色谱
色譜
색보
CHINESE JOURNAL OF CHROMATOGRAPHY
2014年
4期
426-432
,共7页
梁超%乔俊琴%葛欣%练鸿振
樑超%喬俊琴%葛訢%練鴻振
량초%교준금%갈흔%련홍진
反相高效液相色谱%保留时间两点校正%持久性有机污染物%正辛醇-水分配系数
反相高效液相色譜%保留時間兩點校正%持久性有機汙染物%正辛醇-水分配繫數
반상고효액상색보%보류시간량점교정%지구성유궤오염물%정신순-수분배계수
reversed-phase high performance liquid chromatography( RP-HPLC)%dual-point retention time correction( DP-RTC)%persistent organic pollutants( POPs)%n-octanol / water partition coefficient(K ow )
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。
採用改進的反相高效液相色譜法(RP-HPLC)測定瞭持久性有機汙染物( POPs)包括多環芳烴( PAHs)、多氯二苯併二噁英(PCDDs)、多氯二苯併呋喃(PCDFs)和十溴二苯乙烷( DBDPE)等的正辛醇-水分配繫數( logK ow )。採用保留時間雙點校正法(DP-RTC)校正因色譜柱老化等引起的保留時間漂移。以37種有可靠 logK ow 實驗值的苯繫物、PAHs、PCDD / Fs 類似物為模型化閤物,建立瞭 logK ow 和外推至純水相的保留因子 logk w 的定量結構-色譜保留關繫(QSRR)模型,迴歸方程為 logK ow =(1.18±0.02)logk w +(0.36±0.11),其相關繫數(R 2)為0.985,交扠驗證相關繫數(R2 cv )為0.983,標準偏差(SD)為0.16。進而,用4箇已有可靠 logK ow實驗值的驗證化閤物(聯苯、芴、PCDD 1和 PCDF 114)對模型進行瞭外部驗證,錶明 RP-HPLC 測得的 logK ow 值與搖瓶法/慢攪法結果有很好的一緻性,尤其是對疏水性彊的化閤物。採用該模型測定瞭29種特彆受關註的 POPs 的 logK ow 值,這些化閤物的logK ow 實驗值均未見報道。所建立的 DP-RTC-HPLC 是測定彊疏水性 POPs 的 logK ow值的一種值得推薦的方法。
채용개진적반상고효액상색보법(RP-HPLC)측정료지구성유궤오염물( POPs)포괄다배방경( PAHs)、다록이분병이악영(PCDDs)、다록이분병부남(PCDFs)화십추이분을완( DBDPE)등적정신순-수분배계수( logK ow )。채용보류시간쌍점교정법(DP-RTC)교정인색보주노화등인기적보류시간표이。이37충유가고 logK ow 실험치적분계물、PAHs、PCDD / Fs 유사물위모형화합물,건립료 logK ow 화외추지순수상적보류인자 logk w 적정량결구-색보보류관계(QSRR)모형,회귀방정위 logK ow =(1.18±0.02)logk w +(0.36±0.11),기상관계수(R 2)위0.985,교차험증상관계수(R2 cv )위0.983,표준편차(SD)위0.16。진이,용4개이유가고 logK ow실험치적험증화합물(련분、물、PCDD 1화 PCDF 114)대모형진행료외부험증,표명 RP-HPLC 측득적 logK ow 치여요병법/만교법결과유흔호적일치성,우기시대소수성강적화합물。채용해모형측정료29충특별수관주적 POPs 적 logK ow 치,저사화합물적logK ow 실험치균미견보도。소건립적 DP-RTC-HPLC 시측정강소수성 POPs 적 logK ow치적일충치득추천적방법。
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.