Structural characterization of unsaturated phosphatidylcholines using traveling wave ion mobility spectrometry.
Structural characterization of unsaturated phosphatidylcholines using traveling wave ion mobility spectrometry.
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DOI：
10.1021/ac900672a
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发表时间：
2009-10-15
影响因子：
7.4
通讯作者：
Kanik, Isik
中科院分区：
文献类型：
--
作者：
Kim, Hugh I.;Kim, Hyungjun;Pang, Eric S.;Ryu, Ernest K.;Beegle, Luther W.;Loo, Joseph A.;Goddard, William A.;Kanik, Isik
利用电喷雾电离质谱联用行波离子迁移谱法（TWIMS）研究了质量范围为400 ~ 1000 Da的磷脂酰胆碱（PC）阳离子。在N2中饱和磷脂酰胆碱阳离子证明了质量和迁移率之间的高度相关性。不饱和PC阳离子的质量迁移率有明显的偏离。我们发现酰基链上的双键使漂移时间减少了5%。每增加一个双键，漂移时间以约1%的速率减少。PC阳离子的理论碰撞截面与实验计算值吻合良好。利用最近导出的TWIMS堆叠环离子波导（SRIG）中迁移率与漂移时间的关系确定了碰撞截面，并与经验校准方法估计的碰撞截面进行了比较。以非球形N2分子为漂移气体，采用修正轨迹法（TJ）进行计算分析。PC阳离子的估计碰撞截面与理论碰撞截面之间的差异与PC阳离子碰撞截面对离子中性相互作用细节的敏感性有关。利用分子动力学模拟，从分子结构刚度的角度讨论了所观察到的PC阳离子的质量和迁移率之间的相关性和偏差的来源。
A number of phosphatidylcholine (PC) cations spanning a mass range of 400 to 1000 Da are investigated using electrospray ionization mass spectrometry coupled with traveling wave ion mobility spectrometry (TWIMS). A high correlation between mass and mobility is demonstrated with saturated phosphatidylcholine cations in N2. A significant deviation from this mass-mobility correlation line is observed for the unsaturated PC cation. We found that the double bond in the acyl chain causes a 5% reduction in drift time. The drift time is reduced at a rate of ~1% for each additional double bond. Theoretical collision cross sections of PC cations exhibit good agreement with experimentally evaluated values. Collision cross sections are determined using the recently derived relationship between mobility and drift time in TWIMS stacked ring ion guide (SRIG) and compared to estimate collision cross-sections using empiric calibration method. Computational analysis was performed using the modified trajectory (TJ) method with nonspherical N2 molecules as the drift gas. The difference between estimated collision cross-sections and theoretical collision cross-sections of PC cations is related to the sensitivity of the PC cation collision cross-sections to the details of the ion-neutral interactions. The origin of the observed correlation and deviation between mass and mobility of PC cations is discussed in terms of the structural rigidity of these molecules using molecular dynamic simulations.
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影响因子：
7.4
作者：
Kim, Hyungjun;Kim, Hugh I.;Kanik, Isik
通讯作者：
Kanik, Isik
影响因子：
--
作者：
KARPAS, Z;BERANT, Z
通讯作者：
BERANT, Z
影响因子：
1.8
作者：
Beegle, LW;Kanik, I;Hill, HH
通讯作者：
Hill, HH
影响因子：
7.4
作者：
Bagal, Dhanashri;Zhang, Heidi;Schnier, Paul D.
通讯作者：
Schnier, Paul D.
影响因子：
7.4
作者：
GRIFFIN, GW;DZIDIC, I;HORNING, EC
通讯作者：
HORNING, EC