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Electrochemical Measurements (electrochemical + measurement)
Selected AbstractsQuantitative Analysis of Prometrine Herbicide by Liquid,Liquid Extraction Procedures Coupled to Electrochemical MeasurementsELECTROANALYSIS, Issue 6 2009V. Juarez Abstract A sensitive method is proposed for the preconcentration and quantification of the herbicide Prometrine (PROM) at a liquid-liquid interface employing square-wave voltammetry. The preconcentration stage was based on liquid-liquid extraction methodology and the PROM quantification was carried out from the peak current of square-wave voltammograms. Under the experimental conditions employed, linear calibration curves in the concentration range 1.0×10,6,M,5.0×10,5,M, with detection limit equal to 1.5×10,6,M were obtained without pretreatment of the samples. This linear range, as well as detection limit could be extended towards lower concentrations when a pretreatment procedure was employed. In this way, linearity of calibration curves between 8.0×10,8,M and 2.4×10,7,M and detection limit of 1.0×10,7,M, were observed. On the other hand, the standard addition method was also used as an alternative and an appropriated quantification technique for this system. A linear concentration range between 1.0×10,6,M and 2.7×10,5,M, with a correlation coefficient of 0.997, was obtained. This procedure has also a promising application in the separation of herbicides from other interferents, present in real samples, previous to their quantification. [source] Microflow Vessel Improving Reproducibility and Sensitivity of Electrochemical MeasurementsELECTROANALYSIS, Issue 23 2008Jan Krejci Abstract A new microflow system was designed and developed for electrochemical measurements. The electrochemical electrodes prepared using thick film technology were used in this arrangement. Results of various measurements such as simple amperometric measurement on the example of H2O2 detection, measurement with glucose oxidase (GOx) biosensor, soluble enzyme activity measurement etc. carried out using this system are reported. It was observed that the sensitivity and reproducibility of the electrochemical measurements is improved significantly. The new device performance was proved on H2O2 detection, activity of GOx measurement and heavy metals detection (measured concentration range: H2O2 10,9 to 10,1,M, glucose 10,6 to 10,2,M, activity of GOx 10,1 to 102,IU, heavy metals (Cu, Pb) 10,4 to 10,3,M). The microflow insert greatly reduces the overall size of the electrolyte vessel and measurements with sample quantity as low as 2,mL can be accomplished. [source] Working Electrodes from Amalgam Paste for Electrochemical MeasurementsELECTROANALYSIS, Issue 4 2008Bogdan Yosypchuk Abstract Paste electrode with paste amalgam as an active electrode material is described here for the first time. Designed electrode from silver paste amalgam (AgA-PE) is solely metallic and does not contain any organic binder. Mechanical surface regeneration of AgA-PE is performed in the same way as for classical carbon paste electrodes and reproducibility of such regeneration is about 10%. Electrochemical surface regeneration appeared very efficient for most measurements. In dependence on paste metal content, the electrode surface can be liquid (resembling a film) or rather solid. The hydrogen overvoltage on AgA-PE is high, and the electrode allows measurements at highly negative potentials. AgA-PE is well suited for study of reduction or oxidation processes without an accumulation step. Anodic stripping voltammetry of some metals tested on the electrode is influenced by formation of intermetallic compounds. The measurement based on cathodic stripping voltammetry (adenine, cysteine) and on catalytic processes from adsorbed state (complex of osmium tetroxide with 2,2,-bipyridine) can be performed on AgA-PE practically under the same conditions as found earlier for HMDE and for silver solid amalgam electrode. The working electrode from paste amalgam combines the advantages of paste and metal electrodes. [source] Influence of Heat Treatments on In Vitro Degradation Behavior of Mg-6Zn Alloy Studied by Electrochemical Measurements,ADVANCED ENGINEERING MATERIALS, Issue 5 2010Shaoxiang Zhang The influence of heat treatment on the in vitro degradation of Mg-6Zn alloy is studied by electrochemical measurements. After solid-solution treatment, the microstructure of the Mg-6Zn becomes more homogeneous, along with an elevated charge-transfer resistance in SBF and a reduced corrosion current density. After ageing treatment, the discrete intermetallic ,-MgZn phase enhances the cathodic hydrogen evolution and impairs the corrosion resistance of the alloy. Galvanic cells are expected on ageing, but the ageing process makes the microstructure of the alloy homogeneous. Heat treatment alters the in vitro degradation behavior of Mg-6Zn alloy and is applicable in adjusting the biodegradation rate. [source] Electrocatalytic Oxidation of Glucose by the Glucose Oxidase Immobilized in Graphene-Au-Nafion BiocompositeELECTROANALYSIS, Issue 3 2010Kangfu Zhou Abstract Graphene was successfully prepared and well separated to individual sheets by introducing SO3,. XRD and TEM were employed to characterize the graphene. UV-visible