通过碰撞诱导和氧附着解离的双重碎片化,使用水及其基因用于C=C位置解析的脂管组
Hiroaki Takeda1,2, Mami Okamoto3, Hidenori Takahashi3
1Department of Biotechnology and Life Science, Tokyo University of Agriculture and Technology, Koganei, Tokyo, Japan. hiroaki.takeda@aist.go.jp.
Communications chemistry
|May 13, 2025
概括
氧附着解离 (OAD) 现在在脂管学中以负离子模式工作. 新的OAciD方法结合了OAD和碰撞诱导解离 (CID) 以实现更快,更详细的脂质分析,揭示大脑脂质差异.
科学领域:
- 利皮多米克 (Lipidomics) 是一种消化剂.
- 质谱测量质量谱测量
- 生物化学 生物化学
背景情况:
- 氧附着解离 (OAD) 是一种双重质谱 (MS/MS) 技术,用于确定脂质中的双键位置.
- 目前的OAD方法仅限于正离子模式,需要单独的碰撞诱导解离 (CID) 实验来进行全面的脂质分析.
研究的目的:
- 为了适应负离子模式脂管学的OAD.
- 开发一种联合OAD和CID方法 (OAciD),用于同时获取数据.
- 使用MS-DIAL 5加速C=C位置解析的非向性脂管组学.
主要方法:
- 已证明OADMS/MS在负离子模式下对脂胺素,脂糖醇,脂氨酸醇和硫酸盐.
- 优化了同时进行CID和OAD碎片化的条件 (OAciD).
- 在MS-DIAL 5中实现了理论碎片离子用于数据分析.
主要成果:
- 与正离子模式相比,OAD碎片化机制在负离子模式中是一致的.
- 通过OAciD,可以同时获取OAD和CID特定的碎片离子.
- 应用OAciD来分析鱼大脑脂质组,确定大脑区域特定的脂质配置文件和C=C位置异构体比率.
- 发现小脑中含有omega-3脂肪酸的脂质和海马和额叶中含有omega-6脂肪酸的脂质的丰富.
结论:
- 在脂管学中,OAD在负离子模式中有效.
- OAciD方法通过提供C=C位置信息来增强非向性脂管学.
- 这种方法揭示了大脑脂质组成的显著区域差异,特别是多不和脂肪酸.
相关概念视频
01:20Mass Spectrometry: Molecular Fragmentation Overview
2.8K
The ionization of a molecule into a molecular ion inside the mass spectrometer causes instability in the molecule's structure due to the loss of an electron. This eventually leads to the fragmentation or breaking of some bonds in the molecule. The fragmentation occurs predominantly at specific bonds to yield relatively stable fragments.
One type of fragmentation pattern is the cleavage of a single bond in the molecular ion. The cleavage leads to a radical and a cation. The cleavage can...
One type of fragmentation pattern is the cleavage of a single bond in the molecular ion. The cleavage leads to a radical and a cation. The cleavage can...
2.8K
01:01Mass Spectrometry: Carboxylic Acid, Ester, and Amide Fragmentation
1.0K
The fragmentation patterns observed for compounds such as carboxylic acids, esters, and amides in the mass spectra include ⍺-cleavage and McLafferty rearrangement. Fragmentation by ⍺-cleavage preferentially occurs at the carbon-carbon bond at the ⍺-position next to the carboxylic group to generate a neutral radical and a cation. Long chain compounds with hydrogen at their γ-carbon undergo McLafferty rearrangement to give a radical cation and a neutral alkene.
For example,...
For example,...
1.0K
01:18Mass Spectrometry: Long-Chain Alkane Fragmentation
1.5K
The molecular ions of linear alkanes prefer to fragment at the carbon-carbon bond away from the end of the chain since the cleavage of an inner bond creates a stable carbocation and a stable radical. Consequently, the mass signals of linear alkanes feature intense peaks in the middle of the mass-to-charge ratio plot with weaker peaks on either end. The fragmentation of each carbon-carbon bond with the release of a methyl group in each splitting leads to prominent peaks in the mass spectra...
1.5K
01:03Mass Spectrometry: Alcohol Fragmentation
3.2K
Alcohols (R-OH) ionize to lose one non-bonded electron from the oxygen atom, forming molecular ions. Due to their tendency to fragment rapidly, the intensity of the molecular ion peak in the mass spectrum is weak or sometimes absent. The fragmentation patterns for alcohols occur in two ways, i.e. ⍺-cleavage and dehydration. During ⍺-cleavage, the bond at the ⍺-position adjacent to the hydroxyl group cleaves to give a resonance-stabilized cation and a radical. However,...
3.2K
00:54Mass Spectrometry: Cycloalkene Fragmentation
962
The molecular ions of cycloalkenes undergo fragmentation via a retro-Diels–Alder reaction.
962
00:59Mass Spectrometry: Alkene Fragmentation
2.4K
Alkenes lose one electron from the unsaturated π bond upon ionization and form stable molecular ions. Further fragmentation of alkenes occurs through three different reaction pathways. The most prominent fragmentation is the cleavage at the allylic position. The resultant allylic carbocation is resonance stabilized. In the mass spectra of terminal alkenes, this fragment appears at a mass-to-charge ratio of 41. In the internal alkenes, where there are two choices of allylic cleavage, the...
2.4K