Anodic Stripping Voltammetry at Bismuth-Coated and Uncoated Carbon Microdisk Electrodes:Application to Trace Metals Analysis in Flood Samples

This article reports on the performance of a bismuth-coated carbon microdisk electrode (BiFμE) for the determination of trace heavy metals by anodic stripping voltammetry (ASV). The BiFμE was prepared by electrodeposition of a metallic bismuth film onto the microdisk, by applying an in-situ electroplating procedure. To test the performance of the BiFμE, ASV measurements were performed on synthetic solutions containing Cd2+, Pb2+, and Cu2+ as target ions. The results indicated that cadmium and lead gave well-defined ASV peaks with no interference, and their quantitative determination could be carried out straightforwardly. In particular, linear calibration curves over the range 5.0 x 10-8-1.0 x 10-6M for both ions, and detection limits of 7.8 and 2.9 nM, for cadmium and lead, respectively, after applying a 60 sec preconcentration step, were obtained. The reproducibility was also satisfactory, the relative standard deviation (RSD) being within 2.5% for both ions. Copper, instead, gave an ASV response that. in most experimental conditions, overlapped with that of bismuth. This circumstance made the determination of copper at the BiFμE difficult. Since the latter element could be detected reliably at the uncoated carbon microdisk electrode (CμE), both BiFμE and CμE were employed, respectively, for the determination of lead and copper ions in drinking water, wine, and tomato sauce.

Specific Adsorption of Trace Amounts of Calcium and Strontium by Hydrous Oxides of Iron and Aluminum1

Freshly prepared Fe and Al hydrous oxide gels and the amorphous product of heating gibbsite selectively adsorbed traces of Ca and Sr from solutions containing a large excess (∼1M) of NaNO3. The fraction of the added Ca (Sr) adsorbed depended principally on the suspension pH, the amount of solid present, and to a lesser extent on the NaNO3 concentration. Significant Ca and Sr adsorption occurred on the Fe and Al gels, and heated gibbsite, at pH values below the points of zero charge (8.1, 9.4, and 8.3±0.1, respectively), indicating specific adsorption. The pH (± 0.10) at which 50% of the Ca was adsorbed (pH50) occurred at pH 7.15 for the Fe gel (0.093M Fe), 8.35 for the Al gel (0.093M Al), and 6.70 for the heated gibbsite (0.181M Al); for Sr, the pH50 values were 7.10, 9.00, and 6.45, respectively. For the Fe gel and heated gibbsite, an empirical model based on the law of mass action described the pH dependence of adsorption reasonably well and suggested that for each Ca or Sr fraction adsorbed, approximately one proton was released. Failure of the Al gel to fit this model may have resulted from its rapid aging.

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.

Self-assembly of single-stranded RNA on carbon nanotube: Polyadenylic acid to form a duplex structure

All messenger-RNA (mRNA) molecules in eukaryotic cells have a polyadenylic acid [poly (rA)] tail at the 3'-end and human poly (rA) polymerase (PAP) has been considered as a tumor-specific target. A ligand that is capable of recognizing and binding to the poly(M) tail of mRNA might interfere with the full processing of mRNA by PAP and can be a potential therapeutic agent. We report here for the first time that single-walled carbon nanotubes (SWNTs) can cause single-stranded poly (M) to self-structure and form a duplex structure, which is studied by UV melting, atomic force microscopy, circular dichroism spectroscopy, and NMR spectrometry.

Copper(I)-Catalyzed Aryl Bromides To Form Intermolecular and Intramolecular Carbon-Oxygen Bonds

A highly efficient Cu-catalyzed C-O bond-forming reaction of alcohol and aryl bromides has been developed. This transformation was realized through the use of copper(I) iodide as a catalyst, 8-hydroxyquinoline as a ligand, and K3PO4 as a base. A variety of functionalized substrates were found to react under these reaction conditions to provide products in good to excellent yields.

Implantation of Nafion (R) ionomer into polyvinyl alcohol/chitosan composites to form novel proton-conducting membranes for direct methanol fuel cells

A series of cost-effective, proton-conducting composite membranes, comprising of Nafion (R) ionomer, chitosan (CS). and polyvinyl alcohol (PVA), is successfully prepared. By taking advantage of the strong electrostatic interactions between Nafion (R) ionomer and CS component, Nafion ionomer is effectively implanted into the PVA/CS composite membranes, and improves proton conductivity of the PVA/CS composite membranes. Furthermore, this effect dramatically depends on the composition ratio of PVA/CS, and the optimum conductivity is obtained at the PVA/CS ratio of 1:1. The developed composite membranes exhibit much lower methanol permeability compared with the widely used Nafion (R) membrane, indicating that these novel membranes have great potential for direct methanol fuel cells (DMFCs).

Enhanced crystallization of the gamma-form of propylene-ethylene copolymer in its miscible blends with propylene homopolymer

BACKGROUND: How to promote the formation of the gamma-form in a certain propylene-ethylene copolymer (PPR) under atmospheric conditions is significant for theoretical considerations and practical applications. Taking the epitaxial relationship between the alpha-form and gamma-form into account, it is expected that incorporation of some extrinsic alpha-crystals, developed by propylene homopolymer (PPH), can enhance the crystallization of the gamma-form of the PPR component in PPR/PPH blends.RESULTS: The PPH component in the blends first crystallizes from the melt, and its melting point and crystal growth rate decrease with increasing PPR fraction. On the other hand, first-formed alpha-crystals of the PPH component can induce the lateral growth of PPR chains on themselves, indicated by sheaf-like crystal morphology and positive birefringence, which is in turn responsible for enhanced crystallization of the gamma-form of the PPR component.

