Homochirality Originates from the Handedness of Helices

Liu, Shubin

doi:10.1021/acs.jpclett.0c02144

Cited by 48 publications

(81 citation statements)

References 36 publications

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“…3e and 3f, markedly improved correlations can be obtained. These results are in excellent agreement with our previous work about confirmational stability for other systems, 11,14,16,17,20 indicating that it is the electrostatic interaction that plays the dominant role with steric and exchange-correlation effects being minor yet indispensable. These results also suggest that even though those dimers with bulky alkane groups look special, they are indeed no exceptions.…”

supporting

confidence: 92%

“…Patterns of the results emerged from these processes and analyses thereafter should provide us with clues about the origin of their stability. To analyze the results, we employ two schemes of the density-based total energy decomposition, [10][11][12][13][14] information-theoretic approach (ITA), [15][16][17][18] and natural bond orbital (NBO) 19 analyses, whose details are available elsewhere. 20 Figure 1 illustrates the profile of the C-C distance as a function of its flexible rotation from 0 to 360 with the step size of 5.…”

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confidence: 99%

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The Synergetic and Multifaceted Nature of Carbon-Carbon Rotation Reveals the Origin of Stability for Bulky Alkane Dimers

Liu

Wan

et al. 2022

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Designing compounds with as long carbon-carbon bond distances as possible to challenge conventional chemical wisdom is of current interest in the literature. These compounds with exceedingly long bond lengths are commonly believed to be stabilized by dispersion interactions. In this work, we build nine dimeric models with varying sizes of alkyl groups, let the carbon-carbon bond flexibly rotate, and then analyze rotation barriers with energy decomposition and information-theoretic approaches in density functional theory. Our results show that these rotations lead to extraordinarily elongated carbon-carbon bond distances and rotation barriers are synergetic and multifaceted in nature. The dominant factor contributing to the stability of the dimers with bulky alkane groups is not the dispersion force but the electrostatic interaction with steric and exchange-correlation effects playing minor yet indispensable roles.

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confidence: 92%

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confidence: 99%

The Synergetic and Multifaceted Nature of Carbon-Carbon Rotation Reveals the Origin of Stability for Bulky Alkane Dimers

Liu

Wan

et al. 2022

Preprint

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“…Many different mechanisms have been proposed over the years to explain homochirality: the parity violation in weak nuclear interaction for molecular energy levels [3] or ionization by cosmic rays [4], or circularly polarized UV light from active star-forming regions [5]. Another study suggests that the helical structure of biological molecules could be at the root of homochirality, because homochiral structures built of chiral amino acids are thermodynamically more stable than heterochiral structures [6]. While some of these mechanisms could possibly explain an initial chiral bias, these effects are often too small to explain the near complete homochirality of life, which needs to be amplified and maintained dynamically [7].…”

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confidence: 99%

A robust transition to homochirality in complex chemical reaction networks

2022

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Homochirality, i.e. the dominance across all living matter of one enantiomer over the other among chiral molecules, is thought to be a key step in the emergence of life. Building on ideas put forward by Frank and many others, we proposed recently one such mechanism in Laurent et al. (Laurent, 2021 Proc. Natl Acad. Sci. USA 118 , e2012741118. ( doi:10.1073/pnas.2012741118 )) based on the properties of large out of equilibrium chemical networks. We showed that in such networks, a phase transition towards a homochiral state is likely to occur as the number of chiral species in the system becomes large or as the amount of free energy injected into the system increases. This paper aims at clarifying some important points in that scenario, not covered by our previous work. We first analyse the various conventions used to measure chirality, introduce the notion of chiral symmetry of a network and study its implications regarding the relative chiral signs adopted by different groups of molecules. We then propose a generalization of Frank’s model for large chemical networks, which we characterize completely using methods of random matrices. This analysis is extended to sparse networks, which shows that the emergence of homochirality is a robust transition.

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“…Very recently, based on the model results for proteins and DNA to attribute the origin of homochirality, we proposed the Principle of Chirality Hierarchy, 5 which states that the propensity of lower dimension chirality is dictated by that of the higher dimension chirality.…”

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confidence: 99%

“…We have shown that righthanded -helix and 310-helix structures in proteins both favor the L-chiral form of amino acids, whereas deoxyribose sugars in right-handed DNA helical structures prefer the D-chiral form instead. 5 We also identified the existence of strong cooperativity effect, [5][6][7] which is dominated by the favorable electrostatic interaction in the homochiral conformation through the analysis of total energy partition 11,12 and information-theoretic approach. 13,14 In this work, we confirm the validity of the Principle of Chirality Hierarchy in an another axial chirality system, a left-handed three-blade propeller molecule (Scheme 1).…”

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Principle of Chirality Hierarchy in Three-Blade Propeller Systems

Liu

2021

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There are different kinds of molecular chirality, such as zero-dimensional point chirality, one-dimensional axial chirality, 2D planar chirality, and 3D chirality. When they coexist in one system, such as in helical structures of proteins and DNA, they form a chirality hierarchy. Earlier, we showed that the chirality propensity of a lower level in a hierarchy is dictated by that of a higher level and henceforth proposed the Principle of Chirality Hierarchy. In this work, we confirm the validity of this principle in the three-blade propeller molecular system. We consider different choices for the three components of a propeller and systematically investigate the dependence of the stereoisomeric energy difference on these choices. Our results show that the preference of the 0D chirality of a functional group in the propeller system is determined by the 1D chirality, and homochirality is also a remarkable feature for this system. We also unveiled that there exists positive cooperativity and electrostatic interactions play the dominant role in determining the stereoisomeric stability difference while the roles for exchange-correlation and steric effects are minor but indispensable. The establishment and confirmation of the Principle of Chirality Hierarchy from this work should find important applications in asymmetric synthesis, macromolecular assembly, and many others.

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Homochirality Originates from the Handedness of Helices

Cited by 48 publications

References 36 publications

The Synergetic and Multifaceted Nature of Carbon-Carbon Rotation Reveals the Origin of Stability for Bulky Alkane Dimers

The Synergetic and Multifaceted Nature of Carbon-Carbon Rotation Reveals the Origin of Stability for Bulky Alkane Dimers

A robust transition to homochirality in complex chemical reaction networks

Principle of Chirality Hierarchy in Three-Blade Propeller Systems

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