Multivalency-driven liquid-liquid phase separation (LLPS) is essential for biomolecular condensates to facilitate spatiotemporal regulation of biological functions. Providing programmable model systems would help to better understand the LLPS processes in biology and furnish new types of compartmentalized synthetic reaction crucibles that exploit biological principles. Herein, we demonstrate a concept for programming LLPS using transient multivalency between ATP-driven sequence-defined functionalized nucleic acid polymers (SfNAPs), which serve as simple models for membrane-less organelles. Critically, the prominent programmability of the DNA-based building blocks allows to encode distinct molecular recognitions for multiple multivalent systems, enabling sorted LLPS and, thus, multicomponent DNA coacervates. The ATP-driven coacervates are capable for multivalent trapping of micron-scale colloids and biomolecules to generate functions as emphasized for rate enhancements in enzymatic cascades. This work demonstrates ATP-driven multivalent coacervation as a valuable mechanism for dynamic multicomponent and functional biomolecular condensate mimics and for autonomous materials design in general.

多价驱动的液-液相分离（LLPS）对于生物分子凝聚态促进生物功能的时空调节至关重要。提供可编程模型系统将有助于更好地理解生物学中的 LLPS 过程，并提供利用生物学原理的新型分区合成反应坩埚。在此，我们展示了使用 ATP 驱动的序列定义的功能化核酸聚合物 (SfNAP) 之间的瞬时多价性来编程 LLPS 的概念，该聚合物可作为无膜细胞器的简单模型。至关重要的是，基于 DNA 的构建模块具有突出的可编程性，可以​​为多个多价系统编码不同的分子识别，从而实现排序的 LLPS，从而实现多组分 DNA 凝聚。 ATP驱动的凝聚层能够多价捕获微米级胶体和生物分子，以产生强调酶级联速率增强的功能。这项工作证明了 ATP 驱动的多价凝聚是动态多组分和功能生物分子凝聚态模拟以及一般自主材料设计的一种有价值的机制。