Yashima E, Yamada M, Kaida Y, Okamoto Y
Department of Applied Chemistry, School of Engineering, Nagoya University, Japan.
J Chromatogr A. 1995 Mar 10;694(2):347-54. doi: 10.1016/0021-9673(94)01039-h.
The calculation of interaction energies between cellulose trisphenylcarbamate (CTPC) and enantiomers of (+/-)-trans-stilbene oxide (1) and (+/-)-trans-1,2-diphenylcyclopropane (2) was performed using QUANTA/CHARMm and MOLECULAR INTERACTION programs to gain an insight into the chiral recognition mechanism of phenylcarbamate derivatives of cellulose. The structure of CTPC was optimized with the CHARMm force field based on the proposed structure of CTPC by X-ray analysis. In chromatographic enantioseparation on CTPC, 1 was completely resolved (alpha = 1.46) and the (R,R)-(+)-isomer eluted first followed by the (S,S)-(-)-isomer, but 2 was not resolved (alpha approximately 1). The results of calculation of interaction energies between CTPC and the enantiomers 1 suggested that the most important adsorbing site of CTPC for 1 may be the NH protons of the carbamate moieties at the 3-position of glucose units, and the (S,S)-(-)-isomer of 1 may interact more closely than the (R,R)-(+)-isomer with CTPC. In contrast, there was little difference in the minimum interaction energies between the enantiomers 2. These calculations agreed with the observed results for the chromatographic resolution on CTPC.
使用QUANTA/CHARMm和分子相互作用程序计算了三苯基氨基甲酸纤维素酯（CTPC）与（±）-反式氧化苯乙烯（1）和（±）-反式-1,2-二苯基环丙烷（2）对映体之间的相互作用能，以深入了解纤维素苯基氨基甲酸酯衍生物的手性识别机制。基于X射线分析提出的CTPC结构，用CHARMm力场对CTPC的结构进行了优化。在CTPC上进行的色谱对映体分离中，1被完全拆分（α = 1.46），（R,R）-（+）-异构体先洗脱，随后是（S,S）-（-）-异构体，但2未被拆分（α约为1）。CTPC与对映体1之间相互作用能的计算结果表明，CTPC对1的最重要吸附位点可能是葡萄糖单元3位氨基甲酸酯部分的NH质子，并且1的（S,S）-（-）-异构体与CTPC的相互作用可能比（R,R）-（+）-异构体更紧密。相比之下，对映体2之间的最小相互作用能几乎没有差异。这些计算结果与在CTPC上进行色谱拆分的观察结果一致。
