Spongin is a fundamental biopolymer that has played a crucial role in the skeletogenesis of keratosan sponges for over 800 million years. This biomaterial had so far remained chemically unidentified and believed to be an enigmatic type of halogenated collagen-keratin-based bioelastomer. Here we show collagen I and III as the main structural components of spongin. Proteomics, 13C solid state NMR and Raman spectroscopy confirm the identity of collagenous domains in spongin with collagen from mammals. Using an HPLC-MS analysis, we found halogenated di- and tri-tyrosines as crosslinking agents in spongin. Using molecular dynamics modeling, we solvated the crystal structures of collagen mimetic peptides for type I and type III collagens in four different systems, including selected brominated crosslinks. The results underscore the complex interplay between the collagen structures and crosslinks, raising intriguing questions about the molecular mechanisms underlying collagen chemistry within spongin as an ancient biocomposite.

Aix Marseille University Avignon Université CNRS IRD IMBE Marseille France

Center for Advanced Technology Adam Mickiewicz University Poznan Poland

Center for Computational Science and Engineering Schwarzman College of Computing Massachusetts Institute of Technology Cambridge MA USA

Center for Computing in Engineering and Sciences Sao Paulo Brazil

Department of Analytical Chemistry Faculty of Chemical Technology University of Pardubice Pardubice Czech Republic

Department of Civil and Environmental Engineering Massachusetts Institute of Technology Cambridge MA USA

Department of Computational Mechanics School of Mechanical Engineering Universidade Estadual de Campinas Sao Paulo Brazil

Department of Histology and Embryology Poznań University of Life Sciences Poznan Poland

Department of Marine Biology Leon H Charney School of Marine Sciences University of Haifa Haifa Israel

Department of Medical Physics and Biomedical Engineering Faculty of Medicine Carl Gustav Carus Technische Universität Dresden Dresden Germany

Department of Pharmacy National Pirogov Memorial Medical University Vinnytsya Vinnytsia Ukraine

Institute for Nanoscale and Biobased Materials TU Bergakademie Freiberg Freiberg Germany

Institute of Analytical Chemistry TU Bergakademie Freiberg Freiberg Germany

Institute of Chemical Technology and Engineering Faculty of Chemical Technology Poznan University of Technology Poznan Poland

Institute of Chemistry Universidade Estadual de Campinas Sao Paulo Brazil

Institute of Geology Chair of Hydrogeology and Hydrochemistry TU Bergakademie Freiberg Freiberg Germany

Institute of Materials Research and Quantum Engineering Faculty of Materials Engineering and Technical Physics Poznan University of Technology Poznan Poland

International Institute of Biomineralogy GmbH Freiberg Germany

Laboratory for Atomistic and Molecular Mechanics Massachusetts Institute of Technology Cambridge MA USA

Leibniz Institute of Polymer Research Dresden Dresden Germany

Max Planck Institute for Chemical Physics of Solids Dresden Germany

NanoBioMedical Centre Adam Mickiewicz University in Poznań 61 614 Poznań Poland

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