Journal
LANGMUIR
Volume 35, Issue 43, Pages 14060-14073Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.langmuir.9b02683
Keywords
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Funding
- National Science Foundation's Designing Materials to Revolutionize and Engineer Our Future (DMREF) program [DMR-1728947, DMR-1841807]
- National Science Foundation graduate research fellowship [DGE-174604S]
- University of Chicago [DMR-1828629]
- Johns Hopkins University
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Self-assembled supramolecular organic materials with pi-functionalities are of great interest because of their applications as biocompatible nanoelectronics. A detailed understanding of molecular parameters to modulate the formation of hierarchical structures can inform design principles for materials with engineered optical and electronic properties. In this work, we combine molecular-level characterization techniques with all-atom molecular simulations to investigate the subtle relationship between the chemical structure of peptide-pi-peptide molecules and the emergent supramolecular chirality of their spontaneously self-assembled nanoaggregates. We demonstrate through circular dichroism measurements that we can modulate the chirality by incorporating alkyl spacers of various lengths in between the peptides and thienylene-phenylene pi-system chromophores: even numbers of alkyl carbons in the spacer units (0, 2) induce M-type helical character whereas odd numbers (1, 3) induce P-type. Corroborating molecular dynamics simulations and explicating machine learning analysis techniques identify hydrogen bonding and hydrophobic packing to be the principal discriminants of the observed chirality switches. Our results present a molecular-level design rule to engineer chirality into optically and electronically active nanoaggregates of these peptidic building blocks by exploiting systematic variations in the alkyl spacer length.
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