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Title: Phase Transformation Mechanism of Amorphous Calcium Phosphate to Hydroxyapatite Investigated by Liquid-Cell Transmission Electron Microscopy

Journal Article · · Crystal Growth and Design

Crystallization via phase transformation of a metastable precursor is a ubiquitous and effective strategy used by living systems to direct the growth of crystalline nanomaterials with remarkable functional properties. However, determining the exact process by which transformation occurs at the nanoscale is a difficult challenge. In this work, the recrystallization process of amorphous calcium phosphate (ACP) to hydroxyapatite (HAP) is explored by liquid-cell transmission electron microscopy. The effect of confinement in the liquid-cell is found to increase the size of ACP nanoparticles. In the presence of Mg2+, these large ACP nanoparticles transform to HAP by first dissolving from the interior to create a hollow structure, after which HAP forms preferentially on the surface and then subsequently in the bulk solution. We propose that the preferential dissolution within ACP particles is due to a change in the structure and/or chemistry of the ACP surface, likely associated with dehydration before crystallization of HAP. These results imply an important role of the confined environment of the liquid-cell in regulating the size of ACP particles, which then affects the surface structure and the detailed dissolution–recrystallization pathway. Moreover, we stress the key role of Mg2+ in controlling HAP formation by stabilizing ACP via reduction in ACP solubility. This work provides a better understanding of the roles of additives and confinement during the phase transformation of ACP to HAP through dissolution and recrystallization.

Research Organization:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division; National Natural Science Foundation of China (NSFC)
Grant/Contract Number:
AC05-76RL01830
OSTI ID:
1824302
Report Number(s):
PNNL-SA--164157
Journal Information:
Crystal Growth and Design, Journal Name: Crystal Growth and Design Journal Issue: 9 Vol. 21; ISSN 1528-7483
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

References (44)

Biological and Medical Significance of Calcium Phosphates journal September 2002
Solid-State Transformation of Amorphous Calcium Carbonate to Aragonite Captured by CryoTEM journal August 2017
Synergistic Approach to Elucidate the Incorporation of Magnesium Ions into Hydroxyapatite journal December 2014
Establishing the Transitory Existence of Amorphous Phases in Crystallization Pathways by the CLASSIC NMR Technique journal November 2018
Review: Nucleation in solutions revisited journal July 2003
Magnesium stabilization of amorphous calcium phosphate: A kinetic study journal July 1974
Evolution of the magnesium incorporated amorphous calcium phosphate to nano-crystallized hydroxyapatite in alkaline solution journal December 2011
Nonclassical Crystallization of Amorphous Calcium Carbonate in the Presence of Phosphate Ions journal December 2020
Direct Nanoscale Imaging Reveals the Growth of Calcite Crystals via Amorphous Nanoparticles journal March 2016
Synergic Effect of Sr 2+ and Mg 2+ on the Stabilization of Amorphous Calcium Phosphate journal September 2018
Control of Calcium Phosphate Nucleation and Transformation through Interactions of Enamelin and Amelogenin Exhibits the “Goldilocks Effect” journal October 2018
Disordering the Disorder as the Route to a Higher Order: Incoherent Crystallization of Calcium Phosphate through Amorphous Precursors journal July 2019
Short-Range Structure of Amorphous Calcium Hydrogen Phosphate journal April 2019
Formation of Hydroxyapatite via Transformation of Amorphous Calcium Phosphate in the Presence of Alginate Additives journal November 2019
On Grounds of the Memory Effect in Amorphous and Crystalline Apatite: Kinetics of Crystallization and Biological Response journal April 2018
Toward a Detailed Understanding of Magnesium Ions on Hydroxyapatite Crystallization Inhibition journal January 2014
Conversion of amorphous calcium phosphate to microcrystalline hydroxyapatite. A pH-dependent, solution-mediated, solid-solid conversion journal September 1973
Solid-State Phase Transformation and Self-Assembly of Amorphous Nanoparticles into Higher-Order Mineral Structures journal June 2020
Capturing the Moment of Emergence of Crystal Nucleus from Disorder journal January 2021
Mineral Formation in the Larval Zebrafish Tail Bone Occurs via an Acidic Disordered Calcium Phosphate Phase journal October 2016
Amorphous-Phase-Mediated Crystallization of Ni Nanocrystals Revealed by High-Resolution Liquid-Phase Electron Microscopy journal January 2019
New Horizons of Nonclassical Crystallization journal May 2019
Direct Observation of Amorphous Precursor Phases in the Nucleation of Protein–Metal–Organic Frameworks journal January 2020
Size Effect on Nucleation Rate for Homogeneous Crystallization of Nanoscale Water Film journal August 2013
Electron–Water Interactions and Implications for Liquid Cell Electron Microscopy journal September 2014
Evolution of Amorphous Calcium Phosphate to Hydroxyapatite Probed by Gold Nanoparticles journal August 2008
Nonclassical nucleation and growth of inorganic nanoparticles journal June 2016
Onset of heterogeneous crystal nucleation in colloidal suspensions journal March 2004
Calcium carbonate nucleation driven by ion binding in a biomimetic matrix revealed by in situ electron microscopy journal January 2015
Connecting energetics to dynamics in particle growth by oriented attachment using real-time observations journal February 2020
Biomineralization of calcium phosphate revealed by in situ liquid-phase electron microscopy journal November 2018
Insights into the kinetics of thermally induced crystallization of amorphous calcium phosphate journal January 2018
Mystery of the transformation from amorphous calcium phosphate to hydroxyapatite journal January 2010
Size Effect in Heterogeneous Nucleation journal September 1958
Nucleation in aqueous NaCl solutions shifts from 1-step to 2-step mechanism on crossing the spinodal journal March 2019
Transformation and crystallization energetics of synthetic and biogenic amorphous calcium carbonate journal September 2010
Shape-preserving amorphous-to-crystalline transformation of CaCO 3 revealed by in situ TEM journal February 2020
Revealing nanoscale mineralization pathways of hydroxyapatite using in situ liquid cell transmission electron microscopy journal November 2020
Direction-Specific Interactions Control Crystal Growth by Oriented Attachment journal May 2012
In situ TEM imaging of CaCO3 nucleation reveals coexistence of direct and indirect pathways journal September 2014
Amorphous intergranular phases control the properties of rodent tooth enamel journal February 2015
Crystallization by particle attachment in synthetic, biogenic, and geologic environments journal July 2015
Apatite Formation: Why It May Not Work as Planned, and How to Conclusively Identify Apatite Compounds journal January 2013
Demineralization–remineralization dynamics in teeth and bone journal January 2016