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Cited by 134Origins and Evolution of LifeSupramolecular Self-Assembly in MaterialsSupramolecular Chemistry and Complexes

The DOI matches its Crossref record; 61 of the 62 references it cites were found in a registry or an index.

Control over the emerging chirality in supramolecular gels and solutions by chiral microvortices in milliseconds

Open access
Sun, Jiashu, Li, Yike, Yan, Fusheng, Liu, Chao, Sang, Yutao, Tian, Fei, Feng, Qiang, Duan, Pengfei, Zhang, Li, Shi, Xinghua, Ding, Baoquan, Liu, Minghua·2018·Nature Communications
DOI 10.1038/s41467-018-05017-7PMC PMC6030102
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Abstract

The origin of homochirality in life is a fundamental mystery. Symmetry breaking and subsequent amplification of chiral bias are regarded as one of the underlying mechanisms. However, the selection and control of initial chiral bias in a spontaneous mirror symmetry breaking process remains a great challenge. Here we show experimental evidences that laminar chiral microvortices generated within asymmetric microchambers can lead to a hydrodynamic selection of initial chiral bias of supramolecular systems composed of exclusively achiral molecules within milliseconds. The self-assembled nuclei with the chirality sign affected by the shear force of enantiomorphic microvortices are subsequently amplified into almost absolutely chirality-controlled supramolecular gels or nanotubes. In contrast, turbulent vortices in stirring cuvettes fail to select the chirality of supramolecular gels. This study reveals that a laminar chiral microflow can induce enantioselection far from equilibrium, and provides an insight on the origin of natural homochirality.

