Calcite Prisms from Mollusk Shells (Atrina Rigida): Swiss-cheese-like Organic-Inorganic Single-crystal Composites

Calcite Prisms from Mollusk Shells (Atrina Rigida): Swiss-cheese-like Organic-Inorganic Single-crystal Composites
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DOI:
10.1002/adfm.201002709
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发表时间:
2011-06-07
影响因子:
19
通讯作者:
Estroff, Lara A.
Estroff, Lara A.
中科院分区:
材料科学1区
文献类型:
--
作者:
Li, Hanying;Xin, Huolin L.;Estroff, Lara A.

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生物成因的单晶复合材料,如海胆刺和软体动物壳的方解石棱柱,在无机单晶基质中含有有机大分子。然而,人们对这些材料的纳米级内部结构知之甚少,特别是生物大分子如何在晶体内分布而不显著破坏晶格。在这里,环形暗场扫描透射电子显微镜和电子断层扫描显示,在三维空间,生物大分子是如何分布在钙化棱柱从Atrina rigida壳。观察到散射强度与有机夹杂物一致的类方解石纳米片在连续的单晶方解石基质内各向异性排列。这些纳米片优先与方解石的(000 l)平面对齐。沿着晶体学c轴,在数十纳米的长度尺度上存在交替的有机物富集和贫乏区域,而在ab平面中,纳米片的分布更随机和均匀。在这项工作中阐明的结构特征具有相关性的理解的结构-性能关系和形成机制的生物矿物,以及生物启发的策略的发展,以extraminated调整单晶的性能。
Biogenic single-crystal composites, such as sea urchin spines and calcitic prisms from mollusk shells, contain organic macromolecules inside of inorganic single-crystal matrices. The nanoscale internal structure of these materials, however, is poorly understood, especially how the biomacromolecules are distributed within the crystals without significantly disrupting the crystalline lattice. Here, annular dark-field scanning transmission electron microscopy and electron tomography reveal, in three dimensions, how biomacromolecules are distributed within the calcitic prisms from Atrina rigida shells. Disk-like nanopatches, whose scattering intensity is consistent with organic inclusions, are observed to be anisotropically arranged within a continuous, single-crystalline calcite matrix. These nanopatches are preferentially aligned with the (000l) planes of calcite. Along the crystallographic c-axis, there are alternating organic-rich and -poor regions on a length scale of tens of nanometers, while, in the ab plane, the distribution of nanopatches is more random and uniform. The structural features elucidated in this work have relevance to understanding the structure-property relationships and formation mechanisms of biominerals, as well as to the development of bio-inspired strategies to extrinsically tune the properties of single-crystals.