PEG functionalization effect of silicate-containing hydroxyapatite particles on effective collagen fibrillation with hydration layer state change

Abstract

Silicate-containing hydroxyapatite (SiHA) particles were synthesized and functionalized with polyethylene glycol-silane (PEG–silane) for clarifying the effect of the bioceramic surface hydration layer states on the collagen (Col) fibrillation degree. Plate-like SiHA particles were obtained containing the SiO₄⁴⁻ ion inside and/or outside the particles. PEG–silane was successfully functionalized on SiHA particles, and the hydration layer and Col adlayer states on the particles were precisely investigated for exemplifying the importance of the water molecular states at the interface. The ratio of free to intermediate water in the hydration layers of the particles decreased when containing silicate components, and it significantly increased with increasing PEG–silane molecular occupancy, where the asymmetric stretching vibration component ratio in the free water clearly increased. In a quartz crystal microbalance with dissipation (QCM-D) measurement, the frequency change (Δf) and the energy dissipation change (ΔD) values increased with Col adsorption on the particles for 32–34 min and then Δf slightly increased (or stopped increasing) and ΔD dramatically increased, indicating the effective water mobility and state changes with the Col fibrillation at the interface. The Col fibrillation degree evaluated by tan δ and the protein secondary structure of the adlayers clearly increased due to the PEG–silane functionalization, and the tendency was supported by the increase in the fibril density under SEM observation. Surprisingly, it was found that the fibrillation degree based on the protein secondary structure was significantly correlated with the asymmetric stretching vibration component ratio in the free water molecules of the hydration layer on the particles, suggesting the importance of the hydration layer states on bioceramics for controlling Col fibrillation.