Selection of supramolecular chirality by application of rotational and magnetic forces
Abstract
Many essential biological molecules exist only in one of two possible mirror-image structures, either because they possess a chiral unit or through their structure (helices, for example, are intrinsically chiral), but so far the origin of this homochirality has not been unraveled. Here we demonstrate that the handedness of helical supramolecular aggregates formed by achiral molecules can be directed by applying rotational, gravitational and orienting forces during the self-assembly process. In this system, supramolecular chirality is determined by the relative directions of rotation and magnetically tuned effective gravity, but the magnetic orientation of the aggregates is also essential. Applying these external forces only during the nucleation step of the aggregation is sufficient to achieve chiral selection. This result shows that an almost instantaneous chiral perturbation can be transferred and amplified in growing supramolecular self-assemblies, and provides evidence that a falsely chiral influence is able to induce absolute enantioselection.
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The role of the magnetic field in Micali et al.'s experiment is to provide tunable magnetic levitation force and alignment of the supramolecular assemblies, and its direction does not influence the sign of the chiral bias.
“The role of the magnetic field is fundamentally different than that in the MChD effect (Part 3.1(a)) since its direction does not influence the sign of the chiral bias.Its role is to provide tunable magnetic levitation force and alignment of the supramolecular assemblies.”
From Possible chemical and physical scenarios towards biological homochirality (2022) · cites this paper as [161]
Micali et al. demonstrated in 2012 that the combination of gravity, magnetic field and rotation can be used to direct the handedness of supramolecular helices generated upon assembly of an achiral porphyrin monomer (TPPS3).
“Micali et al. demonstrated in 2012 that the combination of gravity, magnetic field and rotation can be used to direct the handedness of supramolecular helices generated upon assembly of an achiral porphyrin monomer (TPPS 3 , Fig. 5).161”
From Possible chemical and physical scenarios towards biological homochirality (2022) · cites this paper as [161]
The observed chirality is correlated to the relative orientation of the angular momentum and the effective gravity, the direction of the former being set by clockwise or anticlockwise rotation.
“The observed chirality is correlated to the relative orientation of the angular momentum and the effective gravity, the direction of the former being set by clockwise or anticlockwise rotation.”
From Possible chemical and physical scenarios towards biological homochirality (2022) · cites this paper as [161]
The handedness of TPPS3 helical assemblies is controlled by the relative orientation of the angular momentum of rotation and the effective gravity.
“Control of the handedness of TPPS 3 helical assemblies by the relative orientation of the angular momentum of rotation (L) and the effective gravity (G eff ).”
From Possible chemical and physical scenarios towards biological homochirality (2022) · cites this paper as [161]
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Separation of enantiomers by their enantiospecific interaction with achiral magnetic substrates
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Symmetry Breaking in Self-Assembled Nanoassemblies
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“(B) Molecular formula of the achiral porphyrin tetraphenylporphyrin sulfonate (TPPS3), experimental set-up and the relationship between the chirality and the applied physical forces.”
BackgroundMethodInfluential
- Authors
- Micali, N., Engelkamp, H., van Rhee, P. G., Christianen, P. C. M., Scolaro, L. M., & Maan, J. C.
- Affiliations
- Institute for Chemical and Physical Processes (IT)
- Radboud University Nijmegen (NL)
- University of Messina (IT)
- Corresponding author
- Scolaro, L. Monsù
- Venue
- Nature Chemistry
- Published
- 2012-02-12
- Volume
- 4
- Issue
- 3
- Pages
- 201-207
- ISSN
- 1755-4330 (ISSN-L)
- 1755-4349
- OpenAlex
- W2096801006
- Cited by
- 259
- References
- 2
- Citations by year
- 2026: 9 · 2025: 12 · 2024: 15 · 2023: 13 · 2022: 20 · 2021: 24 · 2020: 24 · 2019: 19 · 2018: 18 · 2017: 21 · 2016: 17 · 2015: 13 · 2014: 14 · 2013: 22 · 2012: 18
- FWCI
- 8.69
- Type
- journal article
- Language
- en
- Open access
- closed
- Licence
- www.springer.com/tdm (tdm)
- Locations
- Nature Chemistry (publishedVersion)
- PubMed (publishedVersion)
- Radboud Repository (Radboud University) (submittedVersion)
- Funders
- European Commission (228043)
- Stichting voor Fundamenteel Onderzoek der Materie
- Nederlandse Organisatie voor Wetenschappelijk Onderzoek
- Topics
- Physical Sciences › Materials Science › Biomaterials › Supramolecular Self-Assembly in Materials
- Physical Sciences › Physics and Astronomy › Astronomy and Astrophysics › Origins and Evolution of Life
- Physical Sciences › Chemistry › Organic Chemistry › Supramolecular Chemistry and Complexes
- Keywords
- supramolecular chirality, homochirality, enantioselectivity, achiral molecules, self-assembly, nucleation, rotational force, effective gravity, magnetic field alignment, porphyrin assemblies, origin of homochirality
- MeSH terms
- Models, Chemical, Models, Molecular, Porphyrins, Rotation, Stereoisomerism, Thermodynamics, Macromolecular Substances, Magnetic Phenomena
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