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Positive Potentials (positive + potential)
Selected AbstractsAdsorptive Stripping Voltammetric Detection of Tea Polyphenols at Multiwalled Carbon Nanotubes-Chitosan Composite ElectrodeELECTROANALYSIS, Issue 6 2009Deyin Guo Abstract This study reports the catalytic oxidation and detection of tea polyphenols (TPs) at glassy-carbon electrode modified with multiwalled carbon nanotubes-chitosan (MWCNTs-CS) film. The adsorption of TPs at the surface of the MWCNTs through ,,, conjugation prevents the aggregation of nanotubes and induces a stable MWCNTs suspension in water over 30 days. Based on the adsorptive accumulation of polyphenols at MWCNTs, TPs is sensitively and selectively detected by adsorptive stripping voltammetry. The accumulation conditions and pH effect on the adsorptive stripping detection were examined. The linear range was found to be 100 to 1000,mg L,1 with a detection limit of 10,mg L,1 (S/N=3) for 2.5,min accumulation. Additionally, the MWCNTs-CS electrode is easily renewed by applying positive potential to remove the adsorbed TPs. This method was successfully applied to determine TPs in commercially available teas with satisfied result compared with that of conventional spectrometric analysis. [source] Electrochemical Preparation of Poly(Malachite Green) Film Modified Nafion-Coated Glassy Carbon Electrode and Its Electrocatalytic Behavior Towards NADH, Dopamine and Ascorbic AcidELECTROANALYSIS, Issue 14 2007Shen-Ming Chen Abstract Poly(malachite green) film modified Nafion-coated glassy carbon electrodes have been prepared by potentiodynamic cycling in malachite green solution. The pH of polymerisation solution has only minor effect on film formation. Electrochemical quartz crystal microbalance (EQCM) was used to monitor the growth of the poly(malachite green) film. Cyclic voltammogram of the poly(malachite green) film shows a redox couple with well-defined peaks. The redox response of the modified electrode was found to be depending on the pH of the contacting solution. The peak potentials were shifted to a less positive region with increasing pH and the dependence of the peak potential was found to be 56,mV per pH unit. The electrocatalytic behavior of poly(malachite green) film modified Nafion-coated glassy carbon electrodes was tested towards oxidation of NADH, dopamine, and ascorbic acid. The oxidation of dopamine and ascorbic acid occurred at less positive potential on poly(malachite green) film compared to bare glassy carbon electrode. In the case of NADH, the overpotential was reduced substantially on modified electrode. Finally, the feasibility of utilizing poly(malachite green) film electrode in analytical estimation of ascorbic acid was demonstrated in flow injection analysis. [source] Preparation, Characterization and Electrocatalytic Studies on Copper Complex Dye Film Modified ElectrodesELECTROANALYSIS, Issue 13 2007Shen-Ming Chen Abstract Copper complex dye (C.I. Direct Blue 200) film modified electrodes have been prepared by multiple scan cyclic voltammetry. The effect of solution pH and nature of electrode material on film formation was investigated. The optimum pH for copper complex film formation on glassy carbon was found to be 1.5. The mechanism of film formation on ITO seems to be similar to that on GC surface but completely different mechanism followed with gold electrode. Cyclic voltammetric features of our modified electrodes are in consistent with a surface-confined redox process. The voltammetric response of modified electrode was found to be depending on pH of the contacting solution. UV-visible spectra show that the nature of copper complex dye is identical in both solution phase and after forming film on electrode. The electrocatalytic behavior of copper complex dye film modified electrode towards oxidation of dopamine, ascorbic acid and reduction of SO52, was investigated. The oxidation of dopamine and ascorbic acid occurred at less positive potential on film electrode compared to bare glassy carbon electrode. Feasibility of utilizing our modified electrode in analytical estimation of dopamine, ascorbic acid was also demonstrated. [source] Gold Nanoparticles in Nonenzymatic Electrochemical Detection of SugarsELECTROANALYSIS, Issue 19-20 2006Fredy Kurniawan Abstract A nonenzymatic electrochemical sensor for detection of sugars was prepared by layer-by-layer deposition of gold nanoparticles on thin gold electrodes. The deposition was optimized by using of surface plasmon resonance. Voltammetric investigation and impedance spectroscopy of the sensor was performed. Electrical currents caused by glucose on bare gold electrodes and on gold electrodes coated by immobilized gold nanoparticles were compared. The electrodes with nanoparticles display much higher current of glucose oxidation. The oxidation becomes blocked when the swept electrode potential exceeded +0.25,V, during the back scan an oxidation peak is observed again but at less positive potential. The magnitudes of these current peaks