absorption spectra indicated that glucose oxidase (GOx) could keep bioactivity well in the graphene-Au biocomposite. To construct a novel glucose biosensor, graphene, Au and GOx were co-immobilized in Nafion to further modify a glassy carbon electrode (GCE). Electrochemical measurements were carried out to investigate the catalytic performance of the proposed biosensor. Cyclic voltammograms (CV) showed the biosensor had a typical catalytic oxidation response to glucose. At the applied potential +0.4,V, the biosensor responded rapidly upon the addition of glucose and reached the steady state current in 5,s, with the present of hydroquinone. The linear range is from 15,,M to 5.8,mM, with a detection limit 5,,M (based on the S/N=3). The Michaelis-Menten constant was calculated to be 4.4,mM according to Lineweaver,Burk equation. In addition, the biosensor exhibits good reproducibility and long-term stability. Such impressive properties could be ascribed to the synergistic effect of graphene-Au integration and good biocompatibility of the hybrid material. [source] Mixed-Ligand Oxidovanadium(V) Complexes with N, -Salicylidenehydrazides: Synthesis, Structure, and 51V Solid-State MAS NMR Investigation,EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 14 2008Simona Nica Abstract The synthesis and spectroscopic characterization of a series of three oxidovanadium(V) complexes with 8-hydroxyquinoline and Schiff-base ligands derived from salicylaldehyde and ,-hydroxy-functionalized carbohydrazides with different chain lengths are reported. The complex with the hydrazone ligand containing the shortest chain length was crystallographically characterized. This complex crystallizes in the triclinic space group P with two structurally similar but crystallographically independent oxidovanadium(V) complexes. Each vanadium atom is six-coordinate in a distorted-octahedral geometry. The two molecules are assembled through hydrogen-bonding interactions between the hydroxyl groups of the side-chain substituted Schiff-base ligand and the oxido group of one of the two complexes. Electrochemical measurements performed in acetonitrile solution reveal two reversible one-electron reduction steps. The observed pre-wave feature of the second reduction step indicates the presence of dissociation equilibria related to the 8-hydroxyquinoline coligand. Magic-angle spinning solid-state 51V NMR spectroscopy allowed to characterize the full series of complexes with alkyl and hydroxy alkyl-substituted hydrazone ligands that were used. The quadrupolar coupling constants are small with a value of about 4 MHz and show little variation within the series. The asymmetry of the chemical shift tensor indicates a rather axial symmetric environment around the vanadium(V) center. The isotropic chemical shifts observed in the solid state occur at about 30 ppm, which is in the same order of magnitude as the solvent induced variations, about 10 ppm, found for different solvents.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Structural and Electrochemical Studies of Dimerization and Rotational Isomerization in Multi-Iron SilicotungstatesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 9 2005Travis M. Anderson Abstract A structural and electrochemical investigation of dimerization and Baker,Figgis (rotational) isomerization in the tri-ferric-substituted silicotungstates has been undertaken because these phenomena are important in a large number of polyoxometalates. A single-crystal X-ray diffraction analysis of K4Na7[(,-SiFe3W9(OH)3O34)2(OH)3] (,1) has been carried out [a = 12.9709(7) Å, b = 38.720(2) Å, c = 21.4221(12) Å, orthorhombic, Pbcm, R1 = 8.48,%, based on 13809 independent reflections]. The complex is isostructural with [(,-SiFe3W9(OH)3O34)2(OH)3]11, (,1) except that the edge-shared W3O13 caps in each [SiFe3W9(OH)3O34]4, unit are rotated by 60°. Electrochemical measurements, performed in a pH 5 acetate buffer, indicate a positive shift in the FeIII -based peak potential (and no change for the WVI -based potential) upon going from ,1 to its monomeric derivative [(,-Si(FeOH2)3W9(OH)3O34)]4, (,2) (,0.484,±,0.005 V and ,0.474,±,0.005 V, respectively). In contrast, the peak potentials of the FeIII - and WVI -based redox processes of ,1 are both found at more negative values than its rotational isomer ,1. The absolute values of the reduction peak potential differences are 0.022 V for FeIII and 0.162 V for WVI. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] Self-Assembled Graphene,Enzyme Hierarchical Nanostructures for Electrochemical BiosensingADVANCED FUNCTIONAL MATERIALS, Issue 19 2010Qiong Zeng Abstract The self-assembly of sodium dodecyl benzene sulphonate (SDBS) functionalized graphene sheets (GSs) and horseradish peroxidase (HRP) by electrostatic attraction into novel hierarchical nanostructures in aqueous solution is reported. Data from scanning electron microscopy, high-resolution transmission electron microscopy, and X-ray diffraction demonstrate that the HRP,GSs bionanocomposites feature ordered hierarchical nanostructures with well-dispersed HRP intercalated between the GSs. UV-vis and infrared spectra indicate the native structure of HRP is maintained after the assembly, implying good biocompatibility of SDBS-functionalized GSs. Furthermore, the