Pasteur's Tweezers Revisited: On the Mechanism of Attrition-Enhanced Deracemization and Resolution of Chiral Conglomerate Solids
Pasteur's Tweezers Revisited: On the Mechanism of Attrition-Enhanced Deracemization and Resolution of Chiral Conglomerate Solids
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DOI：
10.1021/ja303566g
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发表时间：
2012-08-01
影响因子：
15
通讯作者：
Blackmond, Donna G.
中科院分区：
文献类型：
--
作者：
Hein, Jason E.;Cao, Blessing Huynh;Blackmond, Donna G.
通过晶体尺寸和溶解度测量以及同位素标记实验，深入了解了固体对映体手性化合物的摩擦增强去消旋和拆分机制。这些结果有助于解卷积的各种化学和物理速率过程的现象。晶体尺寸测量强调了晶体的随机、瞬时生长与磨损条件下单一固体对映体的出现之间的明显相关性。的快速传质的溶液和固相之间的摩擦下的分子被证明，和晶体尺寸引起的溶解度驱动力的概念被利用，以克服晶体生长和溶解过程的随机性。非外消旋条件的扩展为手性拆分提供了一种新的方法。实际的手性分离和生物纯手性的起源的影响进行了讨论。
Insights into the mechanism of attrition-enhanced deracemization and resolution of solid enantiomorphic chiral compounds are obtained by crystal size and solubility measurements and by isotopic labeling experiments. Together these results help to deconvolute the various chemical and physical rate processes contributing to the phenomenon. Crystal size measurements highlight a distinct correlation between the stochastic, transient growth of crystals and the emergence of a single solid enantiomorph under attrition conditions. The rapid mass transfer of molecules between the solution and solid phases under attrition is demonstrated, and the concept of a crystal-size-induced solubility driving force is exploited to overcome the stochastic nature of the crystal growth and dissolution processes. Extension to non-racemizing conditions provides a novel methodology for chiral resolution. Implications both for practical chiral separations and for the origin of biological homochirality are discussed.