Chiral symmetry-breaking transition in growth front of crystal phase of 1,1′-binaphthyl in its supercooled melt

被引:15
作者
Asakura, K
Nagasaka, Y
Hidaka, M
Hayashi, M
Osanai, S
Kondepudi, DK
机构
[1] Keio Univ, Dept Appl Chem, Fac Sci & Technol, Kohoku Ku, Yokohama, Kanagawa 2238522, Japan
[2] Wake Forest Univ, Dept Chem, Winston Salem, NC 27109 USA
关键词
chiral autocatalysis; total spontaneous resolution; conglomerate crystallization; racemic mixture; racemic compound; supercooling;
D O I
10.1002/chir.10315
中图分类号
R914 [药物化学];
学科分类号
100701 ;
摘要
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 similar to 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. (C) 2004 Wiley-Liss, Inc.
引用
收藏
页码:131 / 136
页数:6
相关论文
共 26 条
[1]   Role of latent heat in chiral symmetry breaking transition in the crystallization of 1,1′-binaphthyl [J].
Asakura, K ;
Hayashi, M ;
Osanai, S .
CHIRALITY, 2003, 15 (03) :238-241
[2]   GENERATION OF AN OPTICALLY-ACTIVE OCTAHEDRAL COBALT COMPLEX BY A CHIRAL AUTOCATALYSIS [J].
ASAKURA, K ;
KOBAYASHI, K ;
MIZUSAWA, Y ;
OZAWA, T ;
OSANAI, S ;
YOSHIKAWA, S .
PHYSICA D, 1995, 84 (1-2) :72-78
[3]   Probability distributions of enantiomeric excess in unstirred and stirred crystallization of 1,1'-binaphthyl melt [J].
Asakura, K ;
Soga, T ;
Uchida, T ;
Osanai, S ;
Kondepudi, DK .
CHIRALITY, 2002, 14 (01) :85-89
[4]  
Asakura K, 1998, CHIRALITY, V10, P343, DOI 10.1002/(SICI)1520-636X(1998)10:4<343::AID-CHIR9>3.3.CO
[5]  
2-2
[6]   Random chiral asymmetry generation by chiral autocatalysis in a far-from-equilibrium reaction system [J].
Asakura, K ;
Ikumo, A ;
Kurihara, K ;
Osanai, S ;
Kondepudi, DK .
JOURNAL OF PHYSICAL CHEMISTRY A, 2000, 104 (12) :2689-2694
[7]  
BADAR Y, 1965, J CHEM SOC, P1543
[8]  
Calvin Melvin., 1969, CHEM EVOLUTION
[9]   OPTICAL RESOLUTION BY DIRECT CRYSTALLIZATION OF ENANTIOMER MIXTURES [J].
COLLET, A ;
BRIENNE, MJ ;
JACQUES, J .
CHEMICAL REVIEWS, 1980, 80 (03) :215-230
[10]   GROUND-STATE STRAIN AND OTHER FACTORS INFLUENCING OPTICAL STABILITY IN 1,1'-BINAPHTHYL SERIES [J].
COOKE, AS ;
HARRIS, MM .
JOURNAL OF THE CHEMICAL SOCIETY, 1963, (APR) :2365-&