The reaction mechanism of phosphoryl transfer catalyzed
by UMP/CMP-kinase from Dictyostelium discoideum
was investigated by semiempirical AM1 molecular orbital
computations of an active site model system derived from
crystal structures that contain a transition state analog
or a bisubstrate inhibitor. The computational results suggest
that the nucleoside monophosphate must be protonated for
the forward reaction while it is unprotonated in the presence
of aluminium fluoride, a popular transition state analog
for phosphoryl transfer reactions. Furthermore, a compactification
of the active site model system during the reaction and
for the corresponding complex containing AlF3
was observed. For the active site residues that are part
of the LID domain, conformational flexibility during the
reaction proved to be crucial. On the basis of the calculations,
a concerted phosphoryl transfer mechanism is suggested
that involves the synchronous shift of a proton from the
monophosphate to the transferred PO3-group.
The proposed mechanism is thus analogous to the phosphoryl
transfer mechanism in cAMP-dependent protein kinase that
phosphorylates the hydroxyl groups of serine residues.