Usefulness of Derivatization in High-Performance Liquid Chromatography/Tandem Mass Spectrometry of Conjugated Vitamin D Metabolites
Usefulness of Derivatization in High-Performance Liquid Chromatography/Tandem Mass Spectrometry of Conjugated Vitamin D Metabolites
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衍生化在结合维生素 D 代谢物的高效液相色谱/串联质谱分析中的用途
DOI：
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发表时间：
1999
期刊：
影响因子：
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通讯作者：
K. Shimada
中科院分区：
文献类型：
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作者：
T. Higashi;K. Miura;J. Kitahori;K. Shimada
衍生化在高效液相色谱/离子阱串联质谱（电喷雾电离）的共轭维生素D代谢产物的有用性进行了研究。24，25-二羟基维生素D_3 [24，25（OH）_2D_3]-3-和-24-葡萄糖醛酸苷（G）分别与4-苯基-1，2，4-三唑啉-3，5-二酮（PdR）、甲酯和乙酸酯形成加合物。与PdR和甲基化的衍生化的组合提高了在正离子和负离子模式下的检测限。24，25（OH）_2D_3-3G和-24G的PdR加合物在正离子-MS/MS/MS中也有一个特征产物离子，表明了PdR的结合位置，而在完整的PdR加合物中没有观察到这种特征产物离子。25-羟基维生素D_33-硫酸酯在负离子模式下产生去质子化离子，而在正离子模式下未观察到特征离子。与此相反，它的P2 O3加合物以正离子模式给出了分子相关离子，其MS/MS/MS提供了结构信息，即共轭位置和硫酸基团的存在。
The usefulness of derivatization in high-performance liquid chromatography/ion trap tandem mass spectrometry (electro-spray ionization) of conjugated vitamin D metabolites was examined. 24,25-Dihydroxyvitamin D_3 [24,25(OH)_2D_3]-3-and -24-glucuronides (G) were converted to the adducts with 4-phenyl-1,2,4-triazoline-3,5-dione (PTAD), the methyl esters and the acetates. The combination of the derivatization with PTAD and methylation improved the detection limit in both the positive- and negative-ion modes. The PTAD adducts of 24,25(OH)_2D_3-3G and -24G also gave a characteristic product ion indicating the conjugation position by the positive-MS/MS/MS, which was not observed in the intact forms. 25-Hydroxyvitamin D_3 3-sulfate gave the deprotonated ion in the negative-ion mode, but no characteristic ion was observed in the positive-ion mode. On the contrary, its PTAD adduct gave a molecular-related ion in the positive-ion mode, the MS/MS/MS of which provided structural information, that is, the conjugation position and the existence of a sulfuric acid group.