Saikat Mandal

Investigation into the interaction between surface-bound alkylamines and gold nanoparticles

In addition to alkanethiols and phosphine derivatives, alkylamines have been investigated as capping agents in the synthesis of organically dispersible gold nanoparticles. However, reports pertaining to gold nanoparticle derivatization with alkylamines are relatively scarce and their interaction with the underlying gold support is poorly understood. In this paper, we attempt a more detailed examination of this problem and present results on the Fourier transform infrared spectroscopy, thermogravimetry, nuclear magnetic resonance, and X-ray photoemission (XPS) characterization of gold nanoparticles capped with the alkylamines laurylamine (LAM) and octadecylamine (ODA). The capping of the gold nanoparticles with the alkylamines was accomplished during phase transfer of aqueous gold nanoparticles to chloroform containing fatty amine molecules. Thermogravimetry and XPS analysis of purified powders of the amine-capped gold nanoparticles indicated the presence of two different modes of binding of the alkylamines with the gold surface. The weakly bound component is attributed to the formation of an electrostatic complex between protonated amine molecules and surface-bound AuCl4-/AuCl2- ions, while the more strongly bound species is tentatively assigned to a complex of the form [AuCl(NH2R)]. The alkylamine monolayer on the gold nanoparticle surface may be place exchanged with other amine derivatives present in solution.

Water-dispersible tryptophan-protected gold nanoparticles prepared by the spontaneous reduction of aqueous chloroaurate ions by the amino acid.

The synthesis of water-dispersible amino-acid-protected gold nanoparticles by the spontaneous reduction of aqueous chloroaurate ions by tryptophan is described. Water-dispersible gold nanoparticles may also be obtained by the sequential synthesis of the gold nanoparticles by borohydride reduction of chloroauric acid followed by capping with tryptophan. Comparison of the proton NMR spectroscopic signatures from the tryptophan-protected gold nanoparticles obtained by the two processes indicated that the indole group in tryptophan is responsible for reduction of the aqueous chloroaurate ions. The reduction of the metal ions is accompanied by oxidative polymerization of the indole group of the tryptophan molecules and, consequently, some degree of cross-linking of the gold nanoparticles.

Synthesis of a stable gold hydrosol by the reduction of chloroaurate ions by the amino acid, aspartic acid

Development of reliable protocols for the synthesis of nanoparticles of well-defined sizes and good monodispersity is an important aspect of nanotechnology. In this paper, we present details of the synthesis of gold nanoparticles of good monodispersity by the reduction of aqueous chloroaurate ions by the amino acid, aspartic acid. The colloidal gold solution thus formed is extremely stable in time, indicating electrostatic stabilization via nanoparticle surface-bound amino acid molecules. This observation has been used to modulate the size of the gold nanoparticles in solution by varying the molar ratio of chloroaurate ions to aspartic acid in the reaction medium. Characterization of the aspartic acid-reduced gold nanoparticles was carried out by UV-visible spectroscopy, thermogravimetric analysis and transmission electron microscopy. The use of amino acids in the synthesis and stabilization of gold nanoparticle in water has important implications in the development of new protocols for generation of bioconjugate materials.

Open-Mouthed Metallic Microcapsules: Exploring Performance Improvements at Agglomeration-Free Interiors

Although artificial capsule structures have been thoroughly investigated, functionality at the surfaces of their interiors has been surprisingly overlooked. In order to exploit this aspect of capsular structure, we here report the breakthrough fabrication of metallic (platinum) microcapsules with sufficient accessibility and electroactivity at both interior and exterior surfaces (open-mouthed platinum microcapsules), and also we demonstrate improvements in electrochemical and catalytic functions to emphasize the practical importance of our concept. The open-mouthed platinum microcapsules were prepared by template synthesis using polystyrene spheres, where surface-fused crystalline nanoparticles formed a capsule shell. Subsequent removal of the polystyrene spheres induced formation of mouth-like openings. The open-mouthed platinum microcapsules exhibit a substantial increase of their electrode capability for methanol oxidation and catalytic activities for carbon monoxide (CO) oxidation. Notably, activity loss during CO oxidation due to undesirable particle agglomeration can be drastically suppressed using the open-mouthed microcapsules.

