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

• Ryosuke Shinomiya

  Department of Chemistry, University of Tsukuba, Tsukuba, Ibaraki 305-8571 , Japan

• Haruka Araki

  Department of Chemistry, University of Tsukuba, Tsukuba, Ibaraki 305-8571 , Japan

• Atsuya Momotake

  Department of Chemistry, University of Tsukuba, Tsukuba, Ibaraki 305-8571 , Japan

• Hiroaki Kotani

  Department of Chemistry, University of Tsukuba, Tsukuba, Ibaraki 305-8571 , Japan

• Takahiko Kojima

  Department of Chemistry, University of Tsukuba, Tsukuba, Ibaraki 305-8571 , Japan

• Yasuhiko Yamamoto

  Department of Chemistry, University of Tsukuba, Tsukuba, Ibaraki 305-8571 , Japan

Abstract

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.

Journal

• Bulletin of the Chemical Society of Japan

  Bulletin of the Chemical Society of Japan 92 (10), 1729-1736, 2019-07-13

  Oxford University Press (OUP)

Keywords

• General Chemistry

Details

• CRID: 1360846644027272320
• NII Article ID: 130007728639
• DOI: 10.1246/bcsj.20190157
• ISSN: 13480634
• ISSN: 00092673
• Web Site: https://academic.oup.com/bcsj/article-pdf/92/10/1729/56299429/bcsj.20190157.pdf
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