Confinement-induced liquid crystalline transitions in amyloid fibril cholesteric tactoids

Abstract

Chirality is ubiquitous in nature and plays crucial roles in biology, medicine, physics and materials science. Understanding and controlling chirality is therefore an important research challenge with broad implications. Unlike other chiral colloids, such as nanocellulose or filamentous viruses, amyloid fibrils form nematic phases but appear to miss their twisted form, the cholesteric or chiral nematic phases, despite a well-defined chirality at the single fibril level. Here we report the discovery of cholesteric phases in amyloids, using β-lactoglobulin fibrils shortened by shear stresses. The physical behaviour of these new cholesteric materials exhibits unprecedented structural complexity, with confinement-driven ordering transitions between at least three types of nematic and cholesteric tactoids. We use energy functional theory to rationalize these results and observe a chirality inversion from the left-handed amyloids to right-handed cholesteric droplets. These findings deepen our understanding of cholesteric phases, advancing their use in soft nanotechnology, nanomaterial templating and self-assembly.

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Fig. 1: Amyloid fibril preparation and examples of amyloid fibril liquid crystal polymorphs.
Fig. 2: Nematic and cholesteric phases of amyloid fibrils as observed by rotating the sample in the plane between fixed crossed polarizers.
Fig. 3: Determination of 3D cholesteric tactoid shape.
Fig. 4: Nematic tactoid aspect ratio dependence on tactoid volume, tactoid structural transitions and cholesteric pitch dependence on tactoid volume.
Fig. 5: Nematic–cholesteric phase diagram and determination of handedness of cholesteric phase.

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Acknowledgements

We acknowledge support from the Scientific Center for Optical and Electron Microscopy of ETH Zurich (ScopeM). S. Handschin and T. Schwarz are acknowledged for help with the sample rotation stage for polarized optical microscopy and the laser scanning confocal microscopy, respectively. S. Assenza and C. de Michele are acknowledged for discussions.

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G.N. designed and carried out the experiments, analysed data and interpreted the results. M.A. carried out the experiments, analysed data and interpreted the results. R.M. developed the theoretical description, analysed and interpreted the results, and designed and directed the study. All authors discussed the results and contributed to writing.

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Correspondence to Raffaele Mezzenga.

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Supplementary information

Supplementary Information

Supplementary discussion, Supplementary Figures 1–5, captions for Supplementary Videos 1–4.

Supplementary Video 1

Rotation of a cholesteric tactoid around an axis parallel to the observation plane and passing through the poles of the apparent spindle-like droplet.

Supplementary Video 2

Coalescence of two nematic tactoids and their transition into one cholesteric tactoid.

Supplementary Video 3

Right-handed rotation of a cholesteric tactoid.

Supplementary Video 4

Right-handed rotation of a right-handed rod helix.

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Nyström, G., Arcari, M. & Mezzenga, R. Confinement-induced liquid crystalline transitions in amyloid fibril cholesteric tactoids. Nature Nanotech 13, 330–336 (2018). https://doi.org/10.1038/s41565-018-0071-9

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