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Figures

Fig. 1 Microfluidic design for self-assembly of BTAC building blocks in microvortices. a Schematic hypothesis of the emergence of supramolecular chirality after molecules pass through the submarine rock micropores (left), and the imitated design of microfluidic device consisting of ten pairs of inclined microchambers (right) to generate counter-rotating microvortices. The blue (red) streamlines refer to CCW (CW) microvortices in the left (right) microchambers. L (R) indicates the left (right) outlet along the flow direction. Scale bar, 500 μm. The inset is SEM image of the cross-section of microchambers. Scale bar in the inset, 100 μm. b Effect of the shear forces of enantiomorphic microvortices (CW and CCW rotating directions) on the mirror symmetry breaking process of achiral BTAC molecules in DMF/H2O mixtures leading to the formation of BTAC gels. M (P) chirality refers to left-handed (right-handed) helical twists
Fig. 1 Microfluidic design for self-assembly of BTAC building blocks in microvortices. a Schematic hypothesis of the emergence of supramolecular chirality after molecules pass through the submarine rock micropores (left), and the imitated design of microfluidic device consisting of ten pairs of inclined microchambers (right) to generate counter-rotating microvortices. The blue (red) streamlines refer to CCW (CW) microvortices in the left (right) microchambers. L (R) indicates the left (right) outlet along the flow direction. Scale bar, 500 μm. The inset is SEM image of the cross-section of microchambers. Scale bar in the inset, 100 μm. b Effect of the shear forces of enantiomorphic microvortices (CW and CCW rotating directions) on the mirror symmetry breaking process of achiral BTAC molecules in DMF/H2O mixtures leading to the formation of BTAC gels. M (P) chirality refers to left-handed (right-handed) helical twistsCC BY · PubMed Central
Fig. 2 Microvortex selection of supramolecular chirality of BTAC gels. a UV-Vis spectra of BTAC gels. The blue (red) line refers to measurement from the gels collected from the L- (R-) outlet. b CD spectra indicate opposite chirality for BTAC gels collected from different outlets. c, d SEM characterizations show predominantly M and P twists for BTAC gels from the L- and R-outlet, respectively. Size of chiral twists is 295.2 ± 10.8 nm in width, and 869.3 ± 31.1 nm in length (mean ± s.e.m.; n = 40). Scale bars, 1 μm. e CD signals of 28 independent experiments indicate nearly absolute chirality control of BTAC gels by microvortices. The void blue (solid red) circles indicate CD signals of gels from the L- (R-) outlets
Fig. 2 Microvortex selection of supramolecular chirality of BTAC gels. a UV-Vis spectra of BTAC gels. The blue (red) line refers to measurement from the gels collected from the L- (R-) outlet. b CD spectra indicate opposite chirality for BTAC gels collected from different outlets. c, d SEM characterizations show predominantly M and P twists for BTAC gels from the L- and R-outlet, respectively. Size of chiral twists is 295.2 ± 10.8 nm in width, and 869.3 ± 31.1 nm in length (mean ± s.e.m.; n = 40). Scale bars, 1 μm. e CD signals of 28 independent experiments indicate nearly absolute chirality control of BTAC gels by microvortices. The void blue (solid red) circles indicate CD signals of gels from the L- (R-) outletsCC BY · PubMed Central
Fig. 3 TPPS4 J-aggregates with opposite chirality signs selected by microvortices. a Formation of chiral supramolecular nanotubes by the self-assembly of achiral TPPS4 building blocks (blue) and the C2mim+ ionic stabilizer (red) within the microvortices. b UV-Vis spectra exhibit a monomer peak at 433 nm and a J-aggregate peak at 491 nm for TPPS4 assemblies from the L- (blue line) and R-outlet (red line). c CD spectra indicate opposite chirality of the TPPS4 assemblies from the L- (blue line) and R-outlet (red line). d CD signals of 28 independent experiments reveal nearly absolute chirality control over supramolecular TPPS4 assemblies from the L- (void blue circles) and R-outlet (solid red circles). e, f Cryo-EM examinations of TPPS4 aggregates from the L- and R-outlet show the hollow tubular nanostructures with an average diameter of 12.8 ± 0.1 nm (mean ± s.e.m.; n = 40). Scale bars, 50 nm. The insets are the enlarged cryo-EM images. Scale bars in the insets, 20 nm
Fig. 3 TPPS4 J-aggregates with opposite chirality signs selected by microvortices. a Formation of chiral supramolecular nanotubes by the self-assembly of achiral TPPS4 building blocks (blue) and the C2mim+ ionic stabilizer (red) within the microvortices. b UV-Vis spectra exhibit a monomer peak at 433 nm and a J-aggregate peak at 491 nm for TPPS4 assemblies from the L- (blue line) and R-outlet (red line). c CD spectra indicate opposite chirality of the TPPS4 assemblies from the L- (blue line) and R-outlet (red line). d CD signals of 28 independent experiments reveal nearly absolute chirality control over supramolecular TPPS4 assemblies from the L- (void blue circles) and R-outlet (solid red circles). e, f Cryo-EM examinations of TPPS4 aggregates from the L- and R-outlet show the hollow tubular nanostructures with an average diameter of 12.8 ± 0.1 nm (mean ± s.e.m.; n = 40). Scale bars, 50 nm. The insets are the enlarged cryo-EM images. Scale bars in the insets, 20 nmCC BY · PubMed Central
Fig. 4 Analysis of laminar chiral microvortices. a CFD simulation shows that fluid can rotate upward (red curves) or downward (blue curves) to generate laminar P- or M-chiral microvortices in the left microchamber. The color bar indicates the magnitude of flow velocity. The channel height is 50 μm. Scale bar, 100 μm. b A majority (~84%) of microvortices rotate upward, suggesting a predominantly P chirality (red bar) in the left microchamber. c Shear rate gradient from P-chiral microvortices in the left microchamber. Insert: shear rate (black line) obtained from simulation results (void black circles). d Residence time (gray bars) of nuclei within the left microchamber from simulation results
Fig. 4 Analysis of laminar chiral microvortices. a CFD simulation shows that fluid can rotate upward (red curves) or downward (blue curves) to generate laminar P- or M-chiral microvortices in the left microchamber. The color bar indicates the magnitude of flow velocity. The channel height is 50 μm. Scale bar, 100 μm. b A majority (~84%) of microvortices rotate upward, suggesting a predominantly P chirality (red bar) in the left microchamber. c Shear rate gradient from P-chiral microvortices in the left microchamber. Insert: shear rate (black line) obtained from simulation results (void black circles). d Residence time (gray bars) of nuclei within the left microchamber from simulation resultsCC BY · PubMed Central
Fig. 5 Laminar chiral microvortices versus turbulent vortices in stirring cuvettes. a Schematic mechanism of laminar chiral microvortex-selected chirality of BTAC and TPPS4 nuclei. The rapidly formed nuclei (<1 ms) are aligned in the laminar flow, and twisted by a shear force (Fs) to give rise to an initial chiral bias dependent on the rotation sense of microvortices. These primary nuclei then serve as the templates for the subsequent growth into supramolecular assemblies with the predefined chirality. Red, blue, and black axes refer to the spatial distributions of shear rate gradient and viscous shear force along the x, y, and z axes. b CFD simulation of chaotic flows generated by CW stirring at ~1000 rpm in cuvettes. Left: 2D representation of the flow direction (black streamlines) and velocity (color). Right: 3D streamlines display a snapshot of chaotic flows. The color bar indicates the magnitude of flow velocity. Scale bar, 5 mm. c CW stirring in cuvettes shows 9 positive CD signals (P chirality, solid red circles) and 11 negative CD signals (M chirality, void blue circles) of BTAC gels
Fig. 5 Laminar chiral microvortices versus turbulent vortices in stirring cuvettes. a Schematic mechanism of laminar chiral microvortex-selected chirality of BTAC and TPPS4 nuclei. The rapidly formed nuclei (<1 ms) are aligned in the laminar flow, and twisted by a shear force (Fs) to give rise to an initial chiral bias dependent on the rotation sense of microvortices. These primary nuclei then serve as the templates for the subsequent growth into supramolecular assemblies with the predefined chirality. Red, blue, and black axes refer to the spatial distributions of shear rate gradient and viscous shear force along the x, y, and z axes. b CFD simulation of chaotic flows generated by CW stirring at ~1000 rpm in cuvettes. Left: 2D representation of the flow direction (black streamlines) and velocity (color). Right: 3D streamlines display a snapshot of chaotic flows. The color bar indicates the magnitude of flow velocity. Scale bar, 5 mm. c CW stirring in cuvettes shows 9 positive CD signals (P chirality, solid red circles) and 11 negative CD signals (M chirality, void blue circles) of BTAC gelsCC BY · PubMed Central

