Supramolecular Chemistry Laboratory, New Chemistry Unit and School of Advanced Materials (SAMat), Jawaharlal Nehru Centre for Advanced Scientific Research (JNCASR), Jakkur, Bangalore, 560064, India.
Centre for Protolife Research, Centre for Organized Matter Chemistry, School of Chemistry, University of Bristol, Bristol BS81TS, UK.
J Mater Chem B. 2024 Oct 2;12(38):9566-9574. doi: 10.1039/d4tb01558d.
Temporal control over self-assembly processes is a highly desirable attribute that is efficiently exhibited by biological systems, such as actin filaments. In nature, various proteins undergo enzymatically catalysed chemical reactions that kinetically govern their structural and functional properties. Consequently, any stimuli that can alter their reaction kinetics can lead to a change in their growth or decay profiles. This underscores the urgent need to investigate bioinspired, adaptable and controllable synthetic materials. Herein we intend to develop a general strategy for controlling the growth and decay of self-assembled systems enzymatically coupled reactions. We achieve this by the coupling of enzymes phosphokinase/phosphatase with a bolaamphiphilic cationic chromophore (PDI) which selectively self-assembles with ATP and disassembles upon its enzymatic hydrolysis. The aggregation process is efficiently regulated by the controlled generation of ATP, through enzymatic reactions. By carefully managing the ATP generating components, we realize precise control over the self-assembly process. Moreover, we also show self-assembled structures with programmed temporal decay profiles through coupled enzymatic reactions of ATP generation and hydrolysis, essentially rendering the process dissipative. This work introduces a novel strategy to generate a reaction-coupled one-dimensional nanostructure with controlled dimensions inspired by biological systems.
时间控制自组装过程是一种非常理想的属性，生物系统（如肌动蛋白丝）高效地展示了这种属性。在自然界中，各种蛋白质经历酶促催化化学反应，这些反应动力学控制着它们的结构和功能特性。因此，任何能够改变它们反应动力学的刺激都可能导致它们的生长或衰减曲线发生变化。这凸显了研究受生物启发、适应性强和可控的合成材料的迫切需要。在此，我们旨在开发一种控制自组装系统酶偶联反应生长和衰减的通用策略。我们通过将磷酸激酶/磷酸酶与具有选择性与 ATP 自组装并在其酶解时解组装的双亲和阳离子生色团（PDI）偶联来实现这一点。通过酶反应，通过控制 ATP 的产生来有效地调节聚集过程。通过仔细管理生成 ATP 的组件，我们实现了对自组装过程的精确控制。此外，我们还通过 ATP 生成和水解的偶联酶反应展示了具有编程时间衰减曲线的自组装结构，实质上使该过程具有耗散性。这项工作介绍了一种受生物系统启发的、具有控制尺寸的反应偶联一维纳米结构的新策略。
