Li Ling, Zhou Shanshan, Zhao Meirong, Zhang Anping, Peng Hao, Tan Xiaosong, Lin Chunmian, He Hongwu
Research Center of Environmental Science, College of Biological and Environmental Engineering, Zhejiang University of Technology, Hangzhou 310032, China.
Chirality. 2008 Feb;20(2):130-8. doi: 10.1002/chir.20511.
A series of organophosphorous compounds (OPs), 1-(substituted phenoxyacetoxy)alkylphosphonates containing a chiral carbon atom, show notable herbicidal activities. In this study, the enantioselective separation and biological toxicity of all these compounds were investigated. The enantioselective separation on the columns of Chiralpak AD, Chiralpak AS, Chiralcel OD, and Chiralcel OJ were compared under various chromatographic conditions. All the analytes investigated obtained baseline resolution (R(s) > 1.5) on Chiralpak AD column, which showed best chiral separation capacity. Further investigation was carried out on Chiralpak AD to evaluate the influence of the mobile phase composition and column temperature. The effect of the structural features on discrimination was also examined. The resolved enantiomers were distinguished by their signs of circular dichroism. The acute aquatic toxicity of enantiomers and racemate to Daphnia magna (D. magna) were assessed. The in vivo assays showed that compound 3 was about 2-148.5 times more toxic than the other four analogues to D. magna. The racemates of compounds 3 and 5 showed intermediate toxicity compare to their enantiomers, while those of compounds 1, 2, and 4 showed synergistic or antagonistic effect. These results suggest that the biological toxicity of chiral OPs to nontarget organisms is enantioselective and therefore should be evaluated with their pure enantiomers.
一系列含有手性碳原子的有机磷化合物（OPs），即1-（取代苯氧基乙酰氧基）烷基膦酸酯，表现出显著的除草活性。在本研究中，对所有这些化合物的对映体选择性分离和生物毒性进行了研究。比较了在各种色谱条件下，在手性固定相Chiralpak AD、Chiralpak AS、Chiralcel OD和Chiralcel OJ柱上的对映体选择性分离情况。所有研究的分析物在手性固定相Chiralpak AD柱上均获得了基线分离度（R(s)>1.5），该柱显示出最佳的手性分离能力。在手性固定相Chiralpak AD上进一步开展研究，以评估流动相组成和柱温的影响。还考察了结构特征对拆分的影响。通过圆二色性的符号区分拆分得到的对映体。评估了对映体和外消旋体对大型溞（D. magna）的急性水生毒性。体内试验表明，化合物3对大型溞的毒性比其他四种类似物高约2 - 148.5倍。化合物3和5的外消旋体与其对映体相比表现出中等毒性，而化合物1、2和4的外消旋体则表现出协同或拮抗作用。这些结果表明，手性OPs对非靶标生物的生物毒性具有对映体选择性，因此应以其纯对映体进行评估。
