MODELING THE COMPLEXATION OF SUBSTITUTED BENZENES BY A CYCLOPHANE HOST IN WATER

被引:23
作者
JORGENSEN, WL
NGUYEN, TB
机构
[1] Department of Chemistry, Yale University, New Haven
关键词
MOLECULAR RECOGNITION; BINDING AFFINITIES; MONTE-CARLO SIMULATIONS;
D O I
10.1073/pnas.90.4.1194
中图分类号
O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];
学科分类号
07 ; 0710 ; 09 ;
摘要
Monte Carlo statistical mechanics simulations have been used to study the complexation of disubstituted benzenes by Diederich's octamethoxy tetraoxaparacyclophane host. Relative free energies of binding were obtained in water at 25-degrees-C for benzene, p-xylene, p-cresol, p-dicyanobenzene, and hydroquinone from statistical perturbation theory. The computed results agree well with experimental data, including the binding affinity of benzene, which was determined after the calculations were completed. The computed structures for the complexes reveal details that are important for understanding the order of binding affinities. It is found that hydroquinone protrudes from one side of the complex and participates in hydrogen bonds between one hydroxyl group and two water molecules and in an intracomplex hydrogen bond between the other hydroxyl group and ether oxygens. The calculations also show a clear preference for binding p-cresol with the hydroxyl group hydrated rather than inside the host's cavity.
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页码:1194 / 1200
页数:7
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