NEG ION CHEM IONIZATION MASS SPECT CHAR OF PENTAFLUOROBENZYL OXIME DERIVATIVES

五氟苄基肟衍生物的负离子化学电离质谱图

• 批准号: 6665785
• 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/6665785
• 关键词: biological products; biomedical resource; cardiovascular system; enzymes; hematology; immunology; infection; inflammation; proteins; spectrometry; technology /technique

We have reported that activated neutrophils utilize the myeloperoxidase-H2O2-chloride system to convert the amino acid L-tyrosine to p-hydroxyphenylacetaldehyde. We report here that this myeloperoxidase system also catalyzes the oxidation of other amino acids to aldehydes. A sensitive method has been developed to detect these aldehydes as pentafluorobenzyl-oxime (PFBO) derivates by GC/NICI/MS. The reagent pentafluorobenzylhydroxylamine was used to prepare these derivatives. Two geometric isomers are obtained that are separable on GC analysis and exhibit distinguishable NICI mass spectra. Major fragment ions observed in these spectra include (M-HF)-. Loss of HF from the molecular anion may yield a ring intermediate, the subsequent decomposition of which yields other ions in the spectra. These include ions generated by elimination of NO or HCN. Proposed fragmentation pathways are supported by collisionally activated dissociation and tandem mass spectrometry, high reso lution mas s spectrometry, and studies of deuterium-labeled analogs.

我们报道过活化的中性粒细胞利用 髓过氧化物酶-H2O2-氯化物系统转化氨基酸 L-酪氨酸转化为对羟基苯乙醛。 我们在此报告，这 髓过氧化物酶系统还催化其他氨基的氧化 酸转化为醛。 已开发出一种灵敏的方法来检测 这些醛为五氟苄基肟 (PFBO) 衍生物 GC/NICI/MS。 试剂五氟苄基羟胺用于 制备这些衍生物。 得到两种几何异构体： 在 GC 分析中可分离并表现出可区分的 NICI 质量 光谱。 在这些光谱中观察到的主要碎片离子包括 (M-HF)-。 分子阴离子失去 HF 可能会产生环 中间体，随后分解产生其他离子 在光谱中。 这些包括通过消除 NO 或 HCN。 所提出的碎片途径得到了碰撞的支持 活化解离和串联质谱，高分辨率 质谱分析以及氘标记类似物的研究。