The mixing of polymers and nanoparticles is opening pathways for engineering flexible composites that exhibit advantageous electrical, optical, or mechanical properties. Recent advances reveal routes to exploit both enthalpic and entropic interactions so as to direct the spatial distribution of nanoparticles and thereby control the macroscopic performance of the material. For example, by tailoring the particle coating and size, researchers have created self-healing materials for improved sustainability and self-corralling rods for photovoltaic applications. A challenge for future studies is to create hierarchically structured composites in which each sublayer contributes a distinct function to yield a mechanically integrated, multifunctional material.

The organization of inorganic nanostructures within self-assembled organic or biological templates is receiving the attention of scientists interested in developing functional hybrid materials. Previous efforts have concentrated on using such scaffolds to spatially arrange nanoscopic elements as a strategy for tailoring the electrical, magnetic or photonic properties of the material. Recent theoretical arguments have suggested that synergistic interactions between self-organizing particles and a self-assembling matrix material can lead to hierarchically ordered structures. Here we show that mixtures of diblock copolymers and either cadmium selenide- or ferritin-based nanoparticles exhibit cooperative, coupled self-assembly on the nanoscale. In thin films, the copolymers assemble into cylindrical domains, which dictate the spatial distribution of the nanoparticles; segregation of the particles to the interfaces mediates interfacial interactions and orients the copolymer domains normal to the surface, even when one of the blocks is strongly attracted to the substrate. Organization of both the polymeric and particulate entities is thus achieved without the use of external fields, opening a simple and general route for fabrication of nanostructured materials with hierarchical order.

The self-assembly of particles at fluid interfaces, driven by the reduction in interfacial energy, is well established. However, for nanoscopic particles, thermal fluctuations compete with interfacial energy and give rise to a particle-size-dependent self-assembly. Ligand-stabilized nanoparticles assembled into three-dimensional constructs at fluid-fluid interfaces, where the properties unique to the nanoparticles were preserved. The small size of the nanoparticles led to a weak confinement of the nanoparticles at the fluid interface that opens avenues to size-selective particle assembly, two-dimensional phase behavior, and functionalization. Fluid interfaces afford a rapid approach to equilibrium and easy access to nanoparticles for subsequent modification. A photoinduced transformation is described in which nanoparticles, initially soluble only in toluene, were transported across an interface into water and were dispersed in the water phase. The characteristic fluorescence emission of the nanoparticles provided a direct probe of their spatial distribution.

different core block chemistry. The key point for choosing the different chemistries of the two hydrophobic blocks is that the two blocks experience a high degree of mutual immiscibility. In the current experiment, polystyrene (PS) and poly(2,3,4,5,6-pentafluorostyrene) (PPFS) were employed as the different, third hydrophobic blocks in the two triblock copolymers (PAA 94 -b-PMA 103 -b-PS 117 and PAA 93 -b-PMA 99 -b-PPFS 100 ) (29). Equal molar amounts of the two triblock copolymers with different respective third blocks were dissolved in pure THF. EDDA was then added to reach a final 1:1 molar ratio of amine groups to acid groups. The diamines underwent complexation with the PAA blocks, thereby forming aggregates with PAA-diamine cores. Notably, these aggregates contained each of the triblock copolymers with both PS and PPFS hydrophobic blocks because of the simple trapping of unlike hydrophobic blocks in the same aggregate by PAA-diamine complexation. Next, introduction of water into the THF solution to a final ratio of THF:water = 1:2 provided for the formation of cylindrical micelles. However, the existence of the original mixed triblock copolymer aggregates, as a result of PAA and diamine complexation, forced the local co-assembly of unlike third hydrophobic blocks into the same micelle core. In addition, the lack of chain exchange in solution that disallows global chain migration and maintains nonequilibrated micelle structures, combined with the fact that the PAA chains in the corona of the newly formed micelles were still complexed with diamines and were not freely mobile within the micelle, guarantee the stability of the mixed-core micelle. The immiscibility of the two different hydrophobic blocks, PS and PPFS, eventually resulted in internal phase separation on the nanoscale, producing multicompartment micelles. The images shown in Fig. 4, A to D were taken after 4 days of aging a solution of mixed hydrophobic core cylinders. Internal phase separation is clearly indicated by the strong undulations along the cylinder surfaces and the TEM contrast variation along the cylinders. The larger, darker, and more spherical regions within the cylinders are hypothesized to be regions that are concentrated in PAA 94 -b-PMA 103 -b-PPFS 100 triblock copolymer. First, there is a higher interfacial energy between PPFS and PMA, relative to PS and PMA, causing more chain stretching within PPFS-rich core domains so as to limit PPFS interactions with surrounding PMA blocks. Second, the greater electron density of the PPFS block provides a greater ability to scatter electrons and produce darker images in the TEM. The thinner region of the undulating cylinder would then be occupied primarily by PAA 93 -b-PMA 99 -b-PS 117 (Fig. 4G). This internal cylinder phase separation only occurred at relatively higher amounts of water in the mixed solvent solutions. Cryo-TEM showed uniform cylinders without undulation on the surface at only 40% water/THF solution after 4 days (Fig. 4E). However, multicompartment cylinders could be obser...