近日，荷兰阿姆斯特丹大学Reek, J. N. H.团队实现了通过假轮烷形成的外模板降低M12L24纳米球多组分自组装的途径复杂性。这一研究成果于2025年5月12日发表在《自然-化学》杂志上。

通过众多构建块的自组装选择性形成多组分结构在生物系统中无处不在，但合成模拟具有挑战性。更多的组分为具有陷阱状态能力的动力学中间体引入了额外的可能性，阻碍了获得所需产品。在共价化学中，应用模板、试剂和催化剂来创建所需产物形成的替代途径。

类似地，研究组利用外模板来塑造大型多组分超分子结构的形成。 具体而言，带电环与外官能化构建块内的1,5-二氧萘站对接，通过外骨骼模板促进立方八面体Pd₁₂L₂₄纳米球的形成。有了外模板环，纳米球的形成是通过小Pd_x-L_y低聚物进行的，而在没有环的情况下，Pd_x-L_y聚合物的静止状态迅速演变，纳米球形成缓慢。研究组展示了一种动力学模板形式——通过中间失稳——类似于催化中观察到的性质。重要的是，与通常使用的内模板不同，他们证明外模板特别适用于更大、更复杂、自组装的结构。

附：英文原文

Title: Exo-templating via pseudorotaxane formation reduces pathway complexity in the multicomponent self-assembly of M12L24 nanospheres

Author: Bouwens, T., Bobylev, E. O., Antony, L. S. D., Poole, D. A., Alarcn-Llad, E., Mathew, S., Reek, J. N. H.

Issue&Volume: 2025-05-12

Abstract: Selective formation of multicomponent structures via the self-assembly of numerous building blocks is ubiquitous in biological systems but challenging to emulate synthetically. More components introduce additional possibilities for kinetic intermediates with trap-state ability, hampering access to desired products. In covalent chemistry, templates, reagents and catalysts are applied to create alternative pathways for desired product formation. Analogously, we enlist exo-templating to mould the formation of large, multicomponent supramolecular structures. Specifically, a charged ring docks at 1,5-dioxynaphthalene stations within exo-functionalized building blocks to promote formation of cuboctahedral Pd12L24 nanospheres via exoskeletal templating. With the exo-templating ring present, nanosphere formation occurs via small Pdx–Ly oligomers, while in the absence of the ring a Pdx–Ly polymer resting state rapidly evolves, from which nanosphere formation occurs slowly. We demonstrate a form of kinetic templating—via intermediate destabilization—resembling properties observed in catalysis. Importantly, unlike typically employed endo-templates, we demonstrate that exo-templating is particularly suited for larger, complex, self-assembled structures.

DOI: 10.1038/s41557-025-01808-w

Source: https://www.nature.com/articles/s41557-025-01808-w