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Negative Potential (negative + potential)
Selected AbstractsThe sequential processing of visual feature conjunction mismatches in the human brainPSYCHOPHYSIOLOGY, Issue 1 2004Yuping Wang Abstract To clarify the brain mechanism for multifeature stimulus comparison, subjects matched the features of two serial visual stimuli in pairs. Stimulus pairs were of four categories: C,S,, color same, shape same (match); C,S+, color same, shape different (shape mismatch); C+S,, color different, shape same (color mismatch); C+S+, color different, shape different (conjunction mismatches). Subjects matched the stimuli in three different sessions according to different attention tasks: attending to color (Ac), attending to shape (As), or attending to both color and shape (Acs). A negative one-peak brain potential, N270, was elicited in all the mismatch conditions with amplitude enhanced in the task-relevant mismatch. Negative potential with two peaks, N270 and N400, appeared when attending to the conjunction mismatches concurrently. The two serial negativities in response to attended feature conjunctions might reflect the temporal different stages for processing conjunction mismatches or conflicts. [source] Separation and Detection of Nitrophenols at Capillary Electrophoresis Microchips with Amperometric DetectionELECTROANALYSIS, Issue 2 2006Jan Fischer Abstract A miniaturized analytical system for the separation and amperometric detection of toxic nitrophenols, based on the coupling of a micromachined capillary electrophoresis (CE) chip with a glassy carbon detector is described. This microsystem enables a rapid (120,s/sample) simultaneous determination of five priority nitrophenolic pollutants (2-nitrophenol, 3-nitrophenol, 4-nitrophenol, 2,4-dinitrophenol, and 2-methyl-4,6-dinitrophenol). These compounds can be detected down to the 1×10,5,M level using a 15,mM phosphate buffer pH,7.2 (containing 1.3,mM ,-cyclodextrin) as running solution on 77,mm long microchannel by applying a separation voltage of 3000,V and a negative potential of ,0.7,V (vs. Ag /AgCl wire). Applicability to ground water samples was demonstrated. [source] Electrochemically-Induced Deposition of Amine-Functionalized Silica Films on Gold Electrodes and Application to Cu(II) Detection in (Hydro)Alcoholic MediumELECTROANALYSIS, Issue 19 2005Alain Walcarius Abstract Well-adherent amine-functionalized porous silica films have been deposited on gold electrodes by combining the self-assembly technology, the sol,gel process, and the electrochemical modulation of pH at the electrode/solution interface. A partial self-assembled monolayer of mercaptopropyl-trimethoxysilane (MPTMS) was first formed on disposable gold electrodes from recordable CDs (Au-CDtrodes). The so pretreated MPTMS-Au-CDtrodes were immersed in a stable sol solution (pH,3) containing (3-aminopropyl)-triethoxysilane (APTES) and tetraethoxysilane (TEOS). Polycondensation of the APTES and TEOS precursors was then achieved by applying a negative potential for a given period of time to generate a local pH increase at the electrode/solution interface and promote the deposition of the amine functionalized silica film adhering well to the electrode surface owing to the MPTMS monolayer acting somewhat as a "molecular glue". Various parameters affecting the electrodeposition process have been studied and the film permeability to redox probes in solution was characterized by cyclic voltammetry. The amine-functionalized silica film electrodes were then applied to the preconcentration of copper(II) species prior to their electrochemical detection by anodic stripping differential pulse voltammetry. Getting high sensitivity has however required the application of an electrochemical pre-activation step as the majority of the organo-functional groups were in the form of ammonium moieties (because the film was prepared from an acidic sol). This was achieved by applying a sufficiently negative potential to the electrode surface to reduce protons and increase consequently the amine-to-ammonium ratio within the film and, thus, the efficiency of the precocentration process. The resulting device was then optimized for copper(II) determination in hydroalcoholic medium, giving rise to a linear response in the 0.1,10,,M concentration range. [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] Mercury Detection in Seawater Using a Mercaptoacetic Acid Modified Gold Microwire ElectrodeELECTROANALYSIS, Issue 10 2005Antje Widmann Abstract It is demonstrated here that it is possible to determine mercury in chloride containing media like seawater by anodic stripping voltammetry using a modified electrode. A gold microwire electrode is modified using