Amorphous 1-D nanowires of calcium phosphate/pyrophosphate: A demonstration of oriented self-growth of amorphous minerals.
Amorphous 1-D nanowires of calcium phosphate/pyrophosphate: A demonstration of oriented self-growth of amorphous minerals.
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DOI：
10.1016/j.jcis.2023.12.002
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发表时间：
2023-12
影响因子：
9.9
通讯作者：
C. Feng;Bingqiang Lu;Yunshan Fan;Haijian Ni;Yunfei Zhao;Shuo Tan;Zhi Zhou;Lijia Liu;J. Hachtel;D. Kepaptsoglou;Baohu Wu;Denis Gebauer;Shisheng He;Feng Chen
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文献类型：
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作者：
C. Feng;Bingqiang Lu;Yunshan Fan;Haijian Ni;Yunfei Zhao;Shuo Tan;Zhi Zhou;Lijia Liu;J. Hachtel;D. Kepaptsoglou;Baohu Wu;Denis Gebauer;Shisheng He;Feng Chen
无定形无机固体传统上是各向同性的，因此，据信它们在没有调节剂的帮助下仅以非优先方式生长，导致纳米球或纳米颗粒的不规则聚集体的形态。然而，在存在在生物矿化中具有协同作用的（正）磷酸根（Pi）和焦磷酸根离子（PPi）的情况下，高度伸长的无定形纳米线（表示为ACPPN）在无调节剂的水溶液（没有模板、添加剂、有机物等）中形成。基于对形成过程的彻底表征和跟踪（例如，用Cryo-TEM、球差校正高分辨TEM、固态NMR、高能量分辨单色化STEM-EELS等方法研究了薄膜的微观结构及其择优生长行为。在ACPPN中，无定形正磷酸钙和无定形焦磷酸钙分布在分开但靠近的位置。ACPPNs的生长要么是通过1维的方式优先附着102 nm的纳米团簇，要么是通过更大的纳米颗粒的转化，表明了一个内在的驱动力控制的过程。我们建议，各向异性的ACPPNs的微观结构，这是实验证实，导致其定向生长。该研究证明，与传统观点不同的是，非晶态矿物可以在没有外界调控的情况下通过定向生长形成，为非晶态矿物的结构和生长行为提供了新的视角。
Amorphous inorganic solids are traditionally isotropic, thus, it is believed that they only grow in a non-preferential way without the assistance of regulators, leading to the morphologies of nanospheres or irregular aggregates of nanoparticles. However, in the presence of (ortho)phosphate (Pi) and pyrophosphate ions (PPi) which have synergistic roles in biomineralization, the highly elongated amorphous nanowires (denoted ACPPNs) form in a regulator-free aqueous solution (without templates, additives, organics, etc). Based on thorough characterization and tracking of the formation process (e.g., Cryo-TEM, spherical aberration correction high resolution TEM, solid state NMR, high energy resolution monochromated STEM-EELS), the microstructure and its preferential growth behavior are elucidated. In ACPPNs, amorphous calcium orthophosphate and amorphous calcium pyrophosphate are distributed at separated but close sites. The ACPPNs grow via either the preferential attachment of ∼2 nm nanoclusters in a 1-dimension way, or the transformation of bigger nanoparticles, indicating an inherent driving force-governed process. We propose that the anisotropy of ACPPNs microstructure, which is corroborated experimentally, causes their oriented growth. This study proves that, unlike the conventional view, amorphous minerals can form via oriented growth without external regulation, demonstrating a novel insight into the structures and growth behaviors of amorphous minerals.