Ionophore Based Bismuth Film Electrode for Lead

A Nafion/ionophore, 4-tert-butylcalix[4]arene-tetrakis(N,N-dimethylthioacetamide) composite coated and bismuth film modified glassy carbon electrode. (GC/NA-IONO/BiFE) was described to determine trace lead sensitively and selectively. The characteristics of such modified GC/NA-IONO/BiFE were studied by scanning electron microscopy and cyclic voltammetry. The influence of various experimental parameters upon the stripping lead signal at the GC/NA-IONO/BiFE was explored. Under the optimized conditions, the differential pulse voltammetric stripping response is highly linear over the 0.1-8.0 nM lead range examined (180s preconcentration at -1.2V), with a detection limit of 0.044nM and good precision (RSD=5.4% at 0.5nM). Also applicability to seawater samples was demonstrated at such modified electrode. The high selectivity of ionophore coupled with the excellent electrochemical characteristics of bismuth endow the GC/NA-IONO/BiFE a promising and robust tool for monitoring of trace lead rapidly and precisely.

抗癌药长春新碱及其与微管蛋白相互作用的电化学研究

在0.05 mol/L Tris，0.15 mol/L NaCl溶液中，用吸附伏安法研究长春新碱(VCR)，其峰电位在-1.68 V(vs. Ag/AgCl)，峰电流与1.0*10^{-8}～2.0*10^{-7}mol/L VCR浓度成正比，检测限为7.0*l0^{-9} mol/L，用常规脉冲极谱法、线性扫描和循环伏安法等研究该体系的电化学行为，实验表明，电极还原过程为具有吸附特征的不可逆过程。VCR的吸附符合Frumkin吸附等温式。也研究了VCR与微管蛋白的相互作用。实验表明，VCR与微管蛋白形成一电活性的结合物，这一结合物具有吸附性，且还原过程也为不可逆过程。

Reducing organic substances from anaerobic decomposition of hydrophytes

Oxidation-reduction properties of surface sediments are tightly associated with the geochemistry of substances, and reducing organic substances (ROS) from hydrophytes residues may play an important role in these processes. In this study, composition, dynamics, and properties of ROS from anaerobic decomposition of Eichhornia crassipes (Mart.) Solms, Potamogenton crispus Linn, Vallisneria natans (Lour.) Hara, Lemna trisulca Linn and Microcystis flos-aquae (Wittr) Kirch were investigated using differential pulse voltammetry (DPV). The type of hydrophytes determined both the reducibility and composition of ROS. At the peak time of ROS production, the anaerobic decomposition of M. flos-aquae produced 6 types of ROS, among which 3 belonged to strongly reducing organic substance (SROS), whereas there were only 3-4 types of ROS from the other hydrophytes, 2 of them exhibiting strong reducibility. The order of potential of hydrophytes to produce ROS was estimated to be: M. flos-aquae > E. crassipes > L. trisulca > P. crispus approximate to V. natans, based on the summation of SROS and weakly reducing organic substances (WROS). The dynamic pattern of SROS production was greatly different from WROS. The total SROS appeared periodic fluctuation with reducibility gradually weakening with incubation time, whereas the total WROS increased with incubation time. Reducibility of ROS from hydrophytes was readily affected by acid, base and ligands, suggesting that their properties were related to these aspects. In addition to the reducibility, we believe that more attention should be paid to the other behaviors of ROS in surface sediments.

