Impacts of Initial Ca/P on Amorphous Calcium Phosphate

Hoeher, Alexandria J.; Mergelsberg, Sebastian T.; Borkiewicz, Olaf J.; Michel, F. Marc

doi:10.1021/acs.cgd.1c00058

Impacts of Initial Ca/P on Amorphous Calcium Phosphate

Journal Article · Thu Jun 03 00:00:00 EDT 2021 · Crystal Growth and Design

DOI:https://doi.org/10.1021/acs.cgd.1c00058· OSTI ID:1833534

^[1]; ^[2]; Borkiewicz, Olaf J. ^[3]; Michel, F. Marc ^[1]

Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)
Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Argonne National Lab. (ANL), Argonne, IL (United States)

Amorphous calcium phosphate (ACP) is a metastable phase in the crystallization pathway of calcium phosphates. Understanding its chemical and structural properties could provide critical insights into biomineralization mechanisms. Of particular interest is the impact of the initial Ca/P on the structure of ACP. Further, the influence of Ca/P on the size, precipitate chemistry, and transformation of ACP is crucial to understanding the metastability of amorphous phosphates. In situ pair distribution function (PDF) analysis results 5 min after mixing show that the Ca-P bonding geometry varies from predominantly monodentate, to mixed monodentate and bidentate, to predominantly bidentate as Ca/P increases from 0.2 to 5.0. This relationship is consistent across a pH range of 6-11. Samples with only monodentate Ca-P geometries transform directly to hydroxylapatite, while samples some or all bidentate geometries form brushite. Regardless of the initial ratio, the Ca/P of precipitates is close to 1.0. In situ small-angle X-ray scattering shows particle size increases with increasing Ca/P. This is the first evidence of structural variations in ACP and is directly linked to system chemistry. Finally, synthesis of ACP with monodentate Ca-P geometries is a promising method to control the crystallization pathway to form hydroxylapatite at circumneutral pH without stabilizing ions.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE; Virginia Polytechnic Institute and State University (Virginia Tech)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1833534

Journal Information:: Crystal Growth and Design, Journal Name: Crystal Growth and Design Journal Issue: 7 Vol. 21; ISSN 1528-7483

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Amorphous calcium phosphate
brushite
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in situ X-ray total scattering
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Impacts of Initial Ca/P on Amorphous Calcium Phosphate

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