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Crystals 2017, 7(2), 57; doi:10.3390/cryst7020057

Molecular Dynamics Simulations of Hydroxyapatite Nanopores in Contact with Electrolyte Solutions: The Effect of Nanoconfinement and Solvated Ions on the Surface Reactivity and the Structural, Dynamical, and Vibrational Properties of Water

1
Queen Mary University of London, School of Biological and Chemical Sciences, Mile End Road, E1 4NS London, UK
2
Université Paris-Est, Laboratoire Modélisation et Simulation Multi Echelle, MSME UMR 8208 CNRS, 94010 Créteil cedex, France
3
Sri Ramaswamy Memorial University, SRM Research Institute and Department of Chemistry, Kattankulathur 603203, Tamil Nadu, India
4
Université Paris-Est, Laboratoire Modélisation et Simulation Multi Echelle, MSME UMR 8208 CNRS, 77454 Marne-la-Vallée cedex 2, France
5
Cardiff University, School of Chemistry, Main Building, Park Place, Cardiff CF10 3AT, UK
*
Authors to whom correspondence should be addressed.
Academic Editors: Helmut Cölfen and Hugo K. Christenson
Received: 23 October 2016 / Revised: 23 January 2017 / Accepted: 10 February 2017 / Published: 18 February 2017
(This article belongs to the Special Issue Effects of Confinement and Topography on Crystallization)
View Full-Text   |   Download PDF [5912 KB, uploaded 18 February 2017]   |  

Abstract

Hydroxyapatite, the main mineral phase of mammalian tooth enamel and bone, grows within nanoconfined environments and in contact with aqueous solutions that are rich in ions. Hydroxyapatite nanopores of different pore sizes (20 Å ≤ H ≤ 110 Å, where H is the size of the nanopore) in contact with liquid water and aqueous electrolyte solutions (CaCl2 (aq) and CaF2 (aq)) were investigated using molecular dynamics simulations to quantify the effect of nanoconfinement and solvated ions on the surface reactivity and the structural and dynamical properties of water. The combined effect of solution composition and nanoconfinement significantly slows the self-diffusion coefficient of water molecules compared with bulk liquid. Analysis of the pair and angular distribution functions, distribution of hydrogen bonds, velocity autocorrelation functions, and power spectra of water shows that solution composition and nanoconfinement in particular enhance the rigidity of the water hydrogen bonding network. Calculation of the water exchange events in the coordination of calcium ions reveals that the dynamics of water molecules at the HAP–solution interface decreases substantially with the degree of confinement. Ions in solution also reduce the water dynamics at the surface calcium sites. Together, these changes in the properties of water impart an overall rigidifying effect on the solvent network and reduce the reactivity at the hydroxyapatite-solution interface. Since the process of surface-cation-dehydration governs the kinetics of the reactions occurring at mineral surfaces, such as adsorption and crystal growth, this work shows how nanoconfinement and solvation environment influence the molecular-level events surrounding the crystallization of hydroxyapatite. View Full-Text
Keywords: hydroxyapatite; nanoconfinement; electrolyte solution; molecular dynamics hydroxyapatite; nanoconfinement; electrolyte solution; molecular dynamics
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Di Tommaso, D.; Prakash, M.; Lemaire, T.; Lewerenz, M.; de Leeuw, N.H.; Naili, S. Molecular Dynamics Simulations of Hydroxyapatite Nanopores in Contact with Electrolyte Solutions: The Effect of Nanoconfinement and Solvated Ions on the Surface Reactivity and the Structural, Dynamical, and Vibrational Properties of Water. Crystals 2017, 7, 57.

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