Structural Analysis of Unsaturated Glycosphingolipids Using Shotgun Ozone-Induced Dissociation Mass Spectrometry.
Structural Analysis of Unsaturated Glycosphingolipids Using Shotgun Ozone-Induced Dissociation Mass Spectrometry.
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DOI：
10.1007/s13361-017-1772-2
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发表时间：
2017-11
影响因子：
3.2
通讯作者：
Zhang Q
中科院分区：
文献类型：
--
作者：
Barrientos RC;Vu N;Zhang Q
鞘糖脂是广泛分布于生物界的重要生物分子，但由于其组成和结构的复杂性，其研究仍相对不足。虽然多糖头基团一直是大多数研究的主题，但关于脂质部分，特别是不饱和位置的报道很少。本文采用四极杆飞行时间（Q-ToF）行波质谱仪，采用散弹枪法对不饱和鞘糖脂进行了研究。由此产生的高分辨率质谱有助于诊断性OzID产物离子的明确鉴定。用真实标准的[M+Na]+加合物，观察到长链碱和脂肪酰基不饱和对臭氧有明显的反应性。脂肪酰基链的不饱和反应活性比长链碱基的不饱和反应活性高约8倍，这使它们能够直接区分。还观察了头基团、脂肪酰基羟基化和脂肪酰基链长度对双键氧化裂解的影响。将该技术应用于牛脑半乳糖脑苷，揭示了共分离的等压异构体和区域异构体物种，否则仅使用当代碰撞诱导解离（CID）无法完全鉴定。这些结果突出了OzID-MS在鞘糖脂研究中的潜力，它不仅为现有的CID技术提供了补充的结构信息，而且有助于这些复杂生物分子的从头结构测定。
Glycosphingolipids are essential biomolecules widely distributed across biological kingdoms yet remain relatively underexplored owing to both compositional and structural complexity. While the glycan head group has been the subject of most studies, there is paucity of reports on the lipid moiety, particularly the location of unsaturation. In this paper, ozone-induced dissociation mass spectrometry (OzID-MS) implemented in a traveling wave-based quadrupole time-of-flight (Q-ToF) mass spectrometer was applied to study unsaturated glycosphingolipids using shotgun approach. Resulting high resolution mass spectra facilitated the unambiguous identification of diagnostic OzID product ions. Using [M+Na]+ adducts of authentic standards, we observed that the long chain base and fatty acyl unsaturation had distinct reactivity with ozone. The reactivity of unsaturation in the fatty acyl chain was about eight-fold higher than that in the long chain base, which enables their straightforward differentiation. Influence of the head group, fatty acyl hydroxylation and length of fatty acyl chain on the oxidative cleavage of double bonds was also observed. Application of this technique to bovine brain galactocerebrosides revealed co-isolated isobaric and regioisomeric species which otherwise would be incompletely identified using contemporary collision-induced dissociation (CID) alone. These results highlight the potential of OzID-MS in glycosphingolipids research, which not only provides complementary structural information to existing CID technique but also facilitates de novo structural determination of these complex biomolecules.
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鞘糖脂的脂质组学。
影响因子：
4.1
作者：
Farwanah H;Kolter T
通讯作者：
Kolter T
DOI：
10.1016/j.jchromb.2008.12.057
发表时间：
2009-09-15
期刊：
Journal of chromatography. B, Analytical technologies in the biomedical and life sciences
影响因子：
--
作者：
Haynes CA;Allegood JC;Park H;Sullards MC
通讯作者：
Sullards MC
影响因子：
4.7
作者：
ABE, T;NORTON, WT
通讯作者：
NORTON, WT
影响因子：
7.4
作者：
Boutin, Michel;Sun, Ying;Auray-Blais, Christiane
通讯作者：
Auray-Blais, Christiane
影响因子：
7.4
作者：
Kirsch, Stephan;Zarei, Mostafa;Peter-Katalinle, Jasna
通讯作者：
Peter-Katalinle, Jasna