Although tremendous advances have been made in preparing porous crystals from molecular precursors^1,2, there are no general ways of designing and making topologically diversified porous colloidal crystals over the 10–1,000 nm length scale. Control over porosity in this size range would enable the tailoring of molecular absorption and storage, separation, chemical sensing, catalytic and optical properties of such materials. Here, a universal approach for synthesizing metallic open-channel superlattices with pores of 10 to 1,000 nm from DNA-modified hollow colloidal nanoparticles (NPs) is reported. By tuning hollow NP geometry and DNA design, one can adjust crystal pore geometry (pore size and shape) and channel topology (the way in which pores are interconnected). The assembly of hollow NPs is driven by edge-to-edge rather than face-to-face DNA–DNA interactions. Two new design rules describing this assembly regime emerge from these studies and are then used to synthesize 12 open-channel superlattices with control over crystal symmetry, channel geometry and topology. The open channels can be selectively occupied by guests of the appropriate size and that are modified with complementary DNA (for example, Au NPs).

尽管在从分子前体制备多孔晶体方面取得了巨大进步^1,2, 在 10–1,000 nm 长度尺度上，没有通用的方法来设计和制造拓扑多样化的多孔胶体晶体。控制该尺寸范围内的孔隙率将能够定制此类材料的分子吸收和储存、分离、化学传感、催化和光学特性。在这里，报道了一种从 DNA 修饰的空心胶体纳米粒子 (NPs) 合成孔径为 10 至 1,000 nm 的金属开放通道超晶格的通用方法。通过调整中空 NP 几何形状和 DNA 设计，可以调整晶体孔隙几何形状（孔径和形状）和通道拓扑结构（孔隙相互连接的方式）。中空 NP 的组装是由边到边而不是面对面的 DNA-DNA 相互作用驱动的。这些研究中出现了两个描述这种组装机制的新设计规则，然后用于合成 12 个开放通道超晶格，并控制晶体对称性、通道几何形状和拓扑结构。开放通道可以选择性地被适当大小的客体占据，并用互补 DNA（例如，Au NPs）进行修饰。