Kinetics of aggregation and growth processes of PEG-stabilised mono- and multivalent gold nanoparticles in highly concentrated halide solutions.

5-6 nm gold nanoparticles were prepared by hydrolytic decomposition of [NMe4][Au(CF3)2] and functionalized in situ with mono- and multivalent thiolated PEG ligands. Time-dependent changes of the nanoparticles were monitored in aqueous NaCl, NaBr, and NaI solutions by UV-Vis spectroscopy, TEM, and HRTEM. The purely sterically protected particles are stable in ≤1 M NaCl and NaBr solutions, regardless of the valence of the ligands. At higher concentrations (≥2 M), the monovalent stabilized particles show minor reaction limited colloidal aggregation. In NaBr but not in NaCl solutions a minor Ostwald ripening also occurs. The divalent stabilized particles remain colloidally stable in both halide solutions, even if the temperature is raised or the concentration is increased above 2 M. In ≤1 M aqueous NaI solutions the particles remain stable. Above, the monovalent stabilized particles undergo an oxidative reaction, resulting in a time-dependent shift and broadening of the absorbance spectrum. Finally, this process slows down while the width of the spectra slightly narrows. The kinetics of this process can be described by a two-step sigmoidal process, comprising a slow induction period where active species are formed, followed by a fast growth and aggregation process. The increasing concentration of fused structures from the aggregates during this process results in a narrowing of the size distributions. The divalent stabilized particles show only some minor broadening and a slight shift of the absorbance spectra in ≤3 M NaI solutions. These observations confirm the excellent stability of the multivalent stabilized particles from this chloride-free particle synthesis.

Single-source precursors for alloyed gold-silver nanocrystals - a molecular metallurgy approach.

Multiple silver(I)-aurates(I) have been prepared by salt metathesis reactions that act as efficient single-source precursors to colloidal gold silver alloys with the highest possible atom economy in the chemical synthesis of nanostructures. The CF3 group present on the Au cation acts as an in situ reducing agent and can be converted into CO ligands by simple hydrolysis. This ligand-mediated activation and subsequent decomposition of metal-organic precursors impose a molecular control over the nucleation process, producing homogeneously alloyed (Ag-Au) nanoparticles with an atomic Au:Ag ratio of 1:1. The concept also works for the Au-Cu system and acts as a pointer to replace Au (Ag) with less expensive (Cu) metals.

Improved stability of "naked" gold nanoparticles enabled by in situ coating with mono and multivalent thiol PEG ligands.

Unprotected ("naked") gold nanoparticles with high monodispersity ([d], 5.5± 0.5 nm) were obtained in a facile and single-step microwave-assisted hydrolytic decomposition of the molecular precursor [NMe4][Au(CF3)2]. Given their chloride-free surface chemistry, the as-obtained gold nanoparticles were in situ functionalized with mono-, di-, and trivalent thiolated PEG ligands in order to study the influence of multivalent character of the ligands on the stability of the colloidal solutions. For this purpose, a novel tridentate ligand was synthesized and the previously reported syntheses of mono- and divalent thiol ligands were improved. Owing to the pristine character of the Au nanoparticles no ligand exchange was required, and the colloidal and chemical stability of the mono- and multivalent functionalized particles purely depended on the ligating ability of the thiolated groups. In situ-functionalized Au nanoparticles showed a strikingly (2 orders of magnitude higher) improved stability against small nucleophiles such as sodium cyanide compared to gold nanoparticles coated with citrate ligands and functionalized via a ligand-exchange reaction. The monovalent thiol PEG ligand produced most stable colloids against cyanide, which is explained by a strongly increased numerical ligand-density on the surface. Gold colloids stabilized by di- and trivalent ligands exhibited high stability in aqueous solutions with high NaCl concentrations (2 M) in contrast to those functionalized with the monovalent PEG ligand, which were only temporally stable in dilute NaCl solutions. The beneficial effect of the multivalence of the ligands was further demonstrated by the incorporation of an additional chelating ligand (dithiothreitol) to the colloidal dispersions.

[(CF3)4Au2(C5H5N)2]--a new alkyl gold(II) derivative with a very short Au-Au bond.

A new gold(II) species [(CF(3))(4)Au(2)(C(5)H(5)N)(2)] with a very short unsupported Au-Au bond (250.62(9) pm) was generated by photo irradiation of a silver aurate, [Ag(Py)(2)][Au(CF(3))(2)], unambiguously characterized by (19)F and (109)Ag NMR studies.

Ink-jetable patterning of metal-catalysts for regioselective growth of nanowires.

Nanosized (20-30 nm) colloidal gold, silver and their alloys were obtained by reductive transformation of corresponding metal salts. Dispersions of metal nanoparticles (σ < 4%) in aqueous solutions were obtained by appropriate surface functionalization which led to inorganic inks with solid fraction ranging from 0.01-4%. Judicious choice of a polymer additive (polyethylene glycol or carboxymethyl cellulose) was found to be crucial to avoid the agglomeration of nanocrystals in the ink-jetted structures upon solvent evaporation. The versatility of the nanoparticle-based printing technology was demonstrated by fabrication of dot-matrices and circuitry patterns on different substrates. Characterization of printed structures showed a homogeneous topography (AFM) and uniform distribution of metallic nanoparticles (SEM/TEM) within the ink-jetted microdrops. The site-specific patterning on silicon (001) substrates with nanoparticle (mono)layers could also be achieved by printing the linker molecule, aminopropyltriethoxysilane, followed by selective attachment of gold nanoparticles. Positionally ordered and chemically bonded gold catalyst patterns were used for the chemical vapour deposition (CVD) of nanowires, which led to site-specific growth of nanowires via the vapour-liquid-solid (VLS) mechanism and unlike in the case of spin-coated metal colloids no significant lateral diffusion of metal nanoparticles was observed, in chemically anchored Au nanoparticles. Nanoparticle containing inks allow a user-defined dilution to vary the density of CVD grown nanowires, which was utilized to show the differences in catalytic activities of silver and gold catalysts in the VLS growth.