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.

Silver nanocrystals modified microstructured polymer optical fibres for chemical and optical sensing

In-fibre chemical and optical sensors based on silver nanocrystals modified microstructured polymer optical fibres (MPOFs) were demonstrated. The silver nanocrystals modified MPOFs were formed by direct chemical reduction of silver ammonia complex ions on the templates of array holes in the microstructure polymer optical fibres. The nanotube-like and nanoisland-like Ag-modified MPOFs could be obtained by adjusting the conditions of Ag-formation in the air holes of MPOFs. SEM images showed that the higher concentration of the reaction solution (silver ammonia 0.5 mol/L, glucose 0.25 mol/L), gave rise to a tubular silver layer in MPOF, while the lower concentration (silver ammonia 0.1 M, glucose 0.05 M) produced an island-like Ag nanocrystal modified MPOF. The tubular Ag-MPOF composite fibre was conductive and could be directly used as array electrodes in electrochemical analyses. It displayed high electrochemical activity on sensing nitrate or nitrite ions. The enhanced fluorescence of dye molecules was observed when the island-like Ag-modified MPOF was inserted into a fluorescent dye solution. (C) 2007 Elsevier B.V. All rights reserved.

XPS depth profiling study of n/TCO interfaces for p-i-n amorphous silicon solar cells

Detailed X-ray photoelectron spectroscopy (XPS) depth profiling measurements were performed across the back n-layer/transparent conducting oxide (n/TCO) inter-faces for superstrate p-i-n solar cells to examine differences between amorphous silicon (a-Si:H) and microcrystalline silicon (mu c-Si:H) n-layer materials as well as TCO materials ZnO and ITO in the chemical, microstructural and diffusion properties of the back interfaces. No chemical reduction of TCO was found for all variations of n-layer/TCO interfaces. We found that n-a-Si:H interfaces better with ITO, while n-mu c-Si:H, with ZnO. A cross-comparison shows that the n-a-Si:H/ITO interface is superior to the n-mu c-Si:H/ZnO interface, as evidenced by the absence of oxygen segregation and less oxidized Si atoms observed near the interface together with much less diffusion of TCO into the n-layer. The results suggest that the n/TCO interface properties are correlated with the characteristics of both the n-layer and the TCO layer. Combined with the results reported on the device performance using similar back n/TCO contacts, we found the overall device performance may depend on both interface and bulk effects related to the back n/TCO contacts. (c) 2006 Elsevier B.V. All rights reserved.

Surface-enhanced Raman scattering from surfactant-free 3D gold nanowire networks substrates

A useful method for the fabrication of three-dimensional gold nanowire networks based on the chemical reduction of HAuCl4 with trisodium citrate was presented. The coverage of the 3D gold nanowire networks was tunable by altering precursor concentration. The as-prepared 3D gold nanowire networks could be used as surface-enhanced Raman scattering (SERS) substrates and examined by 4-aminothiophenol (4-ATP) as a probe molecules.

Hydrogen Vanadate as an Effective Stabilizer of Pd Nanocatalysts for Formic Acid Electroxidation

In this paper, a simple chemical reduction route is discussed that results in small size, uniform dispersion of Pd nanoparticles supported on carbon black. HVO42-, the tridentate oxoanion with its O-O distance of 2.76 angstrom, closely matching with the Pd-Pd distance (2.75 angstrom), is expected to be an effective stabilizer for Pd according to the lattice size-matching binding model (Finke, R. G.; Ozkar, S. Coord. Chem. Rev. 2004, 248, 135). Because it has never been tested, HVO42- is exploited and found to be a very simple and effective stabilizer.

In situ PEI and formic acid directed formation of Pt NPs/MWNTs hybrid material with excellent electrocatalytic activity

A hybrid material based on Pt nanoparticles (Pt NPs) and multi-walled carbon nanotubes (MWNTs) was fabricated with the assistance of PEI and formic acid. The cationic polyelectrolyte PEI not only favored the homogenous dispersion of carbon nanotubes (CNTs) in water, but also provided sites for the adsorption of anionic ions PtCl42- on the MWNTs' sidewalls. Deposition of Pt NPs on the MWNTs' sidewalls was realized by in situ chemical reduction of anionic ions PtCl42- with formic acid. The hybrid material was characterized with TEM, XRD and XPS. Its excellent electrocatalytic activity towards both oxygen reduction in acid media and dopamine redox was also discussed.

