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Differentiation of dihydroxylated vitamin D3 isomers using tandem mass spectrometry
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Haris, Anisha, Lam, Yuko P. Y., Wootton, Christopher, Theisen, Alina, Marzullo, Bryan P., Schorr, Pascal, Volmer, Dietrich A. and O’Connor, Peter B. (2022) Differentiation of dihydroxylated vitamin D3 isomers using tandem mass spectrometry. Journal of The American Society for Mass Spectrometry, 33 (6). pp. 1022-1030. doi:10.1021/jasms.2c00085 ISSN 1044-0305.
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Official URL: https://doi.org/10.1021/jasms.2c00085
Abstract
Vitamin D compounds are a group of secosteroids derived from cholesterol that are vital for maintaining bone health in humans. Recent studies have shown extraskeletal effects of vitamin D, involving vitamin D metabolites such as the dihydroxylated vitamin D3 compounds 1,25-dihydroxyvitamin D3 and 24,25-dihydroxyvitamin D3. Differentiation and characterization of these isomers by mass spectrometry can be challenging due to the zero-mass difference and minor structural differences between them. The isomers usually require separation by liquid chromatography (LC) prior to mass spectrometry, which adds extra complexity to the analysis. Herein, we investigated and revisited the use of fragmentation methods such as collisional induced dissociation (CID), infrared multiphoton dissociation (IRMPD), electron induced dissociation (EID), and ultraviolet photodissociation (UVPD), available on a 12T Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS) to generate characteristic fragments for the dihydroxylated vitamin D3 isomers that can be used to distinguish between them. Isomer-specific fragments were observed for the 1,25-dihydroxyvitamin D3, which were clearly absent in the 24,25-dihydroxyvitamin D3 MS/MS spectra using all fragmentation methods mentioned above. The fragments generated due to cleavage of the C-6/C-7 bond in the 1,25-dihydroxyvitamin D3 compound demonstrate that the fragile OH groups were retained during fragmentation, thus enabling differentiation between the two dihydroxylated vitamin D3 isomers without the need for prior chromatographic separation or derivatization.
Item Type: | Journal Article | |||||||||||||||||||||||||||||||||
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Subjects: | Q Science > QP Physiology | |||||||||||||||||||||||||||||||||
Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry | |||||||||||||||||||||||||||||||||
SWORD Depositor: | Library Publications Router | |||||||||||||||||||||||||||||||||
Library of Congress Subject Headings (LCSH): | Vitamin D, Ions, Mass spectrometry, Vitamin D in the body, Molecular structure | |||||||||||||||||||||||||||||||||
Journal or Publication Title: | Journal of The American Society for Mass Spectrometry | |||||||||||||||||||||||||||||||||
Publisher: | Springer New York LLC | |||||||||||||||||||||||||||||||||
ISSN: | 1044-0305 | |||||||||||||||||||||||||||||||||
Official Date: | 1 June 2022 | |||||||||||||||||||||||||||||||||
Dates: |
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Volume: | 33 | |||||||||||||||||||||||||||||||||
Number: | 6 | |||||||||||||||||||||||||||||||||
Page Range: | pp. 1022-1030 | |||||||||||||||||||||||||||||||||
DOI: | 10.1021/jasms.2c00085 | |||||||||||||||||||||||||||||||||
Status: | Peer Reviewed | |||||||||||||||||||||||||||||||||
Publication Status: | Published | |||||||||||||||||||||||||||||||||
Access rights to Published version: | Open Access (Creative Commons) | |||||||||||||||||||||||||||||||||
Date of first compliant deposit: | 7 December 2022 | |||||||||||||||||||||||||||||||||
Date of first compliant Open Access: | 8 December 2022 | |||||||||||||||||||||||||||||||||
RIOXX Funder/Project Grant: |
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