保留时间两点校正反相高效液相色谱法测定持久性有机污染物的正辛醇-水分配系数

doi:10.3724/SP.J.1123.2013.10034

色谱 ›› 2014, Vol. 32 ›› Issue (4): 426-432.DOI: 10.3724/SP.J.1123.2013.10034

• 庆祝《色谱》创刊三十周年暨卢佩章院士九十华诞专刊-研究论文 • 上一篇下一篇

保留时间两点校正反相高效液相色谱法测定持久性有机污染物的正辛醇-水分配系数

梁超¹, 乔俊琴^1,2, 葛欣¹, 练鸿振^1,2

1. 南京大学化学化工学院, 江苏南京 210093;
2. 南京大学现代分析中心, 江苏南京 210093

收稿日期:2013-10-29 修回日期:2013-12-10 出版日期:2014-04-08 发布日期:2014-03-28
通讯作者: 葛欣, 练鸿振
基金资助:
国家重点基础研究发展计划（973计划）项目（2009CB421601，2011CB911003）；国家自然科学基金项目（21275069，90913012）.

Determination of n-octanol/water partition coefficients for persistent organic pollutants by reversed-phase high performance liquid chromatography with dual-point retention time correction

LIANG Chao¹, QIAO Junqin^1,2, GE Xin¹, LIAN Hongzhen^1,2

1. School of Chemistry & Chemical Engineering, Nanjing University, Nanjing 210093, China;
2. Center of Modern Analysis, Nanjing University, Nanjing 210093, China

Received:2013-10-29 Revised:2013-12-10 Online:2014-04-08 Published:2014-03-28

摘要/Abstract

摘要：

采用改进的反相高效液相色谱法（RP-HPLC）测定了持久性有机污染物（POPs）包括多环芳烃（PAHs）、多氯二苯并二恶英（PCDDs）、多氯二苯并呋喃（PCDFs）和十溴二苯乙烷（DBDPE）等的正辛醇-水分配系数（logK_ow）。采用保留时间双点校正法（DP-RTC）校正因色谱柱老化等引起的保留时间漂移。以37种有可靠logK_ow实验值的苯系物、PAHs、PCDD/Fs类似物为模型化合物，建立了logK_ow和外推至纯水相的保留因子logk_w的定量结构-色谱保留关系（QSRR）模型，回归方程为logK_ow=（1.18±0.02）logk_w+（0.36±0.11），其相关系数（R²）为0.985，交叉验证相关系数（R_cv²）为0.983，标准偏差（SD）为0.16。进而，用4个已有可靠logK_ow实验值的验证化合物（联苯、芴、PCDD 1和PCDF 114）对模型进行了外部验证，表明RP-HPLC测得的logK_ow值与摇瓶法/慢搅法结果有很好的一致性，尤其是对疏水性强的化合物。采用该模型测定了29种特别受关注的POPs的logK_ow值，这些化合物的logK_ow实验值均未见报道。所建立的DP-RTC-HPLC是测定强疏水性POPs的logK_ow值的一种值得推荐的方法。

关键词: 保留时间两点校正, 持久性有机污染物, 反相高效液相色谱, 正辛醇-水分配系数

Abstract:

n-Octanol/water partition coefficients (logK_ow) for persistent organic pollutants (POPs) including polycyclic aromatic hydrocarbons (PAHs), polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and decabromodiphenylethane (DBDPE) have been determined by a modified method of reversed-phase high performance liquid chromatography (RP-HPLC). A dual-point retention time correction (DP-RTC) was used to rectify chromatographic retention time (t_R) shift resulted from stationary phase aging and so on. Based on this correction, the relationship model between logK_ow and logk_w, the logarithm of the retention factor extrapolated to pure water, was trained by a set of model compounds (a total of 37) with reliable experimental logK_ow as training set, including benzene homologues, PAHs and PCDD/Fs-related compounds. A linear regression equation of logK_ow=(1.18±0.02) logk_w+(0.36±0.11) was established with correlation coefficient (R²) of 0.985, cross-validated correlation coefficient (R_cv²) of 0.983 and standard deviation (SD) of 0.16. This quantitative structure retention relationship (QSRR) model was further validated using four verification compounds, biphenyl, fluorene, PCDD 1 and PCDF 114, with reliable experimental logK_ow values. The RP-HPLC-determined K_ow values showed good consistency with shake-flask (SFM) or slow-stirring (SSM) results, especially for highly hydrophobic compounds. Then, the logK_ow values for 29 POPs of wide interest were evaluated by the improved RP-HPLC method for the first time. The DP-RTC-HPLC method is recommended for the determination of the logK_ow values of POPs with strong hydrophobicity.

Key words: n-octanol/water partition coefficient (K_ow), dual-point retention time correction (DP-RTC), persistent organic pollutants (POPs), reversed-phase high performance liquid chromatography (RP-HPLC)

中图分类号:

O658

梁超, 乔俊琴, 葛欣, 练鸿振. 保留时间两点校正反相高效液相色谱法测定持久性有机污染物的正辛醇-水分配系数[J]. 色谱, 2014, 32(4): 426-432.

LIANG Chao, QIAO Junqin, GE Xin, LIAN Hongzhen. Determination of n-octanol/water partition coefficients for persistent organic pollutants by reversed-phase high performance liquid chromatography with dual-point retention time correction[J]. Chinese Journal of Chromatography, 2014, 32(4): 426-432.

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保留时间两点校正反相高效液相色谱法测定持久性有机污染物的正辛醇-水分配系数

Determination of n-octanol/water partition coefficients for persistent organic pollutants by reversed-phase high performance liquid chromatography with dual-point retention time correction

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