Sorptive interaction between goethite and strongly reducing organic substances from anaerobic decomposition of green manures

Strongly reducing organic substances (SROS) and iron oxides exist widely in soils and sediments and have been implicated in many soil and sediment processes. In the present work, the sorptive interaction between goethite and SROS derived from anaerobic decomposition of green manures was investigated by differential pulse voltammetry (DPV). Both green manures, Astragaltus sinicus (Astragalus) and Vicia varia (Vicia) were chosen to be anaerobically decomposed by the mixed microorganisms isolated from paddy soils for 30 d to prepare different SROS. Goethite used in experiments was synthesized in laboratory. The anaerobic incubation solutions from green manures at different incubation time were arranged to react with goethite, in which SROS concentration and Fe(II) species were analyzed. The anaerobic decomposition of Astragalus generally produced SROS more in amount but weaker in reducibility than that of Vicia in the same incubation time. The available SROS from Astragalus that could interact with goethite was 0.69 +/- 0.04, 0.84 +/- 0.04 and 1.09 +/- 0.03 cmol kg(-1) as incubated for 10, 15 and 30 d, respectively, for Vicia, it was 0.12 +/- 0.03, 0.46 +/- 0.02 and 0.70 +/- 0.02 cmol kg(-1). One of the fates of SROS as they interacted with goethite was oxidation. The amounts of oxidizable SROS from Astragalus decreased over increasing incubation time from 0.51 +/- 0.05 cmol kg(-1) at day 10 to 0.39 +/- 0.04 cmol kg(-1) at day 30, but for Vicia, it increased with the highest reaching to 0.58 +/- 0.04 cmol kg(-1) at day 30. Another fate of these substances was sorption by goethite. The SROS from Astragalus were sorbed more readily than those from Vicia, and closely depended upon the incubation time, whereas for those from Vicia, the corresponding values were remarkably less and apparently unchangeable with incubation time. The extent of goethite dissolution induced by the anaerobic solution from Vicia was greater than that from Astragalus, showing its higher reactivity. (c) 2008 Published by Elsevier Ltd.

Validation and in situ application of an automated dissolved nickel monitor for estuarine studies

The validation of a fully automated dissolved Ni monitor for in situ estuarine studies is presented, based on adsorptive cathodic stripping voltammetry (AdCSV). Dissolved Ni concentrations were determined following on-line filtration and UV digestion, and addition of an AdCSV ligand (dimethyl glyoxime) and pH buffer (N-2-hydroxyethylpiperazine-N′-2-ethanesulphonic acid). The technique is capable of up to six fully quantified Ni measurements per hour. The automated in situ methodology was applied successfully during two surveys on the Tamar estuary (south west Britain). The strongly varying sample matrix encountered in the estuarine system did not present analytical interferences, and each sample was quantified using internal standard additions. Up to 37 Ni measurements were performed during each survey, which involved 13 h of continuous sampling and analysis. The high resolution data from the winter and summer tidal cycle studies allowed a thorough interpretation of the biogeochemical processes in the studied estuarine system.

Stripping voltammetric determination of Pb(II) and Cd(II) based on the multiwalled carbon nanotubes-Nafion-bismuth modified glassy carbon electrodes

In this work, a new method for the simultaneous determination of Pb(II) and Cd(II) on the multiwalled carbon nanotubes (MWNT)-Nafion-bismuth modified glassy carbon electrode (GCE) using square-wave anodic stripping voltammetry has been studied. Scanning electron microscopy was used to investigate the characteristics of the MWNT-Nafion-bismuth modified GCE.

Properties of poly(sodium 4-styrenesulfonate)-ionic liquid composite film and its application in the determination of trace metals combined with bismuth film electrode

A new kind of bismuth film modified electrode to sensitively detect trace metal ions based on incorporating highly conductive ionic liquids 1-butyl-3-methyl-imidazolium hexafluorophosphate (BMIMPF6) in solid matrices at glassy carbon (GC) was investigated. Poly(sodium 4-styrenesulfonate) (PSS), silica, and Nafion were selected as the solid matrices. The electrochemical properties of the mixed films modified GC were evaluated. The electron transfer rate of Fe(CN)(6)(4-)/Fe(CN)(6)(3-) can be effectively improved at the PSS-BMIMPF6 modified GC.

