Evidence for a hydroxide ion bridging two magnesium ions at the active site of the hammerhead ribozyme

Nucleic Acids Res. 1997 Sep 1;25(17):3421-7. doi: 10.1093/nar/25.17.3421.

Abstract

In the presence of magnesium ions, cleavage by the hammerhead ribozyme RNA at a specific residue leads to 2'3'-cyclic phosphate and 5'-OH extremities. In the cleavage reaction an activated ribose 2'-hydroxyl group attacks its attached 3'-phosphate. Molecular dynamics simulations of the crystal structure of the hammerhead ribozyme, obtained after flash-freezing of crystals under conditions where the ribozyme is active, provide evidence that a mu-bridging OH-ion is located between two Mg2+ions close to the cleavable phosphate. Constrained simulations show further that a flip from the C3'- endo to the C2'- endo conformation of the ribose at the cleavable phosphate brings the 2'-hydroxyl in proximity to both the attacked phosphorous atom and the mu-bridging OH-ion. Thus, the simulations lead to a detailed new insight into the mechanism of hammerhead ribozyme cleavage where a mu-hydroxo bridged magnesium cluster, located on the deep groove side, provides an OH-ion that is able to activate the 2'-hydroxyl nucleophile after a minor and localized conformational change in the RNA.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Binding Sites
  • Crystallization
  • Electrochemistry
  • Freezing
  • Hydroxides / chemistry*
  • Magnesium / chemistry*
  • Models, Molecular
  • Molecular Structure
  • Nucleic Acid Conformation
  • RNA, Catalytic / chemistry*
  • RNA, Catalytic / metabolism

Substances

  • Hydroxides
  • RNA, Catalytic
  • hydroxide ion
  • Magnesium