mercaptoacetic acid (MAA) to eliminate the problem of calomel formation, allowing the mercury to become fully removed from the electrode surface after each scan. In a synthetic salt solution of KNO3 the sensitivity for mercury was found to be improved by the surface modification. In seawater the sensitivity was not significantly improved possibly because of complexation of the mercury by the abundant chloride; however, the MAA coating prevented the formation of calomel causing the background scan to be free of mercury. Measurements in seawater at various pH values demonstrated that mercury detection is possible at natural pH (around 8); however, best sensitivity was attained at pH,4.8 with a deposition time of 3,min. A peak for copper occurred at more negative potential but did not interfere at this pH. The calibration was linear between 0 and 37,nM mercury with a limit of detection of 1,nM mercury. [source] Adsorptive Stripping Voltammetric Determination of Amitrole at a Multi-Wall Carbon Nanotubes Paste ElectdrodeELECTROANALYSIS, Issue 5-6 2005M. Chicharro Abstract This work reports the excellent electrocatalytic activity of carbon nanotubes paste electrodes (CNTPE) prepared by dispersion of multi-wall carbon nanotubes (MWNT) within mineral oil toward the oxidation of 3-amino-1H -1,2,4-triazole (amitrole). The quantification is performed by adsorptive stripping voltammetry (AdSV). The influence of the paste composition and surface pretreatments as well as the amitrole accumulation conditions on the adsorption and further electrooxidation of this herbicide is described. After potentiodynamic pretreatment in 0.050,M phosphate buffer pH,7.4 the amitrole oxidation signal shifts 250,mV toward more negative potential and the sensitivity increases 29 fold, demonstrating that pretreated CNTPEs are extremely useful for a highly sensitive determination of amitrole down to the sub-,M levels. The oxidation peak current is proportional to the amitrole concentration over the range from 0.8 to 7.0,,M (5,min accumulation), with a detection limit of 0.6,,M (48,,gL,1) and a precision of 4.3%, n=20. The proposed method was used for the determination of amitrole in spiked river water (Alberche River (Madrid, Spain)) and tap water samples (Madrid, Spain) at levels higher than 0.6,,M. [source] Detection of chlorinated quinones using interdigitated electrodes coupled with capillary electrophoresisELECTROPHORESIS, Issue 6 2003Keith B. Male Abstract An array of eight interdigitated microband gold electrodes (IDEs) has been developed together with electrophoretic separation for analysis of chlorinated hydroquinones (ClHQs) and benzoquinones (ClBQs). The IDE chip positioned very close to the separation capillary outlet served as an amplification/detection system without the requirement for frequent "capillary-electrode" alignment. ClHQs, electrophoretically migrating to the IDE surface, were oxidized at +1.1 V by seven electrodes of the array and then detected by the remaining electrode, poised at ,0.1 V. Conversely, ClBQs were detected at +1.1 V by the detecting electrode after having been reduced at the 7 adjacent electrodes poised at ,0.1 V. There was an amplification effect on both the detecting electrode as well as the adjacent electrodes because of the recycle between ClHQs and ClBQs. The detecting "amplification" current response was dependent on the potentials applied, the position of the detecting electrode on the array, the number of adjacent electrodes being used for recycling and the distance between the oxidative and reductive electrodes. Micellar electrokinetic chromatography (MEKC) separation of the analytes was achieved using 30 mM sodium dodecyl sulfate (SDS) with a detection limit in the range of 2,20 ,M. In addition to a facile "capillary-electrode" alignment, the important aspect described here was the capability of detecting through recycling a reduced compound (in the case of ClHQs) at a negative potential to circumvent fouling and electroactive interferences. An appealing feature was also the concurrent oxidation/reduction detection for each compound to ascertain peak assignment, as interfering compounds are less likely to exhibit the same oxidative/reductive characteristics and electrophoretic mobilities as the target analytes. [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] Biophysical characterization of the interaction of high-density lipoprotein (HDL) with endotoxinsFEBS JOURNAL, Issue 23 2002Klaus Brandenburg The interaction of bacterial endotoxins [lipopolysaccharide (LPS) and the ,endotoxic principle' lipid A], with high-density lipoprotein (HDL) from serum was investigated with a variety of physical techniques and biological assays. HDL exhibited an increase in the gel to liquid