Examination of structurally selective derivatization of vitamin D(3) analogues by electrospray mass spectrometry

The structural specificity of vitamin D derivatization by PTAD (4-phenyl-1,2,4-triazoline-3,5-dione) was probed using synthetic analogues and ion trap mass spectrometry. EB 1089, a vitamin D(3) analogue which contains a second site for Diels--Alder cycloaddition on its side-chain, allowed the examin...

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Bibliographic Details
Published in:Journal of mass spectrometry. 2001-01, Vol.36 (1), p.71
Main Authors: Weiskopf, A S, Vouros, P, Cunniff, J, Binderup, E, Björkling, F, Binderup, L, White, M C, Posner, G H
Format: Article
Language:English
Subjects:
Calcitriol - analogs & derivatives
Calcitriol - chemistry
Cholecalciferol - chemistry
Hydroxylation
Molecular Structure
Spectrometry, Mass, Electrospray Ionization
Triazoles - chemistry
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Summary:The structural specificity of vitamin D derivatization by PTAD (4-phenyl-1,2,4-triazoline-3,5-dione) was probed using synthetic analogues and ion trap mass spectrometry. EB 1089, a vitamin D(3) analogue which contains a second site for Diels--Alder cycloaddition on its side-chain, allowed the examination of derivatization modes and comparisons of ion fragment structures. The origins of a PTAD-vitamin D(3) ion fragment, commonly used in metabolite characterization and quantitation of vitamin D(3) analogues (m/z 314), were established; ion trap mass spectrometry revealed that the PTAD comprises a portion of this diagnostic fragment, and is not lost by a retro-Diels--Alder step. Furthermore, the unique structure of the EB 1089 side-chain also permits facile determination of its side-chain metabolism. Use of PTAD derivatization and detection of metabolite-specific ion fragments identify hydroxylation at the end of the EB 1089 sidechain. It is believed that the results from these studies provide a clearer understanding of the mass spectrometry of triazolinedione derivatives, not only in the specific case of EB 1089, but also in their application to other vitamin D compounds.
ISSN:1076-5174