In situ analysis of electropolymerization of aniline by combined electrochemistry and surface plasmon resonance

The combination of electrochemistry with surface plasmon resonance (SPR) has been used to characterize the growth of polyaniline (PAn) on a gold electrode surface during potential cycling. Potential-modulated SPR characteristics of the PAn film were also revealed. The potential switch between the oxidized and reduced states of PAn can lead to a large change of SPR response due to the variation in the imaginary part of the dielectric constant of PAn film resulting from the transition of the film in conductivity. The redox transition of the PAn film during potential cycling is very profitable to the SPR measurements. Two modes of SPR measurement, SPR angular scan (R-theta) and the time evolution of the reflectivity change at a fixed angle (R-t), were displayed to study the growth process of the PAn film. The angle shift of the resonance minimum recorded at each cathodic limit of cyclic potential scanning allows for the unambiguous measurement of the film growth. During cyclic potential scanning, the R-t curve was repeatedly modulated with the direction of the potential ramp as a result of the redox switch of the PAn film, and the amplitude of potential-modulated reflectivity change was well correlated with the cyclic number. The time differential of the R-t curve permits continuous monitoring of the film growth process. These results illustrate that the combined technique is suitable for studying the electropolymerization process of a conducting polymer.

Simple and rapid voltammetric determination of morphine at electrochemically pretreated glassy carbon electrodes

A simple and rapid method for morphine detection has been described based on electrochemical pretreatment of glassy carbon electrode (GCE) which was treated by anodic oxidation at 1.75 V, following potential cycling in the potential range from 0 V to 1.0 V vs. Ag vertical bar AgCl reference electrode. The sensitivity for morphine detection was improved greatly and the detection limit was 0.2 mu M. The reproducibility of the voltammetric measurements was usually less than 3% RSD for six replicate measurements. Moreover, this method could readily discriminate morphine from codeine. And an electrochemical detection of morphine in spiked urine sample was succeeded with satisfactory results.

Synthesis and properties of ferrocene-functionalised polythiophene derivatives

The ferrocene-functionalised thiophene derivatives (TFn) with different length of oxyethylene chains were synthesized and polymerized chemically with iron (III) chloride as an oxidant. The resulting ferrocene-functionalised polythiophenes (PTFn) show good solubility in most solvents, such as chloroform (CHCl3) tetrahydrofuran (THF), acetone, etc. The structure and properties of the PTFn polymers were confirmed by IR, H-1 NMR, AFM and photoluminescence (PL). The polymers PTFn show good redox activity with no attenuation of the electroactivity after multiple potential cycling. (C) 2009 Elsevier B.V. All rights reserved.

Electro-assisted precipitation of electrolytes in poly(3,4-ethylenedioxythiophene) film

The electrolyte, NaBF4, can be enriched into the matrix of poly(3,4-ethylenedioxythiophene) (PEDOT) film during the p-doping potential cycling between 0.6 and -0.9 V. It has been demonstrated that this enrichment is originated from the mixed ion transfer between doping and dedoping, i.e. BF4- anion migrate into the PEDOT film during the oxidation process, the Ne cation insert into the film during the reduction process, and then, the electrolyte is accumulated into the film matrix after the multiple CV cycling. The quantitative analysis of energy-dispersive X-ray spectroscopy (EDX) confirmed the enrichment of NaBF4 in the PEDOT film.

Effects of a surfactant on the electrocatalytic activity of cobalt hexacyanoferrate modified glassy carbon electrode towards the oxidation of dopamine

The cobalt hexacyanoferrate film (CoHCF) was deposited on the surface of a glassy carbon (GC) electrode with a potential cycling procedure in the presence and absence of the cationic surfactant, cetyl trimethylammonium bromide (CTAB), to form CoHCF modified GC (CoHCF/GC) electrode. It was found that CTAB would affect the growth of the CoHCF film, the electrochemical behavior of the CoHCF film and the electrocatalytic activity of the CoHCF/GC electrode towards the electrochemical oxidation of dopamine (DA). The reasons of the electrochemical behavior of CoHCF/GC electrode influenced by CTAB were investigated using FTIR and scanning electron microscope (SEM) techniques. The apparent rate constant of electrocatalytic oxidation of DA catalyzed by CoHCF was determined using the rotating disk electrode measurements.

Simple preparation method of Pd nanoparticles on an Au electrode and its catalysis for dioxygen reduction

A simple method for the fabrication of Pd nanoparticles is described. The three-dimensional Pd nanoparticle films are directly formed on a gold electrode surface by simple electrodeposition at -200 mV from a solution of 1 M H2SO4+0.01 mM K2PdCl4. X-Ray photoelectron spectroscopy verifies the constant composition of the Pd nanoparticle films. Atomic force microscopy proves that the as-prepared Pd nanoparticles are uniformly distributed with an average particle diameter of 45-60 nm. It is confirmed that the morphology of the Pd nanoparticle films are correlated with the electrodeposition time and the state of the Au substrate. The resulting Pd-nanoparticle-film-modified electrode possesses high catalytic activity for the reduction of dissolved oxygen in 0.1 M KCl solution. Freshly prepared Pd nanoparticles can catalyze the reduction of O-2 by a 4-electron process at -200 mV in 0.1 M KCl, but this system is not very stable. The cathodic peaks corresponding to the reduction of O-2 gradually decrease with potential cycling and at last reach a steady state. Then two well-defined reduction peaks are observed at -390 and -600 mV vs. Ag/AgCl/KCl (sat.). Those two peaks correspond to a 2-step process for the 4-electron reduction pathway of O-2 in this neutral medium.

