TY - JOUR

T1 - Effect of sample matrices on supported liquid membrane

T2 - Efficient electromembrane extraction of cathinones from biological samples

AU - Hong, Changbao

AU - Dong, Ying

AU - Zhu, Ruiqin

AU - Yan, Yibo

AU - Shen, Xiantao

AU - Pedersen-Bjergaard, Stig

AU - Huang, Chuixiu

N1 - Funding Information: This research was funded by National Natural Science Foundation of China (Grant No. 21876055 and 81801875). Publisher Copyright: © 2021 Elsevier B.V.

PY - 2022

Y1 - 2022

N2 - In this work, the effect of sample matrix on electromembrane extraction (EME) was investigated for the first time using cathinones (log P < 1.0) as polar basic model analytes. Ten supported liquid membranes (SLMs) were tested for EME from spiked buffer solutions, urine, and whole blood samples, respectively. For buffer solutions, SLMs containing aromatic solvents provided higher EME recovery than non-aromatic solvents, which confirmed the significance of cation-π interactions for EME of basic substances. Interestingly, when applied to urine and whole blood samples, aromatic SLMs were less efficient, while non-aromatic SLMs containing abundant hydrogen-bond acidity/basicity were efficient. These observations were explained by SLM fouling, and the antifouling property of the SLM was clearly dependent on the nature of the SLM solvent. Accordingly, a binary SLM containing aromatic 1-ethyl-2-nitrobenzene (ENB) and non-aromatic 1-undecanol (1:1 v/v) was developed. This binary SLM was not prone to fouling, and provided high recoveries of cathinones from urine and whole blood. EME based on this SLM was optimized and evaluated in combination with liquid chromatography tandem mass spectrometry (LC-MS/MS), and the linear ranges with R2 ≥ 0.9903 for cathinones in whole blood and urine were 5–200 ng/mL and 1–200 ng/mL, respectively. The LOD and LOQ of cathinones were ranged from 0.12 to 0.54 ng/mL and 0.38–1.78 ng/mL, respectively. The repeatability and accuracy bias at three levels were ≤11% and within 10%, respectively. In addition, the matrix effect ranged from 88% to 118% was also in compliance with guidelines for bioanalytical method validation provided by the European Medicines Agency.

AB - In this work, the effect of sample matrix on electromembrane extraction (EME) was investigated for the first time using cathinones (log P < 1.0) as polar basic model analytes. Ten supported liquid membranes (SLMs) were tested for EME from spiked buffer solutions, urine, and whole blood samples, respectively. For buffer solutions, SLMs containing aromatic solvents provided higher EME recovery than non-aromatic solvents, which confirmed the significance of cation-π interactions for EME of basic substances. Interestingly, when applied to urine and whole blood samples, aromatic SLMs were less efficient, while non-aromatic SLMs containing abundant hydrogen-bond acidity/basicity were efficient. These observations were explained by SLM fouling, and the antifouling property of the SLM was clearly dependent on the nature of the SLM solvent. Accordingly, a binary SLM containing aromatic 1-ethyl-2-nitrobenzene (ENB) and non-aromatic 1-undecanol (1:1 v/v) was developed. This binary SLM was not prone to fouling, and provided high recoveries of cathinones from urine and whole blood. EME based on this SLM was optimized and evaluated in combination with liquid chromatography tandem mass spectrometry (LC-MS/MS), and the linear ranges with R2 ≥ 0.9903 for cathinones in whole blood and urine were 5–200 ng/mL and 1–200 ng/mL, respectively. The LOD and LOQ of cathinones were ranged from 0.12 to 0.54 ng/mL and 0.38–1.78 ng/mL, respectively. The repeatability and accuracy bias at three levels were ≤11% and within 10%, respectively. In addition, the matrix effect ranged from 88% to 118% was also in compliance with guidelines for bioanalytical method validation provided by the European Medicines Agency.

KW - Cation-π interactions

KW - Effect of sample matrix

KW - Electromembrane extraction

KW - Enhancement or suppression

KW - Hydrogen-bond interaction

KW - Supported liquid membrane

U2 - 10.1016/j.talanta.2021.123175

DO - 10.1016/j.talanta.2021.123175

M3 - Journal article

C2 - 34972062

AN - SCOPUS:85121966526

VL - 240

JO - Talanta

JF - Talanta

SN - 0039-9140

M1 - 123175

ER -