DNA has traditionally been used for the programmable design of nanostructures by exploiting its sequence-defined supramolecular recognition. However, control on larger length scales or even hierarchical materials that translate to the macroscale remain difficult to construct. Here, we show that the polymer character of single-stranded DNA (ssDNA) can be activated via a nucleobase-specific lower critical solution temperature, which provides a unique access to mesoscale structuring mechanisms on larger length scales. We integrate both effects into ssDNA multiblock copolymers that code sequences for phase separation, hybridization and functionalization. Kinetic pathway guidance using temperature ramps balances the counteracting mesoscale phase separation during heating with nanoscale duplex recognition during cooling to yield a diversity of complex all-DNA colloids with control over the internal dynamics and of their superstructures. Our approach provides a facile and versatile platform to add mesostructural layers into hierarchical all-DNA materials. The high density of addressable ssDNA blocks opens routes for applications such as gene delivery, artificial evolution or spatially encoded (bio)materials.

DNA 传统上通过利用其序列定义的超分子识别来用于纳米结构的可编程设计。然而，对更大长度尺度甚至转化为宏观尺度的分层材料的控制仍然难以构建。在这里，我们展示了单链 DNA (ssDNA) 的聚合物特性可以通过特定于核碱基的较低临界溶液温度来激活，这提供了在更大长度尺度上获得中尺度结构机制的独特途径。我们将这两种效应整合到编码相分离、杂交和功能化序列的 ssDNA 多嵌段共聚物中。使用温度斜坡的动力学路径引导平衡了加热过程中抵消的中尺度相分离和冷却过程中的纳米级双链体识别，从而产生了多种复杂的全 DNA 胶体，并控制了内部动力学及其上层结构。我们的方法提供了一个简单且多功能的平台，可以将介结构层添加到分层的全 DNA 材料中。高密度的可寻址 ssDNA 块为基因传递、人工进化或空间编码（生物）材料等应用开辟了道路。