武汉理工大学邹朝勇课题组发现，纳米团簇诱导的液态前驱体形成和结晶：原位可视化和三维重建。2025年3月6日，国际知名学术期刊《美国化学会杂志》发表了这一成果。

该研究组引入了羧基功能化金纳米管（Au NCs）作为聚合物的替代品，通过瞬态“Au NCs诱导的液体前驱体”相（类似于“聚合物诱导的液体前驱体”）研究CaCO₃结晶。利用金纳米颗粒的超小尺寸、高密度和稳定的自发荧光特性，该方法可以直接在原位观察液体前驱体形成和动态缔合/解离主题光学显微镜。

结果表明，金纳米粒子被纳入液体前驱体中，并且随着时间的推移，液体前驱体的数量几乎呈线性增加，直到溶液中游离Ca²⁺离子由于方解石的结晶而耗尽。随后，液体前驱体的溶解为进一步的晶体生长提供离子。在共聚焦荧光显微镜下，还可以观察到整个结晶过程中Au纳米粒子在CaCO₃中的遮挡和三维空间分布，证明了CaCO₃在特定晶格平面上的优先吸附。这项研究大大提高了他们对不同晶体面生长速率的差异和金纳米在晶体中的空间分布的理解。

研究人员表示，揭示有机分子调控无机材料的结晶机理在生物矿化、晶体学和材料科学等领域具有广泛的意义。然而，直接可视化有机分子在无机材料结晶过程中的参与仍然是一个重大挑战。

附：英文原文

Title: Nanocluster-Induced Liquid-like Precursor Formation and Crystallization: In Situ Visualization and 3D Reconstruction

Author: Jin Chen, Guanbin Gao, Zijun Zhang, Taolei Sun, Zhengyi Fu, Zhaoyong Zou

Issue&Volume: March 6, 2025

Abstract: Revealing the crystallization mechanism of inorganic materials modulated by organic molecules has broad implications in biomineralization, crystallography, and materials science. However, directly visualizing the participation of organic molecules in the inorganic materials’ crystallization process remains a significant challenge. Here, we introduce carboxyl-functionalized gold nanoclusters (Au NCs) as an alternative to polymers for investigating CaCO₃ crystallization via the transient “Au NCs-induced liquid precursor” phase, similar to “polymer-induced liquid precursor”. Exploiting the ultrasmall size, high density, and stable spontaneous fluorescence properties of Au NCs, this approach enables direct in situ observation of liquid precursor formation and dynamic association/dissociation using light microscopy. Results show that Au NCs are incorporated into the liquid precursor and the quantity of liquid precursor exhibits a nearly linear increase over time until the depletion of free Ca²⁺ ions in solution due to crystallization of calcite. Subsequently, the dissolution of the liquid precursor provides ions for further crystal growth. The occlusion and 3D spatial distribution of Au NCs within CaCO₃ throughout the crystallization process can also be visualized using confocal fluorescence microscopy, demonstrating preferential adsorption on specific lattice planes of CaCO₃. This study substantially enhances our comprehension of the differential growth rates of various crystallographic faces and the spatial distribution of Au NCs within the crystals.

DOI: 10.1021/jacs.4c17643

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.4c17643