Complexation-mediated electromembrane extraction of highly polar basic drugs—a fundamental study with catecholamines in urine as model system

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Title: Complexation-mediated electromembrane extraction of highly polar basic drugs—a fundamental study with catecholamines in urine as model system
Authors: Fernández Martínez, Elena | Vårdal, Linda | Vidal, Lorena | Canals, Antonio | Gjelstad, Astrid | Pedersen-Bjergaard, Stig
Research Group/s: Espectroscopía Atómica-Masas y Química Analítica en Condiciones Extremas
Center, Department or Service: Universidad de Alicante. Departamento de Química Analítica, Nutrición y Bromatología | Universidad de Alicante. Instituto Universitario de Materiales
Keywords: Electromembrane extraction | Polar analytes | Urine samples | Catecholamines
Knowledge Area: Nutrición y Bromatología | Química Analítica
Issue Date: Jul-2017
Publisher: Springer Berlin Heidelberg
Citation: Analytical and Bioanalytical Chemistry. 2017, 409(17): 4215-4223. doi:10.1007/s00216-017-0370-2
Abstract: Complexation-mediated electromembrane extraction (EME) of highly polar basic drugs (log P < −1) was investigated for the first time with the catecholamines epinephrine, norepinephrine, and dopamine as model analytes. The model analytes were extracted as cationic species from urine samples (pH 4), through a supported liquid membrane (SLM) comprising 25 mM 4-(trifluoromethyl)phenylboronic acid (TFPBA) in bis(2-ethylhexyl) phosphite (DEHPi), and into 20 mM formic acid as acceptor solution. EME was performed for 15 min, and 50 V was used as extraction voltage across the SLM. TFPBA served as complexation reagent, and selectively formed boronate esters by reversible covalent binding with the model analytes at the sample/SLM interface. This enhanced the mass transfer of the highly polar model analytes across the SLM, and EME of basic drugs with log P in the range −1 to −2 was shown for the first time. Meanwhile, most matrix components in urine were unable to pass the SLM. Thus, the proposed concept provided highly efficient sample clean-up and the system current across the SLM was kept below 50 μA. Finally, the complexation-mediated EME concept was combined with ultra-high performance liquid chromatography coupled to tandem mass spectrometry and evaluated for quantification of epinephrine and dopamine. Standard addition calibration was applied to a pooled human urine sample. Calibration curves using standards between 25 and 125 μg L−1 gave a high level of linearity with a correlation coefficient of 0.990 for epinephrine and 0.996 for dopamine (N = 5). The limit of detection, calculated as three times signal-to-noise ratio, was 5.0 μg L−1 for epinephrine and 1.8 μg L−1 for dopamine. The repeatability of the method, expressed as coefficient of variation, was 13% (n = 5). The proposed method was finally applied for the analysis of spiked pooled human urine sample, obtaining relative recoveries of 91 and 117% for epinephrine and dopamine, respectively.
Sponsor: The authors would like to thank the Spanish Ministry of Science and Innovation (project n. CTQ2011-23968) and Generalitat Valenciana (Spain) (projects n. GVA/2014/096 and PROMETEO/2013/038) for the financial support. E. Fernández thanks Spanish Ministry of Education for her FPU grant (FPU13/03125) and mobility grant (EST15/00074).
ISSN: 1618-2642 (Print) | 1618-2650 (Online)
DOI: 10.1007/s00216-017-0370-2
Language: eng
Type: info:eu-repo/semantics/article
Rights: © Springer-Verlag Berlin Heidelberg 2017
Peer Review: si
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