Pathway complexity in fibre assembly: from liquid crystals to hyper-helical gelmorphs.

Contreras-Montoya, Rafael; Smith, James P; Boothroyd, Stephen C; Aguilar, Juan A; Mirzamani, Marzieh; Screen, Martin A; Yufit, Dmitry S; Robertson, Mark; He, Lilin; Qian, Shuo; Kumari, Harshita; Steed, Jonathan W; Contreras-Montoya, Rafael; Smith, James P; Boothroyd, Stephen C; Mirzamani, Marzieh; Screen, Martin A; Yufit, Dmitry S; Robertson, Mark; He, Lilin

Abstract

Pathway complexity results in unique materials from the same components according to the assembly conditions. Here a chiral acyl-semicarbazide gelator forms three different gels of contrasting fibre morphology (termed 'gelmorphs') as well as lyotropic liquid crystalline droplets depending on the assembly pathway. The gels have morphologies that are either hyperhelical (HH-Gel), tape-fibre (TF-Gel) or thin fibril derived from the liquid crystalline phase (LC-Gels) and exhibit very different rheological properties. The gelator exists as three slowly interconverting conformers in solution. All three gels are comprised of an unsymmetrical, intramolecular hydrogen bonded conformer. The kinetics show that formation of the remarkable HH-Gel is cooperative and is postulated to involve association of the growing fibril with a non-gelling conformer. This single molecule dynamic conformational library shows how very different materials with different morphology and hence very contrasting materials properties can arise from pathway complexity as a result of emergent interactions during the assembly process. [Abstract copyright: This journal is © The Royal Society of Chemistry.]

Citation

Contreras-Montoya, R., Smith, J. P., Boothroyd, S. C., Aguilar, J. A., Mirzamani, M., Screen, M. A., Yufit, D. S., Robertson, M., He, L., Qian, S., Kumari, H., Steed, J. W., Contreras-Montoya, R., Smith, J. P., Boothroyd, S. C., Mirzamani, M., Screen, M. A., Yufit, D. S., Robertson, M., & He, L. (2023). Pathway complexity in fibre assembly: from liquid crystals to hyper-helical gelmorphs. Chemical Science, 14(41), 11389-11401. https://doi.org/10.1039/d3sc03841f

• Journal Article Type: Article
• Acceptance Date: Sep 25, 2023
• Online Publication Date: Sep 26, 2023
• Publication Date: Oct 1, 2023
• Deposit Date: Dec 4, 2023
• Publicly Available Date: Dec 4, 2023
• Journal: Chemical science
• Print ISSN: 2041-6520
• Electronic ISSN: 2041-6539
• Publisher: Royal Society of Chemistry
• Peer Reviewed: Peer Reviewed
• Volume: 14
• Issue: 41
• Pages: 11389-11401
• DOI: https://doi.org/10.1039/d3sc03841f
• Public URL: https://durham-repository.worktribe.com/output/1904524