Crystallinity and Compositional Changes in Carbonated Apatites: Evidence from P Solid-state NMR, Raman, and AFM Analysis

Overview

Journal J Solid State Chem

Date 2013 Nov 26

PMID 24273344

Citations 22

Authors

John-David P McElderry

Peizhi Zhu

Kamal H Mroue

Jiadi Xu

Barbara Pavan

Ming Fang

Guisheng Zhao

Erin McNerny

David H Kohn

Renny T Franceschi

Mark M Banaszak Holl

Mary M J Tecklenburg

Ayyalusamy Ramamoorthy

Michael D Morris

Affiliations

Soon will be listed here.

Abstract

Solid-state (magic-angle spinning) NMR spectroscopy is a useful tool for obtaining structural information on bone organic and mineral components and synthetic model minerals at the atomic-level. Raman and P NMR spectral parameters were investigated in a series of synthetic B-type carbonated apatites (CAps). Inverse P NMR linewidth and inverse Raman PO ν bandwidth were both correlated with powder XRD crystallinity over the 0.3-10.3 wt% CO range investigated. Comparison with bone powder crystallinities showed agreement with values predicted by NMR and Raman calibration curves. Carbonate content was divided into two domains by the P NMR chemical shift frequency and the Raman phosphate ν band position. These parameters remain stable except for an abrupt transition at 6.5 wt% carbonate, a composition which corresponds to an average of one carbonate per unit cell. This near-binary distribution of spectroscopic properties was also found in AFM-measured particle sizes and Ca/P molar ratios by elemental analysis. We propose that this transition differentiates between two charge-balancing ion-loss mechanisms as measured by Ca/P ratios. These results define a criterion for spectroscopic characterization of B-type carbonate substitution in apatitic minerals.

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