RESUMO
In this study, the use of switchable hydrophilicity solvent with a simple and low-cost lab-made device for the extraction procedure in homogeneous liquid-liquid microextraction is proposed for the first time in the determination of antidepressants in human urine. The antidepressants studied consisted of fluoxetine, amitriptyline, nortriptyline, imipramine, desipramine and sertraline. The optimization of the main parameters that can influence on the extraction efficiency was performed through multivariate approaches. The analytes were separated and identified by gas chromatography coupled to mass spectrometry (GC-MS). The optimal extraction conditions consisted of using N,N-dimethylcyclohexylamine (DMCHA) as the switchable hydrophilicity solvent (SHS), 500⯵L of urine sample previously diluted with ultrapure water at 1:1 ratio (v/v), 200⯵L of a mixture of SHS:HCl 6â¯mol L-1 (1:1 v/v), 600⯵L of NaOH 10â¯mol L-1 and 3â¯min of extraction time. A volume of 40⯵L of diphenylamine at concentration of 500⯵g L-1 (20â¯ng) was used as internal standard. The method developed was in-house validated, providing coefficients of determination higher than 0.995 for all analytes, limits of detection (LOD) from 0.02 to 0.88⯵g L-1, limits of quantification (LOQ) from 0.05 to 2.92⯵g L-1, relative recoveries of 68 to 102%, intra-day precision from 0.5 to 15.9%, inter-day precision from 4.2 to 19.3%, selectivity and robustness. The method proposed was successfully applied in five human urine samples from a Toxicological Information Center located in Porto Alegre (Brazil). The results demonstrated that the µP-SHS-HLLME approach is highly cost-effective, rapid, simple and environmentally-friendly with satisfactory analytical performance.
Assuntos
Antidepressivos/urina , Adulto , Amitriptilina/urina , Cicloexilaminas/química , Desipramina/urina , Fluoxetina/urina , Cromatografia Gasosa-Espectrometria de Massas , Química Verde , Humanos , Interações Hidrofóbicas e Hidrofílicas , Imipramina/urina , Limite de Detecção , Microextração em Fase Líquida , Nortriptilina/urina , Sertralina/urina , Solventes/químicaRESUMO
In this study, the viability of two membrane-based microextraction techniques for the determination of endocrine disruptors by high-performance liquid chromatography with diode array detection was evaluated: hollow fiber microporous membrane liquid-liquid extraction and hollow-fiber-supported dispersive liquid-liquid microextraction. The extraction efficiencies obtained for methylparaben, ethylparaben, bisphenol A, benzophenone, and 2-ethylhexyl-4-methoxycinnamate from aqueous matrices obtained using both approaches were compared and showed that hollow fiber microporous membrane liquid-liquid extraction exhibited higher extraction efficiency for most of the compounds studied. Therefore, a detailed optimization of the extraction procedure was carried out with this technique. The optimization of the extraction conditions and liquid desorption were performed by univariate analysis. The optimal conditions for the method were supported liquid membrane with 1-octanol for 10 s, sample pH 7, addition of 15% w/v of NaCl, extraction time of 30 min, and liquid desorption in 150 µL of acetonitrile/methanol (50:50 v/v) for 5 min. The linear correlation coefficients were higher than 0.9936. The limits of detection were 0.5-4.6 µg/L and the limits of quantification were 2-16 µg/L. The analyte relative recoveries were 67-116%, and the relative standard deviations were less than 15.5%.