Edwards, William and Smith, David Kelham orcid.org/0000-0002-9881-2714 (2018) Chiral Assembly Preferences and Directing Effects in Supramolecular Two-Component Organogels. Gels. ISSN 2310-2861
Abstract
The impact of chirality on the self-assembly of supramolecular gels is of considerable importance, as molecular-scale programming can be translated into nanostructuring and ultimately affect macroscopic performance. This paper explores the effect of chirality on the assembly of two-component gels comprised of a second-generation dendritic lysine peptide acid, containing three chiral centres, and an amine. This combination forms an acid–amine complex that assembles into nanofibres through peptide-peptide hydrogen bonds, leading to organogels. With achiral amines, a racemic mixture of l,l,l and d,d,d dendritic peptide acids surprisingly forms the best gels—more commonly, mixing enantiomers suppresses gelation. Thermodynamic studies demonstrate that depending on the amine, the greater stability of heterochiral gels can either be entropically or enthalpically driven. With amines possessing “R” chirality, the l,l,l peptide acid consistently forms more effective gels than its d,d,d analogue. Furthermore, in mixed gels, l,l,l sometimes imposes its assembly preference onto d,d,d. In summary, this paper demonstrates a rare example in which heterochiral gels are preferred, and also explores directing effects when each component in a two-component gel is chiral.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2018 by the authors. |
Dates: |
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Institution: | The University of York |
Academic Units: | The University of York > Faculty of Sciences (York) > Chemistry (York) |
Depositing User: | Pure (York) |
Date Deposited: | 27 Apr 2018 08:20 |
Last Modified: | 16 Oct 2024 14:41 |
Status: | Published |
Refereed: | Yes |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:130161 |