Polyamines Promote Aragonite Nucleation and Generate Biomimetic Structures
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 a...
| Main Authors: | , , , , , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
Wiley
2023-01-01
|
| Series: | Advanced Science |
| Subjects: | |
| Online Access: | https://doi.org/10.1002/advs.202203759 |
| _version_ | 1797962155676401664 |
|---|---|
| author | Ouassef Nahi Alexander N. Kulak Shuheng Zhang Xuefeng He Zabeada Aslam Martha A. Ilett Ian J. Ford Robert Darkins Fiona C. Meldrum |
| author_facet | Ouassef Nahi Alexander N. Kulak Shuheng Zhang Xuefeng He Zabeada Aslam Martha A. Ilett Ian J. Ford Robert Darkins Fiona C. Meldrum |
| author_sort | Ouassef Nahi |
| collection | DOAJ |
| description | 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. |
| first_indexed | 2024-04-11T01:08:57Z |
| format | Article |
| id | doaj.art-aa3bd28628d443d1a6c7a4361f8a2035 |
| institution | Directory Open Access Journal |
| issn | 2198-3844 |
| language | English |
| last_indexed | 2024-04-11T01:08:57Z |
| publishDate | 2023-01-01 |
| publisher | Wiley |
| record_format | Article |
| series | Advanced Science |
| spelling | doaj.art-aa3bd28628d443d1a6c7a4361f8a20352023-01-04T10:53:44ZengWileyAdvanced Science2198-38442023-01-01101n/an/a10.1002/advs.202203759Polyamines Promote Aragonite Nucleation and Generate Biomimetic StructuresOuassef Nahi0Alexander N. Kulak1Shuheng Zhang2Xuefeng He3Zabeada Aslam4Martha A. Ilett5Ian J. Ford6Robert Darkins7Fiona C. Meldrum8School of Chemistry University of Leeds Woodhouse Lane Leeds LS2 9JT UKSchool of Chemistry University of Leeds Woodhouse Lane Leeds LS2 9JT UKSchool of Chemistry University of Leeds Woodhouse Lane Leeds LS2 9JT UKSchool of Chemistry University of Leeds Woodhouse Lane Leeds LS2 9JT UKSchool of Chemical and Process Engineering University of Leeds Woodhouse Lane Leeds LS2 9JT UKSchool of Chemical and Process Engineering University of Leeds Woodhouse Lane Leeds LS2 9JT UKLondon Centre for Nanotechnology University College London 17–19 Gordon Street London WC1H 0AH UKLondon Centre for Nanotechnology University College London 17–19 Gordon Street London WC1H 0AH UKSchool of Chemistry University of Leeds Woodhouse Lane Leeds LS2 9JT UKAbstract 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.https://doi.org/10.1002/advs.202203759biomineralizationcalcium carbonatemagnesiumnon‐classical crystallizationpolymorph |
| spellingShingle | Ouassef Nahi Alexander N. Kulak Shuheng Zhang Xuefeng He Zabeada Aslam Martha A. Ilett Ian J. Ford Robert Darkins Fiona C. Meldrum Polyamines Promote Aragonite Nucleation and Generate Biomimetic Structures Advanced Science biomineralization calcium carbonate magnesium non‐classical crystallization polymorph |
| title | Polyamines Promote Aragonite Nucleation and Generate Biomimetic Structures |
| title_full | Polyamines Promote Aragonite Nucleation and Generate Biomimetic Structures |
| title_fullStr | Polyamines Promote Aragonite Nucleation and Generate Biomimetic Structures |
| title_full_unstemmed | Polyamines Promote Aragonite Nucleation and Generate Biomimetic Structures |
| title_short | Polyamines Promote Aragonite Nucleation and Generate Biomimetic Structures |
| title_sort | polyamines promote aragonite nucleation and generate biomimetic structures |
| topic | biomineralization calcium carbonate magnesium non‐classical crystallization polymorph |
| url | https://doi.org/10.1002/advs.202203759 |
| work_keys_str_mv | AT ouassefnahi polyaminespromotearagonitenucleationandgeneratebiomimeticstructures AT alexandernkulak polyaminespromotearagonitenucleationandgeneratebiomimeticstructures AT shuhengzhang polyaminespromotearagonitenucleationandgeneratebiomimeticstructures AT xuefenghe polyaminespromotearagonitenucleationandgeneratebiomimeticstructures AT zabeadaaslam polyaminespromotearagonitenucleationandgeneratebiomimeticstructures AT marthaailett polyaminespromotearagonitenucleationandgeneratebiomimeticstructures AT ianjford polyaminespromotearagonitenucleationandgeneratebiomimeticstructures AT robertdarkins polyaminespromotearagonitenucleationandgeneratebiomimeticstructures AT fionacmeldrum polyaminespromotearagonitenucleationandgeneratebiomimeticstructures |