Kinetic model for the chiral symmetry breaking transition in the growth front of a conglomerate crystal phase

被引:12
作者
Asakura, K
Nagasaka, Y
Osanai, S
Kondepudi, DK
机构
[1] Keio Univ, Fac Sci & Technol, Dept Appl Chem, Koho Ku, Yokohama, Kanagawa 2238522, Japan
[2] Wake Forest Univ, Dept Chem, Winston Salem, NC 27109 USA
关键词
D O I
10.1021/jp0470041
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
In its molten phase, 1,1'-binaphthyl is racemic due to its high racemization rate, but it can crystallize as a conglomerate of R and S crystals. Our experiments have indicated that, under some conditions, the crystal growth front of 1, V-binaphthyl shows many of the characteristics of an open system in which chiral symmetry is broken; i.e., the growing solid phase becomes predominantly R or S. Here we present a kinetic model to explain the observed chiral symmetry breaking. The model is based on growth due to attachment of R or S growth units to a crystal surface in a supercooled melt. Chiral symmetry breaking occurs due to chirally autocatalytic formation of R or S growth units on the growth surface. Unlike the many models suggested and studied in the 1980s, there is no cross-inhibition between R- and S-enantiomer in the model presented here. In our model, asymmetric and symmetric steady-state solutions that do not intersect were found. Through linear stability analysis, the critical point, at which a symmetric solution becomes unstable and makes a transition to an asymmetric solution, is determined.
引用
收藏
页码:1586 / 1592
页数:7
相关论文
共 16 条
[1]   Chiral symmetry-breaking transition in growth front of crystal phase of 1,1′-binaphthyl in its supercooled melt [J].
Asakura, K ;
Nagasaka, Y ;
Hidaka, M ;
Hayashi, M ;
Osanai, S ;
Kondepudi, DK .
CHIRALITY, 2004, 16 (02) :131-136
[2]  
BADAR Y, 1965, J CHEM SOC, P1543
[3]  
Belousov B. P., 1958, PERIODIC REACTION IT, P145
[4]   EXPERIMENTAL-EVIDENCE OF A SUSTAINED STANDING TURING-TYPE NONEQUILIBRIUM CHEMICAL-PATTERN [J].
CASTETS, V ;
DULOS, E ;
BOISSONADE, J ;
DEKEPPER, P .
PHYSICAL REVIEW LETTERS, 1990, 64 (24) :2953-2956
[5]   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-&
[6]  
Epstein I. R., 1998, INTRO NONLINEAR CHEM
[7]   ON SPONTANEOUS ASYMMETRIC SYNTHESIS [J].
FRANK, FC .
BIOCHIMICA ET BIOPHYSICA ACTA, 1953, 11 (04) :459-463
[8]  
Kondepudi D., 1998, MODERN THERMODYNAMIC
[9]   CHIRAL-SYMMETRY-BREAKING STATES AND THEIR SENSITIVITY IN NONEQUILIBRIUM CHEMICAL-SYSTEMS [J].
KONDEPUDI, DK ;
NELSON, GW .
PHYSICA A, 1984, 125 (2-3) :465-496
[10]   WEAK NEUTRAL CURRENTS AND THE ORIGIN OF BIOMOLECULAR CHIRALITY [J].
KONDEPUDI, DK ;
NELSON, GW .
NATURE, 1985, 314 (6010) :438-441