Chiral Supramolecular Polymers Assembled by Amphiphilic Oligopeptide-Perylene Diimides and High Electrochemical Sensing

Abstract

Various secondary structures, for example, β-sheet hydrogen bonds formed by oligopeptides exhibiting high directionality and selectivity provide a new avenue to regulate optoelectronic performances of supramolecular assemblies constructed by π-conjugated chromophores. In this work, oligopeptide-perylene diimides (AUPDIs) are synthesized to generate β-sheet strands which guide the formation of chiral supramolecular polymers with a diversity of morphologies in combination with the π–π stacking even in aqueous media. Complex morphology transitions are successfully controlled by simply adjusting the water volume fraction in the binary solvent of water and tetrahydrofuran from spherical hollow aggregates to long helical nanowires and to short nanofibers. The mechanism of the assembly changes from cooperative to the isodesmic model relying on AUPDI concentrations. This originates from the transformation in the β-sheet that regulates profoundly the arrangement of the AUPDI molecules. Prominently efficient and positive electronic sensing to triethylamine for highly helical nanowires engenders due to the highly ordered helical arrangement within the nanowires, fourfold of the short nanofibers.

One‐Dimensional Helical Nanostructures from the Hierarchical Self‐Assembly of an Achiral “Rod−Coil” Alternating Copolymer

“…We expect that the 𝜋−𝜋 electron delocalization in a helical nanowire with well-arranged conjugated segments could enhance the charge separation and transport ability, which could improve the electronic performance (such as carrier mobility) of the self-assembled nanowires. [51,52]…”

Molecularly Selective Polymer Interfaces for Electrochemical Separations

“…Polymer interfaces have been core components in the design of stimuli-responsive systems. In the past, conducting polymers have been extensively studied as electroactive films for anion doping. − Since then, redox-responsive polymers have been applied to numerous applications including electrochemical sensing, catalysis, − and energy storage. , However, despite their intrinsic capabilities for ion-selective interactions, only recently have redox polymers been systematically investigated for the separation of diverse charged molecules, particularly anionic species.…”

Evolution of π-Peptide Self-Assembly: From Understanding to Prediction and Control

“…This attention could be conceived to have originated from the early compositional introductions of Chmielewski, Bäuerle, and Nowick, who joined peptide sequences with π-electron cores. This attention is currently manifest in the many modern day examples showcasing the structures, morphologies, and properties of these hybrid bioelectronic materials. − In general, π-peptide conjugates can self-assemble into hierarchical nanostructures such as tapes and fibrils in line with many standard oligopeptides that are capable of forming amyloid-like nanomaterials. Importantly, they offer the additional ability to foster intermolecular π-stacking of the electronic cores which is required for energy migration in a broad sense.…”