Controlling assembly-induced symmetry-breaking by tuning the vortex-responsive nanostructures
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The generation of chirality in supramolecular structures from achiral building blocks has remained a challenge for a long time. In this study, we present a vortex-assisted chiral supramolecular polymerization from a series of achiral C3-symmetric monomers, where the mechanism of symmetry-breaking is systematically investigated. By increasing the supersaturation, at the early stage of nucleation and growth, highly ordered assemblies can be generated as the initial chiral nuclei. Meanwhile, chiral assemblies from high supersaturation are hard to interwind into clusters, where clusters as nuclei are not conducive to being fractured by sheer force of vortex fluid. Therefore, it is concluded that chiral assemblies in the nucleation stage possess low energy barrier, so that chiral nuclei could be fractured and replicated by the vortex. By enlarging the initial chiral bias, the major chiral nuclei can evolute into the final chiral polymers.
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Controlling assembly-induced symmetry-breaking by tuning the vortex-responsive nanostructures
)
Abstract
The generation of chirality in supramolecular structures from achiral building blocks has remained a challenge for a long time. In this study, we present a vortex-assisted chiral supramolecular polymerization from a series of achiral C3-symmetric monomers, where the mechanism of symmetry-breaking is systematically investigated. By increasing the supersaturation, at the early stage of nucleation and growth, highly ordered assemblies can be generated as the initial chiral nuclei. Meanwhile, chiral assemblies from high supersaturation are hard to interwind into clusters, where clusters as nuclei are not conducive to being fractured by sheer force of vortex fluid. Therefore, it is concluded that chiral assemblies in the nucleation stage possess low energy barrier, so that chiral nuclei could be fractured and replicated by the vortex. By enlarging the initial chiral bias, the major chiral nuclei can evolute into the final chiral polymers.
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Acknowledgements
This work was supported by the National Natural Science Foundation of China (Nos. 52173159 and 92256304), the Beijing Municipal Science and Technology Commission (No. JQ21003), and the National Key R&D Program of the Ministry of Science and Technology of the People’s Republic of China (No. 2021YFA1200303). Numerical computations were performed on Hefei advanced computing center.
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