are linearly dependent on the glucose concentration; this dependence can be used as calibration for analytical applications. The limit of detection for glucose is below 0.5,mM, the sensitivity (normalized to the macroscopic electrode surface) is about 160,,A,cm,2,mM,1. The sensor response is linear till at least 8,mM of glucose concentration. [source] Coupling Capillary Electrophoresis and Pulsed Electrochemical DetectionELECTROANALYSIS, Issue 13 2005Carlos Abstract Pulsed electrochemical detection (PED) is an excellent method for detection of analytes that normally foul electrodes. In PED, the detection electrode is first cleaned at a high positive potential, then reactivated at a negative potential dissolving the surface oxide, and finally used to oxidize the analyte at a moderate positive potential. Due to the advantages and versatility of PED, many different variations of the detection waveform can be found in literature. This review focuses on application of PED to CE and in particular, the most commonly used modes: pulsed amperometric detection (PAD) and integrated pulsed amperometric detection (iPAD). [source] Tuning Specific Biomolecular Interactions Using Electro-Switchable Oligopeptide SurfacesADVANCED FUNCTIONAL MATERIALS, Issue 16 2010Chun L. Yeung Abstract The ability to regulate biomolecular interactions on surfaces driven by an external stimuli is of great theoretical interest and practical impact in the biomedical and biotechnology fields. Herein, a new class of responsive surfaces that rely on electro-switchable peptides to control biomolecular interactions on gold surfaces is presented. This system is based upon the conformational switching of positively charged oligolysine peptides that are tethered to a gold surface, such that bioactive molecular moieties (biotin) incorporated on the oligolysines can be reversibly exposed (bio-active state) or concealed (bio-inactive state) on demand, as a function of surface potential. The dynamics of switching the biological properties is studied by observing the binding events between biotin and fluorescently labeled NeutrAvidin. Fluorescence microscope images and surface plasmon resonance spectral data clearly reveal opposite binding behaviors when +0.3 V or ,0.4 V vs. SCE are applied to the surface. High fluorescence intensities are observed for an applied positive potential, while minimal fluorescence is detected for an applied negative potential. Surface plasmon resonance spectroscopy (SPR) results provided further evidence that NeutrAvidin binding to the surface is controlled by the applied potential. A large SPR response is observed when a positive potential is applied on the surface, while a negative applied potential induces over 90% reduction in NeutrAvidin binding. [source] The triakontatetraneuropeptide TTN increases [Ca2+]i in rat astrocytes through activation of peripheral-type benzodiazepine receptorsGLIA, Issue 2 2001Pierrick Gandolfo Abstract Astrocytes synthesize a series of regulatory peptides called endozepines, which act as endogenous ligands of benzodiazepine receptors. We have recently shown that one of these endozepines, the triakontatetraneuropeptide TTN, stimulates DNA synthesis in astroglial cells. The purpose of the present study was to determine the mechanism of action of TTN on cultured rat astrocytes. Binding of the peripheral-type benzodiazepine receptor ligand [3H]Ro5-4864 to intact astrocytes was displaced by TTN, whereas its C-terminal fragment (TTN[17,34], the octadecaneuropeptide ODN) did not compete for [3H]Ro5-4864 binding. Microfluorimetric measurement of cytosolic calcium concentrations ([Ca2+]i) with the fluorescent probe indo-1 showed that TTN (10,10 to 10,6 M) provokes a concentration-dependent increase in [Ca2+]i in cultured astrocytes. Simultaneous administration of TTN (10,8 M) and Ro5-4864 (10,5 M) induced an increase in [Ca2+]i similar to that obtained with Ro5-4864 alone. In contrast, the effects of TTN (10,8 M) and ODN (10,8 M) on [Ca2+]i were strictly additive. Chelation of extracellular Ca2+ by EGTA (6 mM) or blockage of Ca2+ channels with Ni2+ (2 mM) abrogated the stimulatory effect of TTN. The calcium influx evoked by TTN (10,7 M) or by Ro5-4864 (10,5 M) was not affected by the N- and T-type calcium channel blockers ,-conotoxin (10,6 M) and mibefradil (10,6 M), but was significantly reduced by the L-type calcium channel blocker nifedipine (10,7 M). Patch-clamp studies showed that, at negative potentials, TTN (10,7 M) induced a sustained depolarization. Reduction of the chloride concentration in the extracellular solution shifted the reversal potential from 0 mV to a positive potential. These data show that TTN, acting through peripheral-type benzodiazepine receptors, provokes chloride efflux, which in turn induces calcium influx via L-type calcium channels in rat astrocytes. GLIA 35:90,100, 2001. © 2001 Wiley-Liss, Inc. [source] Long-lasting increased excitability differs in dentate gyrus vs.HIPPOCAMPUS, Issue 3 2002CA1 in freely moving chronic epileptic rats after electrically