Full text

Turn on search term navigation

© 2018. This work is licensed under http://creativecommons.org/licenses/by/4.0/ (the “License”). Notwithstanding the ProQuest Terms and Conditions, you may use this content in accordance with the terms of the License.

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.

Details

Title
Chiral Assembly Preferences and Directing Effects in Supramolecular Two-Component Organogels
Author
Edwards, William; Smith, David K
Publication year
2018
Publication date
Jun 2018
Publisher
MDPI AG
e-ISSN
23102861
Source type
Scholarly Journal
Language of publication
English
ProQuest document ID
2124605690
Copyright
© 2018. This work is licensed under http://creativecommons.org/licenses/by/4.0/ (the “License”). Notwithstanding the ProQuest Terms and Conditions, you may use this content in accordance with the terms of the License.