Identification, structure elucidation and origin of a common pyridinium-thiocyanate intermediate in electrospray mass spectrometry among the benziamidazole-class proton pump inhibitors
During the analysis of benziamidazole-class irreversible proton pump inhibitors, an unusual mass spectral response with the mass-to-charge ratio at [M+10]+ intrigued us, as it couldn't be assigned to any literature known relevant structure, intermediate or adduct ion. Moreover, this mysterious...
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| Format: | Article |
| Language: | English |
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Elsevier
2023-06-01
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| Series: | Journal of Pharmaceutical Analysis |
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| Online Access: | http://www.sciencedirect.com/science/article/pii/S2095177923000722 |
| _version_ | 1797790073649889280 |
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| author | Dong Sun Chunyu Wang Yanxia Fan Jingkai Gu |
| author_facet | Dong Sun Chunyu Wang Yanxia Fan Jingkai Gu |
| author_sort | Dong Sun |
| collection | DOAJ |
| description | During the analysis of benziamidazole-class irreversible proton pump inhibitors, an unusual mass spectral response with the mass-to-charge ratio at [M+10]+ intrigued us, as it couldn't be assigned to any literature known relevant structure, intermediate or adduct ion. Moreover, this mysterious mass pattern of [M+10]+ has been gradually observed by series of marketed proton pump inhibitors, viz. omeprazole, pantoprazole, lansoprazole and rabeprazole. All the previous attempts to isolate the corresponding component were unsuccessful. The investigation of present work addresses this kind of signal to a pyridinium thiocyanate mass spectral intermediate (10), which is the common fragment ion of series of labile aggregates. The origin of such aggregates can be traced to the reactive intermediates formed by acid-promoted degradation. These reactive intermediates tend to react with each other and give raise series of complicated aggregates systematically in a water/acetonitrile solution by electrospray ionization. The structure of the corresponding pyridinium thiocyanate species of omeprazole (10a) has been eventually characterized with the help of synthetic specimen (10a′). Our structural proposal as well as its origin was supported by in situ nuclear magnetic resonance, chemical derivatization and colorimetric experiments. |
| first_indexed | 2024-03-13T01:59:34Z |
| format | Article |
| id | doaj.art-a660d0a15bce4075ba85c73a27ccfd12 |
| institution | Directory Open Access Journal |
| issn | 2095-1779 |
| language | English |
| last_indexed | 2024-03-13T01:59:34Z |
| publishDate | 2023-06-01 |
| publisher | Elsevier |
| record_format | Article |
| series | Journal of Pharmaceutical Analysis |
| spelling | doaj.art-a660d0a15bce4075ba85c73a27ccfd122023-07-02T04:16:32ZengElsevierJournal of Pharmaceutical Analysis2095-17792023-06-01136683688Identification, structure elucidation and origin of a common pyridinium-thiocyanate intermediate in electrospray mass spectrometry among the benziamidazole-class proton pump inhibitorsDong Sun0Chunyu Wang1Yanxia Fan2Jingkai Gu3Research Center for Drug Metabolism, School of Life Sciences, Jilin University, Changchun, 130012, ChinaState Key Laboratory of Supramolecular Structure and Materials, Jilin University, Changchun, 130012, ChinaJilin Institute for Drug Control, Changchun, 130033, China; Corresponding author.Research Center for Drug Metabolism, School of Life Sciences, Jilin University, Changchun, 130012, China; State Key Laboratory of Supramolecular Structure and Materials, Jilin University, Changchun, 130012, China; Beijing Institute of Drug Metabolism, Beijing, 102209, China; Corresponding author. Research Center for Drug Metabolism, School of Life Sciences, Jilin University, Changchun, 130012, China.During the analysis of benziamidazole-class irreversible proton pump inhibitors, an unusual mass spectral response with the mass-to-charge ratio at [M+10]+ intrigued us, as it couldn't be assigned to any literature known relevant structure, intermediate or adduct ion. Moreover, this mysterious mass pattern of [M+10]+ has been gradually observed by series of marketed proton pump inhibitors, viz. omeprazole, pantoprazole, lansoprazole and rabeprazole. All the previous attempts to isolate the corresponding component were unsuccessful. The investigation of present work addresses this kind of signal to a pyridinium thiocyanate mass spectral intermediate (10), which is the common fragment ion of series of labile aggregates. The origin of such aggregates can be traced to the reactive intermediates formed by acid-promoted degradation. These reactive intermediates tend to react with each other and give raise series of complicated aggregates systematically in a water/acetonitrile solution by electrospray ionization. The structure of the corresponding pyridinium thiocyanate species of omeprazole (10a) has been eventually characterized with the help of synthetic specimen (10a′). Our structural proposal as well as its origin was supported by in situ nuclear magnetic resonance, chemical derivatization and colorimetric experiments.http://www.sciencedirect.com/science/article/pii/S2095177923000722Proton pump inhibitorMass spectrometryElectrospray ionizationPseudo-molecular ionPyridinium thiocyanate |
| spellingShingle | Dong Sun Chunyu Wang Yanxia Fan Jingkai Gu Identification, structure elucidation and origin of a common pyridinium-thiocyanate intermediate in electrospray mass spectrometry among the benziamidazole-class proton pump inhibitors Journal of Pharmaceutical Analysis Proton pump inhibitor Mass spectrometry Electrospray ionization Pseudo-molecular ion Pyridinium thiocyanate |
| title | Identification, structure elucidation and origin of a common pyridinium-thiocyanate intermediate in electrospray mass spectrometry among the benziamidazole-class proton pump inhibitors |
| title_full | Identification, structure elucidation and origin of a common pyridinium-thiocyanate intermediate in electrospray mass spectrometry among the benziamidazole-class proton pump inhibitors |
| title_fullStr | Identification, structure elucidation and origin of a common pyridinium-thiocyanate intermediate in electrospray mass spectrometry among the benziamidazole-class proton pump inhibitors |
| title_full_unstemmed | Identification, structure elucidation and origin of a common pyridinium-thiocyanate intermediate in electrospray mass spectrometry among the benziamidazole-class proton pump inhibitors |
| title_short | Identification, structure elucidation and origin of a common pyridinium-thiocyanate intermediate in electrospray mass spectrometry among the benziamidazole-class proton pump inhibitors |
| title_sort | identification structure elucidation and origin of a common pyridinium thiocyanate intermediate in electrospray mass spectrometry among the benziamidazole class proton pump inhibitors |
| topic | Proton pump inhibitor Mass spectrometry Electrospray ionization Pseudo-molecular ion Pyridinium thiocyanate |
| url | http://www.sciencedirect.com/science/article/pii/S2095177923000722 |
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