Superstructures of water-dispersive hydrophobic nanocrystals: specific properties

Abstract

Here, we describe water-soluble superstructures of hydrophobic nanocrystals that have been developed in recent years. We will also report on some of their properties which are still in their infancy. One of these structures, called “cluster structures”, consists of hydrophobic 3D superlattices of Co or Au nanocrystals, covered with organic molecules acting like parachutes. The magnetic properties of Co “cluster structures” a retained when the superstructures is dispersed in aqueous solution. With Au “cluster structures”, the longer wavelength optical scattered spectra are very broad and red-shifted, while at shorter wavelengths the localized surface plasmonic resonance of the scattered nanocrystals is retained. Moreover, the maximum of the long-wavelength signal spectra is linearly dependent on the increase in assembly size. The second superstructure was based on liquid–liquid instabilities favoring the formation of Fe₃O₄ nanocrystal shells (colloidosomes) filled or unfilled with Au 3D superlattices and also spherical solid crystal structures are called supraballs. Colloidosomes and supraballs in contact with cancer cells increase the density of nanocrystals in lysosomes and near the lysosomal membrane. Importantly, the structure of their organization is maintained in lysosomes for up to 8 days after internalization, while the initially dispersed hydrophilic nanocrystals are randomly aggregated. These two structures act as nanoheaters. Indeed, due to the dilution of the metallic phase, the penetration depth of visible light is much greater than that of homogeneous metallic nanoparticles of similar size. This allows for a high average heat load overall. Thus, the organic matrix acts as an internal reservoir for efficient energy accumulation within a few hundred picoseconds. A similar behavior was observed with colloidosomes, supraballs and “egg” structures, making these superstructures universal nanoheaters, and the same behavior is not observed when they are not dispersed in water (dried and deposited on a substrate). Note that colloidosomes and supraballs trigger local photothermal damage inaccessible to isolated nanocrystals and not predicted by global temperature measurements.