Cerium(IV)/Lanthanide(III)/Dextran Ternary Solutions for Efficient and Homogeneous DNA Hydrolysis

References

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• The pseudo-first-order rate constants for the hydrolyses of authentic samples of 3′-and 5′-monophosphate to thymidine were 0.32 and 0.24 h-1, respectively. The hydrolysis of monophosphate are about 100 fold faster than that of TpT
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• When the ratio [monomeric residue of dextran]0/[Ce(IV))]0 is 1.0, homogeneous solutions are obtained for both the Ce(IV)/dextran and the Ce(IV)/Pr(III)/dextran systems. However, these solutions are rather unstable, and gradually become turbid and heterogeneous as the TpT hydrolysis proceeds. The ratio must be 2 or greater, in order to keep the mixtures homogeneous throughout the reactions
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• The HPLC profile for TpT hydrolysis by Ce(IV)/Pr(III)/dextran was presented in ref. 1. The pseudo-first-order rate constants for the hydrolyses of authentic samples of 3′− and 5′−monophosphate were 0.79 and 0.88 h-1, respectively
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• Burgess , J. 1978 . Metal Ions in Solution Horwood In Ce(IV)/dextran binary system, both the acid and the base must be provided by the Ce(IV) ion(s). The cooperation can not be very effective here, since the Ce(IV) ion is intrinsically eminent as an acid but not very active as a base. Consistently, the Pr(III)-bound hydroxide is much stronger a base than the Ce(IV)-bound one (the pKa of Pr(III)-bound water (7.1) is greater than that of Ce(IV)-bound water (∼ 0)) (the pKa of the water bound to lanthanide(III) ions, other than Pr(III), is also between 7 and 9, and thus the corresponding metal-bound hydroxide is sufficiently basic for the catalysis Chichester
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