Self-assembly of the pre-formed inclusion complexes between cyclodextrins and alkanethiols on gold electrodes

A new kind of self-assembled monolayer (SAM) formed in aqueous solution through the pre-formed inclusion complexes (abbreviated CD . C-n) between alpha-, beta-cyclodextrins (CDs) and alkanethiols (CH3(CH2)(n-1)SH, n = 10, 14 and 18) was prepared successfully on gold electrodes. High-resolution H-1 NMR was used to confirm the formation of CD . C-n. X-ray photoelectron spectroscopy, cyclic voltammetry and chronoamperometry were used to characterize the resulting SAMs (denoted as M-CD . Cn). It was found that M-CD . Cn were more stable against repeated potential cycling in 0.5 M H2SO4 than SAMs of CH3(CH2)(n-1)SH (denoted as M-Cn), with a relative sequence of Mbeta-CD . Cn > Malpha-CD . Cn > M-Cn. In addition, an order of blocking the electron transfer between gold electrodes and redox couples (both Fe(CN)(6)(3-) and Ru(NH3)(6)(3+)) in solution, M-CD . C10 > M-CD . C14 > M-CD . C18, was observed. A plausible explanation is provided to elucidate some of the observations. (C) 1997 Elsevier Science S.A.

EFFECTS OF ANODIC-OXIDATION ON THE SURFACE-STRUCTURE OF HIGHLY ORIENTED PYROLYTIC-GRAPHITE REVEALED BY IN-SITU ELECTROCHEMICAL SCANNING-TUNNELING-MICROSCOPY IN H2SO4 SOLUTION

Effects of the potential of anodic oxidation and of potential cycling on the surface structure of a highly oriented pyrolytic graphite (HOPG) electrode were observed by in situ electrochemical scanning tunnelling microscopy (ECSTM) in dilute H2SO4 solution with atomic resolution. With potential cycling between -0.1 V and 1.8 V vs. Ag/AgCl (sat. KCI), some atoms on the top layer of HOPG protrude out of the base plane, and the graphite lattice of these protrusions is still intact but is strained and expanded. With further potential cycling, some protrusions coalesced and some grew larger, and an anomalous superperiodic feature was observed (spacing 90 Angstrom with a rotation 30 degrees relative to atomic corrugations) which superimposed on the atomic corrugation of HOPG. On the topmost of these protrusions, some atoms form oxides and others are still resolved by the ECSTM image. With potential cycling between -0.1 V and + 2.0 V vs. Ag/AgCl (sat. KCl), damage to freshly cleaved HOPG surface is more serious and fast, some ridges are observed, the atomic structure of the HOPG surface is partially and then completely damaged due to the formation of oxide. We also found that anodic oxidation occurred nonuniformly on the surface of HOPG near defects during potential cycling.

PREPARATION OF MODIFIED ELECTRODE WITH MOLYBDOPHOSPHATE ANION AND ITS ELECTROCATALYSIS FOR BROMATE REDUCTION

A molybdophosphate anion modified electrode has been prepared in 2 M sulfuric acid solution containing PMo12O403- by electrochemical cycling scan or simple adsorption on a glassy carbon electrode anodized before modification. The film electrode obtained is very stable upon potential cycling in acid solution. The catalytic effect of the film for reduction of bromate was investigated in detail.

IN-SITU SCANNING-TUNNELING-MICROSCOPY IMAGE OF A HIGHLY ORIENTED PYROLYTIC-GRAPHITE ELECTRODE MODIFIED WITH POTASSIUM BIS(11-MOLYBDOSILICATO) DYSPROSATE(III) IN SODIUM-SULFATE SOLUTION

The variation in molecule adsorption mode on pretreated highly oriented pyrolytic graphite electrodes, modified with the title complex K10H3[Dy(SiMo11O39)(2)] by cyclic voltammetry in the title complex solution, was observed in situ by electrochemical scanning tunnelling microscopy (ECSTM) with molecular resolution in sodium sulphate solution. According to the ECSTM images and the known molecular structure we conclude that the adsorption mode of the title complex modified electrode changed during potential cycling from ''vertical'' to ''inclined'' and then ''horizontal'' or ''flat'' mode, i.e. the title complex adsorbed on the surface of electrode by one ligand of the complex at first, then began to incline and was finally adsorbed by two ligands of the complex. This result indicates that the adsorption mode on the modified electrode surface changed during potential cycling in the sulphate solution and a much more stable molecular layer was formed. The change in adlattice of adsorbates on the modified electrode surface from hexagonal to rectangular was also observed by ECSTM. A plausible model was given to explain this process.

