TY - JOUR

T1 - Kinetic aspects of hollow fiber liquid-phase microextraction and electromembrane extraction

AU - Gjelstad, Astrid

AU - Jensen, Henrik

AU - Rasmussen, Knut Einar

AU - Pedersen-Bjergaard, Stig

N1 - Copyright © 2012 Elsevier B.V. All rights reserved.

PY - 2012/9/12

Y1 - 2012/9/12

N2 - In this paper, extraction kinetics was investigated experimentally and theoretically in hollow fiber liquid-phase microextraction (HF-LPME) and electromembrane extraction (EME) with the basic drugs droperidol, haloperidol, nortriptyline, clomipramine, and clemastine as model analytes. In HF-LPME, the analytes were extracted by passive diffusion from an alkaline sample, through a (organic) supported liquid membrane (SLM) and into an acidic acceptor solution. In EME, the analytes were extracted by electrokinetic migration from an acidic sample, through the SLM, and into an acidic acceptor solution by application of an electrical potential across the SLM. In both HF-LPME and EME, the sample (donor solution) was found to be rapidly depleted for analyte. In HF-LPME, the mass transfer across the SLM was slow, and this was found to be the rate limiting step of HF-LPME. This finding is in contrast to earlier discussions in the literature suggesting that mass transfer across the boundary layer at the donor-SLM interface is the rate limiting step of HF-LPME. In EME, mass transfer across the SLM was much more rapid due to electrokinetic migration. Nevertheless, mass transfer across the SLM was rate limiting even in EME. Theoretical models were developed to describe the kinetics in HF-LPME, in agreement with the experimental findings. In HF-LPME, the extraction efficiency was found to be maintained even if pH in the donor solution was lowered from 10 to 7-8, which was below the pK(a)-value for several of the analytes. Similarly, in EME, the extraction efficiency was found to be maintained even if pH in the donor solution increased from 4 to 11, which was above the pK(a)-value for several of the analytes. The two latter experiments suggested that both techniques may be used to effectively extract analytes from samples in a broader pH range as compared to the pH range recommended in the literature.

AB - In this paper, extraction kinetics was investigated experimentally and theoretically in hollow fiber liquid-phase microextraction (HF-LPME) and electromembrane extraction (EME) with the basic drugs droperidol, haloperidol, nortriptyline, clomipramine, and clemastine as model analytes. In HF-LPME, the analytes were extracted by passive diffusion from an alkaline sample, through a (organic) supported liquid membrane (SLM) and into an acidic acceptor solution. In EME, the analytes were extracted by electrokinetic migration from an acidic sample, through the SLM, and into an acidic acceptor solution by application of an electrical potential across the SLM. In both HF-LPME and EME, the sample (donor solution) was found to be rapidly depleted for analyte. In HF-LPME, the mass transfer across the SLM was slow, and this was found to be the rate limiting step of HF-LPME. This finding is in contrast to earlier discussions in the literature suggesting that mass transfer across the boundary layer at the donor-SLM interface is the rate limiting step of HF-LPME. In EME, mass transfer across the SLM was much more rapid due to electrokinetic migration. Nevertheless, mass transfer across the SLM was rate limiting even in EME. Theoretical models were developed to describe the kinetics in HF-LPME, in agreement with the experimental findings. In HF-LPME, the extraction efficiency was found to be maintained even if pH in the donor solution was lowered from 10 to 7-8, which was below the pK(a)-value for several of the analytes. Similarly, in EME, the extraction efficiency was found to be maintained even if pH in the donor solution increased from 4 to 11, which was above the pK(a)-value for several of the analytes. The two latter experiments suggested that both techniques may be used to effectively extract analytes from samples in a broader pH range as compared to the pH range recommended in the literature.

KW - Antipsychotic Agents

KW - Chromatography, High Pressure Liquid

KW - Diffusion

KW - Droperidol

KW - Electrochemical Techniques

KW - Hydrogen-Ion Concentration

KW - Kinetics

KW - Liquid Phase Microextraction

KW - Membranes, Artificial

KW - Models, Chemical

KW - Porosity

U2 - 10.1016/j.aca.2011.12.039

DO - 10.1016/j.aca.2011.12.039

M3 - Journal article

C2 - 22884201

VL - 742

SP - 10

EP - 16

JO - Analytica Chimica Acta

JF - Analytica Chimica Acta

SN - 0003-2670

ER -