典型环亚胺类毒素大气压化学电离质谱分析

Analysis of Typical Cyclic Imine Toxins by Atmospheric Pressure Chemical Ionization-Mass Spectrometry

利用离子阱质谱技术分析了两种典型环亚胺类毒素(GYM和SPX1)在大气压化学电离(APCI)条件下的质谱裂解特征,并与电喷雾电离(ESI)质谱法进行了比较。GYM和SPX1在APCI一级质谱分析过程中易形成准分子离子[M+H]+峰(基峰);在二级质谱分析过程中,母离子[M+H]+通过丢失H2O中性碎片形成稳定的特征子离子峰;并结合三级质谱分析,推测了两种毒素的裂解途径。结果表明:大气压化学电离质谱法(APCI-MS)的灵敏度好于电喷雾质谱法(ESI-MS);液相色谱-大气压化学电离质谱法(LC-APCI-MS2)分析4种不同基质样品中GYM和SPX1的专属性、重复性、稳定性和抗基质干扰能力均好于液相色谱-电喷雾质谱法(LC-ESI-MS2)。综上,APCI-MS法适于典型环亚胺类毒素的分析,本研究可为LC-APCI-MS定性、定量分析不同基质复杂样品中环亚胺类毒素提供参考和依据。

The fragmentation characteristics of two typical cyclic imine toxins（GYM and SPX1）were analyzed by ion trap-atmospheric pressure chemical ionization-mass spectrometry（IT-APCI-MS）. The results showed that quasi-molecular ion peak[M＋H]＋（base peak）of GYM and SPX1 was detected by APCI-MS.Stability characteristic fragment ions were observed by the neutral loss of H2 O from precursor ions[M＋H]＋for APCI-MS2.Then,the fragmentation pathways of GYM and SPX1 werediscussed based on APCI-MS3 analysis.Based on the comparison of two methods,the sensitivity of APCI-MS is better than ESI-MS for analysis of GYM and SPX1.The matrix interference resistance,specificity,repeatability and stability of the LC-APCIMS2 method are better than LC-ESI-MS2 method for analysis of GYM and SPX1 in four different matix.In conclusion,APCI-MS is suitable for determination of cyclic imine toxins,and this study can provide a good reference and basis for qualitative and quantitative analysis of cyclic imine toxins in different complex matrix samples by LC-APCI-MS.