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Janus nanoparticles with two chemically different compartments have been shown to be a unique class of building blocks in solution. Here we perform mesoscale simulations to explore the self-assembly of Janus nanoparticles with widely varying architectures in diblock copolymers. We demonstrate that the coassembly of these amphiphilic building blocks forms novel and tunable structures at the interfaces of block copolymers, and consequently influences the interface stabilization and structural evolution kinetics. Our simulations suggest that Janus nanoparticle self-assembly at block copolymer interfaces yields considerable control over the creation of polymer nanocomposites with improved shear behavior. In this context, the approach is a viable strategy for creating functional materials with enhanced processing properties.

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The ability to tailor the interfacial behaviors of nanoparticles (NPs) is crucial not only for the design of novel nanostructured materials with superior properties and of interest for many promising applications such as water purification, enhanced oil recovery, and innovative energy transduction, but also for a better insight into many biological systems where nanoscale particles such as proteins or viruses can interact and organize at certain interfaces. As a class of emerging building blocks, Janus NPs consisting of two compartments of different chemistry or polarity are ideal candidates to generate tunable and stable interfacial nanostructures because of the asymmetric nature. However, precise control over such interfacial nanostructures toward a controllable order and even responses to various external stimuli still remains a great challenge as the interfaces do not simply serve as a scaffold but rather induce complex enthalpic and entropic interactions. In this Account, we focus on our efforts on exploiting entropy strategies based on computational design to tailor the spatial distribution and ordering of NPs at the interfaces of various systems. First, we introduce the physical principle of entropic ordering, being the theoretical basis of entropy-directed interfacial self-assembly. The typical types of entropy, which have been harnessed to manipulate the interfacial NP organization, are then summarized, including conformational entropy, shape entropy, and rotational and vibrational entropy. Next, we describe the emerging pathways in the development of novel environmentally responsive systems which involve the use of entropy to access the stimuli-responsive behaviors of interfacial nanostructures. Taking one step further, how molecular architectures can be tailored to tune the entropic contributions to the interfacial self-assembly is demonstrated, through identifying the effects of various intrinsic properties of block segments, such as chain length and stiffness, on entropy-governed precise organization of Janus NPs at block copolymer interfaces. Finally, we detail some key factors for tailoring interfacial organization through entropy. In summary, entropy strategies offer a promising and abundant framework for precisely programming the structural organization of NPs at interfaces. We discuss future directions to signify the framework in tailoring the interfacial organization of NPs. We hope that this Account will promote further efforts toward fundamental research and the wide applications of designed interfacial assemblies in new types of functional nanomaterials and beyond.

The transport of nanoparticles at bio-nano interfaces is essential for many cellular responses and biomedical applications. How two-dimensional nanomaterials, such as graphene and transition-metal dichalcogenides, diffuse along the cell membrane is, however, unknown, posing an urgent and important issue to promote their applications in the biomedical area. Here, we show that the transport of graphene oxides (GOs) sandwiched inside cell membranes varies from Brownian to Lévy and even directional dynamics. Specifically, experiments evidence sandwiched graphene–cell membrane superstructures in different cells. Combined simulations and analysis identify a sandwiched GO–induced pore in cell membrane leaflets, spanning unstable, metastable, and stable states. An analytical model that rationalizes the regimes of these membrane-pore states fits simulations quantitatively, resulting in a mechanistic interpretation of the emergence of Lévy and directional dynamics. We finally demonstrate the applicability of sandwiched GOs in enhanced efficiency of membrane-specific drug delivery. Our findings inform approaches to programming intramembrane transport of two-dimensional nanomaterials toward advantageous biomedical applications.