crystalline phase transition temperature Tc and a rigidification of the acyl chains of the endotoxins as measured by Fourier-transform infrared spectroscopy and differential scanning calorimetry. The functional groups of the endotoxins interacting with HDL are the phosphates and the diglucosamine backbone. The finding of phosphates as target groups is in accordance to measurements of the electrophoretic mobility showing that the zeta potential decreases from ,50 to ,60 mV to ,20 mV at binding saturation. The importance of the sugar backbone as further target structure is in accordance with the remaining negative potential and competition experiments with polymyxin B (PMB) and phase transition data of the system PMB/dephosphorylated LPS. Furthermore, endotoxin binding to HDL influences the secondary structure of the latter manifesting in a change from a mixed ,-helical/,-sheet structure to a predominantly ,-helical structure. The aggregate structure of the lipid A moiety of the endotoxins as determined by small-angle X-ray scattering shows a change of a unilamellar/inverted cubic into a multilamellar structure in the presence of HDL. Fluorescence resonance energy transfer data indicate an intercalation of pure HDL, and of [LPS],[HDL] complexes into phospholipid liposomes. Furthermore, HDL may enhance the lipopolysaccharide-binding protein-induced intercalation of LPS into phospholipid liposomes. Parallel to these observations, the LPS-induced cytokine production of human mononuclear cells and the reactivity in the Limulus test are strongly reduced by the addition of HDL. These data allow to develop a model of the [endotoxin]/[HDL] interaction. [source] Interaction of heparin with Ca2+: A model study with a synthetic heparin-like hexasaccharideISRAEL JOURNAL OF CHEMISTRY, Issue 3-4 2000Jesús Angulo The binding of Ca2+ to synthetic hexasaccharide 1, containing the structural motifs of the regular region of heparin, has been investigated using NMR spectroscopy and molecular modeling. The NMR data of the calcium salt of 1 indicate the existence of specific Ca2+ binding, and molecular modeling results predict three different types of binding sites with different negative potential and preorganized geometry. The presence of Ca2+ does not seem to affect the overall helical structure of hexasaccharide 1, although it seems to have a marked influence on the flexibility of the oligosaccharide backbone. [source] Role of Kinases in Neuronal FunctionBIOTECHNOLOGY JOURNAL, Issue 8 2007Article first published online: 7 AUG 200 Cover illustration: Role of Cdk5 in neuronal function. Crystal structure of indirubin-38-monoxime in complex with Cdk5/p25 [1]. The inhibitor binds in the ATP-binding pocket of the catalytic subunit, mainly through hydrophobic interaction and two hydrogen bonds with Leu83. Indirubin-38-monoxime is shown as a ball-and-stick model, and the molecular surface of Cdk5/p25 is coloured according to electrostatic potential, with blue and red representing positive and negative potential, respectively. The figure was created with the program GRASP [2]. Courtesy of Claudia Crovace, Aldo Tarricone and Andrea Musacchio. [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] Photoelectrochemical Study of Corrosion Resisting Property of Cupronickel B10 in Simulated Cooling WaterCHINESE JOURNAL OF CHEMISTRY, Issue 2 2009Qunjie XU Abstract The corrosion behavior for cupronickel B10 electrode in simulated cooling water has been studied by using cyclic voltammetry, a photocurrent response method and electrochemical impedance spectroscopy (EIS). The cupronickel electrode shows a p-type photoresponse to positive and negative potential scan, which comes from Cu2O layer on its surface, but its iph,max is less than that in borax buffer solution. The corrosion resisting property of the cupronickel B10 electrode appeared worse with the increase in the concentrations of Cl,, SO42, and S2, ions, as well as with increasing pH. The rise in the temperature may result in a photoresponse changes from p-type to n-type, and the corrosion resisting property fell simultaneously. The results of the EIS measurement agree well with those obtained by a photoelectrochemical method. [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] Heterogeneity Of The Properties Of INa in Epicardial And Endocardial Cells Of Rat VentricleCLINICAL AND EXPERIMENTAL PHARMACOLOGY AND PHYSIOLOGY, Issue 3 2002Bonny N Honen SUMMARY 1. Ventricular INa heterogeneity was investigated in adult rat hearts. Differences in transient outward potassium current (Ito) were used to confirm isolation of subepicardial and subendocardial cells. Mean peak Ito was 6.0 ± 0.7 and 1.6 ± 0.45 pA/pF in epicardial and endocardial cells, respectively (P < < 0.01). 