induced status epilepticus Abstract A paired-pulse (PP) stimulation protocol was used to examine changes in field potentials (fEPSPs), locally evoked in CA1 via Schaffer/commissural fiber stimulation and in the dentate gyrus (DG) through angular bundle stimulation, in freely moving epileptic rats. This epilepsy model is characterized by recurrent spontaneous seizures that occur after a latent period of 1,2 weeks following an electrically induced status epilepticus (SE). In the control period, i.e., before induction of SE, the PP stimulation protocol given at the appropriate intensity evoked fEPSPs with a pronounced paired-pulse depression (PPD). In the acute period, immediately after SE, the fEPSPs in the CA1 and DG areas were generally depressed. During the latent period in the CA1 stratum radiatum, the negative fEPSP was followed by a large positive potential that remained for the rest of the recording period. CA1 PPD, observed during the control period, was changed to paired-pulse facilitation (PPF) that remained for the rest of the recording period. Also during the latent period, a broad late component appeared in DG fEPSPs. The initial decrease in PPD was partly restored in the following weeks. Timm staining at different time points after SE showed an increase of mossy-fiber sprouting in the inner molecular layer within 6 days, which was robust within 6 weeks. We noted Timm granules positioned on parvalbumin immunoreactive neurons in the granule-cell layer of rats that had survived SE, suggesting that restoration of PPD could be partly due to reinnervation of a population of GABAergic neurons. The broad late component of DG fEPSPs, which was sensitive to the NMDA receptor antagonist ketamine, was still present for at least 6 weeks into the chronic epileptic phase, indicating lasting increased excitability. These observed changes indicate a lasting increased excitability in CA1 and DG networks that could play a role in the recurrence of spontaneous seizures. Hippocampus 2002;12:311,324. © 2002 Wiley-Liss, Inc. [source] A predicted new type of directional noncovalent interactionINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 12 2007Jane S. Murray Abstract The electrostatic potentials computed on the surfaces of a series of molecules R3X, where X is a Group V atom, show that some of these atoms have regions of positive potential on their outer surfaces, approximately on the extensions of the RX bonds. This suggests the likelihood of weak, directional noncovalent interactions between such atoms and nucleophiles, paralleling what has already been established for Groups VI and VII. The origins and relative strengths of the positive regions are explained in terms of the ,-hole concept, supported by natural bond orbital analyses. MP2/6-311++G(3df,2p) calculations confirm the formation of stable complexes between five such Group V molecules and the model nucleophile HCN. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 [source] The long-range electrostatic interactions control tRNA,aminoacyl-tRNA synthetase complex formationPROTEIN SCIENCE, Issue 6 2003Dmitry Tworowski 3D, three-dimensional; PDB, Protein Data Bank of experimentally determined 3D structures of proteins; aaRS, aminoacyl-tRNA synthetase Abstract In most cases aminoacyl-tRNA synthetases (aaRSs) are negatively charged, as are the tRNA substrates. It is apparent that there are driving forces that provide a long-range attraction between like charge aaRS and tRNA, and ensure formation of "close encounters." Based on numerical solutions to the nonlinear Poisson-Boltzmann equation, we evaluated the electrostatic potential generated by different aaRSs. The 3D-isopotential surfaces calculated for different aaRSs at 0.01 kT/e contour level reveal the presence of large positive patches,one patch for each tRNA molecule. This is true for classes I and II monomers, dimers, and heterotetramers. The potential maps keep their characteristic features over a wide range of contour levels. The results suggest that nonspecific electrostatic interactions are the driving forces of primary stickiness of aaRSs,tRNA complexes. The long-range attraction in aaRS,tRNA systems is explained by capture of negatively charged tRNA into "blue space area" of the positive potential generated by aaRSs. Localization of tRNA in this area is a prerequisite for overcoming the barrier of Brownian motion. [source] Brain potentials in perception: Picture complexity and emotional arousalPSYCHOPHYSIOLOGY, Issue 3 2007Margaret M. Bradley Event-related potentials (ERPs) were measured while participants viewed affectively arousing and neutral pictures depicting either simple figure,ground compositions or more complex scenes to assess the timing and topography of perceptual and emotional modulation. Emotional pictures elicited a larger late positive potential than neutral pictures in a 400,700-ms window over centro-parietal sensors both for pictures with simple figure,ground composition and for more complex scenes. Picture composition affected ERPs beginning earlier (around 150 ms), with simple figure,ground compositions eliciting less positivity over posterior sensors and less negativity over frontal sensors. Emotionality had little effect on modulation of these early ERPs. These data suggest that the late centro-parietal positive potential primarily reflects motivational relevance, and that earlier posterior (and anterior) components reflect, at least in part, differences in a picture's perceptual organization. [source] Semantic integration in videos of real,world events: An electrophysiological investigationPSYCHOPHYSIOLOGY, Issue 1 2003Tatiana Sitnikova Event,related potentials (ERPs) discriminated between contextually appropriate and inappropriate objects appearing in video film clips of common activities. Incongruent objects elicited a larger negative,going deflection, which was similar to the N400 component described previously in association with words and static pictures and which has been argued to reflect the integration of semantic information into a mental representation of the preceding context. The onset of this potential occurred shortly after object presentation, indicating that semantic integration is a rapid online component of real,world perception. In addition, the anomalies in movies evoked a large late positive potential at posterior regions, suggesting that in event perception, semantic incongruity may trigger cognitive processes other than those mediating pure semantic integration. [source] Being before doing: The cultural identity (essence) of occupational therapyAUSTRALIAN OCCUPATIONAL THERAPY JOURNAL, Issue 3 2006Ruth Marguerite Watson Occupational therapists know that culture is relevant to their work, but have failed to understand that while they share a professional foundation, practice cannot assume uniformity, given the cultural uniqueness of different contexts. A discussion of why culture matters forms the basis for appreciating the cultural identity of the profession, which unifies around a belief in the power and positive potential of occupation to transform people's lives. This is the profession's ,essence'. Examples from South Africa are used to show that previous epistemologies must be challenged, and assumptions, values and beliefs adjusted in order to match cultural needs. As people's ,being' is shaped by the culture within which they are situated, the collective cultural practices or ,doing' of occupational therapy should be diversified across the globe. Service options that are driven by these perspectives are suggested as ways of giving due recognition to cultural needs and people's right to occupationally fulfilled lives. [source] Structure of uracil-DNA N -glycosylase (UNG) from Vibrio cholerae: mapping temperature adaptation through structural and mutational analysisACTA CRYSTALLOGRAPHICA SECTION F (ELECTRONIC), Issue 2 2010Inger Lin Uttakleiv Raeder The crystal structure of Vibrio cholerae uracil-DNA N -glycosylase (vcUNG) has been determined to 1.5,Å resolution. Based on this structure, a homology model of Aliivibrio salmonicida uracil-DNA N -glycosylase (asUNG) was built. A previous study demonstrated that asUNG possesses typical cold-adapted features compared with vcUNG, such as a higher catalytic efficiency owing to increased substrate affinity. Specific amino-acid substitutions in asUNG were suggested to be responsible for the increased substrate affinity and the elevated catalytic efficiency by increasing the positive surface charge in the DNA-binding region. The temperature adaptation of these enzymes has been investigated using structural and mutational analyses, in which mutations of vcUNG demonstrated an increased substrate affinity that more resembled that of asUNG. Visualization of surface potentials revealed a more positive potential for asUNG compared with vcUNG; a modelled double mutant of vcUNG had a potential around the substrate-binding region that was more like that of asUNG, thus rationalizing the results obtained from the kinetic studies. [source] Ribosome motions modulate electrostatic propertiesBIOPOLYMERS, Issue 6 2004Joanna Trylska Abstract The electrostatic properties of the 70S ribosome of Thermus thermophilus were studied qualitatively by solving the Poisson,Boltzmann (PB) equation in aqueous solution and with physiological ionic strength. The electrostatic potential was calculated for conformations of the ribosome derived by recent normal mode analysis (Tama, F., et al. Proc Natl Acad Sci USA 2003 100, 9319,9323) of the ratchet-like reorganization that occurs during translocation (Frank, J.; Agrawal, R. K. Nature 2000 406, 318,322). To solve the PB equation, effective parameters (charges and radii), applicable to a highly charged backbone model of the ribosome, were developed. Regions of positive potential were found at the binding site of the elongation factors G and Tu, as well as where the release factors bind. Large positive potential areas are especially pronounced around the L11 and L6 proteins. The region around the L1 protein is also positively charged, supporting