欧洲鲍鱼<i>鲍氏</i>盐囊藻中文石的无序矿物域内的化学异质<i>性</i>,The Journal of Physical Chemistry C

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欧洲鲍鱼鲍氏盐囊藻中文石的无序矿物域内的化学异质性
The Journal of Physical Chemistry C ( IF 3.3 ) Pub Date : 2020-06-02 , DOI: 10.1021/acs.jpcc.0c00280
Widad Ajili ₁ , Guillaume P. Laurent ₁ , Nicolas Menguy ₂ , Axel Gansmuller ₃ , Sylvain Huchette ₄ , Stéphanie Auzoux-Bordenave ₅ , Nadine Nassif ₁ , Thierry Azais ₁

Affiliation

自从2005年在鲍鱼Haliotis laevigata nacre的文石血小板表面观察到无序的矿物层以来，这种生物矿化组织中有机-矿物界面的模型受到了挑战。由于文石晶体核与有机基质之间的直接相互作用不再适合描述这种界面，因此在原子水平上对无序矿物域的结构描述是全面了解珍珠母超微结构的关键。在这里，我们使用欧洲鲍鱼Haliotis tuberculata作为模型，通过高分辨率透射电子显微镜（HR-TEM）和多核固态核磁共振（ssNMR）研究文石珍珠质。通过HR-TEM观察，类似于文盲H. laevigata，显示出文石晶体周围无序畴的存在。通过¹ H，¹³ C，⁴³ Ca和²³ Na ssNMR研究了珍珠质珍珠菌无序矿物环境的结构和离子组成。有趣的是，我们证明珍珠母中的无序矿物域在结构和化学组成方面似乎是异质的，并且与无定形碳酸钙严格匹配不匹配。。至少三个不同的碳酸盐物种证明，包括CO ₃^2-和HCO ₃^-存在于相同的矿物结构域和具有刚性ħ密切相关的₂水分子。这些离子周围的局部紊乱被发现是不均匀的，因为某些CO ₃^{2 –}具有一个烷属环境，并且是有序的（根据其¹³ C共振的位置和线宽），而相反，HCO ₃周围的化学环境^–高度分散。对潜在阳离子作为抗衡离子的分析揭示了无序Ca ²⁺的存在和Na ⁺的存在与HCO ₃^–密切相关。关于这些结构数据的基础上，我们提出在鲍鱼的无序结构域的原子级模型（H.tuberculata）珍珠质，其中碳酸根离子的质子化水平，钠离子的比例和局部紊乱从内增加无序域的外部。这些结果在珍珠质文石片中这种无序矿物域的原子尺度上提供了前所未有的结构观点。

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Chemical Heterogeneities within the Disordered Mineral domains of Aragonite Platelets in Nacre from the European Abalone Haliotis tuberculata

Since the observation in 2005 of a disordered mineral layer at the surface of aragonite platelets in abalone Haliotis laevigata nacre, the model of the organo–mineral interface in such biomineralized tissue has been challenged. As a direct interaction between the aragonite crystalline core and the organic matrix is no longer appropriate to describe such interface, a structural description of the disordered mineral domains at the atomic level is a key for a comprehensive view of nacre ultrastructure. Here, we use European abalone Haliotis tuberculata as a model to investigate aragonite nacre through high-resolution transmission electron microscopy (HR-TEM) and multinuclear solid state nuclear magnetic resonance (ssNMR). The presence of a disordered domain around aragonite crystals is shown through HR-TEM observations similarly to H. laevigata. The structure and the ionic composition of the disordered mineral environments of H. tuberculata nacre are investigated through ¹H, ¹³C, ⁴³Ca, and ²³Na ssNMR. Interestingly, we demonstrate that the disordered mineral domains in nacre seem to be heterogeneous in terms of structure and chemical composition and do not match with amorphous calcium carbonate stricto sensu. At least three different carbonates species are evidenced, including CO₃^2– and HCO₃^– present in the same mineral domain and closely associated with rigid H₂O molecules. The local disorder around these ions is found to be inhomogeneous as some CO₃^2– possess an aragonitic environment and are rather ordered (according to the position and line width of their ¹³C resonance) whereas, in opposition, the chemical environment around HCO₃^– is highly distributed. The analysis of potential cations as counterions revealed the presence of disordered Ca²⁺ and the presence of Na⁺ closely associated with HCO₃^–. On the basis of these structural data, we propose an atomic-level model for the disordered domains in abalone (H.tuberculata) nacre where the protonation level of carbonate ions, the proportion of sodium ions and the local disorder are increasing from the inner to the outer part of disordered domains. These results give an unprecedented structural view at the atomic scale of such disordered mineral domains in nacre aragonite tablets.

更新日期：2020-07-02

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