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

DOI: 10.1039/D3SC03841F

Authors: Rafael Contreras-Montoya (Durham University) , James P. Smith (Durham University) , Stephen Boothroyd (Durham University) , Juan A. Aguilar (Durham University) , Marzieh Mirzamani (University of Cincinnati) , Martin A. Screen (Durham University) , Dmitry S. Yufit (Durham University) , Mark Robertson (University of Southern Mississippi) , Lilin He (Oak Ridge National Laboratory) , Shuo Qian (Oak Ridge National Laboratory) , Harshita Kumari (University of Cincinnati) , Jonathan W. Steed (Durham University)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Chemical Science , VOL 46

State: Published (Approved)
Published: September 2023
Diamond Proposal Number(s): 22240

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.

Subject Areas: Materials, Chemistry


Instruments: I19-Small Molecule Single Crystal Diffraction

Added On: 04/10/2023 13:52

Documents:
d3sc03841f.pdf

Discipline Tags:

Physical Chemistry Chemistry Materials Science Polymer Science

Technical Tags:

Diffraction Single Crystal X-ray Diffraction (SXRD)