Nanocomposite based on depositing platinum nanostructure onto carbon nanotubes through a one-pot, facile synthesis method for amperometric sensing

Platinum nanoparticles (Pt NPs) were deposited onto multi-walled carbon nanotubes (MWNTs) through direct chemical reduction without any other stabilizing agents. Transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry were employed to characterize the morphology of the as-prepared nanocomposite (noted as Pt NPs-MWNTs) and further identify the Pt NPs on the surface of MWNTs. The nanocomposite demonstrated the ability to electrocatalyze the oxidation of hydrogen peroxide and substantially raises the response current. A sensitivity of 591.33 mu A mM(-1) cm(-2) was obtained at Pt NPs-MWNTs modified electrode. Thus, we immobilized glucose oxidase (GOD) as a model enzyme on the nanocomposite-based electrode with a thin layer of Nafion to fabricate a glucose biosensor, which showed sensitive and fast response to glucose. The influence of the GOD loading was investigated and the biosensor with an enzyme loading concentration of 10 mg/mL shows optimal performance for glucose detection, that is, a detection limit of 3 mu M and a response time of 3 s, respectively.

Monodisperse, submicrometer-scale platinum colloidal spheres with high electrocatalytic activity

Monodisperse, submicrometer-scale platinum (Pt) colloidal spheres were prepared through a simple direct chemical reduction of p-phenylenediamine (PPD)-chloroplatinic acid (H2PtCl6) coordination polymer colloids. It was found that the prepared Pt colloids had the similar size and morphology with their coordination polymer precursors, and the prepared Pt colloids with rough surfaces were three-dimensional (3D) structured assemblies of high-density small Pt nanoparticles. The electrochemical experiments confirmed that the prepared Pt colloids possessed a high electrocatalytic activity towards mainly four-electron reduction of dioxygen to water, making the prepared Pt colloids potential candidates for the efficient cathode material in fuel cells.

A New Method for Analysis of Disulfide-Containing Proteins by Matrix-Assisted Laser Desorption Ionization (MALDI) Mass Spectrometry

A simple and high-throughput method for the identification of disulfide-containing peptides utilizing peptide-matrix adducts is described. Some commonly used matrices in MALDI mass spectrometry were found to specifically react with sulfhydryl groups within peptide, thus allowing the observation of the peptide-matrix adduct ion [M + n + n' matrix + H](+) or [M + n + n' matrix + Na](+) (n = the number of cysteine residues, n' = 1, 2, ..., n) in MALDI mass spectra after chemical reduction of disulfide-linked peptides. Among several matrices tested, alpha-cyano-4-hydroxycinnamic acid (CHCA, molecular mass 189 Da) and alpha-cyano-3-hydroxycinnamic acid (3-HCCA) were found to be more effective for MALDI analysis of disulfide-containing peptides/proteins. Two reduced cysteines involved in a disulfide bridge resulted in a mass shift of 189 Da per cysteine, so the number of disulfide bonds could then be determined, while for the other matrices (sinapinic acid, ferulic acid, and caffeic acid), a similar addition reaction could not occur unless the reaction was carried out under alkaline conditions. The underlying mechanism of the reaction of the matrix addition at sulfhydryl groups is proposed, and several factors that might affect the formation of the peptide-matrix adducts were investigated.

Silver nanoparticles coated with adenine: preparation, self-assembly and application in surface-enhanced Raman scattering

We describe herein the preparation of silver nanoparticles (AgNPs) using nucleobase adenine as protecting agent through the in situ chemical reduction of AgNO3 with NaBH4 in an aqueous medium at room temperature. As-prepared AgNPs were characterized by UV-visible spectra, transmission electron microscopy and x-ray photoelectron spectroscopy. All these data confirmed the formation of AgNPs. On the basis of electrostatic interactions between as-prepared AgNPs and anionic polyelectrolyte poly(sodium 4-styrenesulfonate) (PSS), we successfully fabricated (PSS/AgNP)n (n = 0-9) multilayers on a 3-mercaptopropyltrimethoxysilane/AgNP functionalized indium tin oxide (ITO) substrate via the layer-by-layer self-assembly technique and characterized as-formed multilayers with UV-visible spectra. Furthermore, these ITO substrates coated with multilayers of different thickness were investigated as surface-enhanced Raman scattering (SERS)-active substrates using p-aminothiophenol as a probe molecule, implying that these multilayers substrates may be promising for a new type of SERS-active substrate.