HRP,GSs composites are utilized for the fabrication of enzyme electrodes (HRP,GSs electrodes). Electrochemical measurements reveal that the resulting HRP,GSs electrodes display high electrocatalytic activity to H2O2 with high sensitivity, wide linear range, low detection limit, and fast amperometric response. These desirable electrochemical performances are attributed to excellent biocompatibility and superb electron transport efficiency of GSs as well as high HRP loading and synergistic catalytic effect of the HRP,GSs bionanocomposites toward H2O2. As graphene can be readily non-covalently functionalized by "designer" aromatic molecules with different electrostatic properties, the proposed self-assembly strategy affords a facile and effective platform for the assembly of various biomolecules into hierarchically ordered bionanocomposites in biosensing and biocatalytic applications. [source] Synthesis and characterization of a thiadiazole/benzoimidazole-based copolymer for solar cell applicationsJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 20 2010Guan-yu Chen Abstract In this study, we synthesized a new polymer, PCTDBI, containing alternating carbazole and thiadiazole-benzoimidazole (TDBI) units. This polymer (number-average molecular weight = 25,600 g mol,1), which features a planar imidazole structure into the polymeric main chain, possesses reasonably good thermal properties (Tg = 105 °C; Td = 396 °C) and an optical band gap of 1.75 eV that matches the maximum photon flux of sunlight. Electrochemical measurements revealed an appropriate energy band offset between the polymer's lowest unoccupied molecular orbital and that of PCBM, thereby allowing efficient electron transfer between the two species. A solar cell device incorporating PCTDBI and PCBM at a blend ratio of 1:2 (w/w) exhibited a power conversion efficiency of 1.20%; the corresponding device incorporating PCTDBI and PC71BM (1:2, w/w) exhibited a PCE of 1.84%. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010 [source] Synthesis of a [60] fullerene,Functionalized isotactic polypropylene derivativeJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 20 2008Gerardo Martínez Abstract The covalent attachment of [60] fullerene (C60) to isotactic polypropylene (i-PP) is achieved by direct reaction in 1,2,4-trichlorobenzene (TCB) solution in the presence of dicumyl peroxide (DCP). The chemically modified pendant C60/i-PP polymers are soluble in chlorinated solvents and have been characterized by ultraviolet,visible and fourier transform infrared spectroscopy, scanning electron microscopy, X-ray diffraction, differential scanning calorimetry, cyclic voltametry, and thermogravimetric analysis. From the results it can be concluded that the modification of i-PP by grafting via a free-radical reaction competes with the possibility of chain scission of i-PP due to the presence of DCP. The functionalized polymers crystallize in the monoclinic crystal modification, and have high crystallinity. The incorporation of C60 significantly enhances the thermal stability of the i-PP. Electrochemical measurements demonstrate good electron acceptor properties of the fullerenated i-PP samples. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6722,6733, 2008 [source] Synergistic or additive corrosion inhibition of mild steel by a mixture of HEDP and metasilicate at pH 7 and 11MATERIALS AND CORROSION/WERKSTOFFE UND KORROSION, Issue 11 2004D. Mohammedi Abstract Electrochemical measurements (steady-state current-voltage curves and AC impedance) were coupled with mass-loss measurements, SEM examinations, and EDSX analyses to investigate the inhibition of corrosion of a carbon steel by a mixture of phosphonic acid HEDP (acid 1, hydroxyethylene, 1-1 diphosphonic) and sodium metasilicate pentahydrate Na2SiO3. 5H2O in an industrial hard water containing 3.10,3 M Ca2+ ions. At pH 7, HEDP and Ca2+ act in a synergistic manner, by formation of a HEDP and calcium containing layer. Addition of silicate at this pH value, allows to reach an efficiency of 94% due to an additive inhibition effect. At pH 11, metasilicate, HEDP, and Ca2+ ions reinforce the passive layer in a synergistic way. The mixture (1.7 · 10,5 M HEDP + 2.6 · 10 -3 M SiO2,3) in the Ca2+ containing electrolyte is shown to be able to inhibit efficaciously the corrosion of iron at room temperature, considering uniform corrosion at pH 7 or pitting corrosion at pH 11. [source] Crystallographic and Electrochemical Characteristics of La0.7Mg0.3Ni5.0,x(Al0.5Mo0.5)x Hydrogen-Storage Alloys,CHEMPHYSCHEM, Issue 3 2005Xin Bo Zhang Dr. Abstract The structure, hydrogen-storage property and electrochemical characteristics of La0.7Mg0.3Ni5.0,x(Al0.5Mo0.5)x(x=0,0.8) hydrogen-storage alloys have been studied systematically. X-ray diffraction Rietveld analysis shows that all the alloys consist of an La(La,Mg)2Ni9 phase and an LaNi5 phase. The pressure,composition isotherms indicate that the hydrogen-storage capacity first increases and then decreases with increasing x, and the equilibrium pressure decreases with increasing x. Electrochemical measurements show that the maximum discharge capacity and the exchange-current density of the alloy electrodes increase as x increases from 0 to 0.6 and then decrease when x increases further from 0.6 