Yu Shu-Hong, Cölfen Helmut, Antonietti Markus
Max Planck Institute of Colloids and Interfaces, Department of Colloid Chemistry, MPI Research Campus Golm, D-14424 Potsdam, Germany, and Department of Materials Science and Engineering and Structure Research Laboratory of CAS, University of Science and Technology of China, Hefei 230026, P. R. China.
J Phys Chem B. 2003 Jul 31;107(30):7396-405. doi: 10.1021/jp034009+.
Different morphosynthesis strategies for various metal carbonate minerals such as CaCO3, BaCO3, CdCO3, MnCO3, and PbCO3 using double hydrophilic block copolymers (DHBCs) as crystal modifiers are presented. The influence of the DHBCs with different functionalities such as carboxyl, partially phosphonated, and phosphorylated groups on the crystallization and structure formation was investigated. Well-defined crystals with size range from mesoscale to microscale can be easily obtained. More complex higher-order superstructures such as hollow spheres and big spherules with controlled surface structures can also be assembled conveniently. The results show that polymer-controlled mineralization is a versatile tool toward crystal morphogenesis. A time-dependent self-assembly and growth of "sphere-to-rod-to-dumbbell-to-sphere" structures was observed in the case of BaCO3 under the control of DHBCs, adding to the already reported examples of CaCO3 and fluoroapatite. In addition, we found that the influence of the DHBCs while increasing the ionic strength was lost in case of CaCO3, implying that the strong selective interaction between the functional groups of DHBCs and crystals has electrostatic contributions.
本文介绍了使用双亲水嵌段共聚物（DHBCs）作为晶体改性剂，针对各种金属碳酸盐矿物（如碳酸钙、碳酸钡、碳酸镉、碳酸锰和碳酸铅）的不同形态合成策略。研究了具有不同官能团（如羧基、部分膦酸化和磷酸化基团）的DHBCs对结晶和结构形成的影响。可以轻松获得尺寸范围从介观尺度到微观尺度的明确晶体。还可以方便地组装更复杂的高阶超结构，如具有可控表面结构的空心球和大球粒。结果表明，聚合物控制的矿化是实现晶体形态发生的一种通用工具。在DHBCs的控制下，碳酸钡的情况下观察到了“球-棒-哑铃-球”结构的时间依赖性自组装和生长，这增加了已报道的碳酸钙和氟磷灰石的例子。此外，我们发现，在碳酸钙的情况下，增加离子强度时DHBCs的影响消失了，这意味着DHBCs官能团与晶体之间的强选择性相互作用具有静电贡献。
