Polymeric materials produced from fossil fuels have been
intimately
linked to the development of industrial activities in the 20th century
and, consequently, to the transformation of our way of living. While
this has brought many benefits, the fabrication and disposal of these
materials is bringing enormous sustainable challenges. Thus, materials
that are produced in a more sustainable fashion and whose degradation
products are harmless to the environment are urgently needed. Natural
biopolymerswhich can compete with and sometimes surpass the
performance of synthetic polymersprovide a great source of
inspiration. They are made of natural chemicals, under benign environmental
conditions, and their degradation products are harmless. Before these
materials can be synthetically replicated, it is essential to elucidate
their chemical design and biofabrication. For protein-based materials,
this means obtaining the complete sequences of the proteinaceous building
blocks, a task that historically took decades of research. Thus, we
start this review with a historical perspective on early efforts to
obtain the primary sequences of load-bearing proteins, followed by
the latest developments in sequencing and proteomic technologies that
have greatly accelerated sequencing of extracellular proteins. Next,
four main classes of protein materials are presented, namely fibrous
materials, bioelastomers exhibiting high reversible deformability,
hard bulk materials, and biological adhesives. In each class, we focus
on the design at the primary and secondary structure levels and discuss
their interplays with the mechanical response. We finally discuss
earlier and the latest research to artificially produce protein-based
materials using biotechnology and synthetic biology, including current
developments by start-up companies to scale-up the production of proteinaceous
materials in an economically viable manner.