Thermodynamic and nuclear magnetic resonance study of the reactions of alpha- and beta-cyclodextrin with acids, aliphatic amines, and cyclic alcohols

被引:169
作者
Rekharsky, MV
Mayhew, MP
Goldberg, RN
Ross, PD
Yamashoji, Y
Inoue, Y
机构
[1] NIST,DIV BIOTECHNOL,GAITHERSBURG,MD 20899
[2] NIH,MOL BIOL LAB,BETHESDA,MD 20892
[3] OSAKA UNIV,FAC ENGN,DEPT MOL CHEM,SUITA,OSAKA 565,JAPAN
来源
JOURNAL OF PHYSICAL CHEMISTRY B | 1997年 / 101卷 / 01期
关键词
D O I
10.1021/jp962715n
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
Titration calorimetry was used to determine equilibrium constants and standard molar enthalpy, Gibbs energy, and entropy changes for the reactions of a series of acids, amines, and cyclic alcohols with alpha- and beta-cyclodextrin. The results have been examined in terms of structural features in the ligands such as the number of alkyl groups, the charge number, the presence of a double bond, branching, and the presence of methyl and methoxy groups. The values of thermodynamic quantities, in particular the standard molar Gibbs energy, correlate well with the structural features in the ligands. These structural correlations can be used for the estimation of thermodynamic quantities for related reactions. Enthalpy-entropy compensation is evident when the individual classes of substances studied herein are considered, but does not hold when these various classes of ligands are considered collectively. The NMR results indicate that the mode of accommodation of the acids and amines in the alpha-cyclodextrin cavity is very similar, but that the 1-methyl groups in 1-methylhexylamine and in 1-methylheptylamine and the N-methyl group in N-methylhexylamine lie outside the alpha-cyclodextrin cavity. This latter finding is consistent with the calorimetric results. Many of the thermodynamic and NMR results can be qualitatively understood in terms of van der Waals forces and hydrophobic effects.
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页码:87 / 100
页数:14
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