2. Maximum sodium conductance was smaller in subendocardial cells compared with subepicardial cells (2.39 ± 0.11 vs 2.78 ± 0.12 nS/pF, respectively; n = 17 for both; 0.01 < P < 0.05) and 50% activation occurred at a slightly more negative potential (,47.6 ± 0.8 vs,44.9 ± 0.9 mV, respectively; n = 10 for both; 0.01 < P < 0.05). 3. The potential for 50% inactivation was not significantly different in subepicardial compared with subendocardial cells (72.2 ± 1.0 vs 72.8 ± 2.2 mV, respectively; n = 17 for both; NS). 4. Persistent sodium current density appeared smaller in subendocardial (n = 19) compared with subepicardial (n = 11) cells (at a test potential of ,25 mV current, density was 0.118 ± 0.041 vs 0.144 ± 0.085 pA/pF, respectively), although this was not statistically significant due to large variability between cells. 5. Mathematical modelling of the cardiac action potential indicated that the combined effects of differences in current density and voltage dependence of sodium currents are unlikely to contribute to ventricular action potential heterogeneity between epicardial and endocardial cells. [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] Plasma membrane surface potential (,pm) as a determinant of ion bioavailability: A critical analysis of new and published toxicological studies and a simplified method for the computation of plant ,pmENVIRONMENTAL TOXICOLOGY & CHEMISTRY, Issue 12 2006Thomas B. Kinraide Abstract Plasma membranes (PMs) are negatively charged, and this creates a negative PM surface electrical potential ,PM) that is also controlled by the ionic composition of the bathing medium. The ,PM controls the distribution of ions between the PM surface and the medium so that negative potentials increase the surface activity of cations and decrease the surface activity of anions. All cations reduce the negativity of ,PM, and these common ions are effective in the following order: Al3+ > H+ > Cu2+ > Ca2+ , Mg2+ > Na+ , K+. These ions, especially H+, Ca2+, and Mg2+, are known to reduce the uptake and biotic effectiveness of cations and to have the opposite effects on anions. Toxicologists commonly interpret the interactions between toxic cations (commonly metals) and ameliorative cations (commonly H+, Ca2+, and Mg2+) as competitions for binding sites at a PM surface ligand. The ,PM is rarely considered in this biotic ligand model, which incorporates the free ion activity model. The thesis of this article is that ,PM effects are likely to be more important to bioavailability than site-specific competition. Furthermore, ,PM effects could give the false appearance of competition even when it does not occur. The electrostatic approach can account for the bioavailability of anions, whereas the biotic ligand model cannot, and it can account for interactions among cations when competition does not occur. Finally, a simplified procedure is presented for the computation of ,PM for plants, and the possible use of ,PM in a general assessment of the bioavailability of ions is considered. [source] Reduction of [(C5Me5)2Mo2O5] and [(C5Me5)2Mo2O4] in Methanol/Water/Trifluoroacetate Solutions Investigated by Combined On-Line Electrochemistry/Electrospray-Ionization Mass SpectrometryEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 12 2003Jenny Gun Abstract Complexes [Cp*2Mo2O5] (Cp* = ,5 -C5Me5) and [Cp*2Mo2O4] were investigated by combined on-line electrochemical (EC) reduction and electrospray-ionization mass spectrometry (ESI-MS) techniques in a trifluoroacetic acid buffered water/methanol solution. The reduction products at the larger negative potentials are identical for both compounds. The studies reveal the existence of a wide range of previously unknown di- and trinuclear MoV, MoIV, MoIII, and mixed-valence complexes that were identified on the basis of their masses and characteristic isotope patterns. The structures of the initial compounds and the product of electroreduction with m/z = 713,729 were supported by in situ MSn experiments that allowed the elucidation of the fragmentation pathway for the collision-induced dissociation. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003) [source] AMPA/kainate and NMDA-like glutamate receptors at the chromatophore neuromuscular junction of the squid: role in synaptic transmission and skin patterningEUROPEAN JOURNAL OF NEUROSCIENCE, Issue 3 2003Pedro A. Lima Abstract Glutamate receptor types were examined at the chromatophore synapses of the squids Alloteuthis subulata and Loligo vulgaris, where nerve-induced muscle contraction causes chromatophore expansion. Immunoblotting with antibody raised against a squid AMPA receptor (sGluR) demonstrated that AMPA/kainate receptors are present in squid skin. Application of l -glutamate evoked chromatophore muscle contractions in both ventral and dorsal skins, while NMDA was only active on a subpopulation of dorsal chromatophores. In dorsal skin, neurotransmission was partly blocked by either AMPA/kainate receptor antagonists (CNQX and DNQX) or NMDA receptor antagonists (AP-5 and MK-801) or completely blocked by simultaneous application of both classes of antagonists. In isolated muscle fibres, ionophoretic application of l -glutamate evoked fast inward CNQX- and DNQX-sensitive currents with reversal potentials around +14 mV and a high conductance to Na+. In fibres from dorsal skin only, a slower outward glutamate-sensitive current appeared at positive holding potentials. At negative potentials, currents were potentiated by glycine or by removing external Mg2+ and were blocked by AP-5 and MK-801. Glutamate caused a fast, followed by a slow, transient increase in cytoplasmic Ca2+. The slow component was increased in amplitude and duration by glycine or by lowering external Mg2+ and decreased by AP-5 and MK-801. In cells from ventral skin, no ,NMDA-like responses' were detected. Thus, while AMPA/kainate receptors mediated fast excitatory synaptic transmission and rapid colour change over the whole skin, activation of both AMPA/kainate and NMDA-like receptors in a subpopulation of dorsal chromatophores prolonged the postsynaptically evoked Ca2+ elevation causing temporally extended colour displays with behavioural significance. [source] A slowly inactivating sodium current (INa2) in the plateau range in canine cardiac Purkinje single cellsEXPERIMENTAL PHYSIOLOGY, Issue 1 2007Mario Vassalle The action potential of Purkinje fibres is markedly shortened by tetrodotoxin, suggesting the possibility that a slowly inactivating sodium current might flow during the plateau. The aim of the present experiments was to investigate, in canine cardiac Purkinje single cells by means of a whole cell patch clamp technique, whether a sodium current slowly inactivates at less negative potentials and (if so) some of its distinctive characteristics. The results showed that a 500 ms depolarizing step from a holding potential of ,90 mV to ,50 mV induced the fast inward current INa (labelled here INa1). With steps to ,40 mV or less negative values, a slowly decaying component (tentatively labelled here INa2) appeared, which peaked at ,30 to ,20 mV and decayed slowly and incompletely during the 500 ms steps. The INa2 was present also during steps to ,10 mV, but then the transient outward current (Ito) appeared. When the holding potential (Vh) was decreased to ,60 to ,50 mV, INa2 disappeared even if a small INa1 might still be present. Tetrodotoxin (30 ,m), lignocaine (100 ,m) and cadmium (0.2 mm; but not manganese, 1 mm) blocked INa2. During fast depolarizing ramps, the rapid inactivation of INa1 was followed by a negative slope region. During repolarizing ramps, a region of positive slope was present, whereas INa1 was absent. At less negative values of Vh, the amplitude of the negative and positive slopes became gradually smaller. Gradually faster ramps increased the magnitude of the negative slope, and tetrodotoxin (30 ,m) reduced or abolished it. Thus, Purkinje cells have a slowly decaying inward current owing to Na+ entry (INa2) that is different in several ways from the fast INa1 and that appears important for the duration of the plateau. [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] Voltage-activated proton currents in human lymphocytesTHE JOURNAL OF PHYSIOLOGY, Issue 1 2002Tom Schilling Voltage-activated proton currents are reported for the first time in human peripheral blood T and B lymphocytes and in the human leukaemic T cell line Jurkat E6-1. The properties of H+ currents studied using tight-seal voltage-clamp recording techniques were similar in all cells. Changing the pH gradient by one unit caused a 47 mV shift in the reversal potential, demonstrating high selectivity of the channels for protons. H+ current activation upon membrane depolarisation had a sigmoidal time course that could be fitted by a single exponential function after a brief delay. Increasing pHo shifted the activation threshold to more negative potentials, and increased both the H+ current amplitude and the rate of activation. In lymphocytes studied at pHi 6.0, the activation threshold was more negative and the H+ current density was three times larger than at pHi 7.0. Increasing the intracellular Ca2+ concentration to 1 ,m did not change H+ current amplitude or kinetics detectably. Extracellularly applied Zn2+ and Cd2+ inhibited proton currents, slowing activation and shifting the voltage-activation curve to more positive potentials. The H+ current amplitude was 100 times larger in CD19+ B lymphocytes and in Jurkat E6-1 