Engineering Liquid Hierarchical Materials with DNA-Programmed Spherical Nucleic Acids.

Inspired by nature, the orchestration of self-assembling building blocks into hierarchical superstructures offers a transformative approach to functional materials design. While significant advances have been made in engineering solid-state hierarchical materials such as crystals and superlattices, creating dynamic, liquid-like hierarchical materials remains a profound challenge. Herein, a universal and efficient method is introduced to construct spherical nucleic acids (SNAs) functionalized with diverse nucleic acids (NAs), including random DNA sequences, circular DNA (circ-DNA), single guide RNA (sgRNA), messenger RNA (mRNA), and multi-branched DNA independent of sequence, length, or topology. By examining spatial configuration and mechanical rigidity in DNA-mediated bonding, precise hierarchical assembly of SNAs is enabled. Furthermore, using these multivalent SNAs as programmable molecule equivalents, liquid-phase hierarchical materials via phase separation are successfully created, forming microscale SNA droplets. These metal condensates exhibit dynamic liquid-like properties and stimuli-responsiveness, including enhanced photothermal effects in living cells. Our findings provide fundamental insights into the formation and dynamics of liquid hierarchical materials, offering potentials for designing living-matter-inspired systems and advancing applications in biomedicine and responsive materials.