New Chemistry Unit and School of Advanced Materials (SAMat), Jawaharlal Nehru Centre for Advanced Scientific Research (JNCASR), Jakkur, Bangalore 560064, India.
J Am Chem Soc. 2024 May 29;146(21):14844-14855. doi: 10.1021/jacs.4c03588. Epub 2024 May 15.
Nature employs sophisticated mechanisms to precisely regulate self-assembly and functions within biological systems, exemplified by the formation of cytoskeletal filaments. Various enzymatic reactions and auxiliary proteins couple with the self-assembly process, meticulously regulating the length and functions of resulting macromolecular structures. In this context, we present a bioinspired, reaction-coupled approach for the controlled supramolecular polymerization in synthetic systems. To achieve this, we employ an enzymatic reaction that interfaces with the adenosine triphosphate (ATP)-templated supramolecular polymerization of naphthalene diimide monomers (). Notably, the enzymatic production of ATP (template) plays a pivotal role in facilitating reaction-controlled, cooperative growth of the monomers. This growth process, in turn, provides positive feedback to the enzymatic production of ATP, creating an ideal reaction-coupled assembly process. The success of this approach is further evident in the living-growth characteristic observed during seeding experiments, marking this method as the pioneering instance where reaction-coupled self-assembly precisely controls the growth kinetics and structural aspects of supramolecular polymers in a predictive manner, akin to biological systems.
大自然采用了复杂的机制来精确调节生物系统内的自组装和功能，细胞骨架丝的形成就是一个很好的例子。各种酶反应和辅助蛋白与自组装过程耦合，精细调节所得大分子结构的长度和功能。在这方面，我们提出了一种受生物启发的、反应耦合的方法，用于在合成系统中进行受控的超分子聚合。为了实现这一目标，我们采用了一种酶反应，该反应与三磷酸腺苷 (ATP) 模板的萘二酰亚胺单体（）的超分子聚合相接口。值得注意的是，ATP（模板）的酶促生产在促进反应控制的、单体的协同生长中起着关键作用。这种生长过程反过来又为 ATP 的酶促生产提供了正反馈，从而形成了一个理想的反应耦合组装过程。在种子实验中观察到的活生长特性进一步证明了这种方法的成功，这标志着这种方法是首例通过反应耦合自组装以预测的方式精确控制超分子聚合物的生长动力学和结构方面的方法，类似于生物系统。
