Biomimetic pheomelanin to unravel the electronic, molecular and supramolecular structure of the natural product

Wei Cao; Haochuan Mao; Naneki C. McCallum; Xuhao Zhou; Hao Sun; Christopher Sharpe; Joanna Korpanty; Ziying Hu; Qing Zhe Ni; Michael D. Burkart; Matthew D. Shawkey; Michael R. Wasielewski; Nathan C. Gianneschi

doi:10.1039/D2SC06418A

Biomimetic pheomelanin to unravel the electronic, molecular and supramolecular structure of the natural product†

Wei Cao,*^abc Haochuan Mao,^ad Naneki C. McCallum,^a Xuhao Zhou,

^a Hao Sun,

^abcg Christopher Sharpe,

^b Joanna Korpanty,^a Ziying Hu,^a Qing Zhe Ni,

^e Michael D. Burkart,

^e Matthew D. Shawkey,^f Michael R. Wasielewski

^ad and Nathan C. Gianneschi

*^abce

Author affiliations

* Corresponding authors

^a Department of Chemistry, Northwestern University, Evanston, Illinois, USA
E-mail: caowei@bnu.edu.cn, nathan.gianneschi@northwestern.edu

^b Department of Materials Science and Engineering, Northwestern University, Evanston, Illinois, USA

^c Department of Biomedical Engineering, Department of Pharmacology, International Institute for Nanotechnology, Simpson-Querrey Institute, Chemistry of Life Processes Institute, Lurie Cancer Center, Northwestern University, Evanston, Illinois, USA

^d Institute for Sustainability and Energy at Northwestern University, Evanston, Illinois, USA

^e Department of Chemistry & Biochemistry, University of California, San Diego, La Jolla, California, USA

^f Evolution and Optics of Nanostructures Group, Department of Biology, The University of Ghent, Ghent, Belgium

^g Department of Chemistry and Chemical & Biomedical Engineering, Tagliatela College of Engineering, University of New Haven, West Haven, Connecticut, USA

Abstract

Herein, we investigate synthetic routes to a close mimic of natural pheomelanin. Three different oxidative polymerization routes were attempted to generate synthetic pheomelanin, each giving rise to structurally dissimilar materials. Among them, the route employing 5-cysteinyl-dihydroxyphenylalanine (5-CD) as a monomer was verified as a close analogue of extracted pheomelanin from humans and birds. The resulting biomimetic and natural pheomelanins were compared via various techniques, including solid-state Nuclear Magnetic Resonance (ssNMR) and Electron Paramagnetic Resonance (EPR). This synthetic pheomelanin closely mimics the structure of natural pheomelanin as determined by parallel characterization of pheomelanin extracted from multiple biological sources. With a good synthetic biomimetic material in hand, we describe cation-π interactions as an important driving force for pheomelanogenesis, further advancing our fundamental understanding of this important biological pigment.

Chemical Science

Biomimetic pheomelanin to unravel the electronic, molecular and supramolecular structure of the natural product†

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Biomimetic pheomelanin to unravel the electronic, molecular and supramolecular structure of the natural product

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