离子淌度质谱结合轨迹模型确定二糖配合物气相离子结构

doi:10.19894/j.issn.1000-0518.200399

摘要/Abstract

摘要： 二糖的同分异构体由于结构相似难以直接进行区分,与碱金属离子非共价相互作用结合后会使其空间构型发生改变。利用漂移时间离子淌度质谱(Drift Time Ion-Mobility Spectrometry-Mass Spectrometry,DTIMS-MS)对乳糖、麦芽糖、纤维二糖及蔗糖4种二糖的碱金属离子配合物进行测量,结果表明,Cs⁺对纤维二糖和乳糖有较好的区分效果,其双峰分辨率R_p-p=0.39;而K⁺对蔗糖麦芽糖效果较好,R_p-p=0.74。另外,实验利用单场校正的方法对4种二糖金属配合物离子的碰撞截面(Collision Cross-Section,CCS)值进行了测量,同时通过密度泛函理论(Density Functional Theory,DFT)对二糖-金属离子复合物可能的结构进行预测,得到的结构分别通过近似投影(Projection Approximation,PA)模型、精确硬球散射(Exact Hard Sphere Scattering,EHSS)模型和轨迹(Trajectory Method,TM)模型计算其CCS理论值。 3种模型得到的结果和实验值的相对偏差分别为-23.05%、11.79%和0.44%,TM模型与实验值吻合最好。根据此方法可总结出碱金属离子与二糖结构的结合位点,可进一步预测未知二糖离子配合物的结构及其结构,并对二糖同分异构体进行分离识别。

关键词: 漂移时间离子淌度质谱, 碰撞截面积, 轨迹模型, 二糖

Abstract: The isomeric disaccharides are difficult to distinguish due to their similar structures. The non-covalent interaction between disaccharides and alkali metal ions will change their spatial configurations. In this work, drift time ion-mobility spectrometry-mass spectrometry (DTIMS) was used to measure the drift times for alkali metal ion adducts of four disaccharides including lactose, maltose, cellobiose, and sucrose. The results show that Cs⁺ has a better distinguishing effect on cellobiose and lactose, and its bimodal resolution R_p-p is 0.39; while K⁺ has a better effect on sucrose and maltose, and R_p-p is 0.74. Besides, the experiment used a single-field correction method to measure the collision cross-section (CCS) values of those disaccharide alkali metal ion adducts. Contemporary, quantum mechanics density functional theory (DFT) was performed to predict the possible structure of those disaccharide alkali metal ion adducts, followed by the calculation of its theoretical CCS value using three models including the projection approximation (PA), the exact hard-sphere scattering (EHSS) and the trajectory method (TM). The relative deviations obtained by the three models are -23.05%, 11.79%, and 0.44%, respectively, indicating that the TM model agrees best with the experimental values. According to this method, the binding site of alkali metal ion and disaccharide structures can be summarized, and the structure of unknown disaccharide metal ion adduct can be further predicted.

Key words: Drift time ion mobility mass spectrometry, Collision cross-section, Trajectory method, Disaccharide

中图分类号:

O641

房祥雨, 胡军, 吴芳玲, 唐科奇. 离子淌度质谱结合轨迹模型确定二糖配合物气相离子结构[J]. 应用化学, 2021, 38(12): 1655-1662.

FANG Xiang-Yu, HU Jun-Jack, WU Fang-Ling, TANG Ke-Qi. Ion Mobility Mass Spectrometry Combined with the Trajectory Method to Determine Gas Phase Ion Structures of Disaccharide-Alkali Metal Ion Adducts[J]. Chinese Journal of Applied Chemistry, 2021, 38(12): 1655-1662.

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