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Zinc Ions Modify Calcium Oxalate Growth by Distinct Transformation of Crystal Surface Termination

机译:锌离子通过晶体表面终端的不同转化改变草酸钙生长

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Y Calcium oxalate crystals are ubiquitous minerals in biogenic, geological, and synthetic systems. It has been shown that the most naturally abundant form of these crystals, calcium oxalate monohydrate (COM), grows via a classical pathway that can be regulated by crystal growth modifiers. One of the most important occurrences of COM is during human kidney stone disease where the role of zinc in pathological stone formation is not fully understood. There are conflicting claims in the literature that zinc functions either as a promoter or inhibitor of COM stone formation. Here, we examine the role of zinc ions in COM crystal growth using a combination of experimental and modeling techniques to elucidate ion-crystal interactions at macroscopic to atomic length scales. From this, we show that zinc reduces the rate of crystal growth and also induces morphological transformations via the introduction of intergrowths that can potentially accelerate crystal growth. Density functional theory calculations indicate high energetic barriers for zinc incorporation in COM crystals, suggesting that changes in crystal growth are related to zinc interactions with COM crystal surfaces. This was confirmed by in situ atomic force microscopy measurements showing a unique ability of zinc ions to truncate the height of layers on the (100) face, which concomitantly affects both the morphology of surface features and the kinetics of layered growth. Collectively, our study suggests that the role of zinc in pathological crystallization is potentially bimodal, consistent with opposing theories in the literature.
机译:草酸钙晶体是生物、地质和合成系统中普遍存在的矿物。研究表明,这些晶体中最丰富的一种形式,一水草酸钙(COM),通过一种经典的途径生长,该途径可由晶体生长调节剂调节。COM最重要的发生之一是在人类肾结石疾病期间,锌在病理性结石形成中的作用尚不完全清楚。文献中有相互矛盾的说法,即锌是COM结石形成的促进剂或抑制剂。在这里,我们结合实验和建模技术来研究锌离子在COM晶体生长中的作用,以阐明宏观到原子长度尺度上的离子-晶体相互作用。由此,我们发现锌降低了晶体生长速度,并通过引入可能加速晶体生长的共生物诱导形态转变。密度泛函理论计算表明,锌在COM晶体中的掺入存在高能势垒,表明晶体生长的变化与锌与COM晶体表面的相互作用有关。原位原子力显微镜测量结果证实了这一点,表明锌离子具有独特的能力来截断(100)面上的层高度,这同时影响表面特征的形态和分层生长的动力学。总之,我们的研究表明,锌在病理结晶中的作用可能是双峰的,这与文献中的相反理论一致。

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