Phase transitions in biogenic amorphous calcium carbonate
Open accessAbstract
Crystalline biominerals do not resemble faceted crystals. Current explanations for this property involve formation via amorphous phases. Using X-ray absorption near-edge structure (XANES) spectroscopy and photoelectron emission microscopy (PEEM), here we examine forming spicules in embryos of Strongylocentrotus purpuratus sea urchins, and observe a sequence of three mineral phases: hydrated amorphous calcium carbonate (ACC·H 2 O) → dehydrated amorphous calcium carbonate (ACC) → calcite. Unexpectedly, we find ACC·H 2 O-rich nanoparticles that persist after the surrounding mineral has dehydrated and crystallized. Protein matrix components occluded within the mineral must inhibit ACC·H 2 O dehydration. We devised an in vitro, also using XANES-PEEM, assay to identify spicule proteins that may play a role in stabilizing various mineral phases, and found that the most abundant occluded matrix protein in the sea urchin spicules, SM50, stabilizes ACC·H 2 O in vitro.
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Non-classical crystallization is a common route to the formation of carbonate shells and skeletons in invertebrates, as evidenced by transient ACC.
“Growing experimental evidence showed that NCC is a common route to the formation of carbonate shells and skeletons in invertebrates, as evidenced by the presence of transient ACC (Addadi et al., 2003;Gong et al., 2012;Grünewald et al., 2022).”
From A non-classical crystallization mechanism of microbially-induced disordered dolomite (2024) · cites this paper as Gong et al., 2012
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- Authors
- Gong, Y. U. T., Killian, C. E., Olson, I. C., Appathurai, N. P., Amasino, A. L., Martin, M. C., Holt, L. J., Wilt, F. H., & Gilbert, P. U. P. A.
- Affiliations
- University of Wisconsin–Madison (US)
- Lawrence Berkeley National Laboratory (US)
- University of California, Berkeley (US)
- Venue
- Proceedings of the National Academy of Sciences
- Publisher
- National Academy of Sciences
- Published
- 2012-04-04
- Volume
- 109
- Issue
- 16
- Pages
- 6088-6093
- ISSN
- 0027-8424 (ISSN-L)
- 1091-6490
- PMC
- PMC3341025
- OpenAlex
- W2005413325
- Cited by
- 304
- References
- 62
- Citations by year
- 2026: 19 · 2025: 22 · 2024: 20 · 2023: 18 · 2022: 21 · 2021: 26 · 2020: 21 · 2019: 26 · 2018: 16 · 2017: 23 · 2016: 26 · 2015: 20 · 2014: 20 · 2013: 20 · 2012: 5
- FWCI
- 8.43
- Type
- journal article
- Language
- en
- Open access
- bronze
- doi.org
- Locations
- Proceedings of the National Academy of Sciences (publishedVersion)
- PubMed Central (publishedVersion)
- PubMed (publishedVersion)
- Funders
- National Science Foundation (DEAC02-05CH11231, 0613972, 1105167, 0537588)
- U.S. Department of Energy (-AC02-05CH11231, DE‐FG02‐, FG02-07ER15899, 05CH11231, DE AC02 05CH11231, DEFG0207ER15899, DE-AC02-)
- University of Wisconsin-Madison (DE-AC02-05CH11231)
- Division of Materials Research (DMR-1105167)
- Division of Chemistry (DE-AC02-05CH11231)
- Topics
- Physical Sciences › Materials Science › Biomaterials › Calcium Carbonate Crystallization and Inhibition
- Physical Sciences › Environmental Science › Environmental Engineering › Microbial Applications in Construction Materials
- Health Sciences › Medicine › Rheumatology › Bone and Dental Protein Studies
- Keywords
- amorphous calcium carbonate, biomineralization, Strongylocentrotus purpuratus, phase transitions, calcite crystallization, protein matrix
- MeSH terms
- Animals, Biocompatible Materials, Calcification, Physiologic, Calcium Carbonate, Crystallization, Embryo, Nonmammalian, Microscopy, Electron, Minerals, Water, Extracellular Matrix Proteins, Gene Expression Regulation, Developmental, Reverse Transcriptase Polymerase Chain Reaction, Phase Transition, Strongylocentrotus purpuratus, X-Ray Absorption Spectroscopy
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