Co-assembly of Peptide Amphiphiles and Lipids into Supramolecular Nanostructures Driven by Anionâ'Ï€ Interactions

Zhilin Yu, Aykut Erbas, Faifan Tantakitti, Liam C. Palmer, Joshua A. Jackman, Monica Olvera De La Cruz, Nam Joon Cho, Samuel I Stupp

Research output: Contribution to journalArticle

25 Citations (Scopus)

Abstract

Co-assembly of binary systems driven by specific non-covalent interactions can greatly expand the structural and functional space of supramolecular nanostructures. We report here on the self-assembly of peptide amphiphiles and fatty acids driven primarily by anion interactions. The peptide sequences investigated were functionalized with a perfluorinated phenylalanine residue to promote anion interactions with carboxylate headgroups in fatty acids. These interactions were verified here by NMR and circular dichroism experiments as well as investigated using atomistic simulations. Positioning the aromatic units close to the N-terminus of the peptide backbone near the hydrophobic core of cylindrical nanofibers leads to strong anion interactions between both components. With a low content of dodecanoic acid in this position, the cylindrical morphology is preserved. However, as the aromatic units are moved along the peptide backbone away from the hydrophobic core, the interactions with dodecanoic acid transform the cylindrical supramolecular morphology into ribbon-like structures. Increasing the ratio of dodecanoic acid to PA leads to either the formation of large vesicles in the binary systems where the anion interactions are strong, or a heterogeneous mixture of assemblies when the peptide amphiphiles associate weakly with dodecanoic acid. Our findings reveal how co-assembly involving designed specific interactions can drastically change supramolecular morphology and even cross from nano to micro scales.

Original languageEnglish
Pages (from-to)7823-7830
Number of pages8
JournalJournal of the American Chemical Society
Volume139
Issue number23
DOIs
Publication statusPublished - Jun 14 2017

Fingerprint

lauric acid
Amphiphiles
Nanostructures
Lipids
Peptides
Anions
Negative ions
Acids
Fatty acids
Fatty Acids
Nanofibers
Dichroism
Circular Dichroism
Phenylalanine
Hydrophobic and Hydrophilic Interactions
Self assembly
Self Report
Nuclear magnetic resonance

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Co-assembly of Peptide Amphiphiles and Lipids into Supramolecular Nanostructures Driven by Anionâ'Ï€ Interactions. / Yu, Zhilin; Erbas, Aykut; Tantakitti, Faifan; Palmer, Liam C.; Jackman, Joshua A.; De La Cruz, Monica Olvera; Cho, Nam Joon; Stupp, Samuel I.

In: Journal of the American Chemical Society, Vol. 139, No. 23, 14.06.2017, p. 7823-7830.

Research output: Contribution to journalArticle

Yu, Zhilin ; Erbas, Aykut ; Tantakitti, Faifan ; Palmer, Liam C. ; Jackman, Joshua A. ; De La Cruz, Monica Olvera ; Cho, Nam Joon ; Stupp, Samuel I. / Co-assembly of Peptide Amphiphiles and Lipids into Supramolecular Nanostructures Driven by Anionâ'Ï€ Interactions. In: Journal of the American Chemical Society. 2017 ; Vol. 139, No. 23. pp. 7823-7830.
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