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（R 2）为0.985，交叉验证相关系数（R2 cv ）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。
n-Octanol / water partition coefficients ( logKow ) for persistent organic pollutants (POPs)including polycyclic aromatic hydrocarbons( PAHs),polychlorinated dibenzo-p-diox-ins ( PCDDs ), polychlorinated dibenzofurans ( PCDFs ) and decabromodiphenylethane (DBDPE)have been determined by a modified method of reversed-phase high performance liq-uid chromatography(RP-HPLC). A dual-point retention time correction(DP-RTC)was used to rectify chromatographic retention time( tR )shift resulted from stationary phase aging and so on. Based on this correction,the relationship model between logKow and logkw ,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 logKow as training set,including benzene homologues, PAHs and PCDD / Fs-related compounds. A linear regression equation of logKow =(1. 18±0. 02) logkw +(0. 36±0. 11)was established with correlation coefficient(R2 )of 0. 985,cross-validated correlation coefficient( R2cv )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 logKow val-ues. The RP-HPLC-determined Kow values showed good consistency with shake-flask(SFM)or slow-stirring( SSM)results,especially for highly hydrophobic compounds. Then,the logKow 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 logKow val-ues of POPs with strong hydrophobicity.
参考文献
| [1] | Palczewska A;Neagu D;Ridley M.[J].J Cheminf,20135:16. |
| [2] | Pham-The H;Gonzalez-Alvarez I;Bermejo M.[J].Mol Inf,201332:459. |
| [3] | Yadav M;Joshi S;Nayarisseri A.[J].Interdiscip Sci Com-put Life Sci,20135:150. |
| [4] | Sidir Y G;Sidir I.[J].JOURNAL OF MOLECULAR STRUCTURE,20131045:131. |
| [5] | Lammel G;Heil A;Stemmler I.[J].Environmental Science and Technology,201347(20):11616. |
| [6] | Pincemaille J;Schummer C;Heinen E.[J].Food Chemistry,2014145:807. |
| [7] | 吴明红;李刚;徐刚.[J].环境化学,201231(11):1750. |
| [8] | 祝本琼;陈浩;李胜清.[J].色谱,201230(02):201. |
| [9] | Esposito M;Serpe F P;Diletti G.[J].CHEMOSPHERE,201494:62. |
| [10] | Lambert M K;Friedman C;Luey P.[J].Environmental Science and Technology,201145(10):4331. |
| [11] | Hu X B;Xu Z C;Peng X C.[J].ENVIRONMENTAL GEOCHEMISTRY AND HEALTH,201335:593. |
| [12] | Sun Y X;Xu X R;Hao Q.[J].CHEMOSPHERE,201495:442. |
| [13] | Salamova A;Hites R A.[J].Environmental Science and Technology,201347(01):349. |
| [14] | 杨扬;陈建海;常利平.[J].色谱,200826(05):646. |
| [15] | Guideline for Testing of Chemicals,No.107:Par-tition Coefficient(n-octanol/water)-Shake Flask Method[S].,1981. |
| [16] | Brooke D N;Dobbs A J;Williams N.[J].Ecotoxicology and Environmental Safety,198611(03):251. |
| [17] | Guideline for Testing of Chemicals,No.117:Parti-tion Coefficient(n-octanol/water)-High Performance Liq-uid Chromatography Method[S].,1989. |
| [18] | Braumann T.[J].Journal of Chromatography,1986373(02):191. |
| [19] | 卢佩章;卢小明;李秀珍.[J].科学通报,198227(19):1175. |
| [20] | Snyder L R;Dolan J W;Gant J R.[J].Journal of Chromatography,1979165(01):3. |
| [21] | Han S Y;Qiao J Q;Zhang Y Y.[J].CHEMOSPHERE,201183(02):131. |
| [22] | Hansch C;Leo A J.Substituent Constants for Correlation Analysis in Chemistry and Biology[M].New York:Wiley,1979 |
| [23] | Sangster J.[J].Journal of Physical and Chemical Reference Data,198918(03):1111. |
| [24] | De Bruijn J;Busser F;Seinen W.[J].Environmental Toxicology and Chemistry,19898(06):499. |
| [25] | Watarai H;Tanaka M;Suzuki N.[J].Analytical Chemistry,198254(04):702. |
| [26] | Doucette W J;Andren A W.[J].CHEMOSPHERE,198817(02):345. |
| [27] | Banerjee S;Yalkowsky S H;Valvani S C.[J].Environmental Science and Technology,198014(10):1227. |
| [28] | Hansch C;Fujita T.[J].Journal of the American Chemical Society,196486(08):1616. |
| [29] | Demaaged P;Hulscher D;Heuvel H.[J].Environ Toxi-col Chem,199817(02):251. |
| [30] | Helweg C;Nielsen T;Hansen P.[J].CHEMOSPHERE,199734(08):1673. |
| [31] | Kenaga E E;Goring C A I;Eaton J G.Aquatic Toxi-cology[A].,1980:78. |
| [32] | 何艺兵;赵元慧;王连生.[J].环境化学,199413(03):195. |
| [33] | Valsaraj K;Thibodeaux L.[J].Separation Science and Technology,199025(04):369. |
| [34] | Rapaport R A;Eisenreich S J.[J].Environmental Science and Technology,198418(03):163. |
| [35] | Bruggeman W;Van Der Steen J;Hutzinger O.[J].J Chroma-togr,1982238(02):335. |
| [36] | Risby T;Hsu T-B;Sehnert S.[J].Environmental Science and Technology,199024(11):1680. |
| [37] | Gobas F;Lahittete J;Garofalo G.[J].Journal of Pharmaceutical Sciences,198877(03):265. |
| [38] | Sijm D T H M;Wever H;De Vries P J.[J].Chemo-sphere,198919:263. |
| [39] | Sarna L P;Hodge P E;Webster G R B.[J].CHEMOSPHERE,198413(09):975. |
| [40] | Han S Y;Liang C;Qiao J Q.[J].Analytica Chimica Acta,2012713:130. |
| [41] | Lian H Z;Wang W H;Li D N.[J].Journal of Separation Science,200528:1179. |
| [42] | Ming X;Han S Y;Qi Z C.[J].TALANTA,200979(03):752. |
| [43] | Han S Y;Ming X;Qi Z C.[J].Analytical Biochemistry,2010398(06):2731. |
| [44] | Han S Y;Qiao J Q;Zhang Y Y.[J].TALANTA,201297:355. |
| [45] | Han S Y;Liang C;Zou K.[J].TALANTA,2012101:64. |
| [46] | 戚争春;梅少博;练鸿振.[J].中国科学:B 辑,200939(08):806. |
| [47] | Qi Z C;Han S Y;Wu Z Y.[J].Cur Anal Chem,201410:172. |
| [48] | Chen F Y;Cao X W;Han S Y.[J].J Liq Chromatogr Re-lat Technol |
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