Journal
JOURNAL OF PHYSICAL CHEMISTRY B
Volume 118, Issue 29, Pages 8642-8651Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jp504564s
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Funding
- MacDiarmid Institute for Advanced Materials and Nanotechnology, a Rutherford Discovery Fellowship
- Victoria Doctoral Scholarship awarded
- Australian Research Council [LPI30100774]
- Future Fellowship [FT120100101]
- Israel Science Foundation
- Gerhardt M.J. Schmidt Minerva Center of Supramolecular Architecture
- Helen and Martin Kimmel Center for Molecular Design
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Synthetic peptides offer enormous potential to encode the assembly of molecular electronic components, provided that the complex range of interactions is distilled into simple design rules. Here, we report a spectroscopic investigation of aggregation in an extensive series of peptide-perylene diiimide conjugates designed to interrogate the effect of structural variations. By fitting different contributions to temperature dependent optical absorption spectra, we quantify both the thermodynamics and the nature of aggregation for peptides by incrementally varying hydrophobicity, charge density, length, as well as asymmetric substitution with a hexyl chain, and stereocenter inversion. We find that coarse effects like hydrophobicity and hexyl substitution have the greatest impact on aggregation thermodynamics, which are separated into enthalpic and entropic contributions. Moreover, significant peptide packing effects are resolved via stereocenter inversion studies, particularly when examining the nature of aggregates formed and the coupling between it electronic orbitals. Our results develop a quantitative framework for establishing structure function relationships that will underpin the design of self-assembling peptide electronic materials.
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