NMR manifestations and molecular dynamics modeling of chiral recognition of α-pinenes by α-cyclodextrin

被引:20
作者
Dodziuk, H
Kozminski, W
Lukin, O
Sybilska, D
机构
[1] Polish Acad Sci, Inst Phys Chem, PL-01224 Warsaw, Poland
[2] Warsaw Univ, Dept Chem, Warsaw, Poland
[3] Polish Acad Sci, Inst Organ Chem, PL-01224 Warsaw, Poland
关键词
H-1; NMR; C-13; alpha-cyclodextrin; alpha-pinene; chiral recognition; molecular dynamics;
D O I
10.1016/S0022-2860(99)00409-3
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
NMR manifestations of chiral recognition of alpha-pinene enantiomers by alpha-cyclodextrin in D2O have been observed in both proton and carbon spectra. The largest splittings in the former spectra amounted to 0.06 ppm while an unusually high value of 1.3 ppm was found in the corresponding carbon spectra. Different mobilities of the enantiomeric guests in the host cavities have been established in D2O using NOE and ROESY techniques. Molecular dynamics simulations indicated the instability of the complexes of 1:1 stoichiometry both in vacuum and water. However, the corresponding calculations for the 1:2 stoichiometry in vacuum gave incorrectly larger stability of the complex with the (1R,5R)-enantiomer of alpha-pinene. Long simulations of 3.5 ns in water reproduce the stability order of the diastereomeric complexes. (C) 2000 Elsevier Science B.V. All rights reserved.
引用
收藏
页码:205 / 212
页数:8
相关论文
共 32 条
[1]   PRACTICAL ASPECTS OF TWO-DIMENSIONAL TRANSVERSE NOE SPECTROSCOPY [J].
BAX, A ;
DAVIS, DG .
JOURNAL OF MAGNETIC RESONANCE, 1985, 63 (01) :207-213
[2]  
*BIOSYM TECHN INC, INSIGHT 2 VERS 97 0
[3]  
Black DR, 1996, J COMPUT CHEM, V17, P931, DOI 10.1002/(SICI)1096-987X(199606)17:8<931::AID-JCC2>3.0.CO
[4]  
2-S
[5]   NMR DIFFERENTIATION OF ENANTIOMERIC (+)-ALPHA-PINENE AND (-)-ALPHA-PINENE VIA COMPLEXATION WITH CYCLODEXTRINS IN WATER [J].
BOTSI, A ;
YANNAKOPOULOU, K ;
HADJOUDIS, E ;
PERLY, B .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1993, (13) :1085-1086
[6]   (+)- and (-)-alpha-pinene as chiral recognition probes with natural cyclodextrins and their permethylated derivatives. An aqueous NMR study [J].
Botsi, A ;
Perly, B ;
Hadjoudis, E .
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1997, (01) :89-94
[7]   ARYL GROUP PI-FACIAL ELECTROSTATIC ASYMMETRY AS A CONTRIBUTING FACTOR TO CHIRAL RESOLUTION ON BETA-CYCLODEXTRIN HPLC PHASES [J].
CAMILLERI, P ;
EDWARDS, AJ ;
RZEPA, HS ;
GREEN, SM .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1992, (16) :1122-1124
[8]  
Connors K. A, 1987, BINDING CONSTANTS ME
[9]   THE OPTICAL RESOLUTION OF AROMATIC AMINO-ACIDS ON PAPER CHROMATOGRAMS [J].
DALGLIESH, CE .
JOURNAL OF THE CHEMICAL SOCIETY, 1952, (OCT) :3940-3942
[10]   STRUCTURE AND ENERGETICS OF LIGAND-BINDING TO PROTEINS - ESCHERICHIA-COLI DIHYDROFOLATE REDUCTASE TRIMETHOPRIM, A DRUG-RECEPTOR SYSTEM [J].
DAUBEROSGUTHORPE, P ;
ROBERTS, VA ;
OSGUTHORPE, DJ ;
WOLFF, J ;
GENEST, M ;
HAGLER, AT .
PROTEINS-STRUCTURE FUNCTION AND GENETICS, 1988, 4 (01) :31-47