Revealing the Sequence-Structure-Electronic Property Relation of Self-Assembling π-Conjugated Oligopeptides by Molecular and Quantum Mechanical Modeling

Self-assembled nanoaggregates of π-conjugated synthetic peptides present a biocompatible and highly tunable alternative to silicon-based optical and electronic materials. Understanding the relationship between structural morphology and electronic properties of these assemblies is critical for understanding and controlling their mechanical, optical, and electronic response. In this work, we combine all-atom classical molecular simulations with quantum-mechanical electronic structure calculations to ascertain the sequence-structure-electronic property relationship within a family of Asp-X-X- quaterthiophene-X-X-Asp (DXX-OT4-XXD) oligopeptides in which X is one of the five amino acids {Ala, Phe, Gly, Ile, Val} ({A, F, G, I, V}). Molecular dynamics simulations reveal that smaller amino acid substituents (A, G) favor linear stacking within a peptide dimer whereas larger groups (F, I, V) induce larger twist angles between the peptides. Density functional theory calculations on the dimer show the absorption spec...