Evidence for reversible internal hydride/deuteride transfers from sodiated deprotonated fructose-6-phosphate and arginine complex with solvated salt structure
Résumé
Competitive cleavages {as free [F6P-H]$^-$ and [(F6P/R-2H+Na)-C$_3$H$_6$O$_3$]−} of fructose-6-phosphate/sodiated arginine complex anion {i.e., [(F6P/R+Na-H)-H]$^-$} are more complicated than expected. Indeed, the product ions generated from cleavages of [(F6P$_{d6}$/R$_{d7}$-D+Na)-D]$^−$ present (i) D-enrichment of fructose-6-phosphate by hydride transfer from the [Rd7-D+Na] partner via opened ring intermediate during a stepwise pathway and (ii) complementary D-depletion for the second product ion, reinforced by back HDX. As a consequence, the existence of several intermediates results in an unexpected mixture of isomeric structures for the m/z 259 anion (shifted to m/z 264 and m/z 265 from the d11 complex anion) and not only one which should correspond to [F6P-H] as provided from a standard.
Domaines
Chimie analytiqueOrigine | Fichiers produits par l'(les) auteur(s) |
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