ArticleProceedings of the National Academy of Sciences of the United States of America2011
In situ molecular NMR picture of bioavailable calcium stabilized as amorphous CaCO₃ biomineral in crayfish gastroliths.
Article in Proceedings of the National Academy of Sciences of the United States of America, 2011. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 23 papers.
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23 citing papers in PubMed, 89 citations in OpenAlex.
- Synthesis of Nanoscale Precipitated Calcium Carbonate: Additive-Free Precipitation and Chain-like Structure Evolution.Materials (Basel, Switzerland) · 2026Article
- Magnesium- and biopolymer-stabilized ACC and ACP form the body-wall spicules of Baptodoris cinnabarina (Doridida, Gastropoda).Scientific reports · 2026Article
- Exponential crystallization in corals.Nature communications · 2026Article
- The Role of Confinement in Biomineralization.Chemical reviews · 2025Review
- Observation of Transient Prenucleation Species of Calcium Carbonate by DNP-Enhanced NMR.The journal of physical chemistry letters · 2024Article
- Small-Molecular-Weight Additives Modulate Calcification by Interacting with Prenucleation Clusters on the Molecular Level.Angewandte Chemie (International ed. in English) · 2022Article
- In situ carbon dioxide capture to co-produce 1,3-propanediol, biohydrogen and micro-nano calcium carbonate from crude glycerol by Clostridium butyricum.Biotechnology for biofuels and bioproducts · 2022Article
- Self-transformation of solid CaCOIUCrJ · 2022Article
- Inorganic phosphate in growing calcium carbonate abalone shell suggests a shared mineral ancestral precursor.Nature communications · 2022Article
- Faster Crystallization during Coral Skeleton Formation Correlates with Resilience to Ocean Acidification.Journal of the American Chemical Society · 2022Article
- Iron phosphate mediated magnetite synthesis: a bioinspired approach.Chemical science · 2021Article
- Genes encoding putative bicarbonate transporters as a missing molecular link between molt and mineralization in crustaceans.Scientific reports · 2021Article
- Resilient Intracrystalline Occlusions: A Solid-State NMR View of Local Structure as It Tunes Bulk Lattice Properties.Journal of the American Chemical Society · 2020Article
- How corals made rocks through the ages.Global change biology · 2020Review
- The "Missing" Bicarbonate in COJournal of the American Chemical Society · 2018Article
- Minerals in the pre-settled coral Stylophora pistillata crystallize via protein and ion changes.Nature communications · 2018Article
- Calcium phosphate mineralization is widely applied in crustacean mandibles.Scientific reports · 2016Article
- Intraspecific Differences in Biogeochemical Responses to Thermal Change in the Coccolithophore Emiliania huxleyi.PloS one · 2016Article
- Solid-state NMR studies of proteins immobilized on inorganic surfaces.Solid state nuclear magnetic resonance · 2015Review
- NMR investigation of the role of osteocalcin and osteopontin at the organic-inorganic interface in bone.Langmuir : the ACS journal of surfaces and colloids · 2013Article
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Authors and funding
7 authors at 2 institutions in 1 country.
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No grant is acknowledged in the PubMed record.
Abstract
Bioavailable calcium is maintained by some crustaceans, in particular freshwater crayfish, by stabilizing amorphous calcium carbonate (ACC) within reservoir organs--gastroliths, readily providing the Ca(2+) needed to build a new exoskeleton. Despite the key scientific and biomedical importance of the in situ molecular-level picture of biogenic ACC and its stabilization in a bioavailable form, its description has eluded efforts to date. Herein, using multinuclear NMR, we accomplish in situ molecular-level characterization of ACC within intact gastroliths of the crayfish Cherax quadricarinatus. In addition to the known CaCO(3), chitin scaffold and inorganic phosphate (Pi), we identify within the gastrolith two primary metabolites, citrate and phosphoenolpyruvate (PEP) and quantify their abundance by applying solution NMR techniques to the gastrolith "soluble matrix." The long-standing question on the physico-chemical state of ACC stabilizing, P-bearing moieties within the gastrolith is answered directly by the application of solid state rotational-echo double-resonance (REDOR) and transferred-echo double-resonance (TEDOR) NMR to the intact gastroliths: Pi and PEP are found molecularly dispersed throughout the ACC as a solid solution. Citrate carboxylates are found < 5 Å from a phosphate (intermolecular CP distance), an interaction that must be mediated by Ca(2+). The high abundance and extensive interactions of these molecules with the ACC matrix identify them as the central constituents stabilizing the bioavailable form of calcium. This study further emphasizes that it is imperative to characterize the intact biogenic CaCO(3). Solid state NMR spectroscopy is shown to be a robust and accessible means of determining composition, internal structure, and molecular functionality in situ.
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