Chiral acidic amino acids induce chiral hierarchical structure in calcium carbonate.
Chiral acidic amino acids induce chiral hierarchical structure in calcium carbonate.
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DOI：
10.1038/ncomms15066
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发表时间：
2017-04-13
影响因子：
16.6
通讯作者：
McKee MD
中科院分区：
文献类型：
--
作者：
Jiang W;Pacella MS;Athanasiadou D;Nelea V;Vali H;Hazen RM;Gray JJ;McKee MD
手性在生物学中普遍存在，包括在生物矿化中，在无脊椎海洋和陆地生物的许多硬化结构中发现了手性（例如，螺旋腹足动物壳）。在这里，我们表明，碳酸钙（球霰石）的手性，分层组织的架构可以简单地通过添加手性酸性氨基酸（天冬氨酸和谷氨酸）控制。手性，球霰石环形超结构具有“右手”（逆时针）螺旋形态的诱导L-对映体的天冬氨酸和谷氨酸，而“左手”（顺时针）形态诱导D-对映体，氨基酸对映体之间的顺序切换引起的手性开关。手性氨基酸结合后的纳米颗粒倾斜被提出作为手性生长机制，其中“母亲”亚基纳米颗粒产生稍微倾斜的、相应的“女儿”纳米颗粒，其通过在各种长度尺度上放大而产生定向矿物片晶和手性球文石超结构。这些研究结果表明，生物矿化相关的对映异构体可能会施加分级控制，形成扩展的手性超结构的分子机制。手性结构在许多过程中形成，包括碳酸钙的生物矿化。在这里，作者证明了碳酸钙矿物球文石的手性，分层组织的结构可以简单地通过添加手性酸性氨基酸来控制。
Chirality is ubiquitous in biology, including in biomineralization, where it is found in many hardened structures of invertebrate marine and terrestrial organisms (for example, spiralling gastropod shells). Here we show that chiral, hierarchically organized architectures for calcium carbonate (vaterite) can be controlled simply by adding chiral acidic amino acids (Asp and Glu). Chiral, vaterite toroidal suprastructure having a ‘right-handed' (counterclockwise) spiralling morphology is induced by L-enantiomers of Asp and Glu, whereas ‘left-handed' (clockwise) morphology is induced by D-enantiomers, and sequentially switching between amino-acid enantiomers causes a switch in chirality. Nanoparticle tilting after binding of chiral amino acids is proposed as a chiral growth mechanism, where a ‘mother' subunit nanoparticle spawns a slightly tilted, consequential ‘daughter' nanoparticle, which by amplification over various length scales creates oriented mineral platelets and chiral vaterite suprastructures. These findings suggest a molecular mechanism for how biomineralization-related enantiomers might exert hierarchical control to form extended chiral suprastructures. Chiral structures are formed in numerous processes including biomineralization of calcium carbonate. Here, the authors demonstrate that the chiral, hierarchically-organized architecture of the calcium carbonate mineral, vaterite, can be controlled simply by the addition of chiral acidic amino acids.