液相色谱/质谱/质谱法表征乙酰基氨基酸和二乙酰基氨基酸的异构体。

IF 1.9 3区 化学 Q3 BIOCHEMICAL RESEARCH METHODS
Addipilli Ramunaidu, Pallerla Pavankumar, Nagarjunachary Ragi, Rodda Ramesh, Medicharla V. Jagannatham, Prabhakar Sripadi
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引用次数: 0

摘要

氨基酸的乙酰化在分子生物学和生物化学中很重要,因为它们是几种代谢途径的一部分。n -乙酰基氨基酸可以通过n -乙酰基蛋白的降解或特定酶对氨基酸的直接乙酰化形成。α-氨基酸的乙酰化既可以发生在α -NH2上,也可以发生在侧链官能团上,这两种乙酰化产物是同分异构体,可以表现出不同的生物学作用。理论上,所有的蛋白质原α-氨基酸都可能发生乙酰化,它们可能是代谢组的一部分。因此,检测和鉴定所有可能的α-氨基酸乙酰化产物对于非靶向代谢组学研究至关重要。本研究旨在合成并表征天然α-氨基酸的所有乙酰化产物。共合成了20个n - α -乙酰基氨基酸(1-20)、6个侧链乙酰基氨基酸(21-26)和6个双乙酰基氨基酸(27-32),并采用液相色谱-电喷雾电离串联质谱(LC-ESI-MS/MS)对其进行了表征。对所有乙酰氨基酸的[M + H]+离子进行MS/MS实验,获得其结构信息。除了预期的(H2 O + CO)(铵离子)损失外,大多数乙酰基氨基酸特异性地表现出H2 O的损失和[M+H]+离子中酮烯(C2 H2 O)的损失。侧链乙酰基氨基酸显示出清晰的结构特异性片段离子,使其易于与同分异构体n - α -乙酰基氨基酸区分。其他同分异构体/异重乙酰基氨基酸也可以通过质谱分析得到。对乙酰基氨基酸的氨离子进行了质谱分析,其中包括反映母体n - α -乙酰基和侧链乙酰基氨基酸结构的特征产物。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Characterization of isomeric acetyl amino acids and di-acetyl amino acids by LC/MS/MS

Acetylation of amino acids is important in the molecular biology and biochemistry because they are part of several metabolic pathways. N-acetyl amino acids can form through degradation of N-acetyl proteins or direct acetylation of amino acids by specific enzymes. Acetylation of α-amino acids can be either on the alpha –NH2 or on the side-chain functional group, where both the acetyl products are isomeric and can show different biological roles. Theoretically, all proteinogenic α-amino acids are expected to undergo acetylation and they can be a part of metabolome. Thus, it is essential to detect and identify all the possible acetylated products of α-amino acids for untargeted metabolomics studies. In this study, it is aimed to synthesize and characterize all acetylated products of natural α-amino acids. A total of 20 Nα-acetyl amino acids (120), six side-chain acetyl amino acids (2126), and six diacetyl amino acids (2732) were synthesized and characterized by liquid chromatography-electrospray ionizationtandem mass spectrometry (LC–ESI–MS/MS). The [M + H]+ ions of all the acetyl amino acids were subjected to MS/MS experiments to obtain their structural information. Apart from the expected loss of (H2O + CO) (immonium ions), most of the acetyl amino acids specifically showed loss of H2O and loss of a ketene (C2H2O) from [M+H]+ ions. The side-chain acetyl amino acids showed a clear-cut structure specific fragment ions that enabled easy differentiation from their isomeric Nα-acetyl amino acids. The other isomeric/isobaric acetyl amino acids could also be easily distinguished by their MS/MS spectra. The MS/MS of immonium ions of the acetyl amino acids were also studied, and they included characteristic products reflecting the structures of parent Nα-acetyl and side-chain acetyl amino acids.

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来源期刊
Journal of Mass Spectrometry
Journal of Mass Spectrometry 化学-光谱学
CiteScore
5.10
自引率
0.00%
发文量
84
审稿时长
1.5 months
期刊介绍: The Journal of Mass Spectrometry publishes papers on a broad range of topics of interest to scientists working in both fundamental and applied areas involving the study of gaseous ions. The aim of JMS is to serve the scientific community with information provided and arranged to help senior investigators to better stay abreast of new discoveries and studies in their own field, to make them aware of events and developments in associated fields, and to provide students and newcomers the basic tools with which to learn fundamental and applied aspects of mass spectrometry.
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