Directing polymorph specific calcium carbonate formation with de novo protein templates

Fatima A. Davila-Hernandez, Biao Jin (), Harley Pyles, Shuai Zhang, Zheming Wang, Timothy F. Huddy, Asim K. Bera, Alex Kang, Chun-Long Chen, James J. Yoreo () and David Baker ()
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Fatima A. Davila-Hernandez: University of Washington
Biao Jin: Pacific Northwest National Laboratory
Harley Pyles: University of Washington
Shuai Zhang: Pacific Northwest National Laboratory
Zheming Wang: Pacific Northwest National Laboratory
Timothy F. Huddy: University of Washington
Asim K. Bera: University of Washington
Alex Kang: University of Washington
Chun-Long Chen: Pacific Northwest National Laboratory
James J. Yoreo: Pacific Northwest National Laboratory
David Baker: University of Washington

Nature Communications, 2023, vol. 14, issue 1, 1-11

Abstract: Abstract Biomolecules modulate inorganic crystallization to generate hierarchically structured biominerals, but the atomic structure of the organic-inorganic interfaces that regulate mineralization remain largely unknown. We hypothesized that heterogeneous nucleation of calcium carbonate could be achieved by a structured flat molecular template that pre-organizes calcium ions on its surface. To test this hypothesis, we design helical repeat proteins (DHRs) displaying regularly spaced carboxylate arrays on their surfaces and find that both protein monomers and protein-Ca2+ supramolecular assemblies directly nucleate nano-calcite with non-natural {110} or {202} faces while vaterite, which forms first in the absence of the proteins, is bypassed. These protein-stabilized nanocrystals then assemble by oriented attachment into calcite mesocrystals. We find further that nanocrystal size and polymorph can be tuned by varying the length and surface chemistry of the designed protein templates. Thus, bio-mineralization can be programmed using de novo protein design, providing a route to next-generation hybrid materials.

Date: 2023
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DOI: 10.1038/s41467-023-43608-1

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