the idea that L1 may interact with the E-site tRNA during its release from the ribosome after translocation. Functional rearrangement of the ribosome leads to electrostatic changes which may help the translocation of the tRNAs during the elongation stage. © 2004 Wiley Periodicals, Inc. Biopolymers, 2004 [source] Strength in Networks: Employment Rights Organizations and the Problem of Co-OrdinationBRITISH JOURNAL OF INDUSTRIAL RELATIONS, Issue 4 2006Charles Heckscher In recent decades, alternative organizations and movements ,,quasi-unions', have emerged to fill gaps in the US system of representation caused by union decline. We examine the record of quasi-unions and find that although they have sometimes helped workers who lack other means of representation, they have significant limitations and are unlikely to replace unions as the primary means of representation. But networks, consisting of sets of diverse actors including unions and quasi-unions, are more promising. They have already shown power in specific campaigns, but they have yet to do so for more sustained strategies. By looking at analogous cases, we identify institutional bases for sustained networks, including shared information platforms, behavioural norms, common mission and governance mechanisms that go well beyond what now exists in labour alliances and campaigns. There are substantial resistances to these network institutions because of the history of fragmentation and autonomy among both unions and quasi-unions; yet we also identify positive potential for network formation. [source] Optimizing the Quadruple-potential Waveform for the Determination of Gentamicin Sulfate by High Performance Liquid Chromatography with Pulsed Electrochemical DetectionCHINESE JOURNAL OF CHEMISTRY, Issue 9 2005Ya-Qi Cai Abstract In this paper, a quadruple-potential waveform was investigated and optimized for the determination of gentamicin by reversed phase ion-pair chromatography. Instead of a relatively high positive potential, a negative potential was adopted as a potential for the cleaning of gold working electrode. By this way, the formation of gold oxide resulting from the application of high positive potential during the analyte detection and electrode cleaning was greatly reduced, and therefore, the dissolution and recession of gold working electrode was also reduced. The good condition of gold working electrode achieved by this quadruple-potential waveform can help us to obtain a good reproducibility. In order to acquire signal-to-noise ratio as high as possible, several waveform parameters affecting the detection of gentamicin were carefully selected. The analytical method has been applied to the determination of two real gentamicin samples, and good results with low relative standard deviation not more than 4% were obtained. [source] Study on Lead Dioxide Modified Electrode and Its Application in Detection of PhenolsCHINESE JOURNAL OF CHEMISTRY, Issue 2 2003Ai Shi-Yun Abstract The conditions for the preparation of PbO2 modified Pt rotation disc electrode in solutions containing HC104 and Pb(II) were studied, and the morphology and composition of the obtained PbO2 film were characterized by SEM and XRD techniques, respectively. The results show that the modification process of PbO is dependent on the rotation velocity of the electrode and the concentrations of HCIO4 and Pb(II). And it was observed that the obtained PbO2 film was rutile ,-PDO2 structure. At a certain positive potential, HO· and HO2· radicals can be generated on the surface of the modified PbO2/Pt electrode and then oxidize phenols. According to the change of the responding anodic current, the determination of phenols was realizable and good results were obtained. [source] Exponential growth for the wave equation with compact time-periodic positive potentialCOMMUNICATIONS ON PURE & APPLIED MATHEMATICS, Issue 4 2009Ferruccio Colombini We prove the existence of smooth positive potentials V(t, x), periodic in time and with compact support in x, for which the Cauchy problem for the wave equation utt , ,xu + V(t, x)u = 0 has solutions with exponentially growing global and local energy. Moreover, we show that there are resonances, z , ,, |z| > 1, associated to V(t, x). © 2008 Wiley Periodicals, Inc. [source] Voltammetric Determination of Mercury(II) at Poly(3-hexylthiophene) Film Electrode.ELECTROANALYSIS, Issue 24 2007Effect of Halide Ions Abstract The well-known method for the determination of mercury(II), which is based on the anodic stripping voltammetry of mercury(II), has been adapted for applications at the thin film poly(3-hexylthiophene) polymer electrode. Halide ions have been found to increase the sensitivity of the mercury response and shift it more positive potentials. This behavior is explained by formation of mercuric halide which can be easily deposited and stripped from the polymer electrode surface. The procedure was optimized for mercury determination. For 120,s accumulation time, detection limit of 5,ng mL,1 mercury(II) has been observed. The relative