Self-Assembly of a Barnacle Cement Protein (MrCP20) into Adhesive Nanofibrils with Concomitant Regulation of CaCO3 Polymorphism

Harini Mohanram, Tristan Georges, Konstantin Pervushin, Thierry Azaïs, Ali Miserez*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

11 Citations (Scopus)

Abstract

Barnacles are convenient model organisms to study both biomineralization and bioadhesion phenomena. They secrete a proteinaceous adhesive from cement proteins (CPs) to strongly attach to solid immersed substrates. More recently, it has been suggested that some CPs also play a key role in regulating the calcification of barnacles’ protective shells. In this study, combining both solution and solid-state NMR spectroscopy, Raman and infrared spectroscopy studies, and atomic force microscopy (AFM) and transmission electron microscopy (TEM) imaging, we have explored the CaCO3 mineralization pathway regulated by Megabalanus rosa CP 20 (MrCP20). Our data show that MrCP20 can sequestrate inorganic calcium and carbonate ions from the solution state, which quickly coarsen into liquid-like microdroplets and subsequently form protovaterite amorphous CaCO3 (ACC) particles. This pathway leads to the stabilization of the metastable vaterite polymorphism of CaCO3. Simultaneously, AFM and TEM investigations show that MrCP20 undergoes fibrillization triggered by a pH drift arising during CaCO3 mineralization, leading to amyloid-like nanofibrils. Based on protein NMR, this mechanism appears to be stabilized by the reduction of intramolecular disulfide bonds. Collectively, our results demonstrate that MrCP20 plays a synergistic role of regulating CaCO3 biomineralization while concomitantly self-assembling into adhesive nanofibrils.

Original languageEnglish
Pages (from-to)9715-9724
Number of pages10
JournalChemistry of Materials
Volume33
Issue number24
DOIs
Publication statusPublished - Dec 28 2021
Externally publishedYes

Bibliographical note

Publisher Copyright:
© 2021 American Chemical Society.

ASJC Scopus Subject Areas

  • General Chemistry
  • General Chemical Engineering
  • Materials Chemistry

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