Keggin ion-mediated synthesis of aqueous phase-pure Au@Pd and Au@Pt core–shell nanoparticles

Development of simple and reliable protocols for the synthesis of phase-pure core–shell metal nanoparticles is an important problem in nanomaterials synthesis; the synthesis of Au core–Pd/Pt shell nanoparticles is described in this paper. This is accomplished by utilizing Keggin ions bound to the surface of gold nanoparticles as UV-switchable reducing agents. Exposure of Keggin ion-capped gold nanoparticles to aqueous solutions of Pd2+ and Pt4+ ions after UV activation of the Keggin ions results in selective reduction of the metal ions only on the surface of the nanoparticles and thus, to phase-pure core–shell nanostructures. The synthesis of the Au@Pd and Au@Pt core–shell nanoparticles was followed by UV-vis spectroscopy, X-ray photoemission spectroscopy and high-resolution transmission electron microscopy measurements.

Ag+–Keggin ion colloidal particles as novel templates for the growth of silver nanoparticle assemblies

In the work reported in this paper, we demonstrate that Ag+–Keggin ion colloidal particles are excellent templates for the synthesis of organized assemblies of silver nanoparticles, wherein the Keggin ion host plays the role of a UV-switchable reducing agent. More specifically, we investigate the formation of aqueous colloidal particles of Ag+ ions complexed with phosphotungstate (PW12O40)3− Keggin ions and show that they may be used as a new class of inorganic scaffolds in the synthesis of silver nanoparticle assemblies. The crystalline Keggin ion host may be reduced photochemically resulting in electron transfer to the entrapped silver ions and consequent formation of silver nanoparticle assemblies on the underlying colloidal particle surface. Treatment with alkali results in dissolution of the colloidal particle template leaving behind the silver nanoparticle network reasonably intact.

New approaches to the synthesis of anisotropic, core–shell and hollow metal nanostructures

The synthesis of nanomaterials with control over size, shape and chemical composition continues to be a major challenge in nanoscience. The requirements of nanomaterial synthesis are becoming more sophisticated and, in addition to anisotropic structures, there is much excitement surrounding the development of recipes for the synthesis of core–shell and hollow nanostructures. Much of the motivation for research in this direction stems from the unusual optoelectronic and chemical properties exhibited by such nanostructures. In this article, we review the work from this laboratory on the synthesis of flat gold nanostructures at the air–water interface, either by confining the reductant or the precursor metal ions to the air–water interface. We also describe the synthesis of phase-pure core–shell nanoparticles by immobilizing UV- and pH-dependent reducing agents on the surface of the core nanoparticles as well as the synthesis of organically soluble hollow-shell nanostructures via transmetallation reactions.

Silver nanoparticles of variable morphology synthesized in aqueous foams as novel templates

In this paper, we describe the synthesis of silver nanocrystals within aqueous foams as a template. More specifically, we show that aqueous Ag+ions may be electrostatically complexed with the anionic surfactants aerosol OT (sodiumbis-2-ethylhexyl-sulfosuccinate, (AOT) and sodium dodecyl sulphate (SDS)) in a highly stable liquid foam. After drainage of the foam, the silver ions are reducedinsituby introducing sodium borohydride into the foam by capillary flow. This leads to the formation of silver nanoparticles of spherical, tape-and sheet-like morphology in the foam. The structure of the foam is extremely complex and presents reaction sites of different spatial extent. The differences in foam reaction-site geometry are believed to be responsible for the morphology variation in the silver nanoparticles observed. The silver nanoparticles are observed to be extremely stable in solution suggesting that the AOT or SDS molecules stabilize them. This approach appears promising for application in large-scale synthesis of nanoparticles and may be readily extended to other chemical compositions.

Low‐Temperature Remediation of NO Catalyzed by Interleaved CuO Nanoplates

A copper(II)-oxide-based exhaust catalyst exhibits better activity than Pt- and Rh-nanoparticle catalysts in NO remediation at 175 °C. Following theoretical design, the CuO catalyst is rationally prepared; CuO nanoplates bearing a maximized amount of the active {001} facet are arranged in interleaved layers. A field test using a commercial gasoline engine demonstrates the ability of the catalyst to remove NO from the exhaust of small vehicles.

Use of aqueous foams for the synthesis of gold nanoparticles of variable morphology

In this paper we describe the facile synthesis of gold nanocrystals of variable morphology using aqueous foam as a template. The aqueous foams are formed by bubbling an aqueous solution of AuCl−4 ions electrostatically complexed with the surfactant cetyltrimethylammonium bromide (CTAB). The gold ions in the stable foam are then reduced by hydrazine vapours, this process leading to the formation of gold nanoparticles of spherical, flat plate and flake-like structures. The variation in morphology of the gold nanoparticles derived from the foam is believed to arise from the complex spatial structure of reaction sites in the foam. The foam-derived gold nanoparticles were analysed by UV-vis spectroscopy, X-ray diffraction, Fourier transform infrared spectroscopy and transmission electron microscopy.