Deck Leif-Thore, Hosseinalipour Mercedeh Sadat, Mazzotti Marco
Institute of Energy and Process Engineering, ETH Zurich, Zurich 8092, Switzerland.
J Am Chem Soc. 2024 Feb 14;146(6):3872-3882. doi: 10.1021/jacs.3c11332. Epub 2024 Feb 2.
Solid-state deracemization is the amplification of an enantiomeric excess in suspensions of conglomerate-forming chiral compounds. Although numerous chemical and biochemical compounds deracemize, its governing mechanism has remained elusive. We introduce a novel formulation of the classical population-based model of deracemization through temperature cycles to prove that suspensions deracemize whenever a simple and ubiquitous condition is met: crystal dissolution must be faster than crystal growth. Such asymmetry is a known principle of crystallization, hence explaining the generality of deracemization. Through both experiments and a theoretical analysis, we demonstrate that this condition applies even for very small temperature cycles and for random temperature fluctuations. These findings establish solid-state deracemization as an attractive route to the manufacture of enantiopure products and as a plausible pathway toward the emergence of homochirality in nature.
固态外消旋化是在手性化合物聚集体形成的悬浮液中对映体过量的放大。尽管有许多化学和生物化学化合物会发生外消旋化，但其控制机制仍然难以捉摸。我们通过温度循环引入了一种基于经典群体的外消旋化模型的新公式，以证明只要满足一个简单且普遍的条件，悬浮液就会发生外消旋化：晶体溶解必须比晶体生长快。这种不对称性是结晶的一个已知原理，从而解释了外消旋化的普遍性。通过实验和理论分析，我们证明了即使对于非常小的温度循环和随机温度波动，这一条件也适用。这些发现确立了固态外消旋化作为生产对映体纯产品的一条有吸引力的途径，以及作为自然界中同手性出现的一种合理途径。
