中山大学学报(自然科学版)
中山大學學報(自然科學版)
중산대학학보(자연과학판)
ACTA SCIENTIARUM NATURALIUM UNIVERSITATIS SUNYATSENI
2014年
4期
107-113
,共7页
陈安珣%周丽华%唐连凤%姚骏骅%林中祥
陳安珣%週麗華%唐連鳳%姚駿驊%林中祥
진안순%주려화%당련봉%요준화%림중상
电喷雾质谱%离子阱%N-苯甲酰基-脱氢枞胺衍生物
電噴霧質譜%離子阱%N-苯甲酰基-脫氫樅胺衍生物
전분무질보%리자정%N-분갑선기-탈경종알연생물
electrospray mass spectrometry%ionization tandem%N-benzoyl dehydroabietylamine deriva-tive
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-H2 O+H]+, C则更易负离子化。在(+)-ESI-MS/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-H2 O+H]+; A的18位酰基脱水离子峰[ M-H2 O+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-H2 O+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。
利用電噴霧離子阱質譜( ESI-IT-MS)技術,對8箇具有潛在殺菌、抗癌生物活性的三類新型N-苯甲酰基-脫氫樅胺衍生物進行瞭ESI質譜行為研究。結果錶明,由于7位、12位及苯甲酰基上取代基的不同,三類衍生物呈現齣一定的電離及碎裂特性。在(±)-ESI-MS過程中,7-肟基類衍生物( A)和12-硝基類衍生物( C)比7-羥基類衍生物( B)更易產生二聚體;A易產生[ M-H2 O+H]+, C則更易負離子化。在(+)-ESI-MS/MS過程中, A中7-肟基的存在使其易產生特徵離子碎裂峰[ M-35+H]+和[ M-H2 O+H]+; A的18位酰基脫水離子峰[ M-H2 O+H]+失去一分子取代苯甲腈產生繫列偶數碎裂離子峰; A的7-肟基脫水離子峰[ M-H2 O+H]+失去一分子取代苯甲醛產生繫列奇數碎裂離子峰。在(-)-ESI-MS/MS過程中, B比C更穩定,在較高的踫撞能作用下穫得的碎裂片段較少;均可通過丟失中性分子N-取代苯甲酰基亞甲胺、取代苯甲醛或取代苯產生繫列碎裂離子片段; C的彊吸電子基糰12-硝基及4'-硝基的存在使其丟失的中性分子易捕穫電子而離子化。
이용전분무리자정질보( ESI-IT-MS)기술,대8개구유잠재살균、항암생물활성적삼류신형N-분갑선기-탈경종알연생물진행료ESI질보행위연구。결과표명,유우7위、12위급분갑선기상취대기적불동,삼류연생물정현출일정적전리급쇄렬특성。재(±)-ESI-MS과정중,7-우기류연생물( A)화12-초기류연생물( C)비7-간기류연생물( B)경역산생이취체;A역산생[ M-H2 O+H]+, C칙경역부리자화。재(+)-ESI-MS/MS과정중, A중7-우기적존재사기역산생특정리자쇄렬봉[ M-35+H]+화[ M-H2 O+H]+; A적18위선기탈수리자봉[ M-H2 O+H]+실거일분자취대분갑정산생계렬우수쇄렬리자봉; A적7-우기탈수리자봉[ M-H2 O+H]+실거일분자취대분갑철산생계렬기수쇄렬리자봉。재(-)-ESI-MS/MS과정중, B비C경은정,재교고적팽당능작용하획득적쇄렬편단교소;균가통과주실중성분자N-취대분갑선기아갑알、취대분갑철혹취대분산생계렬쇄렬리자편단; C적강흡전자기단12-초기급4'-초기적존재사기주실적중성분자역포획전자이리자화。
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 .