title: Structure Determination of an Ag(I) -Mediated Cytosine-Cytosine Base Pair within DNA Duplex in Solution with (1) H/(15) N/(109) Ag NMR Spectroscopy.
abstract: The structure of an Ag(I) -mediated cytosine-cytosine base pair, C-Ag(I) -C, was determined with NMR spectroscopy in solution. The observation of 1-bond (15) N-(109) Ag J-coupling ((1) J((15) N,(109) Ag): 83 and 84 Hz) recorded within the C-Ag(I) -C base pair evidenced the N3-Ag(I) -N3 linkage in C-Ag(I) -C. The triplet resonances of the N4 atoms in C-Ag(I) -C demonstrated that each exocyclic N4 atom exists as an amino group (-NH2 ), and any isomerization and/or N4-Ag(I) bonding can be excluded. The 3D structure of Ag(I) -DNA complex determined with NOEs was classified as a B-form conformation with a notable propeller twist of C-Ag(I) -C (-18.3±3.0°). The (109) Ag NMR chemical shift of C-Ag(I) -C was recorded for cytidine/Ag(I) complex (δ((109) Ag): 442 ppm) to completed full NMR characterization of the metal linkage. The structural interpretation of NMR data with quantum mechanical calculations corroborated the structure of the C-Ag(I) -C base pair.
authors: School of Pharmaceutical Sciences, Ohu University, 31-1 Misumido, Tomita-machi, Koriyama, Fukushima, 963-8611, Japan. t-dairaku@pha.ohu-u.ac.jp.|Graduate School of Pharmaceutical Sciences, Tohoku University, 6-3 Aza-Aoba, Aramaki, Aoba-ku, Sendai, Miyagi, 980-8578, Japan. t-dairaku@pha.ohu-u.ac.jp.
authors: Takenori
authors: T
authors: Dairaku
authors: Institute for Protein Research, Osaka University, 3-2 Yamadaoka, Suita, Osaka, 565-0871, Japan.
authors: Kyoko
authors: K
authors: Furuita
authors: Application, Bruker BioSpin K. K., 3-9 Moriya-cho, Kanagawa-ku, Yokohama, Kanagawa, 221-0022, Japan.
authors: Hajime
authors: H
authors: Sato
authors: Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, v.v.i., Flemingovo náměstí 2, 16610, Praha 6, Czech Republic.
authors: Jakub
authors: J
authors: Šebera
authors: Faculty of Phamaceutical Scienes, Tokushima Bunri University, Yamashiro-cho, Tokushima, 770-8514, Japan.
authors: Katsuyuki
authors: K
authors: Nakashima
authors: Department of Materials and Life Sciences, Faculty of Science and Technology, Sophia University, 7-1 Kioi-cho, Chiyoda-ku, Tokyo, 102-8554, Japan.
authors: Jiro
authors: J
authors: Kondo
authors: Graduate School of Pharmaceutical Sciences, Tohoku University, 6-3 Aza-Aoba, Aramaki, Aoba-ku, Sendai, Miyagi, 980-8578, Japan.
authors: Daichi
authors: D
authors: Yamanaka
authors: Graduate School of Pharmaceutical Sciences, Tohoku University, 6-3 Aza-Aoba, Aramaki, Aoba-ku, Sendai, Miyagi, 980-8578, Japan.
authors: Yoshinori
authors: Y
authors: Kondo
authors: Department of Material & Life Chemistry, Faculty of Engineering, Kanagawa University, 3-27-1 Rokkakubashi, Kanagawa-ku, Yokohama, Kanagawa, 221-8686, Japan.
authors: Itaru
authors: I
authors: Okamoto
authors: Department of Material & Life Chemistry, Faculty of Engineering, Kanagawa University, 3-27-1 Rokkakubashi, Kanagawa-ku, Yokohama, Kanagawa, 221-8686, Japan.
authors: Akira
authors: A
authors: Ono
authors: Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, v.v.i., Flemingovo náměstí 2, 16610, Praha 6, Czech Republic. vladimir.sychrovsky@marge.uochb.cas.cz.|Czech Technical University in Prague, Faculty of Electrical Engineering, Department of Electrotechnology, Technická 2, 166 27, Praha 6, Czech Republic. vladimir.sychrovsky@marge.uochb.cas.cz.
authors: Vladimír
authors: V
authors: Sychrovský
authors: Institute for Protein Research, Osaka University, 3-2 Yamadaoka, Suita, Osaka, 565-0871, Japan. kojima@protein.osaka-u.ac.jp.
authors: Chojiro
authors: C
authors: Kojima
authors: Graduate School of Pharmaceutical Sciences, Tohoku University, 6-3 Aza-Aoba, Aramaki, Aoba-ku, Sendai, Miyagi, 980-8578, Japan. tanakay@ph.bunri-ac.jp.|Faculty of Phamaceutical Scienes, Tokushima Bunri University, Yamashiro-cho, Tokushima, 770-8514, Japan. tanakay@ph.bunri-ac.jp.
authors: Yoshiyuki
authors: Y
authors: Tanaka
mesh_terms: D020029:Base Pairing; D001483:Base Sequence; D001665:Binding Sites; D003596:Cytosine / Q000737:chemistry*; D004247:DNA / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D015394:Molecular Structure; D009584:Nitrogen / Q000737:chemistry; D009690:Nucleic Acid Conformation; D012834:Silver / Q000737:chemistry*
chemical_list: D012834:Silver; D006859:Hydrogen; D003596:Cytosine; D004247:DNA; D009584:Nitrogen
keywords: DNA; NMR spectroscopy; bioinorganic chemistry; metallo-base-pair; silver