暨南大学宁印报道了共聚物纳米颗粒在方解石晶体中的空间选择性遮挡产生具有可控内部结构的有机-无机杂化材料。相关研究成果于2024年7月2日发表在《德国应用化学》。

将颗粒添加剂有效地嵌入单晶中在材料科学中引起了越来越多的关注，因为它为制造具有新兴性能的晶体纳米复合材料提供了一个反直觉但强大的平台。然而，精确控制客体添加剂在主体晶体内的空间分布仍然极具挑战性。

该文中，研究人员展示了一种独特、直接的方法，通过精确调整用于方解石沉淀的初始[Ca²⁺]浓度，来设计方解石（CaCO₃）单晶中共聚物纳米颗粒的空间分布。更具体地说，采用聚合诱导的自组装来合成定义明确且高度阴离子的，聚（甲基丙烯酸3-磺丙基钾）41嵌段聚（甲基丙烯酸酯苄基酯）500[PPSMA41-PBzMA500]二嵌段共聚物纳米颗粒，其随后在方解石晶体的生长过程中用作模型添加剂。

令人印象深刻的是，根据初始[Ca²⁺]浓度，这种客体纳米颗粒优先被方解石的特定区域包裹。基于系统研究，这些前所未有的现象很可能是由Ca²⁺离子和PSPMA41链之间静电相互作用的动态变化引起的。

该项研究不仅展示了在控制客体纳米颗粒在宿主晶体中的空间分布方面的重大进展，使复合晶体的内部结构能够通过空间选择性遮挡策略合理定制，而且还为生物矿化提供了新的见解。

附：英文原文

Title: Spatioselective Occlusion of Copolymer Nanoparticles within Calcite Crystals Generates Organic-Inorganic Hybrid Materials with Controlled Internal Structures

Author: Wenting Chen, Pei Liu, Xia Sun, Biao Xiong, Huahua Cui, Zhenghong Zhao, Yin Ning

Issue&Volume: 2024-07-02

Abstract: Efficient occlusion of particulate additives into a single crystal has garnered an ever-increasing attention in materials science because it offers a counter-intuitive yet powerful platform to make crystalline nanocomposite materials with emerging properties. However, precisely controlling the spatial distribution of the guest additives within a host crystal remains highly challenging. We herein demonstrate a unique, straightforward method to engineer the spatial distribution of copolymer nanoparticles within calcite (CaCO3) single crystals by judiciously adjusting initial [Ca2+] concentration used for the calcite precipitation. More specifically, polymerization-induced self-assembly is employed to synthesize well-defined and highly anionic poly(3-sulfopropyl methacrylate potassium)41-block-poly(benzyl methacrylate)500 [PSPMA41-PBzMA500] diblock copolymer nanoparticles, which are subsequently used as model additives during the growth of calcite crystals. Impressively, such guest nanoparticles are preferentially occluded into specific regions of calcite depending on the initial [Ca2+] concentration. These unprecedented phenomena are most probably caused by dynamic change in electrostatic interaction between Ca2+ ions and PSPMA41 chains based on systematic investigations. This study not only showcases a significant advancement in controlling the spatial distribution of guest nanoparticles within host crystals, enabling the internal structure of composite crystals to be rationally tailored via a spatioselective occlusion strategy, but also provides new insights into biomineralization.

DOI: 10.1002/anie.202410908

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202410908