Abstract：
Exposure to tobacco smoke is highly correlated to the incidence of different types of cancer due to various carcinogenic compounds present in such smoke. Aromatic amines, such as 1-naphthylamine (1-NA) and 2-naphthylamine (2-NA), are produced in tobacco burning and are linked to bladder cancer. Miniaturized solid phase extraction techniques, such as microporous membrane solid phase extraction (MMSPE), have shown potential for the extraction of aromatic compounds. In this study, a bioanalytical method for the determination of 1-NA and 2-NA in human urine was developed using polypropylene microporous membranes as a sorptive phase for MMSPE. Urine samples were hydrolyzed with HCl for 1 h at 80 °C, after which pH was adjusted to 10. Ultrasound-assisted MMSPE procedure was optimized by factorial design as follows. To each sample, 750 µL of methanol was added, and ultrasound-assisted MMSPE was conducted for 1 h with four devices containing seven 2 mm polypropylene membrane segments. After extraction, the segments were transferred to 400 µL of hexane, and desorption was conducted for 30 min. Extracts were submitted to a simple and fast microwave-assisted derivatization procedure, by the addition of 10 µL of PFPA and heating at 480 W for 3 min, followed by clean-up with phosphate buffer pH 8.0 and GC-MS/MS analysis. Adequate linearity was obtained for both analytes in a range from 25 to 500 µg L-1, while the multiple reaction monitoring approach provided satisfactory selectivity and specificity. Intra-day (n = 6) and inter-day (n = 5) precision and accuracy were satisfactory, below 15 % and between 85 and 115 %, respectively. Recovery rates found were 91.9 and 58.4 % for 1-NA and 2-NA, respectively, with adequate precision. 1-NA was found in first-hand smokers\' urine samples in a concentration range from 20.98 to 89.09 µg in 24 h, while it could be detected in second-hand smoker\'s urine samples, and 2-NA detected in all first and second-hand smokers\' urine samples. The proposed method expands the applicability of low cost MMSPE devices to aromatic amines and biological fluids.
摘要：
暴露于烟草烟雾与不同类型癌症的发病率高度相关,这是由于这些烟雾中存在各种致癌化合物。芳香胺,例如1-萘胺（1-NA）和2-萘胺（2-NA），是在烟草燃烧中产生的，与膀胱癌有关。小型化固相萃取技术，如微孔膜固相萃取(MMSPE)，已经显示出提取芳香族化合物的潜力。在这项研究中,使用聚丙烯微孔膜作为MMSPE的吸附相，开发了一种测定人尿中1-NA和2-NA的生物分析方法。尿样在80°C下用HCl水解1小时，之后将pH调节至10。超声辅助MMSPE程序通过如下析因设计进行优化。对于每个样本，加入750微升甲醇,超声辅助MMSPE使用四个包含七个2mm聚丙烯膜段的设备进行1小时。提取后,将片段转移到400微升的己烷中，和解吸进行30分钟。提取物被提交到一个简单和快速的微波辅助衍生程序，通过添加10微升PFPA并在480W下加热3分钟，然后用磷酸盐缓冲液pH8.0和GC-MS/MS分析净化。两种分析物在25至500µgL-1的范围内都获得了足够的线性，而多反应监测方法提供了令人满意的选择性和特异性。日内（n=6）和日间（n=5）的精度和准确度令人满意，低于15%和85%至115%，分别。1-NA和2-NA的回收率分别为91.9％和58.4％，分别,有足够的精度。在第一手吸烟者的尿液样本中发现1-NA，浓度范围为24小时内20.98至89.09µg，虽然它可以在二手吸烟者的尿液样本中检测到，在所有一手和二手吸烟者的尿液样本中检测到2-NA。所提出的方法将低成本MMSPE设备的适用性扩展到芳族胺和生物流体。
