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2003 Fiscal Year Final Research Report Summary

Creation of structures and functions of artificial DNAs directed towards nano-assembly of metal complexes

Research Project

Project/Area Number 14340206
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Inorganic chemistry
Research InstitutionThe University of Tokyo

Principal Investigator

SHIONOYA Mitsuhiko  The University of Tokyo, Graduate School of Science, Professor, 大学院・理学系研究科, 教授 (60187333)

Co-Investigator(Kenkyū-buntansha) HIRAOKA Shuich  The University of Tokyo, Graduate School of Science, Research Associate, 大学院・理学系研究科, 助手 (10322538)
TANAKA Kentaro  The University of Tokyo, Graduate School of Science, Associate Professor, 大学院・理学系研究科, 助教授 (40281589)
Project Period (FY) 2002 – 2003
KeywordsArtificial DNA / Hydroxypyridone / Multi-nuclear metal / Double helical structure / Metal array / High-order structural control / Molecular wire / Oligonucleotide
Research Abstract

The strategy of replacing DNA natural bases by alternative ones has allowed the modification of DNA in a highly specific and site-selective manner, because DNA has a structural basis to array predesigned building blocks. We have recently envisioned the replacement of hydrogen-bonded base pairing present in natural DNA by metalmediated base pairing. Incorporation of such metal-induced base pairs into DNA would not only affect the assembly-disassembly processes and the structure of DNA double strands but also confer a variety of metal-based functions upon DNA. The chemistry thus interfaces with both life sciences and materials science
Along this line, we designed and synthesized metal-mediated base pairs with nucleosides bearing a phenylenediamine, a catechol, a 2-aminophenol, a pyridine, or a hydroxypyridone as the nucleobase. Some of them were successfully incorporated into DNA and were found to stabilize the duplex or triplex structures. Recently, we reported the synthesis of a series of artificial oligonucleotides, d(5 -GH_nC-3 ) (n = 1-5), using hydroxypyridone nucleobases (H) as flat bidentate ligands. Right-handed double helices of the oligonucleotides, nCu^<2+> d(5 -GH_nC-3 )_2 (n = 1-5), were quantitatively formed through Cu^<2+>-mediated alternative base pairing (H-Cu^<2+>-H), where the Cu^<2+> incorporated into each complex were aligned along the helix axes inside the duplexes with the Cu^<2+>-Cu^<2+> of 3.7 -0.1 angstrom. The Cu^<2+> ions were coupled ferromagnetically with one another through unpaired d electrons to form magnetic chains.

  • Research Products

    (16 results)

All Other

All Publications (16 results)

  • [Publications] M.Tasaka, K.Tanaka, M.Shiro, M.Shionoya: "Toward Nano-Assembly of Metals through Engineered DNAs"Supramolecular Chemistry. 14. 255-261 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] A.Hatano, K.Tanaka, M.Shiro, M.Shionoya: "Synthesis of Nucleic Acid Mimics Designed for Metal-Induced Strand Formation on DNA"Tetrahedron. 58. 2965-2972 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K.Tanaka, Y.Yamada, M.Shionoya: "Formation of Silver(I)-Mediated DNA Duplex and Triplex through an Alternative Base Pair of Pyridine Nucleobases"Journal of the American Chemical Society. 124. 8802-8803 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] S.Aketani, K.Tanaka, K.Yamamoto, A.Ishihama, H.Cao, A.Tengeiji, S.Hiraoka, M.Shiro, M.Shionoya: "Syntheses and Structure-Activity Relationships of Nonnatural β-C-Nucleoside 5'-Triphosphates Bearing an Aromatic Nucleobase with Phenolic Hydroxyl Groups :"Journal of Medicinal Chemistry. 45. 5594-5603 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K.Tanaka, A.Tengeiji, T.Kato, N.Toyama, M.Shiro, M.Shionoya: "Efficient Incorporation of A Copper Hydroxypyridone Base Pair in DNA"Journal of the American Chemical Society. 124. 12494-12498 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] J.Chiba, K.Tanaka, Y.Ohshiro, R.Miyake, S.Hiraoka, M.Shiro, M.Shionoya: "Artificial Nucleosides Possessing Metal Binding Sites at the 3'- and 5'-Positions of the Deoxyribose Moieties"Journal of Organic Chemistry. 68. 331-338 (2003)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K.Tanaka, A.Tengeiji, T.Kato, N.Toyama, M.Shionoya: "A Discrete Self-Assembled Metal Array in Artificial DNA"Science. 299. 1212-1213 (2003)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] S.Aketani, K.Tanaka, K.Yamamoto, A.Ishihama, H.Cao, A.Tengeiji, M.Shionoya: "Role of a non natural a -C-nucleotide unit in DNA as a template for DNA and RNA syntheses and as a substrate for nucleolytic digestion"European Journal of Pharmaceutical Sciences. 20. 43-51 (2003)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] M.Tasaka, K.Tanaka, M.Shiro, M.Shionoya: "Toward Nano-Assembly of Metals through Engineer ed DNAs"Supramolecular Chemistry. 14. 255-261 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M.Tasaka, K.Tanaka, M.Shiro, M.Shionoya: "Synthesis of Nucleic Acid Mimics Designed for Me tal-Induced Strand Formation on DNA"Tetrahedron. 58. 2965-2972 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K.Tanaka, Y.Yamada, M.Shionoya: "Formation of Silver(I)-Mediated DNA Duplex and Triplex through an Alternative Base Pair of Pyridine Nucleobases"Journal of the American Chemical Society. 124. 8802-8803 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] S.Aketani, K.Tanaka, K.Yamamoto, A.Ishihama, H.Cao, A.Tengeiji, S.Hiraoka, M.Shiro, M.Shionoya: "Syntheses and Structure-Activity Relationships of N onnatural β-C-Nucleoside 5'-Triphosphates Bearing an Aromatic Nucleobase with Phenolic Hydroxy Grolips: Inhibitoiy Activities against DNA Polymerases"Journal of Medicinal Chemistry. 45. 5594-5603 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K.Tanaka, A.Tengeiji, T.Kato, N.Toyama, M.Shiro, M.Shionoya: "Efficient Incorporation of A Copper Hydroxypyridone Base Pair in DNA"Journal of the American Chemical Society. 124. 12494-12498 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] J.Chiba, K.Tanaka, Y.Ohshiro, R.Miyake, S.Hiraoka, M.Shiro, M.Shionoya: "Artificial Nucleosides Possessing Metal Binding Site s at the 3'-and 5'-Positions of the Deoxyribose Moieties"Journal of Organic Chemistry. 68. 331-338 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K.Tanaka, A.Tengeiji, T.Kato, N.Toyama, M.Shionoya: "A Discrete Self-Assembled Metal Array in Artificial DNA"Science. 299. 1212-1213 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] S.Aketani, K.Tanaka, K.Yamamoto, A.Ishihama, H.Cao, A.Tengeiji, M.Shionoya: "Role of a non natural β-C-nucleotide unit in DNA as a template for DNA and RNA syntheses and as a substrate for nucleolytic digestion"European Journal of Pharmaceutical Sciences. 20. 43-51 (2003)

    • Description
      「研究成果報告書概要(欧文)」より

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Published: 2005-04-19  

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