Song Chenchen, Dowlatshah Samira, Gaznawi Somayeh, Hay Anne Oldeide, Hasvold Grete, Hansen Frederik André
Department of Pharmacy, University of Oslo, Blindern, P.O. Box 1068, 0316, Oslo, Norway.
School of Chemistry and Chemical Engineering, Henan University of Technology, Zhengzhou, 450001, China.
Anal Bioanal Chem. 2025 Mar;417(7):1293-1303. doi: 10.1007/s00216-024-05503-6. Epub 2024 Aug 29.
The current paper reports two new, robust, and efficient conditions for electromembrane extraction of acidic substances from human plasma. Two systems were developed based on eutectic solvents: A1 ("A" for acid) comprised dodecyl methyl sulfoxide and thymol in 1:2 ratio (w/w) as liquid membrane, while A2 used [6-methylcoumarin:thymol (1:2)]:2-nitrophenyl octyl ether in 2:1 ratio (w/w). The performance of A1 and A2 was characterized by extraction of 31 acidic model analytes (pharmaceutical drugs and nutrients) spiked into 100 µL human plasma diluted 1:1 (v/v) with phosphate buffer pH 7.4. The acceptor solution was 50 mM NHHCO buffer pH 10.0, and extraction was performed at an agitation rate of 750 RPM. Voltage and extraction time were 30 V for 30 min and 10 V for 20 min for A1 and A2, respectively. Under optimal conditions, A1 extracted analytes with 1.8 ≤ log P ≤ 6.0 with an average recovery (R) of 85.1%, while A2 extracted in a range of 0.5 ≤ log P ≤ 6.0 with an average recovery of 79.9%. Meanwhile, extraction current was low at 9 and 26 µA, respectively, which is indicative of good system robustness. Using UHPLC-MS/MS analysis of the acceptor solution, repeatability of the A1 and A2 methods was determined to be 2.8-7.7% and 3.3-9.4% for R > 40%, matrix effects were 82-117% and 84-112%, respectively, and linear calibration curves were obtained. The performance and compatibility with human plasma represent a major improvement over previous state-of-the-art liquid membranes for acidic analytes, namely 1-octanol.
本文报道了两种用于从人血浆中电膜萃取酸性物质的新型、稳健且高效的条件。基于低共熔溶剂开发了两种体系：A1（“A”代表酸）由十二烷基甲基亚砜和百里酚按1:2的比例（w/w）作为液膜组成，而A2使用[6 - 甲基香豆素:百里酚（1:2）]:2 - 硝基苯基辛基醚按2:1的比例（w/w）。A1和A2的性能通过萃取添加到100 μL用pH 7.4的磷酸盐缓冲液1:1（v/v）稀释的人血浆中的31种酸性模型分析物（药物和营养物质）来表征。接受相溶液为50 mM NH₄HCO₃缓冲液，pH 10.0，萃取在750 RPM的搅拌速率下进行。A1和A2的电压和萃取时间分别为30 V 30分钟和10 V 20分钟。在最佳条件下，A1萃取log P为1.8 ≤ log P ≤ 6.0的分析物，平均回收率（R）为85.1%，而A2萃取log P在0.5 ≤ log P ≤ 6.0范围内的分析物，平均回收率为79.9%。同时，萃取电流分别较低，为9和26 μA，这表明系统稳健性良好。通过对接受相溶液进行超高效液相色谱 - 串联质谱分析，对于R > 40%，A1和A2方法的重复性分别为2.8 - 7.7%和3.3 - 9.4%，基质效应分别为82 - 117%和84 - 112%，并获得了线性校准曲线。与先前用于酸性分析物的最先进液膜（即1 - 辛醇）相比，该性能以及与人血浆的兼容性有了重大改进。
