Rocha Bruno Alves, da Costa Bruno Ruiz Brandão, de Albuquerque Nayara Cristina Perez, de Oliveira Anderson Rodrigo Moraes, Souza Juliana Maria Oliveira, Al-Tameemi Maha, Campiglia Andres Dobal, Barbosa Fernando
Laboratório de Toxicologia e Essencialidade de Metais, Faculdade de Ciências Farmacêuticas de Ribeirão Preto, Universidade de São Paulo, 14049-903 Ribeirão Preto, SP, Brazil.
Departmento de Química, Faculdade de Filosofia, Ciências e Letras de Ribeirão Preto, Universidade de São Paulo, 14049-901 Ribeirão Preto, SP, Brazil.
Talanta. 2016 Jul 1;154:511-9. doi: 10.1016/j.talanta.2016.03.098. Epub 2016 Mar 31.
In this study, a novel method combining dispersive liquid-liquid microextraction (DLLME) and fast liquid chromatography coupled to mass spectrometry (LC-MS/MS) was developed and validated for the extraction and determination of bisphenol A (BPA) and six bisphenol analogues, namely bisphenol S (BPS), bisphenol F (BPF), bisphenol P (BPP), bisphenol Z (BPZ), bisphenol AP (BPAP) and bisphenol AF (BPAF) in human urine samples. Type and volume of extraction and disperser solvents, pH sample, ionic strength, and agitation were evaluated. The matrix-matched calibration curves of all analytes were linear with correlation coefficients higher than 0.99 in the range level of 0.5-20.0ngmL(-1). The relative standard deviation (RSD), precision, at three concentrations (1.0, 8.0 and 15.0ngmL(-1)) was lower than 15% with accuracy ranging from 90 to 112%. The biomonitoring capability of the new method was confirmed with the analysis of 50 human urine samples randomly collected from Brazilians. BPA was detected in 92% of the analyzed samples at concentrations ranging <LOQ to 10.4ngmL(-1). The detection rates of BPS (10%), BPAF (4%) and BPF (2%) were much lower than 92%.
在本研究中，开发并验证了一种将分散液液微萃取（DLLME）与快速液相色谱-质谱联用（LC-MS/MS）相结合的新方法，用于萃取和测定人尿液样本中的双酚A（BPA）及六种双酚类似物，即双酚S（BPS）、双酚F（BPF）、双酚P（BPP）、双酚Z（BPZ）、双酚AP（BPAP）和双酚AF（BPAF）。对萃取溶剂和分散剂的类型及体积、样品pH值、离子强度和振荡情况进行了评估。所有分析物的基质匹配校准曲线在0.5 - 20.0 ng mL⁻¹范围内呈线性，相关系数高于0.99。在三个浓度水平（1.0、8.0和15.0 ng mL⁻¹）下，相对标准偏差（RSD）即精密度低于15%，准确度在90%至112%之间。通过对从巴西人那里随机收集的50份人尿液样本进行分析，证实了该新方法的生物监测能力。在92%的分析样本中检测到了BPA，浓度范围为低于定量限至10.4 ng mL⁻¹。BPS（10%）、BPAF（4%）和BPF（2%）的检出率远低于92%。
