@article{SchmittWinterBertinettietal.2015,
  author    = {Schmitt, Clemens Nikolaus Zeno and Winter, Alette and Bertinetti, Luca and Masic, Admir and Strauch, Peter and Harrington, Matthew J.},
  title     = {Mechanical homeostasis of a DOPA-enriched biological coating from mussels in response to metal variation},
  series = {Interface : journal of the Royal Society},
  volume    = {12},
  journal   = {Interface : journal of the Royal Society},
  number    = {110},
  publisher = {Royal Society},
  address   = {London},
  issn      = {1742-5689},
  doi       = {10.1098/rsif.2015.0466},
  pages     = {8},
  year      = {2015},
  abstract  = {Protein metal coordination interactions were recently found to function as crucial mechanical cross-links in certain biological materials. Mussels, for example, use Fe ions from the local environment coordinated to DOPA-rich proteins to stiffen the protective cuticle of their anchoring byssal attachment threads. Bioavailability of metal ions in ocean habitats varies significantly owing to natural and anthropogenic inputs on both short and geological spatio-temporal scales leading to large variations in byssal thread metal composition; however, it is not clear how or if this affects thread performance. Here, we demonstrate that in natural environments mussels can opportunistically replace Fe ions in the DOPA coordination complex with V and Al. In vitro removal of the native DOPA metal complexes with ethylenediaminetetraacetic acid and replacement with either Fe or V does not lead to statistically significant changes in cuticle performance, indicating that each metal ion is equally sufficient as a DOPA cross-linking agent, able to account for nearly 85\% of the stiffness and hardness of the material. Notably, replacement with Al ions also leads to full recovery of stiffness, but only 82\% recovery of hardness. These findings have important implications for the adaptability of this biological material in a dynamically changing and unpredictable habitat.},
  language  = {en}
}
@article{DegtyarHarringtonPolitietal.2014,
  author    = {Degtyar, Elena and Harrington, Matthew J. and Politi, Yael and Fratzl, Peter},
  title     = {The mechanical role of metal ions in biogenic protein-based materials},
  series = {Angewandte Chemie : a journal of the Gesellschaft Deutscher Chemiker ; International edition},
  volume    = {53},
  journal   = {Angewandte Chemie : a journal of the Gesellschaft Deutscher Chemiker ; International edition},
  number    = {45},
  publisher = {Wiley-VCH},
  address   = {Weinheim},
  issn      = {1433-7851},
  doi       = {10.1002/anie.201404272},
  pages     = {12026 -- 12044},
  year      = {2014},
  abstract  = {Protein-metal interactions-traditionally regarded for roles in metabolic processes-are now known to enhance the performance of certain biogenic materials, influencing properties such as hardness, toughness, adhesion, and self-healing. Design principles elucidated through thorough study of such materials are yielding vital insights for the design of biomimetic metallopolymers with industrial and biomedical applications. Recent advances in the understanding of the biological structure-function relationships are highlighted here with a specific focus on materials such as arthropod biting parts, mussel byssal threads, and sandcastle worm cement.},
  language  = {en}
}