UV Spectroscopy Coupled with Partial Least Squares to Determine the Enantiomeric Composition in Chiral Drugs
LI Qian-qian1, WU Li-jun1, LIU Wei1, CAO Jin-li2, DUAN Jia1, HUANG Yue1, MIN Shun-geng1*
1. Department of Applied Chemistry, College of Science, China Agricultural University, Beijing 100193, China 2. Yunnan Dali Tobacco Company, Dali 671000, China
摘要： 利用R和S对映体与蔗糖间手性作用方式不同而产生的紫外吸收光谱差异分别测定了甲霜灵和布洛芬手性对映体的组成。采用偏最小二乘法(partial Least Squares, PLS)分别建立甲霜灵和布洛芬手性对映体摩尔分数的定量模型，并采用外部检验对模型效果进行评价。甲霜灵-蔗糖体系中精甲霜灵摩尔分数的定量模型校正集的决定系数R2为99.98%，标准偏差SEC为0.003;外部检验集的预测值与理论值的相关系数为0.999 8，标准偏差SEP为0.000 4，相对标准偏差RSD为 0.05%。布洛芬-蔗糖体系中S-布洛芬摩尔分数的定量模型校正集的决定系数R2为99.82%，标准偏差SEC为0.007;外部检验集的预测值与理论值的相关系数为0.998 1，标准偏差SEP为0.002，相对标准偏差RSD为0.2%;结果表明本方法可以用于两种药物对映体组成的快速测定，对手性药物质量分析与控制有重要的参考价值。
关键词：蔗糖;偏最小二乘法;紫外光谱法;手性分析;甲霜灵;布洛芬
Abstract：In the present study, sucrose was used as a chiral selector to detect the molar fraction of R-metalaxyl and S-ibuprofen due to the UV spectral difference caused by the interaction of the R- and S-isomer with sucrose. The quantitative model of the molar fraction of R-metalaxyl was established by partial least squares (PLS) regression and the robustness of the models was evaluated by 6 independent validation samples. The determination coefficient R2 and the standard error of calibration set (SEC) was 99.98% and 0.003 respectively. The correlation coefficient of estimated value and specified value, the standard error and the relative standard deviation (RSD) of the independent validation samples was 0.999 8, 0.000 4 and 0.054% respectively. The quantitative models of the molar fraction of S-ibuprofen were established by PLS and the robustness of models was evaluated. The determination coefficient R2 and the standard error of calibration set (SEC) was 99.82% and 0.007 respectively. The correlation coefficient of estimated value and specified value of the independent validation samples was 0.998 1. The standard error of prediction (SEP) was 0.002 and the relative standard deviation (RSD) was 0.2%. The result demonstrates that sucrose is an ideal chiral selector for building a stable regression model to determine the enantiomeric composition.
Key words：Sucrose;Partial least squares;Ultraviolet;Chirality analysis;Metalaxyl;Ibuprofen
李倩倩1，吴丽君1，刘 玮1，曹金莉2，段 佳1，黄 越1，闵顺耕1* . 紫外光谱结合偏最小二乘法测定手性药物对映体的组成[J]. 光谱学与光谱分析, 2012, 32(02): 500-504.
LI Qian-qian1, WU Li-jun1, LIU Wei1, CAO Jin-li2, DUAN Jia1, HUANG Yue1, MIN Shun-geng1* . UV Spectroscopy Coupled with Partial Least Squares to Determine the Enantiomeric Composition in Chiral Drugs. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2012, 32(02): 500-504.
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