Patra Satyajit, Dhiman Shikha, George Subi J
New Chemistry Unit and School of Advanced Materials (SAMat), Jawaharlal Nehru Centre for Advanced Scientific Research(JNCASR), Jakkur, Bangalore, 560064, India.
Department of Chemistry, Johannes Gutenberg University Mainz, Duesbergweg 10-14, Mainz, 55122, Germany.
Angew Chem Int Ed Engl. 2025 Jun 10;64(24):e202500456. doi: 10.1002/anie.202500456. Epub 2025 Apr 14.
Self-sorting of cellular components is essential for maintaining order and function in living systems, enabling complex processes to operate seamlessly. Emulating such self-sorting in synthetic self-assembly, however, has conventionally relied on structural or chirality mismatches of monomers yielding self-sorted systems under thermodynamic conditions. In contrast, reaction-coupled, kinetically controlled self-assembly, ubiquitous in biological systems, is critical for achieving spatiotemporal characteristics. Extending this principle to temporally self-sorted synthetic assemblies is key to developing multi-component biomimetic systems. Herein, we present a strategy towards this direction, to achieve sequential self-sorting of supramolecular assemblies through differences in the chemical-reactivity of monomers, coupled to redox-reactions. This approach exploits the distinct redox potentials of monomers to achieve precise temporal-control over self-sorting, while inherent structural mismatches among monomers ensure the kinetic stability of self-sorted state. Reduction reactions transiently disrupt their assemblies into dormant inactive monomeric states, while subsequent kinetically controlled reassembly occurs via reversible oxidation reactions. Finally, utilizing this sequential self-sorting, we aim to mimic multicomponent cellular self-organization by demonstrating the kinetically controlled growth of self-sorted structures in the presence of model protocells, using lipid vesicles as compartments. Although spatial-distribution remains non-selective, the dormant monomeric states facilitate monomer encapsulation and the unprecedented stepwise-formation of self-sorted assemblies within model protocells.
细胞成分的自我分类对于维持生命系统的秩序和功能至关重要，它能使复杂的过程无缝运行。然而，在合成自组装中模拟这种自我分类，传统上依赖于单体的结构或手性不匹配，从而在热力学条件下产生自我分类的系统。相比之下，反应耦合的、动力学控制的自组装在生物系统中无处不在，对于实现时空特性至关重要。将这一原理扩展到时间上自我分类的合成组装体是开发多组分仿生系统的关键。在此，我们提出了朝着这个方向的一种策略，即通过与氧化还原反应耦合的单体化学反应性差异来实现超分子组装体的顺序自我分类。这种方法利用单体不同的氧化还原电位来实现对自我分类的精确时间控制，而单体之间固有的结构不匹配确保了自我分类状态的动力学稳定性。还原反应会暂时将它们的组装体破坏成休眠的无活性单体状态，而随后的动力学控制的重新组装则通过可逆的氧化反应发生。最后，利用这种顺序自我分类，我们旨在通过使用脂质囊泡作为隔室，在模型原始细胞存在的情况下展示自我分类结构的动力学控制生长，来模拟多组分细胞的自组织。尽管空间分布仍然是非选择性的，但休眠的单体状态有利于单体封装以及在模型原始细胞内前所未有的自我分类组装体的逐步形成。