Analysis of two trace alkaloid isomers in Strychnos nux-vomical by electrospray ionization tandem mass spectrometry

According to their molecular mass and ESI-MSn data, the trace alkaloid isomers pseudostrychnine and strychnine N-oxide in extracts of the total alkaloids from Strychnos nux-vomical were qualitatively analyzed by electrospray ionization tandem mass spectrometry (ESI-MSn) method after rough silica gel-column chromatographic separation. We also investigated the relationship between their fragmentation mechanism and structures of the two alkaloid isomers. A new method for quickly and highly sensitively analyzing the two alkaloid isomers was proposed.

Narion/Poly(sodium 4-styrenesulfonate) mixed coating modified bismuth film electrode for the determination of trace metals by anodic stripping voltammetry

To improve the reproducibility, stability, and sensitivity of bismuth film electrode (BiFE), we studied the performances of a mixed coating of two cation-exchange polymers, Nafion (NA) and poly(sodium 4-styrenesulfonate) (PSS), modified glassy carbon BiFE (GC/NA-PSS/BiFE). The characteristics of GC/NA-PSS/BiFE were investigated by scanning electron microscopy and cyclic voltammetry. Various parameters were studied in terms of their effect on the anodic stripping voltarnmetry (ASV) signals. Under optimized conditions, the limits of detection were 71 ng L-1 for Cd(II) and 93 ng L-1 for Pb(II) with a 10 min preconcentration. The results exhibited that GC/NA-PSS/BiFE can be a reproducible and robust toot for monitor of trace metals by ASV rapidly and environmentally friendly, even in the presence of surface-active compounds.

Evaluation of a sequential extraction for the speciation of thorium in soils from Baotou area, Inner Mongolia

Sequential extraction procedures were widely applied for speciation of radioactive elements. In this study, the sequential extraction procedure developed by Martinez-Aguirre was employed for quantification of different chemical forms of thorium in the soil. The total amount of thorium in contaminated soil was much higher by four-fold than the local background value. The soil properties affect the amount of thoriurn and distribution of fractions in contaminated soil. Results showed that the proportion of thorium in soils from Baotou was found as the residual fraction (F5 + F6) > absorbed fraction (F3), coprecipitated fraction (F4) > carbonates fraction (172) and exchangeable fraction (F1) that could be available to plants. The recovery, calculated by ratio of the sum of the six fractions to the pseudo-total content of thorium, was in the range from 96% to 110%. A comparison was carried out between the sequential extraction and the single extraction to evaluate the selectivity of the extractants. It was found that the amount of thorium of absorbed fraction (H) was higher in the single extraction than that estimated in the sequential extraction, possibly duo to transform of the labile form. While for non-residual fraction analysis, the single extraction scheme was a desirable alternative to the sequential extraction procedure.

Tethered diblock copolymer chains on platelets prepared by semicrystalline ABC triblock copolymers in toluene with trace amounts of water

Lamellar platelets of triblock copolymers grown in dilute toluene solution with trace amounts of water can be used as templates for tethered diblock copolymer chain preparation and analysis. Polystyrene-bpoly(2-vinylpyridine)-b-poly(ethylene oxide) (PS-b-P2VP-b-PEO) with two different block fractions were used as model templates to generate tethered P2VP-b-PS chains on the platelet basal surfaces. In toluene solution the aggregation states of PS-b-P2VP-b-PEO were sensitive to the water content in the solution. For toluene with trace amount of water, spherical micelles were formed in the early stage and large square platelets would gradually grow from these spherical micelles. The hydrogen bonding between water and EO units was responsible for the formation of micelles and subsequent square platelets in the solution. Tethered P2VP-b-PS chains on basal surface of PEO platelets could be regarded as diblock copolymer brushes and the density (or: 0.086-0.36) and height (d: 3.5-14.3 nm) of these tethered chains could be easily modulated by changing the crystallization condition and/ or the molecular weight of each block. The tethered P2VP-b-PS chains were responsive to different solvent vapor.

Effect of the gamma-form crystal on the thermal fractionation of poly(propylene-co-ethylene)

The effect of the gamma-form crystal on the thermal fractionation of a commercial poly(propylene-co-ethylene) (PPE) has been studied by differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD) techniques. Two thermal fractionation techniques, stepwise isothermal crystallization (SIC) and successive self-nucleation and annealing (SSA), have been used to characterize the molecular heterogeneity of the PPE. The results indicate that the SSA technique possesses a stronger fractionation ability than that of the SIC technique. The heating scan of the SSA fractionated sample exhibits 12 endothermic peaks, whereas the scan of the SIC fractionated sample only shows eight melting peaks. The WAXD observations of the fractionated PPE samples prove that the content of the gamma-form crystals formed during the thermal treatment of the SIC technique is much higher than that of the SSA treatment. The former is 57.4%, whereas the later is 12.6%. The effect of they-form crystals on thermal fractionation ability is discussed.