NEGATIVE ION CHEMICAL IONIZATION MASS SPECTROMETRY OF PERFLUOROACYL DERIVATIVES

全氟酰基衍生物的负离子化学电离质谱法

• 批准号: 6665790
• 负责人: FONG-FU HSU
• 金额: $ 15.75万
• 依托单位: WASHINGTON UNIVERSITY
• 依托单位国家: 美国
• 财政年份: 2002
• 资助国家: 美国
• 起止时间: 2002-08-01 至 2003-07-31
• 项目状态: 已结题
• 来源: https://reporter.nih.gov/project-details/6665790
• 关键词: biological products; biomedical resource; musculoskeletal system; proteins; spectrometry

The negative ion chemical ionization (NCI) mass spectra of the pentafluoroproprionyl (PFP) and heptafluorobutyryl (HFB) derivatives of 2-aminophenol contain a base ion which is generated by a mechanism involving the a loss of 44 amu, and ions reflecting this loss are also observed in the NCI spectra of the PFP or HFB derivatives of other ortho hydroxyanilines, including 3-hydroxybenzidine and the n-propyl esters of 2-hydroxyanilinic acid and 2-aminotyrosine. A corresponding ion is not observed in the NCI spectra of the trifluoroacetyl (TFA) derivative of 2-aminophenol or in the spectra of the PFP or HFB derivatives of meta or para isomers of hydroxyaniline or of 2-ethylaminophenol. Examination of the mechanism of this loss by tandem mass spectrometry, linked scanning, and high resolution mass spectrometry revealed that it reflects elimination of CO2 and indicate that the fragmentation pathway involves an initial loss of HF, in which the hydrogen atom is derived from the deriv atized amide nitrogen, followed by formation of a ring intermediate from which CO2 is subsequently eliminated to yield another ring structure. An ion generated by loss of 44 amu is also observed in the NCI spectra of HFB or PFP derivatives of catechols, including L-dopa and catechol itself, and the mechanism of this loss may also involve formation of a ring intermediate from which CO2 is subsequently eliminated. The occurrence of this loss of CO2 can be used to achieve distinction among regio-isomers of hydoxyanilines and to distinguish a catechol from a resorcinol or hydroquinone nucleus.

负离子化学电离（NCI）的质谱 五氟丙二烯基（PFP）和七氟丁酰基（HFB）衍生物 2-氨基苯酚的含有一个由机制产生的碱基离子 涉及44个AMU的A损失，反映这种损失的离子也是 在其他PFP或HFB衍生物的NCI光谱中观察到 邻苯二苯胺，包括3-羟基苯胺和N-丙酰胺 2-羟基苯胺酸和2-氨基酪氨酸的酯。 相应的 在三氟乙酰基（TFA）的NCI光谱中未观察到离子 2-氨基苯酚或PFP或HFB的光谱中的衍生物 羟苯胺或元素异构体的衍生物或 2-乙酰氨基酚。 检查这种损失机制 串联质谱，链接扫描和高分辨率质量 光谱法显示，它反映了消除二氧化碳的消除并指出 碎裂途径涉及HF的初始损失， 氢原子是从中得出的 衍生化的酰胺氮，然后形成环 随后消除二氧化碳的中间体以产生 另一个环结构。 损失44 AMU产生的离子也是 在HFB的NCI光谱中观察到儿茶醇的PFP衍生物， 包括L-DOPA和儿茶酚本身，以及这种损失的机制 也可能涉及形成二氧化碳的环中间体 随后淘汰。 二氧化碳损失的发生可以是 用于在氢氧烷胺的区域异构体之间进行区分 区分儿茶酚与异丙醇或羟基酮核。