Li Meng, He Xin, Chen Jie, Wang Bin, Liu Shubin, Rong Chunying
Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research (Ministry of Education of China), Hunan Normal University, Changsha, Hunan 410081, P.R. China.
Research Computing Center, University of North Carolina, Chapel Hill, North Carolina 27599-3420, United States.
J Phys Chem A. 2021 Feb 11;125(5):1269-1278. doi: 10.1021/acs.jpca.0c10310. Epub 2021 Feb 2.
Homochirality of macromolecules such as proteins and DNA is one of the most striking features in nature; yet, there is still no convincing theory to explain its origin. In a recent work by one of the present authors (. 8690-8696), a general proposal from the viewpoint of thermodynamics has been put forward. It proposes that it is the handedness of helices ubiquitous in biological macromolecules that plays the decisive role. It also unveiled that there exist strong cooperativity effects dominated by favorable electrostatic interactions in the homochiral conformer. In this work, making use of analytical tools, we recently developed a density functional theory and an information-theoretic approach and through four sets of helical structures we designed for the present study, we examine these systems to provide new insights about these properties. We found that the 3-helix and the α-helix are markedly different in cooperativity from the viewpoint of both the total energy and its three components. The electrostatic dominance of homochiral species is manifested by both the electron charge distribution and information gain. At the atomic level, different elements behave significantly differently because they play different roles in the systems. Our results from this work validate that these analytical tools can be applied to homochiral systems, which can be further extended to others with potential interest in asymmetric synthesis and macromolecular assembly where the Principle of Homochirality Hierarchy comes into play.
蛋白质和DNA等大分子的同手性是自然界中最显著的特征之一；然而，仍然没有令人信服的理论来解释其起源。在本文作者之一最近的一项工作中（……8690 - 8696），从热力学的角度提出了一个一般性的提议。该提议认为，生物大分子中普遍存在的螺旋手性起着决定性作用。它还揭示了在同手性构象体中存在由有利的静电相互作用主导的强协同效应。在这项工作中，我们利用最近开发的密度泛函理论和信息论方法等分析工具，并通过为当前研究设计的四组螺旋结构，对这些系统进行研究，以提供关于这些性质的新见解。我们发现，从总能量及其三个组成部分的角度来看，三螺旋和α螺旋在协同性方面有显著差异。同手性物种的静电优势通过电子电荷分布和信息增益得以体现。在原子层面，不同元素的行为差异显著，因为它们在系统中发挥着不同的作用。我们这项工作的结果证实，这些分析工具可应用于同手性系统，这可以进一步扩展到对不对称合成和大分子组装有潜在兴趣的其他系统，在这些系统中同手性层次原理发挥作用。
