Afrose Syed Pavel, Ghosh Chandranath, Das Dibyendu
Department of Chemical Sciences & Centre for Advanced Functional Materials, Indian Institute of Science Education and Research (IISER) Kolkata Mohanpur West Bengal 741246 India
Chem Sci. 2021 Nov 8;12(44):14674-14685. doi: 10.1039/d1sc03492h. eCollection 2021 Nov 17.
Living matter is sustained under non-equilibrium conditions continuous expense of energy which is coordinated by complex organized events. Spatiotemporal control over exquisite functions arises from chemical complexity under non-equilibrium conditions. For instance, extant biology often uses substrate binding events to access temporally stable protein conformations which show acceleration of catalytic rates to subsequently degrade the substrate. Furthermore, thermodynamically activated but kinetically stable esters (GTP) induce the change of conformation of cytoskeleton proteins (microtubules) which leads to rapid polymerization and triggers an augmentation of catalytic rates to subsequently degrade the ester. Importantly, high-energy assemblies composed of non-activated building blocks (GDP-tubulin) are accessed utilizing the energy dissipated from the catalytic conversion of GTP to GDP from the assembled state. Notably, some experimental studies with simple self-assembled systems have elegantly mimicked the phenomena of substrate induced transient generation of catalytic conformations. Through this review, we endeavour to highlight those select studies which have used simple building blocks to demonstrate substrate induced self-assemblies that subsequently show rate acceleration to convert the substrate into waste. The concept of substrate induced self-assembly of building blocks and rate acceleration from the assembled state has the potential to play a predominant role in the preparation of non-equilibrium systems. The design strategies covered in this review can inspire the possibilities of accessing high energy self-assembled structures that are seen in living systems.
生命物质在非平衡条件下得以维持,这需要持续消耗能量,而能量的消耗是由复杂有序的事件协调的。非平衡条件下的化学复杂性产生了对精妙功能的时空控制。例如,现存生物学常常利用底物结合事件来获取时间上稳定的蛋白质构象,这些构象会加速催化速率,进而降解底物。此外,热力学上被激活但动力学上稳定的酯(GTP)会诱导细胞骨架蛋白(微管)的构象变化,这会导致快速聚合,并引发催化速率的提高,从而随后降解酯。重要的是,利用从组装状态下GTP催化转化为GDP过程中耗散的能量,可以获得由未激活的构建块(GDP - 微管蛋白)组成的高能组装体。值得注意的是,一些关于简单自组装系统的实验研究巧妙地模拟了底物诱导催化构象瞬态产生的现象。通过这篇综述,我们力图突出那些使用简单构建块来证明底物诱导自组装的精选研究,这些自组装随后会显示出速率加速,将底物转化为废物。构建块的底物诱导自组装以及从组装状态加速反应速率的概念,有可能在非平衡系统的制备中发挥主导作用。本综述涵盖的设计策略能够激发获得在生命系统中可见的高能自组装结构的可能性。