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Metadata

Authors
Sun, J., Li, Y., Yan, F., Liu, C., Sang, Y., Tian, F., Feng, Q., Duan, P., Zhang, L., Shi, X., Ding, B., & Liu, M.
Affiliations
  • National Center for Nanoscience and Technology (CN)
  • Chinese Academy of Sciences (CN)
Corresponding author
  • Sun, Jiashu
  • Ding, Baoquan
  • Liu, Minghua
ORCID
Venue
Nature Communications
Publisher
Springer Science and Business Media LLC
Published
2018-07-03
Volume
9
Issue
1
Pages
2599-2599
ISSN
2041-1723 (ISSN-L)
DOI
10.1038/s41467-018-05017-7
PMC
PMC6030102
OpenAlex
W2811351535
Cited by
134
References
62
Citations by year
2026: 8 · 2025: 18 · 2024: 18 · 2023: 17 · 2022: 20 · 2021: 16 · 2020: 13 · 2019: 17 · 2018: 7
FWCI
7.10
Type
journal article
Language
en
Open access
Licence
Locations
  • Nature Communications (publishedVersion, cc-by)
  • Europe PMC (PubMed Central) (publishedVersion, other-oa)
  • PubMed Central (publishedVersion, cc-by)
  • PubMed (publishedVersion)
  • RePEc: Research Papers in Economics (submittedVersion)
  • DOAJ (DOAJ: Directory of Open Access Journals) (submittedVersion)
  • DOAJ (DOAJ: Directory of Open Access Journals) (submittedVersion, cc-by-sa)
Funders
  • Chinese Academy of Sciences (2016035)
  • National Natural Science Foundation of China (21622503, 21475028, 91427302)
Topics
  • Physical Sciences › Physics and Astronomy › Astronomy and Astrophysics › Origins and Evolution of Life
  • Physical Sciences › Materials Science › Biomaterials › Supramolecular Self-Assembly in Materials
  • Physical Sciences › Chemistry › Organic Chemistry › Supramolecular Chemistry and Complexes
Keywords
homochirality, origin of homochirality, enantioselectivity, supramolecular gels, supramolecular nanotubes, symmetry breaking, shear force, chiral bias, self-assembly

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