Tandem mass spectra of ammonium ion, metal ion and ligated metal ion adducts of acyclic sugar derivatives.

Abstract

The tandem mass (MS/MS) spectra of ammonium ion, metal ion and ligated metal ion adducts of chain-extended acyclic nitro-containing deoxyglucose and deoxygalactose derivatives have been studied. The ammonium adducts fragment primarily by elimination of ammonia followed by acetic acid, thus not giving much structural information. In contrast, cationization of these compounds by metal ions and ligated metal ions gave structurally informative and useful fragment ions on MS/MS. The metal ions and ligated metal ions play an important role in controlling and directing fragmentation. Retro-aldol fragmentation is facilitated by metal ions such as Li(+), Na(+), Ag(+) and Cu(+), whereas the adducts with higher alkali metal ions such as Rb(+) and Cs(+) fragment to give only the corresponding metal ions. The divalent metal ions such as Cu(2+) and Ba(2+) also induce retro-aldol fragmentation. However, the charge is carried by the aldehyde fragment in the case of Cu(2+) adducts, whereas the nitroalkane fragment carries the charge in the case of Ba(2+) adducts. Ligated metal ions such as ZnCl(+), CuCl(+), InCl(2) (+) and BaCl(+) also behave similarly and induce retro-aldol fragmentation in these acyclic sugars. Both the metal ion and ligated metal ion adducts can fragment by elimination of metal-containing neutral molecules.