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Design of NIR-Luminescent Probes with Long-life Emission on the Basis of Thiacalixarene-Lanthanide-Silver Supramolecular Complexes

Research Project

Project/Area Number 16350039
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Analytical chemistry
Research InstitutionTohoku University

Principal Investigator

IKI Nobuhiko  Tohoku University, Graduate School of Environmental Studies, Associate Professor, 大学院環境科学研究科, 助教授 (50282108)

Co-Investigator(Kenkyū-buntansha) HOSHINO Hitoshi  Tohoku University, Graduate School of Environmental Studies, Professor, 大学院環境科学研究科, 教授 (20124620)
TAKAHASHI Toru  Tohoku University, Graduate School of Environmental Studies, Research Assistant, 大学院環境科学研究科, 助手 (30361166)
Project Period (FY) 2004 – 2006
Project Status Completed (Fiscal Year 2006)
Budget Amount *help
¥13,600,000 (Direct Cost: ¥13,600,000)
Fiscal Year 2006: ¥2,600,000 (Direct Cost: ¥2,600,000)
Fiscal Year 2005: ¥2,400,000 (Direct Cost: ¥2,400,000)
Fiscal Year 2004: ¥8,600,000 (Direct Cost: ¥8,600,000)
KeywordsLuminescent Probe / Near Infrared Luminescence / Lanthanide complex / Thiacalixarenes / Supramolecule / Nd(III) / Yb(III) / Ag(I) / 金赤外発光 / 三元錯体 / テルビウム(III)
Research Abstract

Probes with long-lived luminescence in near-infrared region were obtained with supramolecular formation in lanthanide(III)-silver(I)-thiacalix[4]arene-p-tetrasulfonate (TCAS) ternary systems via following studies.
1.Structural characterization of Tb(III)-Ag(I)-TCAS supramolecular complex with ES-MS : It was clarified that supramolecular complex Ag_2・Tb_2・TCAS (1) was formed at pH 6.5, whereas Ag_2・Tb・TCAS (2) was formed at pH 10.0. Complexes 1 and 2 adopted double-cone structures, in which two Ag(I) ions bridges two cone-shaped TCAS by Ag(I)-S-Ag(I) bridges. In complex 1, TCAS coordinate to Tb(III) with two sets of O,S,O-coordination, whereas in complex 2 each TCAS coordinate to Tb(III) center with two sets of O,O,O,O-coordination.
2.Determination of photophysical properties : For complex 1, determined parameters are as follows: luminescence quantum yield Φ = 0.16, luminescence lifetime τ= 1.09 ms, and number of coordinating water to Tb(III) q = 2.4. For complex 2, Φ (=0.11) was smaller … More than that of 1, but τ (= 4.61 ms) was as large as intrinsic luminescence lifetime of Tb(III) ion (4.7 ms). This owes to the fact that number of coordinating water was almost zero (q = 0.1). Removal of coordinating water from lanthanide center is a key to realize NIR luminescence in aqueous solutions, because coordinating water strongly quenches NIR luminescence via high-energy vibrational modes. Therefore, we selected supramolecular complex 2 as a candidate for NIR probe.
3.Characterization of NIR probes : Yb(III) ion formed supramolecule 2 at pH 9.9, which emitted MIR light at 983 nm with Φ = 2.5x10^<-3>. On the other hand, Nd(III) formed Ag_3 Td TCAS (3) under the same conditions, which exhibited luminescence at 1050 nm (0=2.9x 10^<-4>).
4.Elucidation of kinetic stability : Solvolytic dissociation rate constant for Ag_2 Tb TCAS.( was determined to be 3.1x10^<-3> s^<-1> with a capillary electrophoretic reactor. This corresponds to half-life of 3.8 min, which is rather small from a view point of biological application. It was concluded that improvement of kinetic stability is next challenge for practical application of supramolecular NIR-luminescence probes. Less

Report

(4 results)
  • 2006 Annual Research Report   Final Research Report Summary
  • 2005 Annual Research Report
  • 2004 Annual Research Report
  • Research Products

    (43 results)

All 2007 2006 2005 2004

All Journal Article (43 results)

  • [Journal Article] Di- and tetracarboxylate ligands for highly luminescent terbium(III) complexes on the basis of sulfonylcalix[4]arene scaffold2007

    • Author(s)
      T.Horiuchi
    • Journal Title

      Tetrahedron Lett. 48・5

      Pages: 821-825

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Tetra- and Di-nuclear Copper(II) Complexes with Stereoisomers of Sulfinylcalix[4]arene Arising from the Disposition of Four S=O Groups2007

    • Author(s)
      N.Iki
    • Journal Title

      Bull. Chem. Soc. Jpn. 80・6(印刷中)