Simultaneous electrochemical determination of dopamine, uric acid and ascorbic acid using palladium nanoparticle-loaded carbon nanofibers modified electrode

Palladium nanoparticle-loaded carbon nanofibers (Pd/CNFs) were prepared by electrospinning and subsequent thermal treatment processes. Pd/CNFs modified carbon paste electrode (Pd/CNF-CPE) displayed excellent electrochemical catalytic activities towards dopamine (DA), uric acid (UA) and ascorbic acid (AA). The oxidation overpotentials of DA, UA and AA were decreased significantly compared with those obtained at the bare CPE. Differential pulse voltammetry was used for the simultaneous determination of DA, UA and AA in their ternary mixture.

Determination of Cd2+ and Pb2+ on glassy carbon electrode modified by electrochemical reduction of aromatic diazonium salts

Carbon modified by the reduction of aromatic diazonium derivatives was first used as electrode for the electrochemical stripping analysis of heavy metals. As a model, the glassy carbon electrode was modified with benzoic acid by electrochemical reduction of diazobenzoic acid, and the resulting modified electrodes were used for determination of Cd2+ and Pb2+. The anodic peak currents of cadmium and lead at the benzoic acid-modified glassy carbon electrode are 7.2 and 6 times of that at the bare glassy carbon electrode. A linear response was observed for Pb2+ and Cd2+ in the range of 0.5-50 mu g/l.

Electrochemical Detection of Hydrazine Based on Electrospun Palladium Nanoparticle/Carbon Nanofibers

In this work, we developed an electrochemical method for the detection of hydrazine based oil palladium nanoparticle/carbon nanofibers (Pd/CNFs). Pd/CNFs were prepared by electrospinning technique and subsequent thermal treatments. The electrocatalytic behaviors of Pd/CNFs modified glassy carbon electrode (Pd/CNF-GCE) for hydrazine oxidation were evaluated by cyclic voltammetry (CV), an obvious and well-defined oxidation peak appeared at -0.32 V (vs. Ag/AgCl). The mechanism of the oxidation of hydrazine at Pd/CNF-GCE was also studied, which demonstrated an irreversible diffusion-controlled electrode process and a four-electron transfer involved in the overall reaction. Furthermore, the wide linear range, low detection limit, good reproducibility and excellent storage stability were obtained utilizing differential pulse voltammetry (DPV).

Au nanoparticles grafted sandwich platform used amplified small molecule electrochemical aptasensor

We report a sensitively amplified electrochemical aptasensor using adenosine triphosphate (ATP) as a model. ATP is a multifunctional nucleotide thatis most important as a "molecular currency" of intracellular energy transfer. In the sensing process, duplexes consisting of partly complementary strand (PCS1), ATP aptamer (ABA) and another partly complementary strand (PCS2) were immobilized onto Au electrode through the 5'-HS on the PCS1. Meanwhile, PCS2 was grafted with the Au nanoparticles (AuNPs) to amplify the detection signals. In the absence of ATP, probe methylene blue (MB) bound to the DNA duplexes and also bound to guanine bases specifically to produce a strong differential pulse voltammetry (DPV) signal. But when ATP exists, the ABA-PCS2 or ABA-PCS1 part duplexes might be destroyed, which decreased the amount of MB on the electrode and led to obviously decreased DPV signal.

Combining chemical reduction with an electrochemical technique for the simultaneous detection of Cr(VI), Pb(II) and Cd(II)

This work herein reports the approach for the simultaneous determination of heavy metal ions including cadmium (Cd(II)), lead (Pb(II)), and chromium (Cr(VI)) using a bismuth film electrode (BFE) by anodic stripping voltammertry (ASV). The BFE used was plated in situ. Due to the reduction of Cr(VI) with H2O2 in the acid medium, on one hand, the Cr(III) was produced and Cr(VI) was indirectly detected by monitoring the content of Cr(III) using square-wave ASV. On the other hand, Pb(II) was also released from the complex between Pb(II) and Cr(VI). Furthermore, the coexistence of the Cd(II) was also simultaneously detected with Pb(II) and Cr(VI) in this system as a result of the formation of an alloy with Bi. The detection limits of this method were 1.39 ppb for Cd(II), 2.47 ppb for Pb(II) and 5.27 ppb for Cr(VI) with a preconcentration time of 120 s under optimal conditions (S/N = 3), respectively. Furthermore, the sensitivity of this method can be improved by controlling the deposition time or by using a cation-exchange polymer (such as Nafion) modified electrode.

