Time-Resolved Dynamics of Calcium Oxalate Dihydrate Crystallization

IF 3.2 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY
Vraj P. Chauhan, Gabriel Yazbek Grobman, Netta Vidavsky and Jeffrey D. Rimer*, 
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Abstract

Calcium oxalate is a common biomineral that forms in plants and humans. The deleterious effects associated with the pathological crystallization of calcium oxalate in diseases such as kidney stones and breast cancer depend upon the structural form of the crystal. The majority of studies in the literature focus on understanding and controlling the formation of calcium oxalate monohydrate (COM), which is the most prevalent form in vivo. Relatively fewer studies have examined the crystallization of calcium oxalate dihydrate (COD), which is a less thermodynamically stable hydrate and the focus of this study. Here, we investigate methods of preparing large COD crystals using poly(acrylic acid) as a growth modifier to promote dihydrate nucleation and to generate crystals with a size and morphology that allow for in situ measurements of crystallization in physiologically relevant growth media. Time-resolved dynamics of COD surface growth were tracked in supersaturated calcium oxalate solutions using atomic force microscopy (AFM) to visualize the birth and spreading of unfinished layers on COD {100} crystal surfaces in real time. Our findings reveal that COD growth involves the nucleation and advancement of two-dimensional islands, which is in stark contrast to COM surfaces that grow exclusively from screw dislocations. AFM studies performed over a range of supersaturation indicate that COD grows at a significantly slower rate with a kinetic coefficient that is more than an order of magnitude smaller than that of COM. Similar in situ experiments were performed in the presence of citrate, a known inhibitor of calcium oxalate crystallization. These studies reveal distinct differences in the impact of citrate on COM and COD growth, which may have implications for its efficacy as an administered preventative therapeutic for pathological crystallization.

Abstract Image

二水合草酸钙结晶的时间分辨动力学
草酸钙是一种在植物和人体中形成的常见生物矿物质。在肾结石和乳腺癌等疾病中,草酸钙病理结晶的有害影响取决于晶体的结构形式。文献中的大多数研究都集中在了解和控制草酸钙一水合物(COM)的形成,这是体内最普遍的形式。二水合草酸钙(COD)是一种热力学稳定性较差的水合物,对其结晶的研究相对较少,也是本研究的重点。在这里,我们研究了用聚丙烯酸作为生长调节剂制备大COD晶体的方法,以促进二水成核,并产生具有尺寸和形态的晶体,允许在生理相关的生长介质中进行结晶的原位测量。在过饱和草酸钙溶液中,使用原子力显微镜(AFM)跟踪COD表面生长的时间解析动力学,实时观察COD{100}晶体表面未完成层的生成和扩展。我们的研究结果表明,COD的生长涉及二维岛的成核和推进,这与COM表面完全由螺位错生长形成鲜明对比。在过饱和范围内进行的AFM研究表明,COD的生长速度明显较慢,其动力学系数比COM小一个数量级以上。类似的原位实验在柠檬酸盐的存在下进行,柠檬酸盐是一种已知的草酸钙结晶抑制剂。这些研究揭示了柠檬酸盐对COM和COD生长的影响存在明显差异,这可能意味着其作为一种预防性治疗病理性结晶的功效。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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来源期刊
Crystal Growth & Design
Crystal Growth & Design 化学-材料科学:综合
CiteScore
6.30
自引率
10.50%
发文量
650
审稿时长
1.9 months
期刊介绍: The aim of Crystal Growth & Design is to stimulate crossfertilization of knowledge among scientists and engineers working in the fields of crystal growth, crystal engineering, and the industrial application of crystalline materials. Crystal Growth & Design publishes theoretical and experimental studies of the physical, chemical, and biological phenomena and processes related to the design, growth, and application of crystalline materials. Synergistic approaches originating from different disciplines and technologies and integrating the fields of crystal growth, crystal engineering, intermolecular interactions, and industrial application are encouraged.
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