title: Characterization of Heme-DNA Complexes Composed of Some Chemically Modified Hemes and Parallel G-Quadruplex DNAs.
abstract: Heme {Fe(II)- or Fe(III)-protoporphyrin IX complex [heme(Fe(2+)) or heme(Fe(3+)), respectively]} binds selectively to the 3'-terminal G-quartet of a parallel G-quadruplex DNA formed from a single repeat sequence of the human telomere, d(TTAGGG), through a π-π stacking interaction between the porphyrin moiety of the heme and the G-quartet. The binding affinities of some chemically modified hemes(Fe(3+)) for DNA and the structures of complexes between the modified hemes(Fe(2+)) and DNA, with carbon monoxide (CO) coordinated to the heme Fe atom on the side of the heme opposite the G6 G-quartet, have been characterized to elucidate the interaction between the heme and G-quartet in the complexes through analysis of the effects of the heme modification on the structural properties of the complex. The study revealed that the binding affinities and structures of the complexes were barely affected by the heme modification performed in the study. Such plasticity in the binding of heme to the G-quartet is useful for the versatile design of the complex through heme chemical modification and DNA sequence alteration. Furthermore, exchangeable proton signals exhibiting two-proton intensity were observed at approximately -3.5 ppm in the (1)H nuclear magnetic resonance (NMR) spectra of the CO adducts of the complexes. Through analysis of the NMR results, together with theoretical consideration, we concluded that the heme(Fe(2+)) axial ligand trans to CO in the complex is a water molecule (H2O). Identification of the Fe-bound H2O accommodated between the heme and G-quartet planes in the complex provides new insights into the structure-function relationship of the complex.
authors.affiliation: Department of Chemistry, University of Tsukuba , Tsukuba 305-8571, Japan.
authors.forename: Yasuhiko
authors.initials: Y
authors.lastname: Yamamoto
authors.affiliation: Department of Chemistry, University of Tsukuba , Tsukuba 305-8571, Japan.
authors.forename: Masashi
authors.initials: M
authors.lastname: Kinoshita
authors.affiliation: Department of Chemistry, University of Tsukuba , Tsukuba 305-8571, Japan.
authors.forename: Yuya
authors.initials: Y
authors.lastname: Katahira
authors.affiliation: Department of Chemistry, University of Tsukuba , Tsukuba 305-8571, Japan.
authors.forename: Haruna
authors.initials: H
authors.lastname: Shimizu
authors.affiliation: Department of Chemistry, University of Tsukuba , Tsukuba 305-8571, Japan.
authors.forename: Yue
authors.initials: Y
authors.lastname: Di
authors.affiliation: Department of Chemistry, University of Tsukuba , Tsukuba 305-8571, Japan.
authors.forename: Tomokazu
authors.initials: T
authors.lastname: Shibata
authors.affiliation: Graduate School of Materials Science, Nara Institute of Science and Technology , Ikoma, Nara 630-0192, Japan.
authors.forename: Hulin
authors.initials: H
authors.lastname: Tai
authors.affiliation: Department of Materials Engineering, National Institute of Technology, Nagaoka College , Nagaoka 940-8532, Japan.
authors.forename: Akihiro
authors.initials: A
authors.lastname: Suzuki
authors.affiliation: Department of Physical Chemistry, Graduate School of Pharmaceutical Sciences, Chiba University , Chuoh-Inohana, Chiba 260-8675, Japan.
authors.forename: Saburo
authors.initials: S
authors.lastname: Neya
mesh_terms: D002248:Carbon Monoxide / Q000737:chemistry*; D004247:DNA / Q000737:chemistry*; D054856:G-Quadruplexes; D006418:Heme / Q000737:chemistry*; D007501:Iron / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy
chemical_list: D006418:Heme; D002248:Carbon Monoxide; D004247:DNA; D007501:Iron