Using Catalysis to Drive Chemistry Away from Equilibrium: Relating Kinetic Asymmetry, Power Strokes, and the Curtin-Hammett Principle in Brownian Ratchets.
Using Catalysis to Drive Chemistry Away from Equilibrium: Relating Kinetic Asymmetry, Power Strokes, and the Curtin-Hammett Principle in Brownian Ratchets.
复制标题
DOI：
10.1021/jacs.2c08723
复制
发表时间：
2022-11-09
影响因子：
15
通讯作者：
Roberts, Benjamin M. W.
中科院分区：
文献类型：
--
作者：
Amano, Shuntaro;Esposito, Massimiliano;Kreidt, Elisabeth;Leigh, David A.;Penocchio, Emanuele;Roberts, Benjamin M. W.
化学燃料自主分子机器是由布朗信息棘轮机制控制的催化驱动系统。其运作背后的一个基本原理是动力学不对称性，它量化了分子马达的方向性。然而，合成化学家很难将这一概念应用于分子设计，因为动力学不对称性通常以抽象的数学术语引入，涉及实验无法获得的参数。此外，两个看似矛盾的机制已经提出了化学驱动的自主分子机器：布朗棘轮和动力冲程机制。这一观点解决了这两个问题，提供了方便和实验上有用的设计原则，催化驱动的分子机械。我们与动力学不对称的柯廷-哈米特原则使用合成旋转电机和驱动蛋白步行者作为说明性的例子。我们的方法描述了这些分子马达的布朗棘轮机制，但同时指出化学门控和功率冲程作为可调的设计元素，可以影响动力学不对称。我们解释了为什么这种方法的动力不对称性是一致的，与以前的和大纲条件下，功率冲程可以是有用的设计元素。最后，我们讨论了信息的作用，在文献中使用的不同含义的概念。我们希望，这一观点将访问范围广泛的化学家，澄清的参数，可以有效地控制在分子机器和相关系统的设计和合成。它还可能有助于对生物分子机制进行更全面和跨学科的理解。
Chemically fueled autonomous molecular machines are catalysis-driven systems governed by Brownian information ratchet mechanisms. One fundamental principle behind their operation is kinetic asymmetry, which quantifies the directionality of molecular motors. However, it is difficult for synthetic chemists to apply this concept to molecular design because kinetic asymmetry is usually introduced in abstract mathematical terms involving experimentally inaccessible parameters. Furthermore, two seemingly contradictory mechanisms have been proposed for chemically driven autonomous molecular machines: Brownian ratchet and power stroke mechanisms. This Perspective addresses both these issues, providing accessible and experimentally useful design principles for catalysis-driven molecular machinery. We relate kinetic asymmetry to the Curtin–Hammett principle using a synthetic rotary motor and a kinesin walker as illustrative examples. Our approach describes these molecular motors in terms of the Brownian ratchet mechanism but pinpoints both chemical gating and power strokes as tunable design elements that can affect kinetic asymmetry. We explain why this approach to kinetic asymmetry is consistent with previous ones and outline conditions where power strokes can be useful design elements. Finally, we discuss the role of information, a concept used with different meanings in the literature. We hope that this Perspective will be accessible to a broad range of chemists, clarifying the parameters that can be usefully controlled in the design and synthesis of molecular machines and related systems. It may also aid a more comprehensive and interdisciplinary understanding of biomolecular machinery.
登录
查看更多内容
影响因子：
3.4
作者：
Astumian, R. Dean
通讯作者：
Astumian, R. Dean
影响因子：
3.5
作者：
Astumian, RD;Hänggi, P
通讯作者：
Hänggi, P
影响因子：
3.3
作者：
Astumian, R. Dean
通讯作者：
Astumian, R. Dean
影响因子：
15
作者：
Alvarez-Perez, Monica;Goldup, Stephen M.;Slawin, Alexandra M. Z.
通讯作者：
Slawin, Alexandra M. Z.
影响因子：
16.6
作者：
Blackmond, Donna G.
通讯作者：
Blackmond, Donna G.