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DOI: 10.1039/A708036K (Paper) Reference Section for: J. Chem. Soc., Perkin Trans. 2, 1998, 523-528

Efficient RNA hydrolysis by lanthanide(III)–hydrogen peroxide combinations. Novel aggregates as the catalytic species[hair space]1

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Jun Kamitani, Jun Sumaoka, Hiroyuki Asanuma and Makoto Komiyama

Abstract

Combinations of lanthanum(III) ion and hydrogen peroxide efficiently hydrolyze RNA under physiological conditions, because of a synergetic cooperation. The rate constant for the hydrolysis of adenylyl(3′-5′)adenosine at pH 7.2 and 30 °C is 7.7 × 10–2 min–1, when [LaIII]0 = 10 and [H2O2]0 = 100 mM. This value is 460 times as great as that for the ApA hydrolysis by LaIII alone (1.7 × 10–4 min–1). Hydrogen peroxide is inactive when used separately. A similar synergism operates between NdIII and H2O2. According to the kinetic analysis and the potentiometric titration, a trimeric aggregate of [La(O–O)3La] complex is responsible for the RNA hydrolysis. This result is in contrast with the previous proposal on the hydrolysis of bis(4-nitrophenyl)phosphate that monomeric species of [La(O–O)2La]2+ is the active species (B. K. Takasaki and J. Chin, J. Am. Chem. Soc., 1995, 117, 8582). The discrepancy is ascribed to the difference in the basicities of the leaving groups in the substrates.

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    2La3++ 2H2O2⇌[La(O–O)2]2++ 4H+(6)
    In contrast, our titration has shown absolutely that [La(O–O)3 La], rather than [La(O–O)2 La]2+, is formed in the solutions, at least under the conditions used for the present RNA hydrolysis. Probably, [La(O–O)2 La]2+ further reacts with another H2 O2 molecule to form [La(O–O)3 La], since the concentrations of both the LaIII salt and H2O2 are sufficiently great. The experimental points in Fig. 4 are far from the theoretical line (the broken one), which was calculated by using the parameters reported by Takasaki and Chin.    .
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