Investigating the role of a backbone to substrate hydrogen bond in OMP decarboxylase using a site-specific amide to ester substitution

  • Bijoy J. Desai
    Departments of aBiochemistry and
  • Yuki Goto
    Department of Chemistry, Graduate School of Science, University of Tokyo, Tokyo 113-0033, Japan;
  • Alessandro Cembran
    Department of Chemistry, University of Minnesota, Minneapolis, MN 55455;
  • Alexander A. Fedorov
    Department of Biochemistry, Albert Einstein College of Medicine, Bronx, NY 10461; and
  • Steven C. Almo
    Department of Biochemistry, Albert Einstein College of Medicine, Bronx, NY 10461; and
  • Jiali Gao
    Department of Chemistry, University of Minnesota, Minneapolis, MN 55455;
  • Hiroaki Suga
    Department of Chemistry, Graduate School of Science, University of Tokyo, Tokyo 113-0033, Japan;
  • John A. Gerlt
    Departments of aBiochemistry and

書誌事項

公開日
2014-10
DOI
  • 10.1073/pnas.1411772111
公開者
Proceedings of the National Academy of Sciences

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説明

<jats:title>Significance</jats:title> <jats:p> Orotidine 5′-monophosphate decarboxylase has attracted intense enzymological interest, because it achieves a very large rate enhancement (∼10 <jats:sup>17</jats:sup> ) without the use of cofactors. Previous studies provided evidence that substrate destabilization and vinyl anion intermediate stabilization contribute to the rate enhancement. Using in vitro translation, we generated a backbone amide to ester substitution to evaluate the importance of the hydrogen bond between a backbone amide and the substrate in intermediate stabilization. The hydrogen bond contributes modestly (≤10 <jats:sup>2</jats:sup> ), suggesting that the intermediate is primarily stabilized by electrostatic interactions with the active site. This study establishes a versatile method for generation of backbone amide to ester substitutions in sufficient quantities to investigate the importance of backbone amide hydrogen bonding interactions in enzyme-catalyzed reactions. </jats:p>

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