Self-Assembly of Proteinaceous Shells around Positively Charged Gold Nanomaterials Enhances Colloidal Stability in High-Ionic-Strength Buffers.

The enzyme lumazine synthase (LS) has been engineered to self-assemble into hollow-shell structures that encapsulate unnatural cargo proteins through complementary electrostatic interactions. Herein, we show that a negatively supercharged LS variant can also form organic-inorganic hybrids with gold nanomaterials. Simple mixing of LS pentamers with positively charged gold nanocrystals in aqueous buffer spontaneously affords protein-shelled gold cores. The procedure works well with differently sized and shaped gold nanocrystals, and the resulting shelled complexes exhibit dramatically enhanced colloidal stability over a wide range of pH (4.0-10.0) and at high ionic strength (up to 1 m NaCl). They are even stable over days upon dilution in buffer. Self-assembly of engineered LS shells in this way offers an easy and attractive alternative to commonly used ligand-exchange methods for stabilizing inorganic nanomaterials.

Surface-Engineered Cationic Nanocrystals Stable in Biological Buffers and High Ionic Strength Solutions.

Progress in colloidal synthesis in the last two decades has enabled high-quality semiconductor, plasmonic, and magnetic nanocrystals (NCs). As synthesized, these NCs are usually capped with long-chain apolar ligands. Postsynthetic surface functionalization is required for rendering such NCs colloidally stable in polar media such as water. However, unlike small anionic molecules and polymeric coatings, producing positively charged stable NCs, especially at high ionic strengths, has remained challenging. Here, we present a general approach to achieve aqueously stable cationic NCs using a set of small (<2.5 nm long) positively charged ligands. The applicability of this method is demonstrated for a variety of materials including semiconductor CdSe/CdS core/shell NCs, magnetic Fe@Fe3O4, Fe3O4, and FePt NCs, and three different classes of plasmonic Au NCs including large nanorods. The obtained cationic NCs typically have zeta potential values ranging from +30 to +60 mV and retain colloidal stability for days to months, depending on NC/ligand pair, in several biological buffers at elevated pH and in concentrated salt solutions. This allowed us to demonstrate site-specific staining of cellular structures using fluorescent cationic NCs with several different surface chemistries. Furthermore, colloidal stability of the obtained NCs in the presence of other charged species allowed the assembly of cationic and anionic counterparts driven primarily by electrostatic attraction. With this approach, we prepare highly uniform 3D and 2D binary mixtures of NCs through induced homogeneous aggregation and alternating-charge layer-by-layer deposition, respectively. Such binary mixtures may provide a new route in the engineering of nanocrystalline solids for electronics, thermoelectrics, and photovoltaics.