Centre for Biomaterials and Biopathways and Department of Chemistry, Zhejiang University, Hangzhou, 310027, China.
Nanoscale. 2013 Apr 7;5(7):3006-12. doi: 10.1039/c3nr33782k.
Most spiral coiled biomaterials in nature, such as gastropod shells, are homochiral, and the favoured chiral feature can be precisely inherited. This inspired us that selected material structures, including chirality, could be specifically replicated into the self-similar populations; however, a physicochemical understanding of the material-based heritage is unknown. We study the homochirality by using calcium phosphate mineralization in the presence of racemic amphiphilic molecules and biological protein. The organic-inorganic hybrid materials with spiral coiling characteristics are produced at the nanoscale. The resulted helixes are chiral with the left- and right-handed characteristics, which are agglomerated hierarchically to from clusters and networks. It is interesting that each cluster or network is homochiral so that the enantiomorphs can be separated readily. Actually, each homochiral architecture is evolved from an original chiral helix, demonstrating the heritage of the matrix chirality during the material proliferation under a racemic condition. By using the Ginzburg-Landaue expression we find that the chiral recognition in the organic-inorganic hybrid formation may be determined by a spontaneous chiral separation and immobilization of asymmetric amphiphilic molecules on the mineral surface, which transferred the structural information from the mother matrix to the descendants by an energetic control. This study shows how biomolecules guide the selective amplification of chiral materials via spontaneous self-replication. Such a strategy can be applied generally in the design and production of artificial materials with self-similar structure characteristics.
自然界中大多数螺旋状卷曲的生物材料，如腹足纲贝类，都是手性的，而且所偏好的手性特征可以被精确地继承。这启发我们，包括手性在内的特定材料结构可以被特定地复制到自相似群体中；然而，对于基于物质的遗传的物理化学理解尚不清楚。我们通过在旋光性的两亲性分子和生物蛋白质存在的情况下进行磷酸钙矿化来研究手性。在纳米尺度上产生具有螺旋卷曲特征的有机-无机杂化材料。所得螺旋体具有左手和右手的特征，它们以层级方式聚集形成团簇和网络。有趣的是，每个团簇或网络都是手性的，因此可以很容易地分离出对映异构体。实际上，每个手性结构都是从原始的手性螺旋体进化而来的，这表明在旋光条件下基质手性在手性材料的增殖过程中得到了遗传。通过使用金兹堡-朗道方程，我们发现有机-无机杂化形成中的手性识别可能是由不对称两亲性分子在矿物表面的自发手性分离和固定决定的，这种手性分离和固定将结构信息从母基质传递到后代，从而通过能量控制来实现。本研究展示了生物分子如何通过自发自我复制来指导手性材料的选择性放大。这种策略可以广泛应用于具有自相似结构特征的人工材料的设计和生产。
