McKenna Brandon J, Waite J Herbert, Stucky Galen D
Department of Chemistry and Biochemistry, University of California, Santa Barbara, CA 93106 USA.
Cryst Growth Des. 2009 Oct 7;9(10):4335-4343. doi: 10.1021/cg900166u.
Biomineralization is an intricate process that relies on precise physiological control of solution and interface properties. Despite much research of the process, mechanistic details of biomineralization are only beginning to be understood, and studies of additives seldom investigate a wide space of chemical conditions in mineralizing solutions. We present a ternary diagram-based method that globally identifies the changing roles and effects of polymer additives in mineralization. Simple polyanions were demonstrated to induce a great variety of morphologies, each of which can be selectively and reproducibly fabricated. This chemical and physical analysis also aided in identifying conditions that selectively promote heterogeneous nucleation and controlled cooperative assembly, manifested here in the form of highly organized cones. Similar complex shapes of CaCO(3) have previously been synthesized using double hydrophilic block copolymers. We have found the biomimetic mineralization process to occur interfacially and by the assembly of precursor modules, which generate large mesocrystals with high dependence on pH and substrate surface.
生物矿化是一个复杂的过程，它依赖于对溶液和界面性质的精确生理控制。尽管对该过程进行了大量研究，但生物矿化的机制细节才刚刚开始被理解，并且添加剂的研究很少在矿化溶液中考察广泛的化学条件范围。我们提出了一种基于三元相图的方法，该方法能全面识别聚合物添加剂在矿化过程中不断变化的作用和影响。已证明简单的聚阴离子能诱导出多种形态，每种形态都可以选择性地、可重复地制备。这种化学和物理分析也有助于确定选择性促进异相成核和受控协同组装的条件，在此表现为高度有序的圆锥体形式。此前曾使用双亲水嵌段共聚物合成过类似形状复杂的碳酸钙。我们发现仿生矿化过程在界面处发生，并通过前体模块的组装进行，这会生成对pH值和底物表面高度依赖的大尺寸中晶。
