In Situ Evaluation of Calcium Phosphate Nucleation Kinetics and Pathways during Intra- and Extrafibrillar Mineralization of Collagen Matrices.

In Situ Evaluation of Calcium Phosphate Nucleation Kinetics and Pathways during Intra- and Extrafibrillar Mineralization of Collagen Matrices.
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DOI:
10.1021/acs.cgd.6b00864
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发表时间:
2016
影响因子:
3.8
通讯作者:
Jun, Young-Shin
Jun, Young-Shin
中科院分区:
化学2区
文献类型:
--
作者:
Kim, Doyoon;Lee, Byeongdu;Thomopoulos, Stavros;Jun, Young-Shin

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我们发现胶原原纤维内的成核位点决定了生物矿化过程中磷酸钙(CaP)的成核及其从无定形到结晶板的转化途径。利用原位小角度x射线散射(SAXS),我们研究了胶原基质中CaP的成核和生长,并阐明了成核抑制剂聚天冬氨酸(pAsp)如何在多个长度尺度上控制矿化动力学和途径。没有pAsp的矿化最初导致整个纤维外空间的CaP球形聚集体。随着时间的推移,球形聚集体在胶原基质的最外表面转变成板状,阻止了内部的纤维内矿化。然而,pAsp的成矿作用直接导致了沿基质深度呈空间梯度分布的纤维内CaP板的形成。结果阐明了矿物成核动力学和实时纳米颗粒分布在有机基质中含有体液成分的溶液。由于胶原基质的宏观力学性能取决于其矿物质含量、相和纳米级排列,因此本研究有助于更好地设计和制造用于再生医学的生物材料。
We revealed that nucleation sites within collagen fibrils determined pathways for calcium phosphate (CaP) nucleation and its transformation, from amorphous species to crystalline plates, during the biomineralization process. Using in situ small-angle X-ray scattering (SAXS), we examined the nucleation and growth of CaP within collagen matrices and elucidated how a nucleation inhibitor, polyaspartic acid (pAsp), governs mineralization kinetics and pathways at multiple length scales. Mineralization without pAsp led initially to spherical aggregates of CaP in the entire extrafibrillar spaces. With time, the spherical aggregates transformed into plates at the outermost surface of the collagen matrix, preventing intrafibrillar mineralization inside. However, mineralization with pAsp led directly to the formation of intrafibrillar CaP plates with a spatial distribution gradient through the depth of the matrix. The results illuminate mineral nucleation kinetics and real-time nanoparticle distributions within organic matrices in solutions containing body fluid components. Because the macroscale mechanical properties of collagen matrices depend on their mineral content, phase, and arrangement at the nanoscale, this study contributes to better design and fabrication of biomaterials for regenerative medicine.
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