to 0.8. Moreover, the low-temperature dischargeability of the alloy electrodes increases monotonically with increasing x in the alloys. [source] Diagnostic Implications of Uric Acid in Electroanalytical MeasurementsELECTROANALYSIS, Issue 14 2005Abstract Urate has a long history in clinical analysis and has served as an important diagnostic in a number of contexts. The increasing interest in metabolic syndrome has led to urate being used in combination with a number of other biomarkers in the assessment of cardiovascular risk. The traditional view of urate as principally an interferent in electrochemical measurement is now gradually being replaced with the realization that its measurement could serve as an invaluable secondary (if not primary) marker when monitoring conditions such as diabetes and heart disease. Rather than attempting to wholly exclude urate electrochemistry, many strategies are being developed that can integrate the urate signal within the device architecture such that a range of biomarkers can be sequentially assessed. The present review has sought to rationalize the clinical importance that urate measurements could hold in future diagnostic applications , particularly within near patient testing contexts. The technologies harnessed for its detection and also those previously employed for its removal are reviewed with the aim of highlighting how the seemingly contrasting approaches are evolving to aid the development of new sensing devices for clinical analysis. [source] Hydrogen degradation of structural steels in technical hydrocarbon liquidsMATERIALS AND CORROSION/WERKSTOFFE UND KORROSION, Issue 4 2008B. Swieczko-Zurek Abstract Hydrogen absorption, mechanical testing under different loading mode and electrochemical measurement were done for 0.3C low alloy steels used in the ship engine parts at immersion in the boiler fuel and in the used engine mineral oil at elevated temperatures corresponding to the operating conditions. The hydrogen charging of steels has been found to reach a level causing their plasticity loss. No effect, a plasticity loss and a significant decrease in the number of cycles have been stated in constant load, slow strain rate and fatigue tests, respectively. The results showed the local active plastic deformation proceeded close to the surface of hydrogen ingress to provide the highest possibility for hydrogen induced metal degradation in hydrocarbon environments. Although the source of hydrogen evolved in the case of technical hydrocarbons has been discussed, the promoting effect of formed H2S should be recognized as the important factor influencing the hydrogen charging from those environments. Some variation in the steel microstructure, chemical composition and hardness of steels, even allowed by the standard may affect their susceptibility to hydrogen degradation in hydrocarbons. [source] New Results on the Photochemistry of Biopterin and Neopterin in Aqueous SolutionPHOTOCHEMISTRY & PHOTOBIOLOGY, Issue 1 2009Mariana Vignoni New photochemical studies of the reactivity of biopterin (BPT) and neopterin (NPT) in acidic (pH = 5.5) and alkaline (pH = 10.5) aqueous solutions at 350 nm and room temperature were performed. The photochemical properties of BPT are of particular interest because the photolysis of this compound takes place in the white skin patches of patients affected by vitiligo. The photochemical reactions were followed by UV/VIS spectrophotometry, HPLC, electrochemical measurement of dissolved O2 and enzymatic methods for hydrogen peroxide (H2O2) and superoxide anion (O2,,) determinations. When BPT or NPT are exposed to UVA radiation, a red intermediate, very likely 6-formyl-5,8-dihydropterin, is generated in an O2 -independent process. That product is rapidly oxidized on admission of O2 to yield 6-formylpterin and H2O2. When the photolysis takes place in aerobic conditions, no additional pathways exist. On the other hand, in the absence of O2, the intermediate generated is not stable and leads to the formation of many products. O2,, is also generated during photo-oxidation of BPT and NPT. The quantum yields of reactant consumption depends on the O2 concentration: the higher the O2 concentration, the lower the quantum yields. This behavior is discussed in connection with the excited state of the pterins. [source] ,-Substituted Terthiophene [2]RotaxanesCHEMISTRY - A EUROPEAN JOURNAL, Issue 19 2009Taichi Ikeda Dr. Abstract Towards polythiophene polyrotaxanes: The ,-substituted terthiophene [2]rotaxanes have been synthesized (see figure). Basic optical and electrochemical properties of the synthesized [2]rotaxanes are also reported. Two kinds of ,-substituted terthiophene [2]rotaxanes were synthesized using the host-guest pairs of the electron-deficient cyclophane cyclobis(paraquat- p -phenylene) (CBPQT4+) and the electron-rich terthiophenes with diethyleneglycol chains at the ,-position. One is made from the ,-position non-substituted terthiophene (3,T-,-Rx) and the other is made from the ,-dibromo-substituted terthiophene (3,TBr-,-Rx). The binding constants of the ,-substituted terthiophene threads were confirmed to be smaller than that of the ,-substituted terthiophene analogue. By UV/Vis absorption measurements, we confirmed the charge-transfer (CT) band in the visible