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Proc Natl Acad Sci U S A
2012 Apr 17;10916:6088-93. doi: 10.1073/pnas.1118085109.
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Phase transitions in biogenic amorphous calcium carbonate.
Gong YU
,
Killian CE
,
Olson IC
,
Appathurai NP
,
Amasino AL
,
Martin MC
,
Holt LJ
,
Wilt FH
,
Gilbert PU
.
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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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