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Tandem mass spectra of divalent metal ion adducts of glycosyl sulfides, sulfoxides and sulfones; distinction among stereoisomers
Author(s) -
Madhusudanan K. P.,
Kumar Brijesh,
Kanojiya Sanjeev,
Agnihotri Geetanjali,
Misra Anup Kumar
Publication year - 2006
Publication title -
journal of mass spectrometry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.475
H-Index - 121
eISSN - 1096-9888
pISSN - 1076-5174
DOI - 10.1002/jms.1105
Subject(s) - chemistry , adduct , medicinal chemistry , tandem mass spectrometry , deprotonation , inorganic chemistry , mass spectrometry , organic chemistry , ion , chromatography
The tandem mass spectra of the divalent metal ion (Mg 2+ , Ca 2+ , Sr 2+ , Ba 2+ , Mn 2+ , Ni 2+ , Co 2+ and Zn 2+ ) adducts of acetylated 1,2‐ trans ‐glycosyl sulfides, sulfoxides and sulfones were examined using low energy collision‐induced dissociation on a Quattro II quadrupole tandem mass spectrometer. Abundant doubly charged ions, such as [3M + Met] 2+ and [2M + Met] 2+ , were observed with alkaline earth metal chlorides. The other ions observed were [M + MetCl] + , [M + MetOAc] + , [M + MetO 2 SPh] + and [2M + MetCl] + . The deprotonated metal adducts [M + Met‐H] + were seen only in the sulfones. The divalent metal ion adducts showed characteristic fragmentation pathways for the glycosyl sulfides, sulfoxides and sulfones, depending on the site of metal attachment. The doubly charged metal ion adducts dissociate to two singly charged ions, [M + MetOAc] + and [M − OAc] + , in the sulfides and sulfoxides. In the sulfones, the adducts dissociate to [M + MetO 2 SPh] + and [M − O 2 SPh] + . In contrast to the alkaline earth metals, which attach to the acetoxy functions, the transition metals attach to the sulfide and sulfoxide functions. The metal chloride adducts display characteristic fragmentation for the sulfides, sulfoxides and sulfones. The glucosyl, mannosyl and galactosyl sulfides, sulfoxides and sulfones could be differentiated on the basis of the stereochemically controlled MS/MS fragmentations of the metal chloride adducts. Copyright © 2006 John Wiley & Sons, Ltd.