[Updated on Apr. 18] Integration of CiNii Articles into CiNii Research

Identification of Intermediates in Peroxidase Catalytic Cycle of a DNAzyme Possessing Heme

  • Shinomiya Ryosuke
    Department of Chemistry, University of Tsukuba
  • Araki Haruka
    Department of Chemistry, University of Tsukuba
  • Momotake Atsuya
    Department of Chemistry, University of Tsukuba
  • Kotani Hiroaki
    Department of Chemistry, University of Tsukuba
  • Kojima Takahiko
    Department of Chemistry, University of Tsukuba
  • Yamamoto Yasuhiko
    Department of Chemistry, University of Tsukuba Tsukuba Research Center for Energy Materials Science (TREMS), University of Tsukuba Life Science Center for Survival Dynamics, Tsukuba Advanced Research Alliance (TARA), University of Tsukuba

Abstract

<p>Heme in the ferric state (heme(Fe3+)) binds to G-quadruplex DNAs to form stable complexes that exhibit enhanced peroxidase activities. The complexes are considered DNAzymes possessing heme as a prosthetic group (heme-DNAzymes), and have been extensively investigated as promising catalysts for a variety of applications. On ESR and stopped-flow measurements, an iron(IV)oxo porphyrin π-cation radical known as Compound I was detected in reaction mixtures of heme-DNAzymes and hydrogen peroxide. This finding not only resolved the long-standing issue of the mechanism underlying the enhancement of the peroxidase activity of heme(Fe3+) in the scaffold of a G-quadruplex DNA, but also provided new insights as to the design of novel heme-DNAzymes.</p>

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