standard deviation is 1.3% at 40,ng mL,1 mercury(II). The performance of the polymer film studied in this work was evaluated in the presence of surfactants and some potential interfering metal ions such as cadmium, lead, copper and nickel. [source] Redox Active Two-Component Films of Palladium and Covalently Linked Zinc Porphyrin,Fullerene DyadELECTROANALYSIS, Issue 9 2006Marta Plonska Abstract Redox active films have been generated electrochemically by the reduction of dyads consisting of fullerene C60 covalently linked to zinc meso -tetraphenyloporphyrin, ZnPC60, and palladium acetate. The films are believed to consist of a polymeric network formed via covalent bonds between the palladium atoms and the fullerene moieties. In these films, the zinc porphyrin moiety is covalently linked to the polymeric chains through the pyrrolidine ring of the fullerene. The ZnPC60/Pt films are electrochemically active in both positive and negative potential excursions. At positive potentials, two oxidation steps for the zinc porphyrin are observed. In the negative potential range, electron transfer processes involving the zinc porphyrin and the fullerene entities are observed. Film formation is also accompanied by palladium deposition on the electrode surface. The presence of a metallic phase in the film influences its morphology, structure and electrochemical properties. [source] Solid State Electrochemical Oxidation Mechanisms Of Morin in Aqueous MediaELECTROANALYSIS, Issue 9 2005Patricia Janeiro Abstract The mechanism of electrochemical oxidation of morin has been studied using cyclic, differential pulse and square-wave voltammetry techniques in aqueous electrolyte with solid, insoluble morin hydrate mechanically transferred to a glassy carbon electrode surface, over a wide pH range. The oxidation mechanism proceeds in sequential steps, related with the hydroxyl groups in the three aromatic rings and the oxidation is pH dependent over part of the pH range the oxidation potentials are shifted to lower values with increasing pH. Oxidation of the 2,,4,dihydroxy moiety at the B ring of morin occurs first, at very low positive potentials, and is a one electron one proton reversible reaction. The hydroxyl groups oxidized at more positive potentials were shown to undergo an irreversible oxidation reaction. [source] Early Polarographic Studies on ProteinsELECTROANALYSIS, Issue 13-14 2004Michael Heyrovsky Abstract The first effects of proteins observed with the dropping mercury electrode were catalytic, due to evolution of hydrogen in weakly alkaline solutions. Catalytic lowering of hydrogen overvoltage in presence of cobalt ions, the so-called Brdicka reaction, became the main means for polarographic study of proteins. Apart from that, polarography has been used for following proteins in their adsorption on the electrode surface, in their anodic reaction with mercury at positive potentials, in reduction of the disulfidic bonds of their components, in their complexation with metallic ions in the solution, in electrode reactions of their prosthetic groups and in antigen-antibody interactions. Our review is limited to applications of the dropping mercury electrode. [source] Electrochemical Oxidation of QuercetinELECTROANALYSIS, Issue 22 2003Maria, Oliveira Brett Abstract The mechanism of electrochemical oxidation of quercetin on a glassy carbon electrode has been studied using cyclic, differential pulse and square-wave voltammetry at different pH. It proceeds in a cascade mechanism, related with the two catechol hydroxyl groups and the other three hydroxyl groups which all present electroactivity, and the oxidation is pH dependent. Quercetin also adsorbs strongly on the electrode surface; and the final oxidation product is not electroactive and blocks the electrode surface. The oxidation of the catechol 3,,4,-dihydroxyl electron-donating groups, occurs first, at very low positive potentials, and is a two electron two proton reversible reaction. The hydroxyl group oxidized next was shown to undergo an irreversible oxidation reaction, and this hydroxyl group can form a intermolecular hydrogen bond with the neighboring oxygen. The other two hydroxyl groups also have an electron donating effect and their oxidation is reversible. [source] Electrochemical Behavior and Detection of Dopamine and Ascorbic Acid at an Iron(II)tetrasulfophthalocyanine Modified Carbon Paste MicroelectrodeELECTROANALYSIS, Issue 10 2003Joshua Oni Abstract In this article the electrocatalytic behavior of an iron(II)tetrasulfophthalocyanine modified carbon paste microelectrode for the oxidation of dopamine (DA) and ascorbic acid (AA) is described. Although the oxidation potential of ascorbic acid is shifted by over 100,mV to more positive potentials, no peak separation could be obtained. This can be explained by the immediate homogeneous reduction of the oxidation product of dopamine by ascorbic acid in solution. However, this reaction induces a shift of the half-wave potential as a function of ratio of concentration of dopamine to ascorbic