Markiewicz Grzegorz, Qiu Xujun, Avci Gokay, Wolpert Emma H, Jelfs Kim E, Sanders Jeremy K M, Stefankiewicz Artur R
Center for Advanced Technologies, Adam Mickiewicz University, Uniwersytetu Poznańskiego 10, 61-614 Poznań, Poland.
Faculty of Chemistry, Adam Mickiewicz University, Uniwersytetu Poznańskiego 8, 61-614 Poznań, Poland.
J Am Chem Soc. 2025 Aug 27;147(34):31270-31279. doi: 10.1021/jacs.5c10523. Epub 2025 Aug 15.
One of the main aspects in which artificial capsules and cages still differ from their biological counterparts is symmetry─a fundamental trait that gives natural systems exceptional selectivity in molecular recognition. While the symmetry challenge has been recently addressed within metallosupramolecular or covalent systems, the creation of purely noncovalent capsular assemblies with tunable symmetry remains elusive. One exciting avenue toward reducing symmetry is to avail chirality in chiral-sensitive self-assembly, where symmetry is altered upon component binding. Herein, we report new pathways for the self-assembly of purely noncovalent capsules, wherein both the assembly outcome and symmetry can be finely adjusted through the strategic design of hydrogen bonding motifs and chirality. Specifically, depending on the mixture composition and hydrogen bonding centers embedded on the amino acid-derived benzene-1,3,5-triamide components, the system yields purely noncovalent capsules, ranging from highly symmetrical dimers to reduced symmetry octamers and new heterochiral tetrameric assemblies of low symmetry. The self-assembly processes presented here can be selectively modulated between narcissistic self-sorting pathways and diastereoselective social mixing, as well as toward the creation of social heterocomponent libraries─all yielding distinct capsular products. By showcasing the unique ability for molecular recognition, we believe our approach will pave the way for creating new capsular-type assemblies with unique functionalities and provide a fresh perspective on intricate, nature-inspired molecular dynamics.
人工胶囊和笼子与它们的生物对应物仍存在差异的主要方面之一是对称性——这一基本特征赋予了自然系统在分子识别方面卓越的选择性。虽然最近在金属超分子或共价系统中已经解决了对称性挑战，但创建具有可调对称性的纯非共价胶囊组装体仍然难以实现。减少对称性的一个令人兴奋的途径是在手性敏感的自组装中利用手性，在这种情况下，对称性会在组分结合时发生改变。在此，我们报告了纯非共价胶囊自组装的新途径，其中组装结果和对称性都可以通过氢键基序和手性的策略性设计进行精细调节。具体而言，根据混合物组成以及嵌入在氨基酸衍生的苯 -1,3,5- 三酰胺组分上的氢键中心，该系统会产生纯非共价胶囊，范围从高度对称的二聚体到对称性降低的八聚体以及新的低对称性异手性四聚体组装体。这里展示的自组装过程可以在自恋的自分类途径和非对映选择性的社会混合之间进行选择性调节，以及用于创建社会异组分库——所有这些都会产生不同的胶囊产物。通过展示分子识别这一独特能力，我们相信我们的方法将为创建具有独特功能的新型胶囊型组装体铺平道路，并为复杂的、受自然启发的分子动力学提供新的视角。
