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JBIC Journal of Biological Inorganic Chemistry

, Volume 9, Issue 7, pp 914–921 | Cite as

Molecular design of an acid–base cooperative catalyst for RNA cleavage based on a dizinc complex

Original Article

Abstract

The effects of donor groups of dizinc complexes, formed from a 2:1 mixture of Zn(II) and a dinucleating ligand, on adenylyl(3′-5′)adenosine (ApA) cleavage have been studied. Two dinucleating ligands were used: one had two 2-pyridylmethyl and two 2-hydroxyethyl moieties on the 1,3-diamino-2-propanol linker moiety (2), and the other had two 2-pyridylmethyl and two carboxymethyl moieties on the 1,3-diamino-2-propanol linker moiety (32−). The dizinc complex with 2 [(Zn2+)2-2] showed higher activities toward ApA cleavage than the dizinc complex using an analogous dinucleating ligand having four 2-pyridylmethyl donor moieties [(Zn2+)2-1] at pH 5–8. The former showed a bell-shaped pH–rate constant profile, whereas the latter showed a sigmoidal pattern. The differences in the pH–rate constant profile are attributable to the various distributions of the monohydroxo-dizinc species, i.e. dideprotonated species, which are responsible for ApA cleavage. The monohydroxo species of (Zn2+)2-2 has two acidic protons, which are not present in the corresponding monohydroxo species of (Zn2+)2-1. The existence of both intracomplex acid (ROH or H2O) and base catalysts (RO or OH) in (Zn2+)2-2 can explain its higher activity toward ApA cleavage than that of (Zn2+)2-1. In contrast, (Zn2+)2-32− showed lower activity toward ApA cleavage at pH 7.0, which can be ascribed to the absence of the monohydroxo-dizinc species under these conditions.

Keywords

Acid–base cocatalyst Dinucleating ligands Dizinc(II) complexes Kinetics and mechanism RNA hydrolysis 

Abbreviations

ApA

adenylyl(3′-5′)adenosine

BNPP

bis(4-nitrophenyl) phosphate

Notes

Acknowledgements

We thank Prof. Kazuhiko Saigo. This work was partially supported by the Tokyo Ohka Foundation for the Promotion of Science and Technology.

Supplementary material

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Copyright information

© SBIC 2004

Authors and Affiliations

  1. 1.Department of Applied Chemistry, Faculty of EngineeringTokyo Polytechnic UniversityKanagawa Japan
  2. 2.Department of Chemistry and Biotechnology, Graduate School of EngineeringThe University of TokyoTokyo Japan

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