Abstract
Self-assembling oligopeptides present a means to fabricate biocompatible supramolecular aggregates with engineered electronic and optical functionality. We conducted molecular dynamics simulations of self-assembling synthetic oligopeptides with Asp-X (Formula presented.) -X (Formula presented.) -X (Formula presented.) - (Formula presented.) -X (Formula presented.) -X (Formula presented.) -X (Formula presented.) -Asp architectures. Dimerisation and trimerisation free energies were computed for a range of Asp-X (Formula presented.) -X (Formula presented.) -X (Formula presented.) amino acid sequences, and for perylenediimide (PDI) and naphthalenediimide (NDI) conjugated (Formula presented.) cores that mediate hydrophobic stacking and electron delocalisation within the self-assembled nanostructure. The larger PDI cores elevated oligomerisation free energies by a factor of 2-3 relative to NDI and also improved alignment of the oligopeptides within the stack. Training of a quantitative structure–property relationship (QSPR) model revealed key physicochemical determinants of the oligomerisation free energies and produced a predictive model for the oligomerisation thermodynamics. Oligopeptides with moderate dimerisation and trimerisation free energies of (Formula presented.) (-25) (Formula presented.) produced aggregates with the best in-register parallel stacking, and we used this criterion within our QSPR model to perform high-throughput virtual screening to identify promising candidates for the spontaneous assembly of ordered nanoaggregates. We identified a small number of oligopeptide candidates for direct testing in large scale molecular simulations, and predict a novel chemistry DAVG-PDI-GVAD previously unstudied by experiment or simulation to produce well-aligned nanoaggregates expected to possess good optical and electronic functionality.
Original language | English (US) |
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Pages (from-to) | 930-945 |
Number of pages | 16 |
Journal | Molecular Simulation |
Volume | 44 |
Issue number | 11 |
DOIs | |
State | Published - Jul 24 2018 |
Keywords
- -conjugated oligopeptides
- molecular dynamics simulation
- quantitative structure-property relationships
- self-assembly
- supramolecular peptides
ASJC Scopus subject areas
- General Chemistry
- Information Systems
- Modeling and Simulation
- General Chemical Engineering
- General Materials Science
- Condensed Matter Physics