Molecular-Level Control over Plasmonic Properties in Silver Nanoparticle/Self-Assembling Peptide Hybrids

The plasmonic properties of silver nanoparticle (AgNP) arrays are directly controlled by AgNP size, shape, and spatial arrangement. Reported here is a strategy to prepare chiral AgNP arrays templated by two constitutionally isomeric aromatic peptide amphiphiles (APAs), KsC'EKs and C'EKsKs (K-s = S-aroylthiooxime-modified lysine, C' = citrulline, and E = glutamic acid). In phosphate buffer, both APAs initially self-assembled into nanoribbons with a similar geometry. However, in the presence of silver ions and poly(sodium 4-styrenesulfonate) (PSSS), one of the nanoribbons (KsC'EKs) turned into nanohelices with a regular twisting pitch, while the other (C'EKsKs) remained as nanoribbons. Both were used as templates for synthesis of arrays of similar to 8nm AgNPs to understand how small changes in molecular structure affect the plasmonic properties of these chiral AgNP/APA hybrids. Both hybrids showed improved colloidal stability compared to pure AgNPs, and both showed enhanced sensitivity as surface-enhanced Raman spectroscopy (SERS) substrates for model analytes, with nanohelices showing better SERS performance compared to their nanoribbon counterparts and pure AgNPs.