title: Multi-scale thermal stability of a hard thermoplastic protein-based material.
abstract: Although thermoplastic materials are mostly derived from petro-chemicals, it would be highly desirable, from a sustainability perspective, to produce them instead from renewable biopolymers. Unfortunately, biopolymers exhibiting thermoplastic behaviour and which preserve their mechanical properties post processing are essentially non-existent. The robust sucker ring teeth (SRT) from squid and cuttlefish are one notable exception of thermoplastic biopolymers. Here we describe thermoplastic processing of squid SRT via hot extrusion of fibres, demonstrating the potential suitability of these materials for large-scale thermal forming. Using high-resolution in situ X-ray diffraction and vibrational spectroscopy, we elucidate the molecular and nanoscale features responsible for this behaviour and show that SRT consist of semi-crystalline polymers, whereby heat-resistant, nanocrystalline β-sheets embedded within an amorphous matrix are organized into a hexagonally packed nanofibrillar lattice. This study provides key insights for the molecular design of biomimetic protein- and peptide-based thermoplastic structural biopolymers with potential biomedical and 3D printing applications.
authors.affiliation: Department of Biomaterials, Max Planck Institute of Colloids and Interfaces, Research Campus Golm, Potsdam 14424, Germany.
authors.forename: Victoria
authors.initials: V
authors.lastname: Latza
authors.affiliation: School of Materials Science and Engineering, Nanyang Technological University, Singapore 639798, Singapore.|Energy Research Institute at Nanyang Technological University (ERI@N), Singapore 637553, Singapore.
authors.forename: Paul A
authors.initials: PA
authors.lastname: Guerette
authors.affiliation: School of Materials Science and Engineering, Nanyang Technological University, Singapore 639798, Singapore.
authors.forename: Dawei
authors.initials: D
authors.lastname: Ding
authors.affiliation: School of Materials Science and Engineering, Nanyang Technological University, Singapore 639798, Singapore.
authors.forename: Shahrouz
authors.initials: S
authors.lastname: Amini
authors.affiliation: School of Biological Science, Nanyang Technological University, Singapore 639798, Singapore.
authors.forename: Akshita
authors.initials: A
authors.lastname: Kumar
authors.affiliation: Department of Biomaterials, Max Planck Institute of Colloids and Interfaces, Research Campus Golm, Potsdam 14424, Germany.
authors.forename: Ingo
authors.initials: I
authors.lastname: Schmidt
authors.affiliation: MIT Media Lab, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA.
authors.forename: Steven
authors.initials: S
authors.lastname: Keating
authors.affiliation: MIT Media Lab, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA.
authors.forename: Neri
authors.initials: N
authors.lastname: Oxman
authors.affiliation: Wyss Institute for Biologically Inspired Engineering, Harvard University, Cambridge, Massachusetts 02138, USA.
authors.forename: James C
authors.initials: JC
authors.lastname: Weaver
authors.affiliation: Department of Biomaterials, Max Planck Institute of Colloids and Interfaces, Research Campus Golm, Potsdam 14424, Germany.
authors.forename: Peter
authors.initials: P
authors.lastname: Fratzl
authors.affiliation: School of Materials Science and Engineering, Nanyang Technological University, Singapore 639798, Singapore.|School of Biological Science, Nanyang Technological University, Singapore 639798, Singapore.
authors.forename: Ali
authors.initials: A
authors.lastname: Miserez
authors.affiliation: Department of Biomaterials, Max Planck Institute of Colloids and Interfaces, Research Campus Golm, Potsdam 14424, Germany.
authors.forename: Admir
authors.initials: A
authors.lastname: Masic
mesh_terms: D000818:Animals; D001704:Biopolymers / Q000737:chemistry*; D049832:Decapodiformes / Q000737:chemistry; D006244:Hardness; D006358:Hot Temperature; D055550:Protein Stability; D011506:Proteins / Q000737:chemistry*; D014961:X-Ray Diffraction
chemical_list: D001704:Biopolymers; D011506:Proteins