Programming of Supercrystals Using Replicable DNA‐Functionalized Colloids

Abstract The development of self‐replicating systems is of great importance in research on the origin of life. As the most iconic molecules, nucleic acids have provided prominent examples of the fabrication of self‐replicating artificial nanostructures. However, it is still challenging to construct sophisticated synthetic systems that can create large‐scale or three‐dimensionally ordered nanomaterials using self‐replicating nanostructures. By integrating a template system containing DNA‐functionalized colloidal seeds with a simplified DNA strand‐displacement circuit programmed subsystem to produce DNA‐functionalized colloidal copies, we developed a facile enthalpy‐mediated strategy to control the replication and catalytic assembly of DNA‐functionalized colloids in a time‐dependent manner. The replication efficiency and crystal quality of the resulting superlattice structures can be effectively increased by regulating the molar ratio of the template to the copy colloids. By constructing binary systems from two types of gold nanoparticles (or proteins), superlattice structures with different crystal symmetries can be obtained through the replication and catalytic assembly processes. This programmable enthalpy‐mediated approach was easily leveraged to achieve the phase transformation and catalytic amplification of colloidal crystals starting from different initial template crystals. This work offers a potential way to construct self‐replicating artificial systems that exhibit complicated phase behaviors and can produce large‐scale superlattice nanomaterials.