Temperature protocols to guide selective self-assembly of competing structures.
Temperature protocols to guide selective self-assembly of competing structures.
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DOI：
10.1073/pnas.2119315119
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发表时间：
2022-02-22
影响因子：
11.1
通讯作者：
Sastry S
中科院分区：
文献类型：
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作者：
Bupathy A;Frenkel D;Sastry S
设计具有可切换特性的功能材料是材料科学中非常受欢迎的目标。我们调查的计算设计的多组分自组装系统，可以引导到形成两个预定义的竞争结构之一，通过简单的温度协议。我们的研究揭示了设计的限制，应观察，以避免形成假的或嵌合的聚集体，并最大限度地提高目标结构的选择性。我们证明，可以设计的温度协议，导致任何一个目标结构的形成具有高选择性。我们讨论了二次聚集的产品，我们称之为“残留的聚集体所发挥的重要作用。”多组分自组装混合物提供了用同一组相互作用组分编码多个目标结构的可能性。选择性检索的存储结构之一已被尝试通过准备一个初始状态，有利于所需的目标，通过播种，浓度模式，或相互作用强度的具体选择的组装。这在可能需要构建块的动态重新配置以切换功能的实验中可能是不可能的。在本文中，我们探索的多组分，自组装的混合物能够编码两个竞争的结构，可以通过简单的温度协议的逆设计的原则。我们设计的目标结构，以实现通用的情况下，其中一个目标具有较低的成核势垒，而另一个是全球更稳定。我们观察到，为了避免形成假的或嵌合的聚集体，在这两种结构中出现的相邻组件对的数量应该是最小的。我们的设计还需要包含仅属于其中一个目标结构的组件。然而，我们观察到，为了最大限度地提高检索的选择性，组件库本身应该最大限度地由两个目标共享，在这样的约束。我们证明，可以设计的温度协议，导致任何一个目标结构的形成具有高选择性。我们讨论了二次聚集产物在提高选择性方面所起的重要作用，我们称之为“残留聚集体”。
Designing functional materials with switchable properties is a highly sought-after goal in materials science. We investigate the computational design of a multicomponent self-assembly system that can be guided into forming one of two predefined competing structures through simple temperature protocols. Our investigation reveals design constraints that should be observed in order to avoid formation of spurious or chimeric aggregates and to maximize selectivity of the target structure. We demonstrate that temperature protocols can be designed that lead to the formation of either one of the target structures with high selectivity. We discuss the important role played by secondary aggregation products, which we term “vestigial aggregates.” Multicomponent self-assembly mixtures offer the possibility of encoding multiple target structures with the same set of interacting components. Selective retrieval of one of the stored structures has been attempted by preparing an initial state that favors the assembly of the required target, through seeding, concentration patterning, or specific choices of interaction strengths. This may not be possible in an experiment where on-the-fly reconfiguration of the building blocks to switch functionality may be required. In this paper, we explore principles of inverse design of a multicomponent, self-assembly mixture capable of encoding two competing structures that can be selected through simple temperature protocols. We design the target structures to realize the generic situation in which one of the targets has the lower nucleation barrier, while the other is globally more stable. We observe that, to avoid the formation of spurious or chimeric aggregates, the number of neighboring component pairs that occur in both structures should be minimal. Our design also requires the inclusion of components that are part of only one of the target structures. We observe, however, that to maximize the selectivity of retrieval, the component library itself should be maximally shared by the two targets, within such a constraint. We demonstrate that temperature protocols can be designed that lead to the formation of either one of the target structures with high selectivity. We discuss the important role played by secondary aggregation products in improving selectivity, which we term “vestigial aggregates.”