region with an extinction coefficient of ,102 (M,1,cm,1). Strong, but not quantitative, quenching of the terthiophene fluorescence was confirmed for the [2]rotaxanes. Although the ,-substituted terthiophene thread was electrochemically polymerizable, the [2]rotaxane 3,T-,-Rx was not polymerizable. This result indicates that the interlocked CBPQT4+ macrocycle effectively suppresses the electrochemical polymerization of the terthiophene unit because electrostatic repulsive and steric effects of CBPQT4+ hinder the dimerization of the terthiophene radical cations. In the electrochemical measurement, we confirmed the shift of the first reduction peak towards less negative potential compared to free CBPQT4+ and the splitting of the second reduction peak. These electrochemical behaviors are similar to those observed for the highly-constrained [2]rotaxanes. The ,-substituted terthiophene [2]rotaxanes reported herein are important key compounds to prepare polythiophene polyrotaxanes. [source] Voltammetric Sizing of a SphereCHEMPHYSCHEM, Issue 10 2006Nicole Fietkau Abstract The size of a glass sphere positioned in the center of a microdisk electrode is determined by using a simple electrochemical procedure and is confirmed, additionally, by a microscopical measurement of the sphere at the time of the electrochemical measurement. The cyclic voltammetric response of the naked electrode and of the electrode with the sphere positioned in its center is recorded over a wide range of scan rates (0.002,1.5 V,s,1). The size of the sphere is then determined by comparison of the experimental voltammogram with simulations for each individual scan rate. [source] Microflow Vessel Improving Reproducibility and Sensitivity of Electrochemical MeasurementsELECTROANALYSIS, Issue 23 2008Jan Krejci Abstract A new microflow system was designed and developed for electrochemical measurements. The electrochemical electrodes prepared using thick film technology were used in this arrangement. Results of various measurements such as simple amperometric measurement on the example of H2O2 detection, measurement with glucose oxidase (GOx) biosensor, soluble enzyme activity measurement etc. carried out using this system are reported. It was observed that the sensitivity and reproducibility of the electrochemical measurements is improved significantly. The new device performance was proved on H2O2 detection, activity of GOx measurement and heavy metals detection (measured concentration range: H2O2 10,9 to 10,1,M, glucose 10,6 to 10,2,M, activity of GOx 10,1 to 102,IU, heavy metals (Cu, Pb) 10,4 to 10,3,M). The microflow insert greatly reduces the overall size of the electrolyte vessel and measurements with sample quantity as low as 2,mL can be accomplished. [source] Stripping Analysis at Bismuth Electrodes: A ReviewELECTROANALYSIS, Issue 15-16 2005Joseph Wang Abstract For many years mercury electrodes were the transducer of choice in stripping voltammetry of trace metals owing to their high sensitivity, reproducibility, and renewability. However, because of the toxicity of mercury, alternative (,environmentally friendly') electrode materials are highly desired for both centralized and field applications. Recently introduced bismuth electrodes offer a very attractive alternative to commonly used mercury electrodes. Such electrodes display well-defined, undistorted and highly reproducible response, favorable resolution of neighboring peaks, high hydrogen evolution, with good signal-to-background characteristics comparable to those of common mercury electrodes. The attractive stripping behavior of bismuth electrodes reflects the ability of bismuth to form ,fused' multicomponent alloys with heavy metals. Bismuth stripping electrodes thus hold great promise for decentralized metal testing, with applications ranging from continuous remote sensing to single-use measurements. Fundamental studies aimed at understanding the behavior of bismuth film electrodes should lead to rational preparation and operation of reliable alternative (,non,mercury') stripping electrodes that would have a major impact upon electroanalysis of trace metals. This article reviews the development, behavior, scope and prospects of bismuth electrodes for stripping-based electrochemical measurements of trace metals. [source] Sensitive Electrochemical Detection of Native and Aggregated ,-Synuclein Protein Involved in Parkinson's DiseaseELECTROANALYSIS, Issue 13-14 2004Michal Masa Abstract The aggregation of ,-synuclein, a 14,kDa protein, is involved in several human neurodegenerative disorders, including Parkinson's disease. We studied native and in vitro aggregated ,-synuclein by circular dichroism (CD), atomic force microscopy (AFM) and electrochemical methods. We used constant current chronopotentiometric stripping analysis (CPSA) to measure hydrogen evolution catalyzed by ,-synuclein (peak H) at hanging mercury drop electrodes (HMDE) and square-wave stripping voltammetry (SWSV) to monitor tyrosine oxidation at carbon paste electrodes (CPE). To decrease the volume of the analyte, most of the electrochemical measurements were performed by adsorptive transfer (medium exchange) from 3,6,,L drops of ,-synuclein samples. With both CPE and HMDE we observed changes in electrochemical responses of ,-synuclein