cells than in CD3+ T lymphocytes. Following stimulation with the phorbol ester PMA, the H+ current density in peripheral blood T lymphocytes and Jurkat T cells increased. In contrast, the H+ current density of phorbol ester (PMA)-stimulated B lymphocytes was reduced and activation became slower. The pattern of expression of H+ channels in lymphocytes appears well suited to their proposed role of charge compensation during the respiratory burst. [source] Quercetin as a novel activator of L-type Ca2+ channels in rat tail artery smooth muscle cellsBRITISH JOURNAL OF PHARMACOLOGY, Issue 7 2002Simona Saponara The aim of this study was to investigate the effects of quercetin, a natural polyphenolic flavonoid, on voltage-dependent Ca2+ channels of smooth muscle cells freshly isolated from the rat tail artery, using either the conventional or the amphotericin B-perforated whole-cell patch-clamp method. Quercetin increased L-type Ca2+ current [ICa(L)] in a concentration- (pEC50=5.09±0.05) and voltage-dependent manner and shifted the maximum of the current-voltage relationship by 10 mV in the hyperpolarizing direction, without, however, modifying the threshold and the equilibrium potential for Ca2+. Quercetin-induced ICa(L) stimulation was reversible upon wash-out. T-type Ca2+ current was not affected by quercetin. Quercetin shifted the voltage dependence of the steady-state inactivation and activation curves to more negative potentials by about 5.5 and 7.5 mV respectively, in the mid-potential of the curves as well as increasing the slope of activation. Quercetin slowed both the activation and the deactivation kinetics of the ICa(L). The inactivation time course was also slowed but only at voltages higher than 10 mV. Moreover quercetin slowed the rate of recovery from inactivation. These results prove quercetin to be a naturally-occurring L-type Ca2+ channel activator. British Journal of Pharmacology (2002) 135, 1819,1827; doi:10.1038/sj.bjp.0704631 [source] Characterization of two Bunodosoma granulifera toxins active on cardiac sodium channelsBRITISH JOURNAL OF PHARMACOLOGY, Issue 6 2001Cyril Goudet Two sodium channel toxins, BgII and BgIII, have been isolated and purified from the sea anemone Bunodosoma granulifera. Combining different techniques, we have investigated the electrophysiological properties of these toxins. We examined the effect of BgII and BgIII on rat ventricular strips. These toxins prolong action potentials with EC50 values of 60 and 660 nM and modify the resting potentials. The effect on Na+ currents in rat cardiomyocytes was studied using the patch-clamp technique. BgII and BgIII slow the rapid inactivation process and increase the current density with EC50 values of 58 and 78 nM, respectively. On the cloned hH1 cardiac Na+ channel expressed in Xenopus laevis oocytes, BgII and BgIII slow the inactivation process of Na+ currents (respective EC50 values of 0.38 and 7.8 ,M), shift the steady-state activation and inactivation parameters to more positive potentials and the reversal potential to more negative potentials. The amino acid sequences of these toxins are almost identical except for an asparagine at position 16 in BgII which is replaced by an aspartic acid in BgIII. In all experiments, BgII was more potent than BgIII suggesting that this conservative residue is important for the toxicity of sea anemone toxins. We conclude that BgII and BgIII, generally known as neurotoxins, are also cardiotoxic and combine the classical effects of sea anemone Na+ channels toxins (slowing of inactivation kinetics, shift of steady-state activation and inactivation parameters) with a striking decrease on the ionic selectivity of Na+ channels. British Journal of Pharmacology (2001) 134, 1195,1206; doi:10.1038/sj.bjp.0704361 [source] F90927: A New Member in the Class of Cardioactive SteroidsCARDIOVASCULAR THERAPEUTICS, Issue 3 2007Markus Keller ABSTRACT F90927 is a newly developed cardioactive drug with a steroid-like structure. It acts directly and agonistically on the cardiac L-type Ca2+ channel by shifting its voltage-dependent activation toward more negative potentials. This leads to an increased influx of Ca2+ and, therefore, to a stronger contraction; however, no arrhythmias occur. Calcium current stimulation can already be observed at nanomolar concentrations, but higher concentrations of F90927 elevate intracellular Ca2+ concentration, causing a reduction of the myocardial compliance and an increased diastolic blood pressure. Vessels also react to F90927 and contract in its presence. Binding of F90927 with the L-type Ca2+ channel presumably occurs in the vicinity of the transmembrane domains III and IV of the ,1 subunit. F90927 exhibits no use dependence and interacts with Ca2+ channel