超高效液相色谱-三重四极杆质谱法同时测定美术颜料中33种游离态初级芳香胺

建立了超高效液相色谱-三重四极杆质谱法(UPLC-MS/MS)同时测定水粉画颜料、油画颜料、丙烯画颜料等美术颜料中33种初级芳香胺(PAAs)的检测方法。样品中的初级芳香胺用乙腈提取,经离心分离、氮吹浓缩后,以甲醇-水(1:9, v/v)定容至2 mL, 0.22 μm膜过滤后上机检测。采用BEH Phenyl柱(100 mm×2.1 mm, 1.7 μm),以含0.07%(v/v)甲酸的甲醇溶液-水(1:9, v/v)为流动相,梯度洗脱分离,UPLC-MS/MS多反应监测模式(MRM)检测,同位素内标法定量。方法优化了色谱分离条件、质谱碎裂电压、碰撞能量等,并考察了提取时间、提取溶剂、浓缩方式等对回收率的影响。33种初级芳香胺的方法检出限为5~50 μg/kg,定量限为15~150 μg/kg, 3种不同基质样品在3个添加水平的平均回收率为70.1%~115.8%,相对标准偏差(RSD)为2.1%~15%。本方法操作简便、快速、准确、灵敏度高,能满足相关测定的要求。

Simultaneous determination of 33 primary aromatic amines of free state in fine pigments by ultra-performance liquid chromatography coupled with triple quadrupole mass spectrometry

A comprehensive analytical method based on ultra-performance liquid chromatography coupled with triple quadrupole mass spectrometry (UPLC-MS/MS) has been developed for the simultaneous determination of 33 primary aromatic amines (PAAs) in fine pigments such as gouache paint, oil painting pigment and acrylic paint. The primary aromatic amines in samples were extracted with acetonitrile. Then the extract was concentrated by centrifugation and nitrogen blow, finally diluted to 2 mL with methanol-water (1:9, v/v) and filtered through 0.22 μm membrane before UPLC-MS/MS analysis. The analytes were separated on a BEH Phenyl column (100 mm×2.1 mm, 1.7 μm) with 0.07% (v/v) formic acid in methanol-water as mobile phases in gradient elution. The PAAs were detected by UPLC-MS/MS under multiple reaction monitoring (MRM) mode and quantified by the internal standard method. The separation conditions, fragment voltages and collision energies were optimized. The impacts of extraction times, extraction solvents and concentration methods on recoveries were studied. The limits of detection and limits of quantitation for the 33 primary aromatic amines were 5-50 μg/kg and 15-150 μg/kg respectively. The mean recoveries of three different dye products at three spiked levels were 70.1%-115.8%. The relative standard deviations were 2.1%-15%. The experimental results indicated that the method is simple, rapid, sensitive, accurate and can meet the requirements for the determination.