Random chiral asymmetry generation by chiral autocatalysis in a far-from-equilibrium reaction system

被引:34
作者
Asakura, K
Ikumo, A
Kurihara, K
Osanai, S
Kondepudi, DK
机构
[1] Keio Univ, Fac Sci & Technol, Dept Appl Chem, Yokohama, Kanagawa 2238522, Japan
[2] Wake Forest Univ, Dept Chem, Winston Salem, NC 27109 USA
关键词
D O I
10.1021/jp9936796
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
If the growth in a local concentration due to an autocatalytic process overcomes diffusion, a concentration fluctuation in a small volume will grow. In a chirally autocatalytic system, this phenomenon could produce a large variation in the enantiomeric excess (ee). Here we report kinetic studies that show such stochastic behavior in the synthesis of an autocatalytic chiral cobalt complex. The established values of the kinetic parameters indicate that temperature inhomogeneities in the form of local hot spots can have a significant effect on the progress of the reaction as well as the ee of the final product. Stochastic kinetics of this type are in stark contrast to deterministic kinetics that are usually encountered in chemistry; in these systems random fluctuations play an important role in determining the product distribution. In the present case we find large random fluctuations in the ee.
引用
收藏
页码:2689 / 2694
页数:6
相关论文
共 29 条
[1]   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
[2]   Formation of the intermediate, aquohydroxobis (ethylenediamine)cobalt(III) complex, in the preparation of cis-bromoamminebis (ethylenediamine)cobalt(III) bromide by the reaction of bis[bis(ethylenediamine)cobalt(III)-μ-dihydroxo]diaquocobalt(II) sulfate with ammonium bromide in water [J].
Asakura, K ;
Inoue, K ;
Osanai, S ;
Kondepudi, DK .
JOURNAL OF COORDINATION CHEMISTRY, 1998, 46 (02) :159-164
[3]  
Asakura K, 1998, CHIRALITY, V10, P343, DOI 10.1002/(SICI)1520-636X(1998)10:4<343::AID-CHIR9>3.3.CO
[4]  
2-2
[5]   ENANTIOSELECTIVE AUTOCATALYSIS - SPONTANEOUS RESOLUTION AND THE PREBIOTIC GENERATION OF CHIRALITY [J].
BONNER, WA .
ORIGINS OF LIFE AND EVOLUTION OF THE BIOSPHERE, 1994, 24 (01) :63-78
[6]   THE ORIGIN AND AMPLIFICATION OF BIOMOLECULAR CHIRALITY [J].
BONNER, WA .
ORIGINS OF LIFE AND EVOLUTION OF BIOSPHERES, 1991, 21 (02) :59-111
[7]  
BROWN DD, 1953, J CHEM SOC, P2673
[8]   COMPETITION STUDIES AND STEREOCHEMISTRY FOR BASE HYDROLYSIS AND INDUCED AQUATION OF SOME ACIDOAMMINEBIS(ETHYLENEDIAMINE)COBALT(3) IONS [J].
BUCKINGHAM, DA ;
OLSEN, II ;
SARGESON, AM .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1968, 90 (24) :6654-+
[9]  
Calvin Melvin., 1969, CHEM EVOLUTION
[10]   Enantiomeric excesses in meteoritic amino acids [J].
Cronin, JR ;
Pizzarello, S .
SCIENCE, 1997, 275 (5302) :951-955