to a chemical reaction. Furthermore, it is demonstrated that biomineralization principles can be exploited for the generation of advanced functional materials, such as pigments with novel complex morphology and different properties. Stable PY181 microspheres of nanoplates in the , -phase were obtained in mixed solvents of water and isopropanol by direct azo coupling under the directing influence of a designed copolymer additive aminobenzoylaminobenzamide-acetoacetyl-poly(ethylene imine)- block -poly(ethylene glycol) (ABABA-acetoacetyl-PEI- b -PEG). [source] Mineral precipitation associated with vertical fault zones: the interaction of solute advection, diffusion and chemical kineticsGEOFLUIDS (ELECTRONIC), Issue 1 2007CHONGBIN ZHAO Abstract This article is concerned with chemical reactions that occur between two interacting parallel fluid flows using mixing in vertical faults as an example. Mineral precipitation associated with fluid flow in permeable fault zones results in mineralization and chemical reaction (alteration) patterns, which in turn are strongly dependent on interactions between solute advection (controlled by fluid flow rates), solute diffusion/dispersion and chemical kinetics. These interactions can be understood by simultaneously considering two dimensionless numbers, the Damköhler number and the Z -number. The Damköhler number expresses the interaction between solute advection (flow rate) and chemical kinetics, while the Z -number expresses the interaction between solute diffusion/dispersion and chemical kinetics. Based on the Damköhler and Z -numbers, two chemical equilibrium length-scales are defined, dominated by either solute advection or by solute diffusion/dispersion. For a permeable vertical fault zone and for a given solute diffusion/dispersion coefficient, there exist three possible types of chemical reaction patterns, depending on both the flow rate and the chemical reaction rate. These three types are: (i) those dominated by solute diffusion and dispersion resulting in precipitation at the lower tip of a vertical fault and as a thin sliver within the fault, (ii) those dominated by solute advection resulting in precipitation at or above the upper tip of the fault, and (iii) those in which advection and diffusion/dispersion play similar roles resulting in wide mineralization within the fault. Theoretical analysis indicates that there exists both an optimal flow rate and an optimal chemical reaction rate, such that chemical equilibrium following focusing and mixing of two fluids may be attained within the fault zone (i.e. type 3). However, for rapid and parallel flows, such as those resulting from a lithostatic pressure gradient, it is difficult for a chemical reaction to reach equilibrium within the fault zone, if the two fluids are not well mixed before entering the fault zone. Numerical examples are given to illustrate the three possible types of chemical reaction patterns. [source] | |||||||||||||||||||||||||||||||||||||||||||||||||