In this study, a rapid and straightforward approach based on magnetic ionic liquids (MIL) as extraction phases and dispersive liquid-liquid microextraction (DLLME) was developed to analyze the hormones estriol, 17-β-estradiol, 17-α-ethynylestradiol, and estrone in human urine samples. This is the first report of an application of manganese-based MILs compatible with HPLC to extract compounds of biological interest from urine samples. The hydrophobic MILs trihexyltetradecylphosphonium tetrachloromanganate (II) ([P_6,6,6,14⁺]₂[MnCl₄²⁻]) and aliquat tetrachloromanganate (II) ([Aliquat⁺]₂[MnCl₄²⁻]) were employed and the optimized extraction conditions were comprised of 5 mg of MIL ([P_6,6,6,14⁺]₂[MnCl₄²⁻]), 5 μL of methanol (MeOH) as disperser solvent, and an extraction time of 90 s at sample pH 6. The analytical parameters of merit were determined under optimized conditions and very satisfactory results were achieved, with LODs of 2 ng mL⁻¹ for all analytes, determination coefficients (R²) ranging from 0.9949 for 17-β-estradiol to 0.9998 for estrone. In addition, good results of method precision were achieved with the intraday (n = 3) varying from 4.7% for 17-β-estradiol to 19.5% for estriol (both at 5 ng mL⁻¹) and interday precision (evaluated at 100 ng mL⁻¹) ranging from 11.4% for estrone to 17.7% for 17-α-ethynylestradiol and analyte relative recovery evaluated in three real samples ranged from 67.5 to 115.6%. The proposed DLLME/MIL-based approach allowed for a reliable, environmentally friendly and high-throughput methodology with no need for a centrifugation step.

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在这项研究中，开发了一种基于磁性离子液体（MIL）作为萃取相和分散液-液微萃取（DLLME）的快速而直接的方法来分析雌三醇，17-β-雌二醇，17-α-乙炔雌二醇和人尿液样品中的雌酮。这是首次将与HPLC兼容的锰基MIL应用于从尿液样品中提取具有生物学意义的化合物的报道。疏水性MILs四氯_锰酸三己基_{十四烷基phosph}（II）（[P _6,6,6,14 ⁺ ] ₂ [MnCl ₄ ^2- ]）和脂基四氯化锰（II）（[Aliquat ⁺ ] ₂ [MnCl ₄ ^2-]），最佳提取条件包括5 mg MIL（[P _6,6,6,14 ⁺ ] ₂ [MnCl ₄ ^2- ]），5μL甲醇（MeOH）作为分散剂，以及在样品pH为6的条件下，萃取时间为90 s。在优化条件下测定了优异的分析参数，并获得了令人满意的结果，所有分析物的检测限为2 ng mL ^-1，测定系数（R ²）为0.9949，适用于17种-β-雌二醇为0.9998，为雌酮。此外，当日（n  = 3）从17-β-雌二醇的4.7％到雌三醇的19.5％（均为5 ng mL ^-1）变化时，均获得了良好的方法精度结果。）和日间精密度（评估为100 ng mL ^-1），从雌酮的11.4％到17-α-乙炔基雌二醇的17.7％，在三个真实样品中评估的分析物相对回收率在67.5到115.6％之间。所提出的基于DLLME / MIL的方法无需离心步骤即可实现可靠，环保和高通量的方法。

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