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Anisotropic diffusion of water molecules in hydroxyapatite nanopores

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Abstract

New insights into the dynamical properties of water in hydroxyapatite (HAP) nanopores, a model system for the fluid flow within nanosize spaces inside the collagen-apatite structure of bone, were obtained from molecular dynamics simulations of liquid water confined between two parallel HAP surfaces of different sizes (20 Å ≤ H ≤ 240 Å). Calculations were conducted using a core-shell interatomic potential for HAP together with the extended simple point charge model for water. This force field gives an activation energy for water diffusion within HAP nanopores that is in excellent agreement with available experimental data. The dynamical properties of water within the HAP nanopores were quantified in terms of the second-order water diffusion tensor. Results indicate that water diffuses anisotropically within the HAP nanopores, with the solvent molecules moving parallel to the surface twice as fast as the perpendicular direction. This unusual dynamic behaviour is linked to the strong polarizing effect of calcium ions, and the synergic interactions between the water molecules in the first hydration layer of HAP with the calcium, hydroxyl, and phosphate ions, which facilitates the flow of water molecules in the directions parallel to the HAP surface.

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Acknowledgements

The authors are grateful to the “Institut des sciences de l’ingénierie et des systèmes” (INSIS) of the “Centre national de la recherche scientifique” (CNRS) for financial support through the “HAP-W Nanopores” PEPS grant. The authors are also grateful to “Université Paris-Est Créteil” (UPEC) for the support of the French-English consortium. Finally, Dr. Muthuramalingam Prakash thanks UPEC for the funding of his post-doctoral research grant. This research utilised Queen Mary’s MidPlus computational facilities, supported by QMUL Research-IT, and funded by EPSRC Grant EP/K000128/1.

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  1. Laboratoire Modélisation et Simulation Multi Echelle, MSME UMR 8208 CNRS, Université Paris-Est, Créteil Cedex, 94010, France

    Muthuramalingam Prakash, Thibault Lemaire, Matthieu Caruel & Salah Naili

  2. School of Chemistry, Cardiff University, Main Building, Park Place, Cardiff, CF10 3AT, UK

    Nora H. de Leeuw

  3. Laboratoire Modélisation et Simulation Multi Echelle, MSME UMR 8208 CNRS, Université Paris-Est, 77454, Marne la Vallée Cedex 2, France

    Marius Lewerenz

  4. School of Biological and Chemical Sciences, Queen Mary University of London, Mile End Road, London, E1 4NS, UK

    Devis Di Tommaso

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  1. Muthuramalingam Prakash
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Prakash, M., Lemaire, T., Caruel, M. et al. Anisotropic diffusion of water molecules in hydroxyapatite nanopores. Phys Chem Minerals 44, 509–519 (2017). https://doi.org/10.1007/s00269-017-0878-1

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