Wu Shifan, Zhu Ruiqin, Dong Ying, Huang Chuixiu, Shen Xiantao
Department of Forensic Medicine, Huazhong University of Science and Technology, Hangkong Road #13, Wuhan, 430030, Hubei, China.
Department of Forensic Medicine, Huazhong University of Science and Technology, Hangkong Road #13, Wuhan, 430030, Hubei, China.
Anal Chim Acta. 2020 Sep 8;1129:118-125. doi: 10.1016/j.aca.2020.07.040. Epub 2020 Jul 25.
In this fundamental work, tributyl phosphate (TBP) with zero hydrogen-bond acidity was for the first time discovered as an efficient supported liquid membrane (SLM) for EMEof acidic drugs (barbiturates) due to its high polarity-polarizability. This discovery indicated that strong dipole-dipole interaction induced by high polarity-polarizability played an important role for efficient EME of acidic drugs. In addition, three barbiturates were successfully extracted for the first time from human whole blood and urine samples by EME with recoveries up to 90%. Interestingly, efficient EME of barbiturates from biological samples required much lower extraction voltage than that from buffer samples. This was due to the significant contribution from LPME during the EME process, when EME was conducted from the samples with just partially ionized analytes. EME combined with HPLC-UV and LC-MS were validated using whole blood and urine, respectively. In all cases, the linearity (R) was >0.99 within the reported linear range. Repeatability at three concentrations was satisfactory (<12%), and the limits of detection (LOD, S/N = 3) were in the ranges of 0.44-4.30 ng mL and 0.14-0.69 μg mL for EME-LC-MS and EME-HPLC-UV, respectively. Finally, the validated methods were successfully applied for the identification and quantification of barbiturates in whole blood and urine samples for a forensic case, indicating that EME could be used in routine toxicological analysis. Thus, we believe that EME has great potential as a green, efficient and alternative sample preparation method not only in the field of analytical chemistry but also in the fields of forensic science and clinical medicine.
在这项基础性工作中，首次发现零氢键酸度的磷酸三丁酯（TBP）因其高极性-极化率而成为用于酸性药物（巴比妥类药物）电迁移萃取（EME）的高效支撑液膜（SLM）。这一发现表明，高极性-极化率诱导的强偶极-偶极相互作用对酸性药物的高效电迁移萃取起着重要作用。此外，首次通过电迁移萃取从人全血和尿液样本中成功萃取了三种巴比妥类药物，回收率高达90%。有趣的是，从生物样本中高效萃取巴比妥类药物所需的萃取电压远低于从缓冲液样本中萃取时所需的电压。这是由于在电迁移萃取过程中，当从仅含有部分离子化分析物的样本中进行电迁移萃取时，液相微萃取（LPME）起到了重要作用。分别使用全血和尿液对电迁移萃取与高效液相色谱-紫外检测联用（EME-HPLC-UV）以及电迁移萃取与液相色谱-质谱联用（EME-LC-MS）进行了验证。在所有情况下，在所报道的线性范围内线性度（R）均>0.99。三种浓度下的重复性良好（<12%），电迁移萃取-液相色谱-质谱联用（EME-LC-MS）和电迁移萃取-高效液相色谱-紫外检测联用（EME-HPLC-UV）的检测限（LOD，S/N = 3）分别在0.44 - 4.30 ng/mL和0.14 - 0.69 μg/mL范围内。最后，经过验证的方法成功应用于一起法医案件中全血和尿液样本中巴比妥类药物的鉴定和定量分析，表明电迁移萃取可用于常规毒理学分析。因此，我们认为电迁移萃取不仅在分析化学领域，而且在法医学和临床医学领域都具有作为一种绿色、高效且替代性的样品制备方法的巨大潜力。
