Asakura Kouichi, Nagasaka Yasushi, Hidaka Masashi, Hayashi Masato, Osanai Shuichi, Kondepudi Dilip K
Department of Applied Chemistry, Faculty of Science and Technology, Keio University, Hiyoshi, Kohoku, Yokohama, Japan.
Chirality. 2004 Feb;16(2):131-6. doi: 10.1002/chir.10315.
Although the theory of spontaneous chiral symmetry-breaking in open systems was proposed some time ago, experimental realization of this phenomenon has not been achieved. In this article, we note that the crystal growth front of 1,1'-binaphthyl shows many of the characteristics of an open system in which chiral symmetry-breaking has occurred. We studied the temperature profiles of the crystallizing surface and obtained X-ray diffraction data of the crystals grown from the melt under controlled conditions. The data show that, under appropriate conditions, the observed bimodal probability distribution of enantiomeric excess (ee) with maxima approximately 60% is due exclusively to chiral crystals and not due to racemic crystals of 1,1'-binaphthyl that can also form at large supercooling. The mass independence of the ee shows that the growing front maintains a constant ee, which is a clear signature of open systems in steady state. Chirality 16:131-136, 2004.
尽管开放系统中自发手性对称性破缺的理论早在一段时间之前就已提出,但这一现象的实验实现尚未达成。在本文中,我们注意到1,1'-联萘的晶体生长前沿展现出了许多已发生手性对称性破缺的开放系统的特征。我们研究了结晶表面的温度分布,并获取了在可控条件下从熔体中生长出的晶体的X射线衍射数据。数据表明,在适当条件下,所观察到的对映体过量(ee)呈现出最大值约为60%的双峰概率分布,这完全是由于手性晶体所致,而非由于在大过冷度下也能形成的1,1'-联萘的外消旋晶体。ee的质量独立性表明生长前沿维持着恒定的ee,这是稳态开放系统的一个明确标志。《手性》第16卷,第131 - 136页,2004年。