Microenvironment control of porphyrin binding, organization, and function in peptide nanofiber assemblies

Lee A. Solomon, Anna R. Wood, Matthew E. Sykes, Benjamin T. Diroll, Gary P. Wiederrecht, Richard D. Schaller, H. Christopher Fry

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

To take peptide materials from predominantly structural to functional assemblies, variations in cofactor binding sites must be engineered and controlled. Here, we have employed the peptide sequence c16-AHX 3 K 3 -CO 2 H where X 3 represents the aliphatic structural component of the peptide design that dictates β-sheet formation and upon self-assembly yields a change in the overall microenvironment surrounding the Zn protoporphyrin IX ((PPIX)Zn) binding site. All peptides studied yield β-sheet rich nanofibers highlighting the materials' resiliency to amino acid substitution. We highlight that the (PPIX)Zn binding constants correlate strongly with amino acid side chain volume, where X = L or I yields the lowest dissociation constant values (K D ). The resulting microenvironment highlights the materials' ability to control interchromophore electronic interactions such that slip-stacked cofacial arrangements are observed via exciton splitting in UV/visible and circular dichroism spectroscopy. Steady state and time-resolved photoluminescence suggests that greater interchromophore packing yields larger excimer populations and corresponding longer excimer association lifetimes (τ A ) which directly translates to shorter exciton diffusion lengths. In comparison to synthetic porphyrin molecular assemblies, this work demonstrates the ability to employ the peptide assembly to modulate the degree of cofactor arrangement, extent of excimer formation, and the exciton hopping rates all while in a platform amenable for producing polymer-like materials.

Original languageEnglish
Pages (from-to)5412-5421
Number of pages10
JournalNanoscale
Volume11
Issue number12
DOIs
Publication statusPublished - Mar 28 2019

ASJC Scopus subject areas

  • Materials Science(all)

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    Solomon, L. A., Wood, A. R., Sykes, M. E., Diroll, B. T., Wiederrecht, G. P., Schaller, R. D., & Fry, H. C. (2019). Microenvironment control of porphyrin binding, organization, and function in peptide nanofiber assemblies. Nanoscale, 11(12), 5412-5421. https://doi.org/10.1039/c8nr09556f