Molecular Engineering of Colloidal Atoms

Abstract

Creation of architectures with exquisite hierarchies actuates the germination of revolutionized functions and applications across a wide range of fields. Hierarchical self‐assembly of colloidal particles holds the promise for materialized realization of structural programing and customizing. This review outlines the general approaches to organize atom‐like micro‐ and nanoparticles into prescribed colloidal analogs of molecules by exploiting diverse interparticle driving motifs involving confining templates, interactive surface ligands, and flexible shape/surface anisotropy. Furthermore, the self‐regulated/adaptive co‐assembly of simple unvarnished building blocks is discussed to inspire new designs of colloidal assembly strategies.

DNA-mediated regioselective encoding of colloids for programmable self-assembly

“…The amount of DNA on a particle determines its coordination number, which is analogous to the valence of an atom in a molecule system. [34][35][36][37][38] Since then, a variety of DNA-mediated regioselective surface encoding approaches have been developed to explore novel assembled structures both in experiment and simulation (Fig. 1).…”

Colloidal Self‐Assembly: From Passive to Active Systems

“…[30] Compared to atoms and molecules, the interactions between colloids are usually spherically symmetric. Various techniques, such as template-assisted assembly, ligand-mediated assembly, and anisotropy-regulated assembly, [31][32][33] have been developed to break the interaction symmetry for desired structures. For instance, templated assembly involves using prefabricated microwells to create spatial confinement, where various geometric colloidal molecules can be created by using differently shaped microwells (Figure 3a).…”

Site-Specific Chemistry on Gold Nanorods: Curvature-Guided Surface Dewetting and Supracolloidal Polymerization

“…Nanoparticle (NP) assemblies have been considered as a prototype for artificial molecules/atoms; − however, the level of their structural complexity and hierarchy is far less than those in molecular or atomic systems. , Unlike molecules with asymmetric shapes and bond polarization, colloidal synthesis favors high symmetry, , often leading to isotropic interparticle interactions and the formation of close-packing assemblies. , As pointed out by Glotzer and others, , the key structural feature to create directional interaction, but not yet included in those colloidal building blocks, is anisotropy. Despite notable progress in the controlled synthesis of colloidal NPs in terms of their size, , shape, − and chemical composition, precise control of interparticle interactions (direction and strength), ,− even for anisotropic NP building blocks, remains at its early stage in comparison with their covalent counterparts such as atomic or molecular bonding.…”