Chirality transfer from a 3D macro shape to the molecular level by controlling asymmetric secondary flows

Abstract

Homochirality is a fundamental feature of living systems, and its origin is still an unsolved mystery. Previous investigations showed that external physical forces can bias a spontaneous symmetry breaking process towards deterministic enantioselection. But can the macroscopic shape of a reactor play a role in chiral symmetry breaking processes? Here we show an example of chirality transfer from the chiral shape of a 3D helical channel to the chirality of supramolecular aggregates, with the handedness of the helical channel dictating the direction of enantioselection in the assembly of an achiral molecule. By combining numerical simulations of fluid flow and mass transport with experimental data, we demonstrated that the chiral information is transferred top-down thanks to the interplay between the hydrodynamics of asymmetric secondary flows and the precise spatiotemporal control of reagent concentration fronts. This result shows the possibility of controlling enantioselectively molecular processes at the nanometer scale by modulating the geometry and the operating conditions of fluidic reactors.

Chiral self-organization of the TPPS4 porphyrin assisted by molecular rotations

“…Our results evidence the importance of the chiral bias at the very beginning of the aggregation, as pointed out in different experimental approaches based on microfluidic devices. [37][38][39] Supramolecular chirality may eventually emerge and be amplified by non-covalent interactions.…”

Fundamental Cause of Bio-Chirality - Space-Time Symmetry: Concept Review

“…The occurrence of such connection is bearing by the hieratical chain of chirality transfer [Dyakin et al2017-A). Notable that the stereo-divergent chain of chirality transfer between hierarchical levels of biological organization was observed experimentally, including in Bottom UP and Top-Down directions [Chiccoli et al 2013;Huang et al 2021;Cheng et al 2021;Zhang et al 2022;Sevim et al 2022].…”

Uncovering Origin of Chirality of Gold Nanoparticles Prepared through the Conventional Citrate Reduction Method

“…2,12−14 This mechanism on the chiral origin of artificial nanoparticles is easy to be understood and accepted. In the absence of chiral reagents, chiral templates 15,16 or circularly polarized light 17 were usually needed to induce the generation of chiral nanoparticles.…”

“…The general strategy for the synthesis of chiral nanoparticles is based on the nucleation and growth in liquid media in the presence of chiral ligands, and the chiral ligands as stabilizers are capped on the nanoparticles’ surface. ,− In this strategy, the chirality of the inorganic nanoparticles usually comes from the used chiral ligands, and the chirality of ligand molecules is directly transferred to the nanoparticles. ,− This mechanism on the chiral origin of artificial nanoparticles is easy to be understood and accepted. In the absence of chiral reagents, chiral templates , or circularly polarized light were usually needed to induce the generation of chiral nanoparticles.…”