acid (cDA/cAA). Therefore it was possible to determine the cAA and cDA from this potential shift and the experimental peak current. Detection limits of 4.5±0.2×10,7 and 7.5±0.5×10,7,mol,L,1 were obtained respectively for dopamine and ascorbic acid for cDA/cAA>0.01. [source] Complexes of glutathione with heavy metal ions as a new biochemical marker of aquatic environment pollution,ENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 3 2010Jiri Baloun Abstract Reduced glutathione (GSH) plays a number of key roles in many biochemical pathways. This peptide is highly reactive and forms conjugates with other molecules via its sulfhydryl moiety. The interactions of the common heavy metal pollutant Cd(II) with GSH were determined by using the Brdicka reaction to evaluate whether this technique would be suitable as a biomarker. After GSH interaction with Cd(II) ions, two characteristic changes in the measured voltammogram were observed: Cat2 signal height decreased, and a new signal called P1 was found. The observed signal probably relates to the formation of a GSH,heavy metal ion complex adsorbed on the surface of the working electrode. When the interaction of GSH with cisplatin was studied, the same characteristic changes in the voltammogram were observed, which confirmed our hypothesis. Moreover, changes in the height of P1 and Cat2 signals with increasing time of GSH interaction with Cd(II) ions and/or cisplatin were also investigated. Cat2 peak height decreased proportionally with increasing time of interaction. This decrease can be explained by shielding of free sulfhydryl moiety by heavy metal ions, so it cannot catalyze the evolution of hydrogen from the supporting electrolyte. In addition, we found that, with increasing time of the interaction, the P1 signal was enhanced and shifted to more positive potentials for both Cd(II) ions and cisplatin. Environ. Toxicol. Chem. 2010;29:497,500. © 2009 SETAC [source] Structural, Spectroscopic, and Proton-Coupled Electron-transfer Behavior of Pyrazolyl-3,5-bis(benzimidazole)-Bridged Homo- and Heterochiral RuIIRuII, OsIIOsII, and OsIIRuII 2,2,-Bipyridine ComplexesEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 4 2010Sujoy Baitalik Abstract The homo- and heterobimetallic complexes [(bpy)2MII(H2pzbzim)M,II(bpy)2](ClO4)3·nH2O (1, 3, 5) and their corresponding deprotonated complexes [(bpy)2MII(pzbzim)M,II(bpy)2](ClO4)·nH2O (2, 4, 6) [where MII, M,II = Ru (1, 2) = Os (3, 4); MII = Os and M,II = Ru (3, 5); bpy = 2,2,-bipyridine; H3pzbzim = pyrazole-3,5-bis(benzimidazole)] were synthesized, separated to their heterochiral (a, ,,/,,) and homochiral (b, ,,/,,) diastereoisomers, and characterized by elemental analyses, ESI-MS, and 1H NMR spectroscopy. The X-ray structures of 1a, 3a, and 5a show the involvement of two pyridine rings of two bpy ligands in strong intramolecular nonbonded ,,, interaction. The occurrence of a C,H···, interaction between an aromatic C,H and the ,-cloud of a pyridine ring leads to strong electronic shielding of this proton (1H NMR). In all cases, the two diastereoisomers show practically no differences in their absorption spectra, redox potentials, and pK values. The large shifts in the E1/2 values to less positive potentials and substantial redshifts in the MLCT bands that occur on deprotonation of 1, 3, and 5 are energetically correlated. From the profiles of E1/2(1), (2) vs. pH over the pH range 1,12, the equilibrium constants and standard redox potentials for all the complex species in the metal oxidation states II·II, II·III, and III·III and the bridged ligand in the protonation states H2pzbzim,, Hpzbzim2,, and pzbzim3, have been evaluated. Using these values the bond dissociation free energies for the benzimidazole N,H bonds have been estimated. Spectroelectrochemical studies have been carried out for 1a, 3a, and 5a in the range 400,1100 nm. With stepwise oxidation of the metal centers replacement of MLCT bands by LMCT bands occur gradually with the observation of sharp isosbestic points. In the case of 1a, a band observed at ,max = 910 nm for the RuIIRuIII species has been ascribed to intervalence charge transfer (IVCT) transition. [source] Synthesis, X-ray Crystal Structures and Electrochemistry of (Indenyl)ruthenium Complexes Containing dppf and Heterocyclic Thiolato/Thione LigandsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 1 2008Sin Yee Ng Abstract A number of (indenyl)ruthenium complexes containing dppf [1,1,-bis(diphenylphosphanyl)ferrocene] and heterocyclic thiolato/thione ligands have been synthesized. All the complexes were fully characterized by microanalytical and spectroscopic techniques, together with X-ray diffraction analyses for those containing the benzothiazolato (thiolato) and the thiadiazole (thione) ligands. Cyclic voltammetry (CV) experiments indicated that these complexes can be oxidized in three one-electron processes at positive potentials. Differences in chemical reversibility observed during variable-temperature CV experiments indicated that it was likely that the oxidation