A new quantitative structure-retention relationship (QSRR) model is developed for polychlorinated dibenzofurans (PCDFs) based on molecular interaction field (MIF) analysis. The MIF of all 135 PCDFs is calculated using DRY, C1= and C3 probe, characterizing the hydrophobic and steric interaction between PCDFs and different groups of stationary phase. Then QSRR model is constructed by multiblock partial least squares (MBPLS), and the significance of each block is evaluated by the block importance in the prediction (BIP) method. The model used for prediction is statistically significant, with calibration and cross-validation correlation coefficients 0.9990 and 0.9980 respectively, and relative error less than 1.0%. The results of MBPLS and BIP show that the steric properties have dominant influence on the retention behavior of PCDFs, and then the hydrophobic effects.
提出了基于分子相互作用力场(MIF)、应用偏最小二乘(PLS)与多区组偏最小二乘(MBPLS)分析相结合,建立并检验多氯代二苯并二噁英(PCDD)定量结构-色谱保留关系(QSRR)模型的研究方法。分别以表征van der Waals、氢键和疏水效应的C3、H和DRY探针,计算75种PCDD的分子相互作用力场,并与其气相色谱Kov偄ts保留指数进行PLS与MBPLS分析,建立了拟合与预测效果良好的QSRR模型。其中MBPLS模型相关系数r2为0.998;交叉验证的相关系数q2为0.994。采用投影变量重要性方法判断了各种效应在PCDD色谱保留中的贡献。结果表明:van der Waals作用的影响最大,其次为疏水效应,而氢键效应影响较小。
