Polyamines Promote Aragonite Nucleation and Generate Biomimetic Structures.
Polyamines Promote Aragonite Nucleation and Generate Biomimetic Structures.
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DOI：
10.1002/advs.202203759
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发表时间：
2022-11-20
期刊：
影响因子：
15.1
通讯作者：
Meldrum, Fiona C.
中科院分区：
文献类型：
--
作者：
Nahi, Ouassef;Kulak, Alexander N.;Zhang, Shuheng;He, Xuefeng;Aslam, Zabeada;Ilett, Martha A.;Ford, Ian J.;Darkins, Robert;Meldrum, Fiona C.
碳酸钙生物矿化对于生物体以完美的保真度生产方解石或霰石的能力而言是显着的，这通常归因于特定的阴离子生物大分子。然而，事实证明很难使用合成或生物阴离子有机分子来模拟这种行为。研究表明，从小分子到大聚电解质的阳离子多胺可以对碳酸钙多晶型物发挥特殊的控制作用，在极低浓度下促进文石成核，但在高浓度下抑制其生长，从而形成方解石或球霰石。文石晶体通过颗粒组装形成，产生类似于生物文石的纳米颗粒结构，随后的生长产生与发育珍珠质中所见结构相当的堆叠文石片晶。这种多晶型选择性的机制是在基于这些竞争成核和生长效应的理论模型中捕获的，并且与镁离子的活性完全不同，镁离子通过抑制方解石生成文石。受益于这些对比机制，随后证明多胺和镁离子可以结合起来对霰石的形成提供前所未有的控制。这些结果深入了解了方解石/文石多晶型，并提出了生物体利用富含胺的有机分子和镁离子来控制碳酸钙多晶型的可能性。多胺，包括小分子和聚电解质，被证明对方解石/文石多晶型具有显着的控制作用，它们通过与镁离子完全不同的机制起作用，并在极低的浓度下促进文石成核。文石晶体表现出类似于生物文石的颗粒结构，并且通过颗粒组装生长产生类似于正在发育的珍珠母的文石片叠层。
Calcium carbonate biomineralization is remarkable for the ability of organisms to produce calcite or aragonite with perfect fidelity, where this is commonly attributed to specific anionic biomacromolecules. However, it is proven difficult to mimic this behavior using synthetic or biogenic anionic organic molecules. Here, it is shown that cationic polyamines ranging from small molecules to large polyelectrolytes can exert exceptional control over calcium carbonate polymorph, promoting aragonite nucleation at extremely low concentrations but suppressing its growth at high concentrations, such that calcite or vaterite form. The aragonite crystals form via particle assembly, giving nanoparticulate structures analogous to biogenic aragonite, and subsequent growth yields stacked aragonite platelets comparable to structures seen in developing nacre. This mechanism of polymorph selectivity is captured in a theoretical model based on these competing nucleation and growth effects and is completely distinct from the activity of magnesium ions, which generate aragonite by inhibiting calcite. Profiting from these contrasting mechanisms, it is then demonstrated that polyamines and magnesium ions can be combined to give unprecedented control over aragonite formation. These results give insight into calcite/aragonite polymorphism and raise the possibility that organisms may exploit both amine‐rich organic molecules and magnesium ions in controlling calcium carbonate polymorph. Polyamines, including small molecules and polyelectrolytes, are shown to exert remarkable control over calcite/aragonite polymorphism, where they operate by an entirely different mechanism to magnesium ions and promote aragonite nucleation at exceptionally low concentrations. The aragonite crystals exhibit granular structures analogous to biogenic aragonite and growth via particle assembly yields stacks of aragonite platelets that resemble developing nacre.
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影响因子：
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