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生体物質と希土類錯体のかかわり

Research Project

Project/Area Number 06241103
Research Category

Grant-in-Aid for Scientific Research on Priority Areas

Allocation TypeSingle-year Grants
Research InstitutionThe University of Tokyo

Principal Investigator

小宮山 真  東京大学, 大学院・工学系研究科, 教授 (50133096)

Co-Investigator(Kenkyū-buntansha) 築部 浩  大阪市立大学, 理学部, 教授 (00144725)
井上 祥平  東京理科大学, 工学部, 教授 (20010762)
辻 章夫  昭和大学, 薬学部, 名誉教授 (80053784)
Project Period (FY) 1996
Project Status Completed (Fiscal Year 1996)
Budget Amount *help
¥35,800,000 (Direct Cost: ¥35,800,000)
Fiscal Year 1996: ¥15,800,000 (Direct Cost: ¥15,800,000)
Fiscal Year 1995: ¥10,000,000 (Direct Cost: ¥10,000,000)
Fiscal Year 1994: ¥10,000,000 (Direct Cost: ¥10,000,000)
Keywords希土類錯体 / DNA / 蛍光 / 不斉認識 / アミノ酸 / 核酸 / イムノアッセイ / セリウムイオン / RNA / 抗原抗体反応
Research Abstract

種々の生体分子を効率的に分子認識し、また化学変換する材料の重要性は大きい。すでに、本重点研究において、希土類錯体が特異的な機能を有し、これらの目的に対して優れた特性を持つことを明らかにしてきた。本年度は、最終年度であることを鑑み、これまでに得られた知見を集約するとともに、さらなる進展を図った。まず、Ce(IV)とPr(III)あるいはCe(IV)とNd(III)とを組み合わせると、DNAに対する切断活性が、Ce(IV)を単独で使用した場合よりも飛躍的に(約10倍)大きくなるという興味ある現象を見いだした。Pr(III)単独では触媒活性は全くない。これらの複数希土類イオン混合系の触媒効果は、非酵素系のDNA切断触媒としてはこれまでで最大であり、加速効果は実に10兆倍にも達する。また、希土類イオンを触媒とすることにより、二酸化炭素を効率的に結合すると同時に活性化し、これを用いて新たな有機合成系を構築した。
一方、希土類イオン配位数が大きく、その周囲の化学環境を制御しやすいことに着目し、アミノ酸類を不斉選択的に結合し、また輸送することに成功した。さらにゲスト分子の光学活性を、光情報として取り出した。また、希土類錯体の蛍光が、波長範囲が狭く、しかも寿命が長いことを活用して、生体分子を高感度で分析する手法を開発した。さらに、複数の生体分子の同時分析にも成功した。以上のように、希土類イオンならびにその錯体の特性を活用して、生化学に対して極めて有効な知見を蓄積することが出来た。

Report

(3 results)
  • 1996 Annual Research Report
  • 1995 Annual Research Report
  • 1994 Annual Research Report
  • Research Products

    (22 results)

All Other

All Publications (22 results)

  • [Publications] H.Shigekawa et al.: "Core level photoelectron spectroscopy on the lanthanide-induced hydrolysis of DNA." Appl.Phys.Lett.68. 1433-1435 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] N.Takeda,et al.: "Unprecedentedly fast DNA hydrolysis by the synergism of the cerium(IV)-praseodymium(III)and cerium(IV)-neodymium(III)combinations." Chem.Lett.599-600 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] M.Komiyama et al.: "RNA hydrolysis by the combination of lanthanum(III)ion and hydrogen peroxide." Chem.Lett.869-870 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] H.Yajima et al.: "Enormous cooperative catalyses of two metal ions for the hydrolysis of adenosine 3′,5′-cyclic monophosphate." Nucleic Acids,Symp.Ser.35. 139-140 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] J.Kamitani et al.: "RNA hydrolysis by lanthanide/H_2O_2 systems." Nucleic Acids,Symp.Ser.35. 141-142 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] M.Yashiro et al: "Dinuclear lanthanum(III)complex for efficient hydrolysis of RNA." J.Biochem.120. 1067-1069 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] H.Tsukube et al.: "Unique Carrier Properties of Neutral Lanthanide Complexes Toward Inorganic Anions" J.Mambrane Sci.114. 187-191 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] H.Tsukube et al.: "Enantioselective Binding and Extraction of Zwitterionic Amino Acid by Chiral Lanthanide Complex" J.Chem Soc.,Chem.Commun.477-478 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] H.Tsukube et al.: "Efficient Transport of Aliphatic Amino Acids Mediates by Lanthanide Complex Carrier Under Neutral Conditions" Chem.Lett.969-970 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] H.Tsukube et al.: "Recognition of Metal Complex Guest:Supramolecular Extraction of Water Soluble Lanthanide Complexes by Biological Lasalocid Ionophore" Inorg.Chim.Acta. 251. 1-3 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] H.Tsukube et al.: "Moleculer Recognition with Lanthanide Complex-Type Receptor:A Review" Bol.Soc.Chile Quim,in press.

    • Related Report
      1996 Annual Research Report
  • [Publications] M.Komiyama: "Efficient and oxygen-independent hydrolysis of single-stranded DNA by Ceciv)ion" Journal of Chemcal Societyaty,Perkin Transaction 2. 1995. 269-274 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] M.Irisawa: "Hydrolysis of DNA and RNA through cooperation of two metal ions:Anovel mimic of phosphoesterases" Journal of Biochemistry. 117. 465-466 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] M.Komiyama: "Seguence-selective hydrolytic scission of DNA and RNA and by lanthanide complex-oligo DNA by bybrids." Journal of Biochemistry. 118. 665-670 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] M.Yashiro: "Lanthanide complexes with high stability and eHiciency for the hydrolysis of a ribonucleotide dimer" Chemistry Letlers. 1995. 665-666 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] J.Sumaoka: "Acetylacetorato-lanthanide complexes as emikent catalytic sites for artificial ribonucleases" Nucleic Acids,Symposium Series. 34. 83-84 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Jun Sumaoka: "Enormous acceleration by cerium(IV) for the hydrolysis of nucleoside 3´,5´-cyclic monophosphates" J.Chem.Sec,Chem.Commun.1755-1756 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Morio Yashiro: "Cerium(IV)-cyclodextrin complex for peptide hydrolysis in neutral homogeneous solutions" J.Chem.Sec,Chem.Commun.1757-1758 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Makoto Komiyama: "Selective hydrolysis of tRNA by ethylenediamine bound to a DNA oligomer" J.Bivchem.116. 719-720 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Kazunari Matsumura: "Lanthanide complex-oligoDNA hybrid for sequenceselective hydrolysis of RNA" J.Chem.Sec,Chem. Commun.2019-2020 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Kazunari Matsumura: "Lanthanide(III) complex-oligoDNA hybrid as artificial hydrolytic nuclease" Nucleic Acids,Symp.Ser.31. 201-202 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Morio Yashiro: "Solubilization of lanthanide metal ions by cyclodextrins in basic agueous solutions" J.Incl.Phenom.Molec.Recog.17. 393-397 (1994)

    • Related Report
      1994 Annual Research Report

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Published: 1994-04-01   Modified: 2016-04-21  

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