Isomeric discrimination and quantification of thyroid hormones, T3 and rT3, by the single ratio kinetic method using electrospray ionization mass spectrometry
Isomeric discrimination and quantification of thyroid hormones, T3 and rT3, by the single ratio kinetic method using electrospray ionization mass spectrometry
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DOI：
10.1016/j.jasms.2009.07.004
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发表时间：
2010
影响因子：
3.2
通讯作者：
Avvaru Praveen Kumar;Hua Jin;S. Jo;Changdae Kim;S. Nam;Yong‐Ill Lee
中科院分区：
文献类型：
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作者：
Avvaru Praveen Kumar;Hua Jin;S. Jo;Changdae Kim;S. Nam;Yong‐Ill Lee
基于单电荷过渡金属离子结合的三聚体配合物[MII（A）（ref*）2-H]+的竞争性单分子解离动力学，将单比率动力学方法应用于气相中甲状腺激素异构体3，5，3 ′-三碘甲状腺原氨酸和3，3 ′，5 ′-三碘甲状腺原氨酸的鉴别和定量（MII=二价过渡金属离子; A= T3或rT 3; ref* =参比配体）。使用电喷雾电离质谱法产生三聚络合物离子，并且离子经历碰撞活化以从形成二聚络合物[MII（A）（ref*）-H]+和[MII（ref*）2-H]+的两个片段途径的分支比实现异构体区分。发现两种异构体Riso的各个支化比的比率强烈依赖于参考和金属离子。通过从氨基酸、取代的氨基酸和二肽中选择参考物并与从五种过渡金属离子（CoII、CuII、MnII、NiII和ZnII）中选择的中心金属离子组合，尝试了本实验中复合物的各种组。结果进行了比较方面的异构体歧视的T3/rT 3对。校准曲线通过将支化比的比率与它们的混合物的异构体组成相关联来构建，以允许样品对的快速定量异构体分析。此外，该方法的仪器依赖性进行了研究，通过比较两组结果，一个从四极杆离子阱质谱仪和其他从四极杆飞行时间质谱仪。
The single ratio kinetic method is applied to the discrimination and quantification of the thyroid hormone isomers, 3,5,3′-triiodothyronine and 3,3′,5′-triiodothyronine, in the gas phase, based on the kinetics of the competitive unimolecular dissociations of singly charged transition-metal ion-bound trimeric complexes [MII(A)(ref*)2-H]+(MII= divalent transition-metal ion; A=T3or rT3; ref* = reference ligand). The trimeric complex ions are generated using electrospray ionization mass spectrometry and the ions undergo collisional activation to realize isomeric discrimination from the branching ratio of the two fragment pathways that form the dimeric complexes [MII(A)(ref*)-H]+and [MII(ref*)2-H]+. The ratio of the individual branching ratios for the two isomers Risois found strongly dependent on the references and the metal ions. Various sets are tried by choosing the reference from amino acids, substituted amino acids, and dipeptides in combination with the central metal ion chosen from five transition-metal ions (CoII, CuII, MnII, NiII, and ZnII) for the complexes in this experiment. The results are compared in terms of the isomeric discrimination for the T3/rT3pair. Calibration curves are constructed by relating the ratio of the branching ratios against the isomeric composition of their mixture to allow rapid quantitative isomer analysis of the sample pair. Furthermore, the instrument-dependence of this method is investigated by comparing the two sets of results, one obtained from a quadrupole ion trap mass spectrometer and the other from a quadrupole time-of-flight mass spectrometer.