Pourbaix-Guided Mineralization and Site-Selective Photoluminescence Properties of Rare Earth Substituted B-Type Carbonated Hydroxyapatite Nanocrystals.

ABSTRACT: Rare-earth labeling in biological apatite could provide critical information for the pathologic transition (osteoclastic) and physiologic regeneration (osteogenesis) of bone and teeth because of their characteristic site-sensitive fluorescence in different coordinative conditions of various tissues in many biological processes. However, the rare-earth labeling method for biological apatites, i.e., carbonated-hydroxyapatite, has been rarely found in the literature. In this paper, we report a Pourbaix-diagram guided mineralizing strategy to controllable carbonation and doping of rare-earth ions in the hydroxyapatite (HA) lattice. The carbonation process of hydroxyapatite was achieved by controllable mineralization in hydrothermal condition with K₂CO₃ as the carbonate source, which results into the pure B-type carbonated hydroxyapatite (CHA) with tunable carbonate substitution degree. All of the as-synthesized materials crystalized into P63/m (No. 176) space group with the lattice parameter of a decreases and c increases with the increasing of carbonate content in the reactants. Structural refinement results revealed that the substitution of planar CO₃^2- is superimposed on one of the faces of PO₄^3- tetrahedral sub-units with a rotation angle of 30° in reference to c-axis. All of the hydrothermally synthesized CHA nanocrystals show hexagonal rod-like morphology with the length of 70-110 nm and diameter of 21-35 nm, and the decreasing length/diameter ratio from 3.61 to 2.96 from low to high carbonated level of the samples. Five rare-earth cations, of Pr³⁺, Sm³⁺, Eu³⁺, Tb³⁺, and Ho³⁺, were used as possible probe ions that can be doped into either HA or CHA lattice. The site-preference of Tb³⁺ doping is the same in the crystallographic site of HA and CHA according to characteristic emission peaks of ⁵D₄-⁷F_j (j = 3-6) transitions in their photoluminescent spectroscopy. Our work provides a controllable carbonation method for rare-earth labeling hydroxyapatite nanomaterials with potential biologically active implant powders for bone repair and tissue regeneration.

SUBMITTER: Liu P 

PROVIDER: S-EPMC7864488 | biostudies-literature | 2021 Jan

REPOSITORIES: biostudies-literature