A molecular view of peptoid-induced acceleration of calcite growth

Zhang, Mingyi; Chen, Ying; Wu, Chunhui; Zheng, Renyu; Xia, Ying; Saccuzzo, Emily G.; Trinh, Thi Kim Hoang; Mondarte, Evan Angelo Quimada; Nakouzi, Elias; Rad, Behzad; Legg, Benjamin A.; Shaw, Wendy J.; Tao, Jinhui; De Yoreo, James J.; Chen, Chun-Long

doi:10.1073/pnas.2412358121

Title: A molecular view of peptoid-induced acceleration of calcite growth

Journal Article · Tue Oct 29 00:00:00 UTC 2024 · Proceedings of the National Academy of Sciences of the United States of America

DOI: https://doi.org/10.1073/pnas.2412358121 · OSTI ID:2475449

^[1];

^[1]; Wu, Chunhui ^[2]; Zheng, Renyu ^[2]; Xia, Ying ^[3]; Saccuzzo, Emily G. ^[1];

^[1]; Mondarte, Evan Angelo Quimada ^[1];

^[1];

^[4]; Legg, Benjamin A. ^[1];

^[1]; Tao, Jinhui ^[1]; De Yoreo, James J. ^[2];

^[2]

Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); Univ. of Washington, Seattle, WA (United States)
Univ. of Washington, Seattle, WA (United States)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Molecular Foundry

The extensive deposits of calcium carbonate (CaCO₃) generated by marine organisms constitute the largest and oldest carbon dioxide (CO₂) reservoir. These organisms utilize macromolecules like peptides and proteins to facilitate the nucleation and growth of carbonate minerals, serving as an effective method for CO₂ sequestration. However, the precise mechanisms behind this process remain elusive. In this study, we report the use of sequence-defined peptoids, a class of peptidomimetics, to achieve the accelerated calcite step growth kinetics with the molecular level mechanistic understanding. By designing peptoids with hydrophilic and hydrophobic blocks, we systematically investigated the acceleration in step growth rate of calcite crystals using in situ atomic force microscopy (AFM), varying peptoid sequences and concentrations, CaCO₃ supersaturations, and the ratio of Ca²⁺/ HCO₃-. Mechanistic studies using NMR, three-dimensional fast force mapping (3D FFM), and isothermal titration calorimetry (ITC) were conducted to reveal the interactions of peptoids with Ca²⁺ and HCO₃- ions in solution, as well as the effect of peptoids on solvation and energetics of calcite crystal surface. Our results indicate the multiple roles of peptoid in facilitating HCO₃- deprotonation, Ca²⁺ desolvation, and the disruption of interfacial hydration layers of the calcite surface, which collectively contribute to a peptoid-induced acceleration of calcite growth. These findings provide guidelines for future design of sequence-specific biomimetic polymers as crystallization promoters, offering potential applications in environmental remediation (such as CO₂ sequestration), biomedical engineering, and energy storage where fast crystallization is preferred.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: US Department of Energy; USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22), Scientific User Facilities Division (SC-22.3 ); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-05CH11231; AC05-76RL01830

OSTI ID:: 2475449

Report Number(s):: PNNL-SA--199782; https://escholarship.org/uc/item/338279pm; ark:/13030/qt338279pm

Journal Information:: Proceedings of the National Academy of Sciences of the United States of America, Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Issue: 45 Vol. 121; ISSN 1091-6490; ISSN 0027-8424

Publisher:: National Academy of SciencesCopyright Statement

Country of Publication:: United States

Language:: English

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