PEG functionalization effect of silicate-containing hydroxyapatite particles on effective collagen fibrillation with hydration layer state change
PEG functionalization effect of silicate-containing hydroxyapatite particles on effective collagen fibrillation with hydration layer state change
复制标题
含硅酸盐羟基磷灰石颗粒的 PEG 功能化对水化层状态变化的有效胶原纤维化的影响
DOI：
10.1039/d1cp04768j
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发表时间：
2022
影响因子：
3.3
通讯作者：
Tagaya Motohiro
中科院分区：
文献类型：
--
作者：
Yamada Shota;Chai Yadong;Tagaya Motohiro
合成了含硅酸盐羟基磷灰石（SiHA）颗粒，并用聚乙二醇-硅烷（PEG-硅烷）对SiHA颗粒进行了功能化修饰，研究了生物陶瓷表面水化层状态对胶原（Col）原纤化程度的影响。获得在颗粒内部和/或外部含有SiO 44 −离子的板状SiHA颗粒。成功地将PEG-硅烷功能化在SiHA颗粒上，并精确地研究了颗粒上的水化层和吸附层状态，以举例说明界面处水分子状态的重要性。当含有硅酸盐组分时，颗粒的水合层中的自由水与中间水的比率降低，并且随着PEG-硅烷分子占据率的增加而显著增加，其中自由水中的不对称伸缩振动组分的比率明显增加。在石英晶体微天平（QCM-D）中，随着Col在颗粒上吸附32-34 min，频率变化（Δf）和能量耗散变化（ΔD）值均增大，随后Δf略有增大（或停止增大），ΔD急剧增大，表明Col在界面处的纤化导致了有效水的迁移和状态变化。通过tan δ评估的Col原纤化程度和吸附层的蛋白质二级结构由于PEG-硅烷官能化而明显增加，并且在SEM观察下原纤密度的增加支持了这种趋势。 令人惊讶的是，发现基于蛋白质二级结构的原纤化程度与颗粒上的水合层的自由水分子中的不对称拉伸振动分量比率显著相关，这表明生物陶瓷上的水合层状态对于控制Col原纤化的重要性。
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.