Nahi, O, Kulak, A orcid.org/0000-0002-2798-9301, Zhang, S et al. (6 more authors) (2023) Polyamines Promote Aragonite Nucleation and Generate Biomimetic Structures. Advanced Science, 10 (1). 2203759. ISSN 2198-3844
Abstract
Calcium carbonate biomineralization is remarkable for the ability of organisms to produce calcite or aragonite with perfect fidelity, where this is commonly attributed to specific anionic biomacromolecules. However, it is proven difficult to mimic this behavior using synthetic or biogenic anionic organic molecules. Here, it is shown that cationic polyamines ranging from small molecules to large polyelectrolytes can exert exceptional control over calcium carbonate polymorph, promoting aragonite nucleation at extremely low concentrations but suppressing its growth at high concentrations, such that calcite or vaterite form. The aragonite crystals form via particle assembly, giving nanoparticulate structures analogous to biogenic aragonite, and subsequent growth yields stacked aragonite platelets comparable to structures seen in developing nacre. This mechanism of polymorph selectivity is captured in a theoretical model based on these competing nucleation and growth effects and is completely distinct from the activity of magnesium ions, which generate aragonite by inhibiting calcite. Profiting from these contrasting mechanisms, it is then demonstrated that polyamines and magnesium ions can be combined to give unprecedented control over aragonite formation. These results give insight into calcite/aragonite polymorphism and raise the possibility that organisms may exploit both amine-rich organic molecules and magnesium ions in controlling calcium carbonate polymorph.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2022 The Authors. Advanced Science published by Wiley-VCH GmbH. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited. |
Keywords: | biomineralization; calcium carbonate; magnesium; non-classical crystallization; polymorph |
Dates: |
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Institution: | The University of Leeds |
Academic Units: | The University of Leeds > Faculty of Engineering & Physical Sciences (Leeds) > School of Chemical & Process Engineering (Leeds) The University of Leeds > Faculty of Engineering & Physical Sciences (Leeds) > School of Chemistry (Leeds) > Inorganic Chemistry (Leeds) |
Funding Information: | Funder Grant number EPSRC (Engineering and Physical Sciences Research Council) EP/R018820/1 EU - European Union 788968 EPSRC (Engineering and Physical Sciences Research Council) EP/T006331/1 |
Depositing User: | Symplectic Publications |
Date Deposited: | 04 Nov 2022 15:27 |
Last Modified: | 25 Jun 2023 23:08 |
Status: | Published |
Publisher: | Wiley Open Access |
Identification Number: | 10.1002/advs.202203759 |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:192761 |