Submicrometre scale single-crystalline gold plates of nanometre thickness: synthesis through a nucleobase process and growth mechanism

Synthesis of submicrometre scale single-crystalline gold plates of nanometre thickness in the presence of nucleobase guanine through chemical reduction of HAuCl4 was investigated. The elemental composition of the as-prepared gold nanoplates was estimated using energy-dispersive x-ray spectroscopy. The as-prepared gold plates were composed of essentially (111) lattice planes, as revealed by both x-ray diffraction (XRD) and transmission electron microscopy (TEM) results. It was found that the molar ratio of HAuCl4 to guanine played a very important role in the formation of gold nanoplates. Gold nanoplates could be produced at a molar ratio of [HAuCl4]/[guanine] = 50: 1 while only smaller gold spherical nanoparticles were obtained at molar ratios of [HAuCl4]/[guanine] <= 20:1. A possible growth mechanism of the as-prepared gold nanoplates is proposed and discussed. The results and conclusion presented in this work may be valuable for our further understanding of the roles of precursor ligands in the control of nanoparticles aggregation states and the preparation of shape-controlled nanoparticles.

Thermal annealing of Au nanorod self-assembled nanostructured materials: Morphology and optical properties

Three-dimensional Au nanorod and An nanoparticle nanostructured materials were prepared by layer-by-layer self-assembly. The plasmonic properties of the An nanorod and An nanoparticle self-assembled nanostructured materials (abbreviated as AuNR and AuNP SANMs) are tunable by the controlled self-assenibly process. The effect of thermal annealing at 180 and 500 degrees C to the morphologies, plasmonic properties and surface-enhanced Raman scattering (SERS) responses of these SANMs were investigated. According to the experimental results, these properties correlate with the structure of the SANMs.

Synthesis, characterization, and self-assembly of protein lysozyme monolayer-stabilized gold nanoparticles

Lysozyme monolayer-protected gold nanoparticles (Au NPs) which are hydrophilic and biocompatible and show excellent colloidal stability at low temperature, ca. 4 degrees C, were synthesized in aqueous medium by chemical reduction of HAuCl4 with NaBH4 in the presence of a familiar small enzyme, lysozyme. UV-vis spectra, transmission electron microscopy (TEM), atomic force microscopy, and X-ray photoelectron spectroscopy characterization of the as prepared nanoparticles revealed the formation of well-dispersed An NPs of ca. 2 nm diameter. Moreover, the color change of the An NP solution as well as UV-vis spectroscopy and TEM measurements have also demonstrated the occurrence of Ostwald ripening of the nanoparticles at low temperature. Further characterization with Fourier transform infrared spectroscopy (FTIR) and dynamic light scattering indicated the formation of a monolayer of lysozyme molecules on the particle surface. FTIR data also indicated the intactness of the protein molecules coated on An NPs. All the characterization results showed that the monodisperse An NPs are well-coated directly with lysozyme. Driven by the dipole-dipole attraction, the protein-stabilized Au NPs self-assembled into network structures and nanowires upon aging under ambient temperature.

Room temperature preparation of carbon supported Pt-Ru catalysts

A carbon supported Pt-Ru (Pt-Ru/C-T) catalyst can be prepared by a chemical reduction method in an aqueous solution with tetrahydrofuran (THF) at room temperature. The Pt-Ru particles possess high alloying, small average size and a low relative crystallinity. The electrocatalytic activity of the prepared Pt-Ru/C catalyst for methanol oxidation is much higher than that of commercial Pt-Ru/C (Pt-Ru/C-E) catalysts which have a similar average size and relative crystallinity, but the alloying extent is much lower than that in our Pt-Ru/C-T catalyst. The results illustrate that the alloying extent of Pt and Ru in the Pt-Ru/C catalyst plays an important role in the electrocatalytic activity of the Pt-Ru/C catalyst for methanol oxidation.

Electrocatalytic performance of Pt-TiO2/C complex catalysts for oxidation of methanol

It is reported for the first time that the Pt-TiO2/C catalyst prepared with chemical reduction and sol-gel method showed the excellent electrocatalytic activity and stability for the electrooxidation of methanol. When the atom ratio of Ti to Pt in the catalysts is 1/2, the catalysts showed the best electrocatalytic properties. After the catalyst is treated at 500 degreesC, the performance is further improved. It is hopeful to use the catalyst in the pratical DMFC.