Detection of oligonucleotide gas-phase conformers: H/D exchange and ion mobility as complementary techniques

Detection of oligonucleotide gas-phase conformers: H/D exchange and ion mobility as complementary techniques
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DOI:
10.1016/j.jasms.2008.03.018
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发表时间:
2008-07-01
影响因子:
3.2
通讯作者:
De Pauw, Edwin
De Pauw, Edwin
中科院分区:
化学3区
文献类型:
--
作者:
Balbeur, Dorothee;Widart, Joelle;De Pauw, Edwin

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在傅里叶变换离子回旋共振(FTICR)质谱仪的第二个六极杆中进行小寡核苷酸(dTG、dC 6和Q)与CD 30 D的气相氢/氘交换。离子活化实验进行加速的H/D交换池的入口处的条件下,促进专门的碰撞异构化的离子。这些实验使我们能够评估几种构象的存在,并探测分离这些构象的异构化障碍的高度。还进行了离子迁移率实验。其结果与H/D交换数据一致。提出了一个考虑竞争异构化和H/D交换反应的模型。比较H/D交换和离子迁移率的离子加速实验表明,最紧凑的构象显示最快的H/D交换。这一观察结果表明,H/D交换和离子迁移率为我们提供了互补的信息,因为氢的可及性和大分子的紧凑性不是唯一相关的。
Gas-phase hydrogen/deuterium exchange of small oligonucleotides (dTG, dC6 and Q with CD30D was performed in the second hexapole of a Fourier transform ion-cyclotron resonance (FTICR) mass spectrometer. Ion activation experiments were conducted by accelerating the ions at the entrance of the H/D exchange cell under conditions promoting exclusively collisional isomerization. These experiments allowed us to assess the presence of several conformers, and to probe the height of the isomerization barrier separating these conformers. Ion mobility experiments were also performed. Their results were consistent with the H/D exchange data. A model accounting for the competing isomerization and H/D exchange reactions is proposed. Comparing the ion acceleration experiments for H/D exchange and for ion mobility reveals that the most compact conformer displays the fastest H/D exchange. This observation shows that H/D exchange and ion mobility provide us with complementary information because hydrogen accessibility and macromolecule compactness are not univocally associated.