拭子喷雾电离-四极杆/静电场轨道阱高分辨质谱法快速筛查化妆品中19种防晒剂

Rapid Screening of 19 UV Filters in Cosmetics Using Swab Touch Spray Ionization Coupled with Quadrupole/Orbitrap High-Resolution Mass Spectrometry

本研究建立了拭子喷雾电离与四极杆/静电场轨道阱高分辨质谱(Q/Orbitrap HRMS)联用法快速筛查化妆品中19种防晒剂。化妆品样品无需前处理,直接用拭子蘸取样品,滴加30μL甲醇-乙腈混合溶剂(4∶1,V/V),施加5.0 kV电压,通过拭子喷雾电离方式产生带电液滴。四极杆/静电场轨道阱高分辨质谱采用一级全扫描与平行反应监测模式进行检测。结果表明,19种防晒剂的方法检出限为0.01~2.0 mg/kg,方法重复性在1.4%~9.9%之间(n=6),单个样品的检测时间小于1 min。该方法简便快速、准确可靠,适用于化妆品中防晒剂的快速筛查。

An analytical method combining swab touch spray ionization and quadrupole/Orbitrap high-resolution mass spectrometry(Q/Orbitrap HRMS)was developed for rapid screening of nineteen UV filters in cosmetics.Upon investigation of various spray solvents such as methanol,acetonitrile,tetrahydrofuran,acetone and isopropanol,methanol and acetonitrile were found to be the optimal solvents for positive and negative ionization modes,respectively.For further optimization,methanol-acetonitrile mixture solvents with different volumetric ratios(4∶1,3∶2,2∶3,1∶4,V/V)were compared.A methanol-acetonitrile mixture solvent(4∶1,V/V)was selected as the spray solvent.Moreover,the spray voltages ranging from 3.5 to 6.5 kV were optimized,among which 5.0 kV was found to be the optimum voltage.The position of the swab was another critical parameter.If the swab was placed too close to the MS inlet,electric discharge could occur.On the other hand,a distant swab position may result in unstable or even no signals.The position of the swab was optimized to be 0.8 cm horizontally and 0.5 cm vertically from the MS inlet.Under the optimized experimental conditions,the cosmetic samples were gently picked up using the swab and mounted in front of the MS inlet without the need of sample pretreatment.30μL methanol-acetonitrile mixture solvent(4∶1,V/V)was added to the swab.Afterwards,a high voltage of 5.0 kV was applied to the metallic swab handle.In this way,the charged droplets produced from the swab tip were subjected to the Q/Orbitrap HRMS analysis under the full-scan/parallel reaction monitoring acquisition mode.Experimental results showed that the limits of detection of the nineteen UV filters were between 0.01 and 2.0 mg/kg.Satisfactory repeatability was obtained ranging from 1.4%to 9.9%(n=6).The analysis of a single sample could be completed within 1 min.The established method is simple,fast,accurate,reliable,and suitable for the rapid screening of UV filters in cosmetics.