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Novel Functions of π-Electron Systems in a Heme-DNA Complex

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Chemical Science of π-Electron Systems

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Abstract

While DNA is largely double helical, guanine-rich sequences can exist in an alternative structural form known as the G-quadruplex. The G-quadruplex is stabilized by the formation of the G-quartet composed of four guanine bases that are cyclically associated through Hoogsteen hydrogen bonding. The size and planarity of the G-quartet are well suited for interaction with heme, the most ubiquitous cofactor found in nature, through π-π stacking, and hemes and various G-quadruplex DNAs have been reported to form stable heme-DNA complexes that exhibit spectroscopic and functional properties remarkably similar to those of hemoproteins. These findings paved the way to a new research field involving the exploitation of the heme reactivity in the scaffold of the DNA structure. The heme electronic structure can be indirectly tuned through DNA sequence alterations that change the interaction between the heme and the surrounding DNA moiety and be directly affected by chemical modification of heme peripheral side chains. Therefore, the combined use of these two approaches enables us to control the function of a heme-DNA complex, as the function of hemoproteins is controlled through the heme environment furnished by nearby amino acid residues and electronic tuning of the intrinsic heme reactivity.

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Authors and Affiliations

  1. Department of Chemistry, University of Tsukuba, Tsukuba, 305-8571, Japan

    Yasuhiko Yamamoto & Tomokazu Shibata

Authors
  1. Yasuhiko Yamamoto
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  2. Tomokazu Shibata
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Correspondence to Yasuhiko Yamamoto .

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Editors and Affiliations

  1. Foundation for Advancement of International Science, Tsukuba, Japan

    Takeshi Akasaka

  2. Kyoto University, Kyoto, Japan

    Atsuhiro Osuka

  3. Department of Chemistry and Nano Science,, Ewha Womans University, Seoul, Korea (Republic of)

    Shunichi Fukuzumi

  4. Nagoya Institute of Technology, Nagoya, Japan

    Hideki Kandori

  5. Osaka University, Suita, Japan

    Yoshio Aso

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Yamamoto, Y., Shibata, T. (2015). Novel Functions of π-Electron Systems in a Heme-DNA Complex. In: Akasaka, T., Osuka, A., Fukuzumi, S., Kandori, H., Aso, Y. (eds) Chemical Science of π-Electron Systems. Springer, Tokyo. https://doi.org/10.1007/978-4-431-55357-1_43

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