Surface reconstruction and decahedral structure of bimetallic nanoparticles

We report on energetic surface reconstruction phenomena observed on bimetallic nanoparticle systems of AuPd and AuCu, similar to a resolidification effect observed during the cooling process in lead clusters. These binary alloy nanoparticles show the fivefold edges truncated, resulting in [100] facets on decahedral structures, an effect largely envisioned and reported theoretically, with no experimental evidence so far. We demonstrate experimentally as well as by computational simulations that this new eutectic structure is favored in such nanoalloy systems.     

Synthesis and structure determination of bimetallic Au/Cu nanoparticles

The synthesis of bimetallic nanoparticles has become so important in recent times due to its multi-faceted applications. The structure of the synthesised particles influences directly their properties. In this paper, we report the synthesis of Au/Cu nanoparticles by a simultaneous reduction method, considering three different molar concentrations (AuCu, AuCu₃ and Au₃Cu) of the components. In order to determine the size and structure of the obtained clusters, the particles were examined by optical spectroscopy, transmission electron microscopy and high-resolution transmission electron microscopy. One of the major factors, the minimum bimetal formation energy, was calculated by an embedded-atom method. The relation between the Au/Cu proportions has been demonstrated to affect the size of the particles and the corresponding structures. From the basic structural analysis it is found that the particles were fcc-like, multiple twin or multiple defect particles for the different Au/Cu concentrations. The smallest particles were identified for the Au/Cu sample with 50% of each, and the most crystalline structures were also obtained in the same sample. PACS 61.46.+w; 61.16.-d; 31.15.Qg     

Preparation of Ultrafine Colloidal Gold Particles using a Bioactive Molecule

Synthesis of nanometer-sized particles with new physical properties is an area of tremendous interest. In metal particles, the changes in size modify the electron density in the particles, which shifts the plasmon band. The most significant size effects occur when the particles are ultrafine (size is <10 nm). Thus the synthesis of ultrafine metal particles is enormously important to exploit their unique and selective application. Here we report a novel method for the synthesis of ultrafine gold particles in the size range of 0.5–3 nm using dopamine hydrochloride (dhc), an important neurotransmitter. This is the first time where such an important bioactive molecule like dhc has been used as a reagent for the transformation of Au(III) to Au(0). The synthesis is carried out, for the first time, either in simple aqueous or in a nonionic micellar (for example Triton X-100 (TX-100)) medium. The gold sol has a beautiful yellow–brown color showing _max at 470 nm. The appearance of the absorption peak at substantially shorter wavelength (usually gold sol absorbs at 520 nm) indicates that the particles are very small. The method discussed here is very simple, reproducible and does not involve any reagent, which contains 'P' or 'S' atoms. Also in this case no polymer or dendrimer or thiol-related stabilizer is used. The effects of different parameters (such as the presence or absence of O₂, temperature, TX-100 concentration and dhc concentration) on the formation of ultrafine gold particles are discussed. The effects of 3-mercapto propionic acid and pyridine on the ultrafine gold sol are also studied and compared with those on photochemically prepared gold sol. It is observed that 3-mercapto propionic acid dampens the plasmon absorption at 470 nm of ultrafine gold particles. Pyridine, on the other hand, has no effect on the particles.     

Structural and functional analogue of the active site of polysulfide reductase from Wolinella succinogenes

Synthesis of [PPh4]2[Mo(SPh)2(S2C2(CN)2)2] (2) from [PPh4]2[MoO(S2C2(CN)2)2] (1) has been achieved to mimic the postulated [Mo(S)6] core of polysulfide reductase with two thiolates and two bis(ene-dithiolate) ligands. Compound 2 reacts with polysulfide to yield H2S, modeling the function of polysulfide reductase. The facile conversion of 2 back to 1 in moist solvent suggests that the interconversion of the [MoIV = O] and [MoIV - X] (X = O-Ser, S-Cys, Se-Cys) moieties might occur in the DMSO reductase class of enzymes under appropriate hydrophobic/hydrophilic conditions.     

Solution phase evolution of AuSe nanoalloys in Triton X-100 under UV-photoactivation

A solution phase UV-irradiation technique has been exploited to produce an AuSe nanoalloy through fusion of preformed Au (photoproduced) and Se (chemically prepared) in a micellar (TX-100) medium.     

Contents of Volume 2 (2003)

Volume Contents

Contents of Volume 2 (2003)     

Studies on CdS nanoparticles dispersed in silica matrix prepared by sol-gel technique

SiO₂/CdS-nanoparticle composite films (SiO₂:CdS=85:15, 80:20, 75:25 and 70:30) were prepared by the sol-gel route. The films were characterized by studying microstructural (XRD and TEM) and optical (transmittance and photoluminescence) properties. Band gaps of these films annealed at different temperatures (373-473 K) for different times (10-120 min) indicated that the signature of nanocrystallinity is retained throughout the range of our experimental conditions. A thermal diffusion process controlled growth in the crystallite size with increasing annealing time and temperature. The average radii of the nanoparticles varied as the cube root of the annealing time but showed exponential dependence on the inverse of annealing temperature. Photoluminescence (PL) studies of the composite films indicated excitonic transitions. Theoretical analysis of the line shapes of the PL peaks recorded at 300 K and 80 K could be accounted for by the combined effects of size distribution and phonon broadening. It was observed that the deformation potential (E _d) effectively controlled the line shapes of the PL measurements. Received 24 May 2002 Published online 27 January 2003 RID="a" ID="a"e-mail: msakp@mahendra.iacs.res.in     

A dimeric pervanadyl (VO2+) complex with a tridentate Schiff base ligand

A di(-oxo)-bridged dinuclear complex, [VO₂(pamh)]₂ was isolated by reacting bis(acetylacetonato)vanadium(IV) and the Schiff base, N-(anisoyl)-N-(picolinylidene)-hydrazine (Hpamh) in acetonitrile. The complex crystallizes in the space group ;1; (#2) on crystallographic inversion center. Crystal data: a = 8.2202(12) Å, b = 9.8389(19) Å, c = 10.1907(17) Å, = 68.245(15)°, = 74.47(2)°, = 66.710(19)°, V = 696.0(2) ų, and Z = 1. The physical properties of the complex and the structural parameters are consistent with the +5 oxidation state of the metal ions. The monomeric VO₂(pamh) unit is square-pyramidal. The planar mononegative ligand (pamh^–) coordinates the metal ion via the pyridine-N, the imine-N, and the amide-O atoms. One of the oxo groups completes the NNOO basal plane and also participates in the Vndash;Ondash ;V bridge formation. The other oxo group satisfies the fifth apical coordination site. The molecular structure of the dimeric complex, [VO₂(pamh)]₂ can be described as two edge-shared distorted VO₄N₂ octahedra.