corresponding to protein fibrillization detectable by CD, fluorescence and AFM. Aggregation-induced changes in peak H at HMDE were relatively large in strongly aggregated samples, suggesting that this electrochemical signal may find use in the analysis of early stages of ,-synuclein aggregation. This assumption was documented by marked changes in the peak H potential and height in samples withdrawn at the end of the lag and the beginning of the elongation phase. Native ,-synuclein can be detected down to subnanomolar concentrations by CPSA. [source] Divanadium(V) and Trapped Valence Linear Tetravanadium(IV,V,V,IV) ComplexesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 35 2009Anindita Sarkar Abstract In an acetonitrile/water mixture, reactions of the N,N,-bis(diacetyl)hydrazine (H2diah), bis(acetylacetonato)oxidovanadium(IV) [VO(acac)2] and monodentate N -coordinating heterocycles (hc) in a 1:2:2 mol ratio provide yellow divanadium(V) complexes of formula [(hc)O2V(,-diah)VO2(hc)] (1, hc = imidazole; 2, hc = pyrazole; 3, hc = 3,5-dimethyl pyrazole). On the other hand, in the same solvent mixture reactions of the same reagents in a 1:4:2 mol ratio produce green linear tetravanadium(IV,V,V,IV) complexes of formula [(acac)2OV(,-O)VO(hc)(,-diah)(hc)OV(,-O)VO(acac)2] (4, hc = imidazole; 5, hc = pyrazole; 6, hc = 3,5-dimethyl pyrazole). The complexes 1,6 have been characterized by elemental analysis, magnetic susceptibility, and various spectroscopic and electrochemical measurements. The X-ray crystal structures of 1, 3 and 6 have been determined. In all three structures, the diazine ligand diah2, is in trans configuration. Metal-centred bond parameters are consistent with the localized electronic structure of the two trans -bent {OV(,-O)VO}3+ cores present in 6. The pentavalent metal centres in 1, 3 and 6 are in a distorted trigonal-bipyramidal N2O3 coordination environment, while the terminal tetravalent metal centres in 6 are in a distorted octahedral O6 coordination sphere. The eight-line EPR spectra of the tetravanadium species (4,6) in dimethyl sulfoxide at ambient temperature indicate the rare valence localized electronic structure in the fluid phase. All the complexes are redox active and display metal-centred electron transfer processes in dimethyl sulfoxide solution. A reduction within ,0.78 to ,0.94 V (vs. Ag/AgCl) is observed for the divanadium(V) species 1,3, while a reduction and an oxidation are observed in the potential ranges ,0.82 to ,0.90 V and 0.96 to 1.12 V (vs. Ag/AgCl), respectively, for the tetravanadium species 4,6. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) [source] Influence of Heat Treatments on In Vitro Degradation Behavior of Mg-6Zn Alloy Studied by Electrochemical Measurements,ADVANCED ENGINEERING MATERIALS, Issue 5 2010Shaoxiang Zhang The influence of heat treatment on the in vitro degradation of Mg-6Zn alloy is studied by electrochemical measurements. After solid-solution treatment, the microstructure of the Mg-6Zn becomes more homogeneous, along with an elevated charge-transfer resistance in SBF and a reduced corrosion current density. After ageing treatment, the discrete intermetallic ,-MgZn phase enhances the cathodic hydrogen evolution and impairs the corrosion resistance of the alloy. Galvanic cells are expected on ageing, but the ageing process makes the microstructure of the alloy homogeneous. Heat treatment alters the in vitro degradation behavior of Mg-6Zn alloy and is applicable in adjusting the biodegradation rate. [source] Highly Emissive and Electrochemically Stable Thienylene Vinylene Oligomers and Copolymers: An Unusual Effect of Alkylsulfanyl SubstituentsADVANCED FUNCTIONAL MATERIALS, Issue 10 2010Shehzad Jeeva Abstract The synthesis, unexpected efficient photoluminescence, and reversible electrochemical p- and n-doping of new conjugated thienylene vinylene materials functionalized with alkylsulfanyl substituents poly(trithienylene vinylene) (PTTV) and poly(dithienylvinyl- co -benzothiadiazole) (PDTVB) along with dithienylvinylene-based oligomers is reported. The materials are studied by thermal and X-ray diffraction analysis, optical spectroscopy, cyclic voltammetry, and spectroelectrochemistry. Organic field-effect transistors (OFETs) are fabricated with PTTV and PDTVB. The polymers, prepared by Stille polycondensation, exhibit good thermal stability and a photoluminescent quantum yield in the range 34%,68%. Low bandgaps (1.5,1.8,eV), estimated by optical and electrochemical measurements along with high stability of both redox states, suggest that these structures are promising materials for photovoltaic applications. OFETs fabricated with PDTVB reveal a hole mobility of 7,×,10,3,cm2 V,1 s,1 with on/off ratio 105, which are comparatively high values for completely amorphous polymer semiconductors. [source] Ethanol and Acetaldehyde Adsorption on a Carbon-Supported Pt Catalyst: A Comparative DEMS StudyFUEL CELLS, Issue 1-2 2004H. Wang Abstract The adsorption of ethanol and acetaldehyde on carbon Vulcan supported Pt fuel cell catalyst and the electrochemical desorption of the adsorption products were studied, using electrochemical measurements and differential electrochemical mass spectrosmetry (DEMS), under continuous flow conditions. Faradaic current adsorption transients