Characterization of Long-Chain Fatty Acid as N-(4-Aminomethylphenyl) Pyridinium Derivative by MALDI LIFT-TOF/TOF Mass Spectrometry.

Characterization of Long-Chain Fatty Acid as N-(4-Aminomethylphenyl) Pyridinium Derivative by MALDI LIFT-TOF/TOF Mass Spectrometry.
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DOI:
10.1007/s13361-018-1993-z
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发表时间:
2018-08
影响因子:
3.2
通讯作者:
Hsu FF
Hsu FF
中科院分区:
化学3区
文献类型:
--
作者:
Frankfater C;Jiang X;Hsu FF

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电荷远程碎裂(CRF)是KeV高能CID裂解过程的重要标志,它是长链脂肪酸脂肪族尾部CnH_2n+2残基的消除。这是一条重要的裂解途径,导致用CID串联质谱仪表征生物分子的结构。在这份报告中,我们描述了MALDI Lift TOF TOF质谱学方法来研究各种脂肪酸(FA),这些脂肪酸被衍生化成N-(4-氨基甲基苯基)吡啶(AMPP)衍生物,并在有或没有基质的情况下被激光解吸为M+离子。不出所料,FA-AMPP的高能MALDI Lift TOF-TOF质谱图中包含的碎片离子主要来自CnH_2n+2残基的CRF裂解。这些离子与涉及分子内官能团的特定键断裂的离子(S)一起提供了比使用线性离子陷阱仪器的低能CID/HCD产生的更完整的结构鉴定。然而,这种Lift TOF TOF质谱学方法继承了低灵敏度,这是高能CID串联质谱学的典型特征。由于目前的Lift TOF-TOF技术缺乏具有足够灵敏度的单位质量前体离子选择,所以对于混合物中具有一个或两个双键的相同链长脂肪酸的产物离子光谱是无法区分的。
Charge remote fragmentation (CRF) elimination of CnH2n+2 residues along the aliphatic tail of long chain fatty acid is hall mark of keV high energy CID fragmentation process. It is an important fragmentation pathway leading to structural characterization of biomolecules by CID tandem mass spectrometry. In this report, we describe MALDI LIFT TOF TOF mass spectrometric approach to study a wide variety of fatty acids (FAs), which were derivatized to N-(4-aminomethylphenyl) pyridinium (AMPP) derivative, and desorbed as M+ ions by laser with or without matrix. The high energy MALDI LIFT TOF-TOF mass spectra of FA-AMPP contain fragment ions mainly deriving from CRF cleavages of CnH2n+2 residues, as expected. These ions together with ions from specific cleavages of the bond(s) involving the functional group within the molecule provide more complete structural identification than those produced by low energy CID/HCD using a linear ion-trap instrument. However, this LIFT TOF TOF mass spectrometric approach inherits low sensitivity, a typical feature of high-energy CID tandem mass spectrometry. Because of the lack of unit mass precursor ion selection with sufficient sensitivity of the current LIFT TOF-TOF technology, product ion spectra from same chain length fatty acids with difference in one or two double bonds in a mixture are not distinguishable.
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