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Pathway complexity in fibre assembly from liquid crystals to hyper-helical gelmorphs [dataset] Open Access

A chiral acyl-semicarbazide gelator 1RR/SS undergoes self-assembly to give three different supramolecular gels of differing fibre morphology (‘gelmorphs’) as well as lyotropic liquid crystalline droplets depending on the assembly pathway. The three gels have either hyperhelical (HH-gel), tape-fibre (TF-gel) or thin fibrils derived from the liquid crystalline phase (LC-gels). The gels exhibit very different rheological properties with elastic modulus, G′, and yield stress decreasing in the order HH > TF > LC and separated by an order of magnitude in each case. The gelator 1RR/SS exists as three slowly interconverting conformers (termed conformers C, B and A) in solution in the ratio 78:21:1, respectively and are self-associated in solution. XRPD data on the freeze dried gels show that all three gels comprise the unsymmetrical, intramolecular hydrogen bonded conformer B which is the least soluble component. In the solid state, however, material comprising conformer B is unstable and slowly converts to crystalline conformer A, an extended linear form which is the minor component in solution. The kinetics of gel fibre assembly have been monitored by circular dichroism spectroscopy which show that formation of the remarkable HH-gels by sonication at 25 oC is cooperative and may well involve association of the growing fibril with major conformer C as a chaperone. In contrast, formation of the TF-gels at 70 oC is isodesmic. This single molecule dynamic conformational library shows how very different materials with different morphology and hence very different materials properties can arise from pathway complexity as a result of emergent interactions during the assembly process.

Descriptions

Resource type

Dataset

Contributors

Creator: Steed, Jonathan William ¹
Contact person: Steed, Jonathan William ¹
Editor: Steed, Jonathan William ¹
Contreras-Montoya, Rafael ²

¹ Durham University, UK
² Edinburgh University, UK

Funder

Engineering and Physical Sciences Research Council

Research methods

XRPD, X-ray crystallography, circular dichroism spectroscopy, SEM, rheology

Other description

Keyword

Gel
Self-assembly
Soft materials
Urea

Subject

Chemistry, Organic
Chemistry, materials
Self-assembly

Location

Language

Cited in

Identifier

ark:/32150/r2sf268517p
doi:10.15128/r2sf268517p

Rights

Creative Commons Attribution 4.0 International (CC BY)

Publisher

Durham University

Date Created

File Details

Depositor

J.W. Steed

Date Uploaded

28 November 2022, 15:11:54

Date Modified

17 March 2023, 13:03:12

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Audits have not yet been run on this file.

Characterization

File format: zip (ZIP Format)

Mime type: application/zip

File size: 83904510

Last modified: 2023:03:17 13:52:57+00:00

Filename: Pathway complexity v2.zip

Original checksum: 89f83b703372553b81c15efc9d6e2ae9