Self-assembly of particles—The regulatory role of particle flexibility

Aspects of the self-assembly of particles, which uses nanometer or micrometer sized building blocks to bridge the gap between microscopic and macroscopic scales, are reviewed. Particle self-assembly has been the focus of considerable research in recent years because it can lead to superstructures with a complexity inaccessible by molecular self-assembly, and functionalities entirely different from or superior to those of the primary particles. Examples in molecular self-assembly suggests that anisotropic interactions could be useful in promoting particle self-assembly, with the exception of colloidal crystallization, which requires particles of uniform size and shape. Anisotropic particles prepared by surface modification of precursor particles are often rigid and submicron or micron sized, and thus relatively strong isotropic van der Waals interactions tend to resist self-assembly into regular superstructures. In addition, the relatively large contact area between particles needed for a sufficient binding enthalpy to stabilize a superstructure is difficult for rigid spherical particles. In contrast, flexible anisotropic polymeric particles dispersed in solvents have been shown to self-assemble into various superstructures. The flexibility of primary anisotropic particles enables them to fuse and stabilize into a superstructure. Some flexible and multi-component particles that are isotropic in common solvents can undergo deformation and sufficient material redistribution to anisotropically self-assemble into regular superstructures in selective solvents. The self-assembly is also driven by anisotropic interactions, which is induced during self-assembly rather than in the particles as synthesized. This review focuses on recent achievements in soft particle self-assembly and describes briefly the advancements in rigid particle self-assembly. The presentation is divided into discussion of self-assembly by the colloidal crystallization of isotropic rigid particles, anisotropic rigid particles, anisotropic soft particles and isotropic soft particles, in that order.