Penocchio Emanuele, Gu Geyao, Albaugh Alex, Gingrich Todd R
Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, United States.
Department of Chemical Engineering and Materials Science, Wayne State University, 5050 Anthony Wayne Drive, Detroit, Michigan 48202, United States.
J Am Chem Soc. 2025 Jan 8;147(1):1063-1073. doi: 10.1021/jacs.4c14481. Epub 2024 Dec 20.
For several decades, molecular motor directionality has been rationalized in terms of the free energy of molecular conformations visited before and after the motor takes a step, a so-called power stroke mechanism with analogues in macroscopic engines. Despite theoretical and experimental demonstrations of its flaws, the power stroke language is quite ingrained, and some communities still value power stroke intuition. By building a catalysis-driven motor into simulated numerical experiments, we here systematically report on how directionality responds when the motor is modified accordingly to power stroke intuition. We confirm that the power stroke mechanism generally does not predict motor directionality. Nevertheless, the simulations illustrate that the relative stability of molecular conformations should be included as a potential design element to adjust the motor directional bias. Though power strokes are formally unimportant for determining directionality, we show that practical attempts to alter a power stroke have side effects that can in fact alter the bias. The change in the bias can align with what power stroke intuition would have suggested, offering a potential explanation for why the flawed power stroke mechanism can retain apparent utility when engineering specific systems.
几十年来,分子马达的方向性一直根据马达迈出一步前后所经历的分子构象的自由能来解释,这是一种在宏观发动机中有类似情况的所谓动力冲程机制。尽管有理论和实验证明了其缺陷,但动力冲程的说法却根深蒂固,一些群体仍然重视动力冲程的直觉。通过在模拟数值实验中构建一个催化驱动的马达,我们在此系统地报告了当根据动力冲程直觉对马达进行相应修改时,方向性是如何响应的。我们证实,动力冲程机制通常无法预测马达的方向性。然而,模拟表明,分子构象的相对稳定性应作为调整马达方向偏置的一个潜在设计要素纳入考虑。虽然动力冲程在形式上对确定方向性并不重要,但我们表明,改变动力冲程的实际尝试会产生副作用,实际上可能会改变偏置。偏置的变化可能与动力冲程直觉所暗示的一致,这为有缺陷的动力冲程机制在设计特定系统时为何仍能保留明显效用提供了一种潜在解释。