Reversible synthesis of sub-10 nm spherical and icosahedral gold nanoparticles from a covalent Au(CN) ₂ ^- precursor and recycling of cyanide to form ferric ferrocyanide for cell staining

A solution approach based on Au(CN) ₂ ^- chemistry is reported for the formation of nanoparticles. The covalent character of the Au(CN) ₂ ^- precursor was exploited in the formation of sub-10 nm nanospheres (≈2.4 nm) and highly monodisperse icosahedral Au nanoparticles (≈8 nm) at room temperature in a one-pot aqueous synthesis. The respective spherical and icosahedral Au morphologies can be controlled by either the absence or presence of the polymer polyvinylpyrrolidone (PVP). Using Au(CN) ₂ ^- as a metal ion source, our findings suggest that the addition of citrate ions is necessary to enhance the particle formation rate as well as to generate a more homogeneous colloidal dispersion. Because of the presence of oxygen and the operation of a CN ^- etching process associated with Au(CN) ₂ ^- complex formation, an interesting reversible formation-dissolution process was observed, which allowed us to repeatedly prepare spherical and icosahedral Au nanoparticles. Time-dependent TEM images and UV/Vis spectra were carefully acquired to study the reversibility of this formation-dissolution process. In view of the accompanying generation of toxic cyanide anions, we have developed a protocol to recycle cyanide in the presence of citrate ions through ferric ferrocyanide formation. After completion of particle formation, the residual solutions containing citrate ions and cyanide ions were processed to stain iron oxide nanoparticles endocytosized in cells. Additionally, the as-prepared 8 nm Au icosahedra could be isolated and grown to larger 57 nm-sized icosahedra using the seed-mediated growth approach. Reversible nanoparticle formation: A one-pot synthesis of nanospheres (≈2.4 nm) and highly monodisperse icosahedral Au nanoparticles (≈8 nm) in aqueous solution using Au(CN) ₂ ^- as a precursor at room temperature is reported. The Au(CN) ₂ ^- chemistry involves a reversible formation-dissolution process that repeatedly produces Au nanospheres and icosahedra (see scheme).