at different constant adsorption potentials, which also include CO adsorption for comparison, show pronounced effects of the adsorption potential and the nature of the reactant molecule. Acetaldehyde adsorption is much faster than ethanol adsorption at all potentials. Pronounced Had induced blocking effects for ethanol adsorption are observed at very cathodic adsorption potentials, < 0.16,V, while for acetaldehyde adsorption this effect is much less significant. Comparison of the adsorption charge for CO adsorption with the H-upd charge allows differentiation between H-displacement and double-layer charging effects. Continuous bulk oxidation is observed for both reactants at potentials > 0.31,V; for acetaldehyde adsorption, increasing bulk reduction is found at low potentials. Based on the electron yield per CO2 molecule formed and on the similarity with the CO stripping characteristics the dominant stable adsorbate is CO, coadsorbed with smaller amounts of (partly oxidized) hydrocarbon decomposition fragments, which are also oxidized at higher potentials (> 0.85,V) and which can be reductively desorbed as methane or, to a very small extent, as ethane. The presence of small amounts of adsorbed C2 species and the oxidative dissociation of these species in the main CO oxidation potential range is clearly demonstrated by increased methane desorption after a potential shift to 0.85,V. The data demonstrate that the Pt/Vulcan catalyst is very reactive for C-C bond breaking upon adsorption of these reactants. [source] The Energy of Charge-Transfer States in Electron Donor,Acceptor Blends: Insight into the Energy Losses in Organic Solar CellsADVANCED FUNCTIONAL MATERIALS, Issue 12 2009Dirk Veldman Abstract Here, a general experimental method to determine the energy ECT of intermolecular charge-transfer (CT) states in electron donor,acceptor (D,A) blends from ground state absorption and electrochemical measurements is proposed. This CT energy is calibrated against the photon energy of maximum CT luminescence from selected D,A blends to correct for a constant Coulombic term. It is shown that ECT correlates linearly with the open-circuit voltage (Voc) of photovoltaic devices in D,A blends via eVoc,=,ECT,,,0.5,eV. Using the CT energy, it is found that photoinduced electron transfer (PET) from the lowest singlet excited state (S1 with energy Eg) in the blend to the CT state (S1,,,CT) occurs when Eg,,,ECT,>,0.1,eV. Additionally, it is shown that subsequent charge recombination from the CT state to the lowest triplet excited state (ET) of D or A (CT,,,T1) can occur when ECT,,,ET,>,0.1,eV. From these relations, it is concluded that in D,A blends optimized for photovoltaic action: i) the maximum attainable Voc is ultimately set by the optical band gap (eVoc,=,Eg,,,0.6,eV) and ii) the singlet,triplet energy gap should be ,EST,<,0.2,eV to prevent recombination to the triplet state. These favorable conditions have not yet been met in conjugated materials and set the stage for further developments in this area. [source] Highly Stable Nickel Hexacyanoferrate Nanotubes for Electrically Switched Ion Exchange,ADVANCED FUNCTIONAL MATERIALS, Issue 15 2007W. Chen Abstract Nickel hexacyanoferrate (NiHCF) nanotubes are fabricated by an electrokinetic method based on the distinct surface properties of porous anodic alumina. By this method, nanotubes can be formed rapidly with the morphologies faithfully replicating the nanopores in the template. The prepared nanotubes were carefully characterized using SEM and TEM. Results from IR, UV, EDX, and electrochemical measurements show that the NiHCF nanotubes exist only in the form of K2Ni[Fe(CN)6]. Because of this single composition and unique nanostructure, NiHCF nanotubes show excellently stable cesium-selective ion-exchange ability. The capacity for electrodes modified with NiHCF nanotubes after 500,potential cycles retains 95.3,% of its initial value. Even after 1500 and 3000 cycles, the NiHCF nanotubes still retain 92.2,% and 82.9,%, respectively, of their ion-exchange capacity. [source] Synthesis, characterization, and in vitro antimicrobial activities of organotin(IV) complexes of Schiff bases with ONO-type donor atomsHETEROATOM CHEMISTRY, Issue 6 2010Gülgün Yeni, ehirli A new series of diorganotin complexes of the type R2SnL (L1: N -(2-hydroxy-5-chlorophenyl)- 3-ethoxysalicylideneimine, R = Me, (Me2SnL1), R = n -Bu, (n -Bu2SnL1), R = Ph, (Ph2SnL1), L2: N -(2-hydroxy-4-nitro-5-chlorophenyl)-3-ethoxysalicylideneimine, R = Ph, Ph2SnL2, L3: N -(2-hydroxy-4-nitrophenyl)-3-methoxysalicylideneimine, R = Me, (Me2SnL3), R = n -Bu, (n -Bu2SnL3), L4: N -(2-hydroxy-4-nitrophenyl)-3-ethoxysalicylideneimine, R = Me, (Me2SnL4), R = n -Bu, (n -Bu2SnL4)) were synthesized and characterized by elemental analysis, infrared (IR), 1H, and 13C NMR mass spectroscopic techniques, and electrochemical measurements. Ph2SnL1 and Ph2SnL2 were also characterized by X-ray diffraction analysis and were found to show a fivefold C2NO2 coordination geometry nearly halfway between a trigonal bipyramidal and distorted square pyramidal arrangement. The CSnC angles in the complexes were calculated using Lockhart's equations with the 1J(117/119Sn- 13C) and 2J(117/119Sn- 1H) values from the 1H NMR and 13C NMR spectra. Biocidal activity tests against