Coordination chemistry of Ca sites at the surface of nanosized hydroxyapatite: interaction with H₂O and CO

Philosophical Transactions. Series A, Mathematical, Physical, and Engineering Sciences
Vera BolisNorberto Roveri

Abstract

The affinity towards water of a selection of well-defined, nanostructured hydroxyapatite (HA) samples was investigated by H(2)O vapour adsorption microcalorimetry and infrared (IR) spectroscopy. A large hydrophilicity of all investigated materials was confirmed. The surface features of hydrated HA were investigated on the as-synthesized samples pre-treated in mild conditions at T=303 K, whereas dehydrated HA features were characterized on samples activated at T=573 K. The relatively large hydrophilicity of the hydrated surface (-Δ(ads)H~100-50 kJ mol(-1)) was due to the interaction of water with the highly polarized H(2)O molecules strongly coordinated to the surface Ca(2+) cations. At the dehydrated surface, exposing coordinatively unsaturated (cus) Ca(2+) cations, H(2)O was still molecularly adsorbed but more strongly (-Δ(ads)H~120-90 kJ mol(-1)). The use of CO adsorption to quantify the Lewis acidic strength of HA surface sites revealed only a moderate strength of cus Ca(2+) cations, as confirmed by both microcalorimetric and IR spectroscopic measurements and ab initio calculations. This result implies that the large HA/H(2)O interaction energy is due to the interplay between cus Ca(2+) sites and nearby hydrophilic PO(4) gro...Continue Reading

References

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Citations

Feb 22, 2012·Philosophical Transactions. Series A, Mathematical, Physical, and Engineering Sciences·A N Cormack, A Tilocca
Aug 31, 2013·Journal of Nanoparticle Research : an Interdisciplinary Forum for Nanoscale Science and Technology·Lukasz Pajchel, Waclaw Kolodziejski
Jul 15, 2015·Applied Spectroscopy·Joanna KolmasWaclaw Kolodziejski
Nov 7, 2013·Nature Materials·Yan WangNadine Nassif
Aug 23, 2017·Scientific Reports·Pavlo IvanchenkoYuriy Sakhno

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