title: Development of negligible depletion hollow fiber membrane-protected liquid-phase microextraction for simultaneous determination of partitioning coefficients and acid dissociation constants.
abstract: A new method based on negligible depletion hollow fiber-protected liquid-phase microextraction coupled with high-performance liquid chromatography (HPLC) was developed for the simultaneous determination of partitioning coefficients (K(OW)) and acid dissociation constants (pK(a)), by using phenol, 4-chlorophenol and 2,4-dichlorophenol as model compounds. A 37-mm length polypropylene hollow fiber membranes (600 microm inner diameter, 200 microm wall-thickness, 0.2 microm pore size, approximately 70% porosity) with two-end sealed were filled with 1-octanol by ultrasonic agitation to prepare the extraction device. The extraction device was deployed in sample solutions, prepared by spiking target analytes in 1-octanol saturated aqueous solutions (500 mL), for negligible depletion extraction. After equilibrium was reached ( approximately 5h), the 1-octanol in the lumen of the hollow fiber membrane was collected for HPLC determination of the target analytes. As the depletion of the analytes in aqueous samples was negligible, the distribution coefficient (D(OW)) could be calculated based on the measured equilibrium concentration in 1-octanol (C(O)) and the initial concentration (C(W)) in the aqueous sample of the target analyte (D(OW)=C(O)/C(W)). The D(OW) values measured at various pH values were nonlinearly regressed with pH to obtain the K(OW) and pK(a) values of a compound. Results showed that the measured values of the K(OW) and pK(a) of these model compounds agreed well with literature data.
authors.affiliation: State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing, China. jfliu@rcees.ac.cn
authors.forename: Jing-fu
authors.initials: JF
authors.lastname: Liu
authors.forename: Xiao-qiang
authors.initials: XQ
authors.lastname: Cai
authors.forename: Zi-fu
authors.initials: ZF
authors.lastname: Li
authors.forename: Gui-bin
authors.initials: GB
authors.lastname: Jiang
mesh_terms: D020003:1-Octanol / Q000737:chemistry; D005591:Chemical Fractionation / Q000295:instrumentation* / Q000379:methods*; D002851:Chromatography, High Pressure Liquid / Q000379:methods*; D006863:Hydrogen-Ion Concentration; D010636:Phenols / Q000032:analysis / Q000737:chemistry; D012044:Regression Analysis
chemical_list: D010636:Phenols; D020003:1-Octanol