processes occurred at two electronically noncommunicating sites within the molecules. One site could be assigned as the oxidation of the Ru ion (two one-electron processes), whilst the second site was assigned as the oxidation of the dppf (one one-electron process). (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Episodic ataxia type 1 mutations in the KCNA1 gene impair the fast inactivation properties of the human potassium channels Kv1.4-1.1/Kv,1.1 and Kv1.4-1.1/Kv,1.2EUROPEAN JOURNAL OF NEUROSCIENCE, Issue 11 2006Paola Imbrici Abstract Episodic ataxia type 1 (EA1) is an autosomal dominant neurological disorder characterized by constant muscle rippling movements (myokymia) and episodic attacks of ataxia. Several heterozygous point mutations have been found in the coding sequence of the voltage-gated potassium channel gene KCNA1 (hKv1.1), which alter the delayed-rectifier function of the channel. Shaker -like channels of different cell types may be formed by unique hetero-oligomeric complexes comprising Kv1.1, Kv1.4 and Kv,1.x subunits. Here we show that the human Kv,1.1 and Kv,1.2 subunits modulated the functional properties of tandemly linked Kv1.4-1.1 wild-type channels expressed in Xenopus laevis oocytes by (i) increasing the rate and amount of N-type inactivation, (ii) slowing the recovery rate from inactivation, (iii) accelerating the cumulative inactivation of the channel and (iv) negatively shifting the voltage dependence of inactivation. To date, the role of the human Kv1.4-1.1, Kv1.4-1.1/Kv,1.1 and Kv1.4-1.1/Kv,1.2 channels in the aetiopathogenesis of EA1 has not been investigated. Here we also show that the EA1 mutations E325D, V404I and V408A, which line the ion-conducting pore, and I177N, which resides within the S1 segment, alter the fast inactivation and repriming properties of the channels by decreasing both the rate and degree of N-type inactivation and by accelerating the recovery from fast inactivation. Furthermore, the E325D, V404I and I177N mutations shifted the voltage dependence of the steady-state inactivation to more positive potentials. The results demonstrate that the human Kv,1.1 and Kv,1.2 subunits regulate the proportion of wild-type Kv1.4-1.1 channels that are available to open. Furthermore, EA1 mutations alter heteromeric channel availability which probably modifies the integration properties and firing patterns of neurones controlling cognitive processes and body movements. [source] The molecular interactions of pyrethroid insecticides with insect and mammalian sodium channels,PEST MANAGEMENT SCIENCE (FORMERLY: PESTICIDE SCIENCE), Issue 10 2001Horia Vais Abstract Recent progress in the cloning of , (para) and , (TipE) Na channel sub-units from Drosophila melanogaster (fruit fly) and Musca domestica (housefly) have facilitated functional expression studies of insect Na channels in Xenopus laevis oocytes, assayed by voltage clamp techniques. The effects of Type I and Type II pyrethroids on the biophysical properties of these channels are critically reviewed. Pyrethroid resistance mutations (termed kdr and super-kdr) that reduce the sensitivity of the insect Na channel to pyrethroids have been identified in a range of insect species. Some of these mutations (eg L1014F, M918T and T929I) have been incorporated into the para Na channel of Drosophila, either individually or in combination, to investigate their effects on the sensitivity of this channel to pyrethroids. The kdr mutation (L1014F) shifts the voltage dependence of both activation and steady-state inactivation by ,5,mV towards more positive potentials and facilitates Na channel inactivation. Incorporation of the super-kdr mutation (M918T) into the Drosophila Na channel also increases channel inactivation and causes a >100-fold reduction in deltamethrin sensitivity. These effects are shared by T929I, an alternative mutation that confers super-kdr -like resistance. Parallel studies have been undertaken using the rat IIA Na channel to investigate the molecular basis for the low sensitivity of mammalian brain Na channels to pyrethroids. Rat IIA channels containing the mutation L1014F exhibit a shift in their mid-point potential for Na activation, but their overall sensitivity to permethrin remains similar to that of the wild-type rat channel (ie both are 1000-fold less sensitive than the wild-type insect channel). Mammalian neuronal Na channels have an isoleucine rather than a methionine at the position (874) corresponding to the super-kdr (M918) residue of the insect channel. Replacement of the isoleucine of the wild-type rat IIA Na channel with a methionine (I874M) increases deltamethrin sensitivity 100-fold. In this way, studies of wild-type and mutant Na channels of insects and mammals are providing a molecular understanding of kdr and super-kdr resistance in insects, and of the low pyrethroid sensitivity of most mammalian Na channels. They are also giving valuable insights into the binding sites for pyrethroids on these channels. © 2001 Society of Chemical Industry [source] | |||||||||||||||||||