质谱学报
質譜學報
질보학보
2010年
1期
12-17
,共6页
储艳秋%蒋公羽%姜丹%王青%丁传凡
儲豔鞦%蔣公羽%薑丹%王青%丁傳凡
저염추%장공우%강단%왕청%정전범
氨基酸%谷胱甘肽%非共价复合物%碰撞诱导解离%碎片化反应
氨基痠%穀胱甘肽%非共價複閤物%踫撞誘導解離%碎片化反應
안기산%곡광감태%비공개복합물%팽당유도해리%쇄편화반응
amino acid%glutathione%non-covalent complexes%collision induced dissociation%fragmentation process
为了探讨非共价复合物的碎片化反应机理,选择谷胱甘肽和氨基酸复合物研究影响碎片化反应的主要因素.串级质谱结果表明,碰撞气体密度(CGT)和碰撞能量是影响非共价复合物碎片化反应的两个主要因素,对谷胱甘肽复合物碎片化产物的生成途径会有明显的影响.当碰撞气体密度恒定在50×10~(13) molecules/cm~2,碰撞能量在小于100 eV范围内,复合物His-GSH都能发生碎裂,断裂位点容易发生在非共价键上,生成原来组分[His+H]~+和[GSH+H]~+ 离子,但没有发生进一步碎裂.当碰撞能量一定(恒定为30 eV),碰撞气体密度为50×10~(13) molecules/cm~2时,His-GSH复合物碎裂后的产物同样为[His+H]~+和[GSH+H]~+.然而,当碰撞气体密度上升至75×10~(13) molecules/cm~2时,除非共价键发生碎裂外,共价键也会发生碎裂,产生更小的碎片离子y2,b2.当碰撞气体密度上升为175×10~(13) molecules/cm~2时,His也开始碎裂,生成m/z 110[His-H_2O-CO+H]~+.三级串级质谱MS~3实验确认,Lys-GSH复合物中谷胱甘肽碎裂后产生的y2碎片离子会进一步碎裂.
為瞭探討非共價複閤物的碎片化反應機理,選擇穀胱甘肽和氨基痠複閤物研究影響碎片化反應的主要因素.串級質譜結果錶明,踫撞氣體密度(CGT)和踫撞能量是影響非共價複閤物碎片化反應的兩箇主要因素,對穀胱甘肽複閤物碎片化產物的生成途徑會有明顯的影響.噹踫撞氣體密度恆定在50×10~(13) molecules/cm~2,踫撞能量在小于100 eV範圍內,複閤物His-GSH都能髮生碎裂,斷裂位點容易髮生在非共價鍵上,生成原來組分[His+H]~+和[GSH+H]~+ 離子,但沒有髮生進一步碎裂.噹踫撞能量一定(恆定為30 eV),踫撞氣體密度為50×10~(13) molecules/cm~2時,His-GSH複閤物碎裂後的產物同樣為[His+H]~+和[GSH+H]~+.然而,噹踫撞氣體密度上升至75×10~(13) molecules/cm~2時,除非共價鍵髮生碎裂外,共價鍵也會髮生碎裂,產生更小的碎片離子y2,b2.噹踫撞氣體密度上升為175×10~(13) molecules/cm~2時,His也開始碎裂,生成m/z 110[His-H_2O-CO+H]~+.三級串級質譜MS~3實驗確認,Lys-GSH複閤物中穀胱甘肽碎裂後產生的y2碎片離子會進一步碎裂.
위료탐토비공개복합물적쇄편화반응궤리,선택곡광감태화안기산복합물연구영향쇄편화반응적주요인소.천급질보결과표명,팽당기체밀도(CGT)화팽당능량시영향비공개복합물쇄편화반응적량개주요인소,대곡광감태복합물쇄편화산물적생성도경회유명현적영향.당팽당기체밀도항정재50×10~(13) molecules/cm~2,팽당능량재소우100 eV범위내,복합물His-GSH도능발생쇄렬,단렬위점용역발생재비공개건상,생성원래조분[His+H]~+화[GSH+H]~+ 리자,단몰유발생진일보쇄렬.당팽당능량일정(항정위30 eV),팽당기체밀도위50×10~(13) molecules/cm~2시,His-GSH복합물쇄렬후적산물동양위[His+H]~+화[GSH+H]~+.연이,당팽당기체밀도상승지75×10~(13) molecules/cm~2시,제비공개건발생쇄렬외,공개건야회발생쇄렬,산생경소적쇄편리자y2,b2.당팽당기체밀도상승위175×10~(13) molecules/cm~2시,His야개시쇄렬,생성m/z 110[His-H_2O-CO+H]~+.삼급천급질보MS~3실험학인,Lys-GSH복합물중곡광감태쇄렬후산생적y2쇄편리자회진일보쇄렬.
To explore the fragmentation reactions of non-covalent complex, the complex of glutathione(GSH) and amino acids were chosen to investigate the main factors affecting the fragmentation process. The secondary tandem mass spectrometry(MS~2) results indicated that collision gas thickness(CGT) and collision energy are two important conditions affecting the fragmentation pathway of glutathione complex. When the CGT maintained at 50×10~(13) molecules/cm~2, increasing collision energy from 5 eV to 80 eV, the dissociation of His-GSH complex took place, leading to the formation of [His+H]~+ and [GSH+H]~+. However, it could be seen that no further dissociation of GSH occurred, and the fragmentation of noncovalent bond was the main pathway of the complex. When CGT rose up to 75×10~(13) molecules/cm~2, the covalent bond also began to dissociate, leading to the formation of y2 and b2 for glutathione. Such phenomena could be also observed in Lys-GSH complex. To confirm the fragment ion y2 of glutathione, MS~3 was also performed and y1 was detected.