Journal article

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Tuning the solubility of hepta(p-benzamide)s via the monomer sequence

    23.11.2012
Published in:
  • Tetrahedron Letters. - 2012
English The automated synthesis of hepta(p-benzamide) hetero sequences on solid support using a modified peptide synthesizer is reported. The oligomers are synthesized from 4-aminobenzoic acid and 4-amino-2-(hexyloxy)benzoic acid, the latter carrying a solubilizing hexyl side chain. It is known from previous studies that both the unsubstituted hepta(p-benzamide) and the fully hexyloxy-substituted hepta(p-benzamide) are insoluble in all common organic solvents. Heterosequences in which both types of monomers alternate are, however, soluble in polar organic solvents such as DMSO. The heterosequence heptamers behave as strong organogelators when DMSO solutions are left at room temperature for several hours. Transmission electron microscopic (TEM) investigations revealed that the gelation was due to the oligomers forming long entangled fibers via a non-covalent aggregation mechanism. We explain these phenomena by a heterosequence triggered switch of aggregation mechanism. The unsubstituted oligomers strongly aggregate via a directional hydrogen-bond driven mechanism which changes to a less directional π-interaction driven aggregation mechanism for the substituted oligomers.We thereby demonstrate that designed hetero sequences in non-natural oligoamides can lead to materials with distinctly different conformations which directly affects the intermolecular interactions and their supramolecular organization.
Faculty
Faculté des sciences et de médecine
Department
Département de Chimie
Language
  • English
Classification
Chemistry
License
License undefined
Identifiers
Persistent URL
https://folia.unifr.ch/unifr/documents/302647
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