Single-wall carbon nanotube-based voltammetric sensor and biosensor

The pH-sensitive property of the single-wall carbon nanotube modified electrode based oil the electroactive group on the single-wall carbon nanotube was explored by differential pulse voltammetry technique. In pH range 1-13 investigated in Britton-Robinson (B-R) buffer, the anodic peak shifted negatively along with the increase of pH exhibiting a reversible Nernstian response. Experiments were carried out to investigate the response of the single-wall carbon nanotube (SWNT) modified electrode to analytes associated with pH change. The response behavior of the modified electrode to ammonia was studied as an example. The potential response could reach equilibrium within 5 min. The modified electrode had good operational stability. Voltammetric urease and acetylcholinesterase biosensors were constructed by immobilizing the enzymes with sol-get hybrid material. The maximum potential shift could reach 0.130 and 0.220V for urea and acetylthiocholine, respectively. The methods for preparing sensor and biosensor were simple and reproducible and the range of analytes could be extended to substrates of other hydrolyases and esterases.

Simultaneous determination of dopamine and ascorbic acid at an in-site functionalized self-assembled monolayer on gold electrode

The in-site functionalization of 4-aminothiophenol (4-ATP) self-assembled monolayer on gold electrode at physiological pH yields a redox active monolayer of 4'-mercapto-N-phenylquinone diimine (MNPD). The functionalized electrode exhibits excellent electrocatalytic responses towards dopamine (DA) and ascorbic acid (AA), reducing the overpotentials by about 0.22 V and 0.34 V, respectively, with greatly enhanced current responses. Due to its different catalytic activities toward DA and AA, the modified electrode resolves the overlapping voltammetric responses of DA and AA into two well-defined voltammetric peaks by differential pulse voltammetry (DPV), which can be used for the simultaneous determination of these species in a mixture. The catalytic peak current obtained from DPV was linearly related to DA and AA concentration in the ranges of 5.0 x 10-6 - 1.25 x 10-4 M and 8.0 x 10-6 - 1.3 x 10-4 M with correlation coefficient of 0.999 and 0.998, respectively. The detective limits (3sigma) for DA and AA were found to be 1.2 x 10-6 M and 2.4 x 10-6 M, respectively.

IrO2/SnO2 electrodes: prepared by sol-gel process and their electrocatalytic for pyrocatechol

IrO2/SnO2 (10%:90%, molar ratio) electrodes (ITEs) were prepared by the sol-gel method as an alternative to the electrode-position and thermal decomposition process. The electrodes were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), atomic force microscope (AFM), cyclic voltammetry (CV) and electrochemical impedance spectra (EIS). From the results of XRD, oxide films prepared at low temperature were in amorphous state, while hydrous IrO2 crystal and cassiterite phase SnO2 were formed at 300 degreesC or even to 500 degreesC. The highly porous structure was confirmed by AFM. The electrochemical experiments demonstrated that the sol-gel method made the ITEs having a fast electron transfer process with good stability and the optimal preparation temperature was 400 degreesC for the highest electroactivity. Furthermore, the electrocatalysis of pyrocatechol on the electrodes was investigated. A quasi-reversible process occurred and a linear range over three orders magnitude (1 x 10(-2) - 10 mM) was obtained by differential pulse voltammetry (DPV). Meanwhile the detection limit of pyrocatechol was 5 x 10(-3) mM. This study indicated that the sol-gel method was an appropriate route to prepare the IrO2/SnO2 electrodes for the electrocatalytic of pyrocatechol.