Isotope effect analyses provide evidence for an altered transition state for RNA 2′-O-transphosphorylation catalyzed by Zn2+

Shuming Zhang; Hong Gu; Haoyuan Chen; Emily Strong; Edward W. Ollie; Daniel Kellerman; Danni Liang; Masaru Miyagi; Vernon E. Anderson; Joseph A. Piccirilli; Darrin M. York; Michael E. Harris

doi:10.1039/C5CC10212J

Isotope effect analyses provide evidence for an altered transition state for RNA 2′-O-transphosphorylation catalyzed by Zn²⁺†

Shuming Zhang,^a Hong Gu,^a Haoyuan Chen,^b Emily Strong,^a Edward W. Ollie,^a Daniel Kellerman,^a Danni Liang,^a Masaru Miyagi,^c Vernon E. Anderson,^a Joseph A. Piccirilli,^d Darrin M. York^b and Michael E. Harris*^a

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* Corresponding authors

^a Department of Biochemistry, Case Western Reserve University School of Medicine, Cleveland, OH 44106, USA
E-mail: meh2@cwru.edu
Tel: +1 216-368-4779

^b Center for Integrative Proteomics Research, BioMaPS Institute for Quantitative Biology and Department of Chemistry and Chemical Biology, Rutgers University Piscataway, NJ 08854, USA

^c Case Center for Proteomics and Bioinformatics, Case Western Reserve University, Cleveland, OH, USA

^d Department of Chemistry and Department of Biochemistry and Molecular Biology, The University of Chicago, Chicago, IL 60637, USA

Abstract

Solvent D₂O and ¹⁸O kinetic isotope effects on RNA 2′-O-transphosphorylation catalyzed by Zn²⁺ demonstrate an altered transition state relative to specific base catalysis. A recent model from DFT calculations involving inner sphere coordination to the non-bridging and leaving group oxygens is consistent with the data.

Chemical Communications

Isotope effect analyses provide evidence for an altered transition state for RNA 2′-O-transphosphorylation catalyzed by Zn²⁺†

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Isotope effect analyses provide evidence for an altered transition state for RNA 2′-O-transphosphorylation catalyzed by Zn²⁺

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