Entropic control of nanoparticle self-assembly through confinement.

Entropy can be the sole driving force for the construction and regulation of ordered structures of soft matter systems. Specifically, under confinement, the entropic penalty could induce enhanced entropic effects which potentially generate visually ordered structures. Therefore, spatial confinement or a crowding environment offers an important approach to control entropy effects in these systems. Here, we review how spatial confinement-mediated entropic effects accurately and even dynamically control the self-assembly of nanoscale objects into ordered structures, focusing on our efforts towards computer simulations and theoretical analysis. First, we introduce the basic principle of entropic ordering through confinement. We then introduce the applications of this concept to various systems containing nanoparticles, including polymer nanocomposites, biological macromolecular systems and macromolecular colloids. Finally, the future directions and challenges for tailoring nanoparticle organization through spatial confinement-mediated entropic effects are detailed. We expect that this review could stimulate further efforts in the fundamental research on the relationship between confinement and entropy and in the applications of this concept for designer nanomaterials.