新型N-苯甲酰基-脱氢枞胺衍生物的电喷雾离子阱质谱行为研究  

Analysis of Novel N-benzoyl Dehydroabietylamine Derivatives through Electrospray Ionization Tandem Mass Spectrometry

作　　者：陈安珣[1] 周丽华[1] 唐连凤[1] 姚骏骅[2] 林中祥[3] 

机构地区：[1]广东工业大学轻工化工学院,广东广州510006 [2]中山大学测试中心,广东广州510275 [3]南京林业大学化学工程学院,南京江苏210037

出　　处：《中山大学学报（自然科学版）》2014年第4期107-113,共7页Acta Scientiarum Naturalium Universitatis Sunyatseni

基　　金：国家自然科学基金资助项目(41301264;31170536);广东省自然科学基金资助项目(S2011010004991)

摘　　要：利用电喷雾离子阱质谱(ESI-IT-MS)技术,对8个具有潜在杀菌、抗癌生物活性的三类新型N-苯甲酰基-脱氢枞胺衍生物进行了ESI质谱行为研究。结果表明,由于7位、12位及苯甲酰基上取代基的不同,三类衍生物呈现出一定的电离及碎裂特性。在(±)-ESI-MS过程中,7-肟基类衍生物(A)和12-硝基类衍生物(C)比7-羟基类衍生物(B)更易产生二聚体;A易产生[M-H_2O+H]^+,C则更易负离子化。在(+)-ESIMS/MS过程中,A中7-肟基的存在使其易产生特征离子碎裂峰[M-35+H]^+和[M-H_2O+H]^+;A的18位酰基脱水离子峰[M-H_2O+H]^+失去一分子取代苯甲腈产生系列偶数碎裂离子峰;A的7-肟基脱水离子峰[M-H_2O+H]^+失去一分子取代苯甲醛产生系列奇数碎裂离子峰。在(-)-ESI-MS/MS过程中,B比C更稳定,在较高的碰撞能作用下获得的碎裂片段较少;均可通过丢失中性分子N-取代苯甲酰基亚甲胺、取代苯甲醛或取代苯产生系列碎裂离子片段;C的强吸电子基团12-硝基及4'-硝基的存在使其丢失的中性分子易捕获电子而离子化。Eight novel N-benzoyl dehydroabietylamine derivatives with potential sterilization and antican-cer biological activities were analyzed through electrospray ionization tandem mass spectrometry （ ESI-IT-MS） .The results indicated that three types of derivatives exhibited their own typical ionization and frag -mentation process , due to their different 7-and 12-substituents on the dehydroabietylamine ring and differ-ent substituents on the benzoyl ring .In （ ±）-ESI-MS, the dimer ions of 7-oxime derivatives （ A） and 12-nitro derivatives （ C） could be more readily formed than that of 7-hydroxy derivatives （ B） .[ M-H2 O＋H] ＋of A was observed in the positive-ion mode.C were prone to be ionized in the negative-ion mode. Two typical fragmentation peaks of [ M-35＋H] ＋and [ M-H2 O＋H] ＋were observed in （ ＋） -ESI-MS/MS spectra of 7-oxime dehydroabietylamine derivatives .The ion of [ M-H2 O＋H] ＋formed from 18-acyl of （ A） could induce some even fragmentation ion peaks by loss of substituted benzonitrile .The ion of [M-H2O＋H] ＋formed from 7-oxime of （A） can induce some odd fragmentation ion peaks by loss of substituted benzaldehyde .（B） showed more stability than （C） in （-）-ESI-MS/MS process.Fe-wer fragmentation ions of （ B） were obtained even though （ B） derivatives were collided with higher ener-gy.Ion fragmentation of （ B） and （ C） derivatives were induced by loss of neutral molecules of N-substi-tuted benzoyl methylene amine , substituted benzaldehyde or substituted benzene .Due to the strong elec-tron-withdrawing ability of 12-and 4＇-nitro of （ C） derivatives , the neutral molecules lost from （ C） deriv-atives can be ionized by capturing one electron .

关 键 词：电喷雾质谱 离子阱 N-苯甲酰基-脱氢枞胺衍生物 

分 类 号：O657.63[理学—分析化学]