inhibitors of all three known classes of channel modulators (dihydropyridines, phenylalkylamines, and benzothiazepines), suggesting that it is a member of a new class of Ca2+ channel modulators. Due to its adverse effects on blood pressure and vessel contraction, F90927 is not an ideal drug candidate. It has, however, some unique properties, which makes it a promising tool to study the function of the L-type Ca2+ channel. [source] Synthesis and Electrochemical Studies of Bingel,Hirsch Derivatives of M3N@Ih -C80 (M=Sc, Lu)CHEMISTRY - A EUROPEAN JOURNAL, Issue 16 2010Julio Abstract Bingel,Hirsch derivatives of the trimetallic nitride template endohedral metallofullerenes (TNT-EMFs) Sc3N@Ih -C80 and Lu3N@Ih -C80 were prepared by reacting these compounds with 2-bromodiethyl malonate, 2-bromo-1,3-dipyrrolidin-1-ylpropane-1,3-dionate bromide, and 9-bromo fluorene. The mono-adducts were isolated and their 1H,NMR spectra showed that the addition occurred with high regioselectivity at the [6,6] bonds of the Ih -C80 fullerene cage. Electrochemical analysis showed that the reductive electrochemistry behavior of these derivatives is irreversible at a scan rate of 100,mV,s,1, which is comparable to the behavior of the pristine fullerene species. The first reduction potential of each derivative is either cathodically or anodically shifted by a different value, depending on the attached addend. Bis-adducts containing EtOOC-C-COOEt and HC-COOEt addends were isolated by HPLC and in the case of Sc3N@Ih -C80 the first reduction potential exhibits a larger shift towards negative potentials when compared to the mono-adduct. This observation is important for designing acceptor materials for the construction of bulk heterojunction (BHJ) organic solar cells, since the polyfunctionalization not only increases the solubility of the fullerene species but also offers a promising approach for bringing the LUMO energy levels closer for the donor and the acceptor materials. [source] Reactivity of Molecular Dioxygen towards a Series of Isostructural Dichloroiron(III) Complexes with Tripodal Tetraamine Ligands: General Access to ,-Oxodiiron(III) Complexes and Effect of ,-Fluorination on the Reaction KineticsCHEMISTRY - A EUROPEAN JOURNAL, Issue 22 2008Nasser Abstract We have synthesized the mono, di-, and tri-,-fluoro ligands in the tris(2-pyridylmethyl)amine (TPA) series, namely, FTPA, F2TPA and F3TPA, respectively. Fluorination at the ,-position of these nitrogen-containing tripods shifts the oxidation potential of the ligand by 45,70,mV per added fluorine atom. The crystal structures of the dichloroiron(II) complexes with FTPA and F2TPA reveal that the iron center lies in a distorted octahedral geometry comparable to that already found in TPAFeCl2. All spectroscopic data indicate that the geometry is retained in solution. These three isostructural complexes all react with molecular dioxygen to yield stable ,-oxodiiron(III) complexes. Crystal structure analyses are reported for each of these three ,-oxo compounds. With TPA, a symmetrical structure is obtained for a dicationic compound with the tripod coordinated in the ,4N coordination mode. With FTPA, the compound is a neutral ,-oxodiiron(III) complex with a ,3N coordination mode of the ligand. Oxygenation of the F2TPA complex gave a neutral unsymmetrical compound, the structure of which is reminiscent of that already found with the trifluorinated ligand. On reduction, all ,-oxodiiron(III) complexes revert to the starting iron(II) species. The oxygenation reaction parallels the well-known formation of ,-oxo derivatives from dioxygen in the chemistry of porphyrins reported almost three decades ago. The striking feature of the series of iron(II) precursors is the effect of the ligand on the kinetics of oxygenation of the complexes. Whereas the parent complex undergoes 90,% conversion over 40,h, the monofluorinated ligand provides a complex that has fully reacted after 30,h, whereas the reaction time for the complex with the difluorinated ligand is only 10,h. Analysis of the spectroscopic data reveals that formation of the ,-oxo complexes proceeds in two distinct reversible kinetic steps with k1,10,k2. For TPAFeCl2 and FTPAFeCl2 only small variations in the k1 and k2 values are observed. By contrast, F2TPAFeCl2 exhibits k1 and k2 values that are ten times higher. These differences in kinetics are interpreted in the light of structural and electronic effects, especially the Lewis acidity at the metal center. Our results suggest coordination of dioxygen as an initial step in the process leading to formation of ,-oxodiiron(III) compounds, by contrast with an unlikely outer-sphere reduction of dioxygen, which generally occurs at negative potentials. [source] | |||||||||||||||||||