Impact of Mg2+and pH on amorphous calcium carbonate nanoparticle formation: Implications for biomineralization and ocean acidification
成果类型：
Article
署名作者：
Kuhrts, Lucas; Shaked, Hadar; Sklar, Johanna; Prudnikov, Elena; Prevost, Sylvain; Manna, Gouranga; Sztucki, Michael; Katsman, Alexander; Pokroy, Boaz
署名单位：
Technion Israel Institute of Technology; Institut Laue-Langevin (ILL); European Synchrotron Radiation Facility (ESRF)
刊物名称：
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
ISSN/ISSBN：
0027-12460
DOI：
10.1073/pnas.2421961122
发表日期：
2025-05-13
关键词：
small-angle
in-situ
crystal-growth
amino-acids
caco3
water
crystallization
DYNAMICS
摘要：
Crystallization by amorphous calcium carbonate (ACC) particle attachment (CPA) is a prevalent biomineralization mechanism among calcifying organisms. A narrow, controlled size distribution of ACC nanoparticles is essential for macroscopic crystal formation via CPA. Using in situ synchrotron small-angle X-ray scattering, we demonstrate that synthetic magnesium-stabilized ACC (Mg-ACC) nanoparticles form with an exceptionally narrow size distribution near the spinodal line during liquid-liquid phase separation. We monitored ACC formation kinetics at pH 8.4 to 8.9 and Mg2+ contents of 50 to 80%, observing a 2-order magnitude rise in nucleation kinetics for a 0.1 pH increase and a 6-order magnitude rise for a 10% Mg2+ decrease. Within the binodal region, faster nucleation kinetics result in more monodisperse particles, narrowing the particle size distribution by factors of 2 for a pH increase of merely 0.1 and by a factor of 3 for a 10% Mg2+ decrease. While the influence of Mg2+ on calcite biomineralization is well studied, its effect on Mg-ACC formation and particle size distribution-an essential parameter in CPA-based biomineralization pathways-remained unexplored. These findings highlight the delicate interplay of pH and Mg2+ in controlling the kinetics and thermodynamics of Mg-ACC formation, significantly impacting particle size distribution.