several micro-organisms and some fungi indicate that all the complexes are mildly active against Gram (+) bacteria and the fungi, A. niger and inactive against Gram (,) bacteria. © 2010 Wiley Periodicals, Inc. Heteroatom Chem 21:373,385, 2010; View this article online at wileyonlinelibrary.com. DOI 10.1002/hc.20628 [source] Evaluation of antioxidant properties of dermocosmetic creams by direct electrochemical measurementsINTERNATIONAL JOURNAL OF COSMETIC SCIENCE, Issue 5 2005C. Guitton Cyclic voltammetry and linear sweep voltammetry were preliminarily used in order to evaluate the global antioxidant properties of dermocosmetic creams. Experiments were performed by introducing electrodes directly into the creams without any pretreatment of the samples. Current,potential curves showed significant anodic current depending on the antioxidant-containing cream studied. In comparison, little amperometric response was recorded with an antioxidant-free cream base. Aqueous solutions of the corresponding antioxidants showed analogous anodic waves and similar peak potentials. A correlation between the global anodic peak and the presence of the antioxidant species in the cream was made with eleven skin creams, attesting to the reliability of the method. Among the tested electrode materials, platinum gave the best results in terms of electrochemical kinetics and measurement precision (current peak standard deviation <5%). Exposure of a depilatory cream to oxidizing agents (e.g. hydrogen peroxide, air, or light) caused a decrease in peak current as expected. This methodology enabled us to evaluate the evolution of the total antioxidant capacity under oxidative stress and gives encouragement to further development of a voltammetric method to quantify cream antioxidant power. [source] A block-on-ring tribocorrosion setup for combined electrochemical and friction testingLUBRICATION SCIENCE, Issue 3 2007M.S. Jellesen Abstract The combined action of corrosion and wear can cause degradation of equipment, and thereby financial losses related to the renewal or repair of damaged equipment. In the food industry, metal degradation is a major concern since metal release eventually can cause health risks for consumers. This study describes a block-on-ring testing facility used to determine sliding wear, and additionally allowing for electrochemical measurements, such as potentiodynamic polarization curves and potentiostatic monitoring of current and potential. To verify the reliability and reproducibility of this block-on-ring tribocorrosion setup, the tribological and electrochemical behaviour of stainless steel sliding against a ceramic ring in sulphuric acid has been determined. Furthermore, a case taken from the food industry has been examined. The study shows that results made on the described block-on-ring testing facility are reliable and can provide improved information about material properties when the material is exposed to combined chemical and mechanical degradation. Copyright © 2007 John Wiley & Sons, Ltd. [source] Galvanisches Verzinken von MagnesiumlegierungenMATERIALWISSENSCHAFT UND WERKSTOFFTECHNIK, Issue 2 2007H. Pokhmurska magnesium alloy; zinc coating; electro plating of zinc; corrosion behaviour Abstract Magnesiumlegierungen sind sehr korrosionsanfällig, was ihre Anwendung unter korrosiven Bedingungen einschränkt. Eine Möglichkeit, um Magnesium vor aggressiven Umweltbedingungen zu schützen, ist das Beschichten. Es werden Ergebnisse über das Korrosionsverhalten der aus verschiedenen Elektrolyten galvanisch verzinkten Magnesiumknetlegierung AZ31 gezeigt. Die Bewertung der Korrosionsprozesse in chloridhaltigen Lösungen erfolgte durch elektrochemische Messungen. Durch einstündige Auslagerung der beschichteten Proben wurde festgestellt, dass dicke und dichte galvanische Zinkschichten auf AZ31 die Korrosionseigenschaften verbessern. Eine Erhöhung der Immersionszeit führt jedoch zu einer Verschlechterung der Korrosionseigenschaften. Elektrolytische Zinkschichten, die durch einen konsekutiven alkalisch / sauren Prozess erzeugt werden, stabilisieren die Schicht und verbessern somit die Korrosionsbeständigkeit des beschichteten AZ31. Zinc-Plating of Magnesium Alloys Magnesium alloys are highly susceptible to corrosion that limits their application when exposure to corrosive service conditions is needed. One of the ways to prevent corrosion is to coat the magnesium-based substrate to avoid a contact with an aggressive environment. Results concerning corrosion behaviour of wrought AZ31 magnesium alloy with electrolytic zinc coatings deposited from different electrolyte solutions are described. Evaluation of corrosion processes in chlorides containing solutions was performed by electrochemical measurements. It was found that thick and dense electrolytic zinc coatings formed on AZ31 significantly improve the corrosion behaviour of magnesium alloy after one hour immersion of zinc coated magnesium alloys in corrosive media. Further increase of immersion time leads to relatively fast decrease of corrosion properties. Electrolytic zinc coatings obtained in consecutive alkaline / acidic process demonstrate an improvement of corrosion resistance of coated AZ31. The time to coating degradation strongly increases. [source] | ||||||||||||||||||||||||||||