Journal
MOLECULAR SIMULATION
Volume 42, Issue 12, Pages 955-975Publisher
TAYLOR & FRANCIS LTD
DOI: 10.1080/08927022.2015.1125997
Keywords
-conjugated oligopeptides; molecular dynamics simulation; supramolecular peptides; self-assembly; Markov state model
Funding
- U.S. Department of Energy, Office of Science, Basic Energy Sciences [DE-SC0004857]
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Synthetic oligopeptides containing-conjugated cores self-assemble novel materials with attractive electronic and photophysical properties. All-atom, explicit solvent molecular dynamics simulations of Asp-Phe-Ala-Gly-OPV3-Gly-Ala-Phe-Asp peptides were used to parameterise an implicit solvent model to simulate early-stage self-assembly. Under low-pH conditions, peptides assemble into -sheet-like stacks with strongly favorable monomer association free energies of . Aggregation at high-pH produces disordered aggregates destabilised by Coulombic repulsion between negatively charged Asp termini (). In simulations of hundreds of monomers over 70 ns we observe the spontaneous formation of up to undecameric aggregates under low-pH conditions. Modeling assembly as a continuous-time Markov process, we infer transition rates between different aggregate sizes and microsecond relaxation times for early-stage assembly. Our data suggests a hierarchical model of assembly in which peptides coalesce into small clusters over tens of nanoseconds followed by structural ripening and diffusion limited aggregation on longer time scales. This work provides new molecular-level understanding of early-stage assembly, and a means to study the impact of peptide sequence and aromatic core chemistry upon the thermodynamics, assembly kinetics, and morphology of the supramolecular aggregates.
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