Hydrolysis of phosphomonoesters in nucleotides by cerium(IV) ions. Highly selective hydrolysis of monoester over diester in concentrated buffers
Abstract
Phosphomonoesters in nucleotides are efficiently hydrolysed by
CeIV ions under physiological conditions. The half-lives of
the residues at pH 7.2 and 50 °C
([CeIV] = 10 mM) are around 10 min.
Phosphomonoester hydrolysis by CeIV ions is faster than the
hydrolysis of phosphodiesters. Significantly, the selectivity for
monoester hydrolysis over diester hydrolysis is remarkably increased by
using concentrated buffer solutions (TRIS and HEPES). In 500
mM TRIS buffer, pdA and dAp are hydrolysed 500- and 580-fold
faster than is d(ApA), whereas the corresponding ratios in 50
mM TRIS buffer are 85 and 90 respectively. Selective removal
of the terminal monophosphate from d(pApA) is achieved by
CeIV in these concentrated buffers.
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