ELECTROCHEMICAL-BEHAVIOR OF MOLIBDOSILICIC HETEROPOLY COMPLEX WITH DYSPROSIUM AND ITS DOPED POLYPYRROLE FILM-MODIFIED ELECTRODE

In this paper, the electrochemical behaviour of molibdosilicic heteropoly complex with dysprosium K10H3[Dy(SiMo11O39)(2)]. xH(2)O [denoted as Dy(SiMo11)(2)] was studied. Voltammetric behavior of this complex was greatly influenced by pH of solutions. The polypyrrole (PPy) film doped with this complex was prepared by electropolymerization of pyrrole in the presence of Dy(SiMo11)(2) under potential cycling conditions. The microenvironment within the PPy film has an effect on the electrochemical behavior of Dy(SiMo11)(2) entrapped in the film. The film electrode can catalyze the reduction of ClO3- and BrO3-.

PREPARATION AND CHARACTERIZATION OF ISOPOLYMOLYBDIC ANIONS DOPED POLYPYRROLE (IPOMO/PPY) FILM ELECTRODE

Isopolymolybdic anion doped polypyrrole film electrode was prepared by electrochemical polymerization of pyrrole in 0.5 mol.L-1 H2SO4 aqueous solution containing isopolymolybdic anions. The film thus prepared has good stability upon potential cycling in s

STUDY OF A 1/12 PHOSPHOMOLYBDIC ANION DOPED POLYPYRROLE FILM ELECTRODE AND ITS CATALYSIS

A phosphomolybdic anion doped polypyrrole (PMo12O403- + PPy) film electrode has been prepared by electrochemical polymerization of pyrrole in an aqueous solution of 0.5 mol l-1 H2SO4 or 0.5 mol l-1 KNO3 containing PMo12O403- anions, and characterized by scanning electron microscopy and in-situ UV-visible spectroelectrochemical methods. The film electrode obtained is very stable upon potential cycling in acidic solution, but not in neutral solution. The catalytic effect of the film electrode on the reduction of ClO3- and BrO3- was studied.

情绪干扰下焦虑水平对执行抑制的影响机制——事件相关电位研究

Behavioral inhibition model suggests the generation of anxiety is related with over-inhibition. For knowing about anxiety better, we used event-related potential (ERP) technique to explore the underlying mechanism of executive inhibition under the emotional distracter in high and low trait-anxious groups. Firstly, we set up the Chinese affective picture system (CAPS) as the stimuli of subsequent experiments. Secondly, we screened the high and low trait-anxious participants using the State-Trait Anxiety Inventory. In the first ERP study, a modified oddball paradigm was used with the positive, neutral and negative pictures as novel stimuli and the potentials evoked by three types pictures were analyzed. In the second ERP study, the same paradigm with higher task load was employed to examine the interaction of anxious level and emotion. Main results as follows: 1. CAPS consisted of 852 pictures was assessed via three dimensionalities, valence, arousal and dominance. The standard deviation of scores on valence and dominance was more than the standard deviation of scores on dimension of arousal. Scatter plot showed that the score distributing on the dimension of valence and arousal was wide in CAPS. 2. In both high and low trait-anxiety groups, the amplitudes of N2 and P3 of negative pictures were greater and smaller respectively as compared with neutral and positive pictures, which suggested all participants no matter what anxious level required more inhibition processing to negative information than others. 3. With increasing of task load, the P3 amplitudes of negative pictures in high anxious group were reduced relative to neutral pictures. In addition, in high anxious group, the P3 amplitudes of positive pictures had the same changes as those of negative ones. Whereas, the reduced P3 of positive pictures were not observed in low anxious group. The results showed the high anxious participants employed the same inhibitory strategy to the positive distracter as the negative distracter, which possibly the over-inhibition processing was involved in this group. 4. Dipole source analysis found cingulate may be involved in executive inhibition processing. In sum, as for the inhibition, high and low anxious group both is sensitive to negative information. However, in the high load situation, due to the shortness of cognitive resources, the high anxious individual represents the general sensitivity to all emotional information. These results gave the electrophysiological evidence for over-inhibition in high trait-anxiety group.

Comparative studies of AOT and NaDEHP by fluorescence technique and z-potential (ζ) measurements

The aggregation behaviors of two surfactants with the same hydrophobic tail, sodium bis(2-ethylhexyl)sulfosuccinate (AOT) and sodium bis(2-ethylhexyl)phosphate (NaDEHP), have been investigated by the fluorescence technique and z-potential (ζ) measurements. Five fine peaks of the pyrene molecule fluorescence spectroscopy appear in the surfactant solution, and the micropolarity at which pyrene locates is monitored from the intensity ratio of the first (I1) and the third peak (I3). A wide peak around 475 nm, the emission spectra of the excimer of pyrene molecules, is observed in the NaDEHP solution, while this is not found for the AOT system. The value of I1/I3 decreases in a more limited concentration range for the AOT system than for NaDEHP, indicating that small aggregates can be more easily formed by NaDEHP molecules. The z-potential results for the aggregates formed by the two surfactants show that the interaction between AOT and PVP is stronger than that between NaDEHP and PVP.