International Joint Research Center for Persistent Toxic Substances (IJRC-PTS), College of Biological and Environmental Engineering, Zhejiang University of Technology, Hangzhou 310014, China.
J Chromatogr A. 2013 Mar 15;1281:26-31. doi: 10.1016/j.chroma.2013.01.016. Epub 2013 Jan 18.
Chiral separation mechanism determination and absolute configuration assignment are fundamental to the development of chiral stationary phases (CSPs) and the evaluation of both the enantioselective bioactivity and fate of chiral compounds. This work investigated the process of chiral separation and the assignment of the absolute configurations of malathion, malaoxon, and isomalathion using chiral high performance liquid chromatography (HPLC) coupled with chiral detector-binding energy computations. Hydrogen bonding was found to be a very important factor in the chiral separation of isomalathion on Chiralpak AD, although it did not exhibit a significant effect on the chiral separation of malathion and malaoxon on Chiralcel OJ. Based on the sign of a chiral detector, the relationships between the cotton effect, optical dispersion and absolute configuration were established for individual enantiomers of malathion, malaoxon, and isomalathion. The elution orders of the enantiomers of malathion and malaoxon on Chiralcel OJ and the stereoisomers of isomalathion on Chiralpak AD predicted by binding energy computations were found to coincide precisely with those observed in the chiral separation experiments. The result suggests that binding energy computations can be used to assign the absolute configuration of the enantiomers of chiral compounds eluted on CSPs.
手性分离机制的确定和绝对构型的赋值对于手性固定相（CSP）的发展以及手性化合物的对映选择性生物活性和命运的评估至关重要。本工作研究了使用手性高效液相色谱（HPLC）与手性检测剂结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合结合分离过程，并在手性 HPLC 测定马拉硫磷、马拉氧磷和异马拉硫磷的绝对构型。尽管氢键在手性分离马拉硫磷和马拉氧磷时没有表现出显著的影响，但它在手性分离异马拉硫磷时是一个非常重要的因素。基于手性检测剂的符号，建立了马拉硫磷、马拉氧磷和异马拉硫磷各个对映体的比旋光、光学色散和绝对构型之间的关系。通过结合能计算预测的马拉硫磷和马拉氧磷对映体在 Chiralcel OJ 上以及异马拉硫磷的立体异构体在 Chiralpak AD 上的洗脱顺序与在手性分离实验中观察到的完全吻合。结果表明，结合能计算可用于在手性固定相上洗脱的手性化合物对映体的绝对构型赋值。