    • NAID

      10019586450

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Transition metal and lanthanide cluster complexes constructed with thiacalix[n]arene and its derivatives2007

    • Author(s)
      T.Kajiwara
    • Journal Title

      Coord. Chem. Rev. (印刷中)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Di-and tetracarboxylate ligands for highly luminescent terbium(III) complexes on the basis of sulfonylcalix[4]arene scaffold2007

    • Author(s)
      T.Horiuchi
    • Journal Title

      Tetrahedron Lett. 48(5)

      Pages: 821-825

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Tetra-and Di-nuclear Copper(II) Complexes with Stereoisomers of Sulfinylcalix[4]arene Arising from the Disposition of Four S=O Groups2007

    • Author(s)
      N.Iki
    • Journal Title

      Bull.Chem.Soc.Jpn. 80(6)(in press)

    • NAID

      10019586450

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Transition metal and lanthanide cluster complexes constructed with thiacalix[n]arene and its derivatives2007

    • Author(s)
      T.Kajiwara
    • Journal Title

      Coord.Chem.Rev. (in press)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Di- and tetracarboxylate ligands for highly luminescent terbium(III) complexes on the basis of sulfonylcalix[4]arene scaffold2007

    • Author(s)
      T.Horiuchi
    • Journal Title

      Tetrahedron Letters 48・5

      Pages: 821-825

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Highly-symmetrical tetra-nuclear cluster complexes supported by p-tert-butylsulfonylcalix[4]arene as a cluster-forming ligand2006

    • Author(s)
      T.Kajiwara
    • Journal Title

      Eur. J. Inorg. Chem. 2006・9

      Pages: 1765-1770

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Topological Variation between Hexa-and Trithiacalix[6]arene-Copper(II) complexes : from Sphere to Wheel by Reducing the Number of the Sulfur Bridges2006

    • Author(s)
      N.Kon
    • Journal Title

      Chem. Lett. 35・4

      Pages: 430-431

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Supramolecular assembly based on π-π stacking and π-cation interactions between thiacalix[6]arene and DMF2006

    • Author(s)
      F.Hamada
    • Journal Title

      Tetrahedron Lett. 47・31

      Pages: 5591-5593

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Conformation-Controlled Luminescent Properties of Lanthanide Clusters Containing p-tert-Butylsulfonylcalix[4]arene2006

    • Author(s)
      T.Kajiwara
    • Journal Title

      Inorg. Chem. 45・13

      Pages: 4880-4882

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Dodeca-Lanthanide Wheel Supported by p-tert-Butylsulfonylcalix[4]arene2006

    • Author(s)
      T.Kajiwara
    • Journal Title

      Chem. Asian J. 1・3

      Pages: 349-351

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Thiacalixarenes2006

    • Author(s)
      N.Morohashi
    • Journal Title

      Chem. Rev. 106・12

      Pages: 5291-5316

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Highly-symmetrical tetra-nuclear cluster complexes supported by p-tert-butylsulfonylcalix[4]arene as a cluster-forming ligand2006

    • Author(s)
      T.Kajiwara
    • Journal Title

      Eur.J.Inorg.Chem. 2006(9)

      Pages: 1765-1770

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Topological Variation between Hexa- and Trithiacalix[6]arene-Copper(II) complexes : from Sphere to Wheel by Reducing the Number of the Sulfur Bridges2006

    • Author(s)
      N.Kon
    • Journal Title

      Chem.Lett. 35(4)

      Pages: 430-431

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Supramolecular assembly based on π-π stacking and at-cation interactions between thiacalix[6]arene and DMF2006

    • Author(s)
      F.Hamada
    • Journal Title

      Tetrahedron Lett. 47(31)

      Pages: 5591-5593

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Conformation-Controlled Luminescent Properties of Lanthanide Clusters Containing p-tert-Butylsulfonylcalix[4]arene2006

    • Author(s)
      T.Kajiwara
    • Journal Title

      Inorg.Chem. 45(13)

      Pages: 4880-4882

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Dodeca-Lanthanide Wheel Supported by p-tert-Butylsulfonylcalix[4]arene2006

    • Author(s)
      T.Kajiwara
    • Journal Title

      Chem.Asian J. 1(3)

      Pages: 349-351

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Thiacalixarenes2006

    • Author(s)
      N.Morohashi
    • Journal Title

      Chem.Rev. 106(12)

      Pages: 5291-5316

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Highly-symmetrical tetra-nuclear cluster complexes supported by p-tert-butylsulfonylcalix[4]arene as a cluster-forming ligand2006

    • Author(s)
      T.Kajiwara
    • Journal Title

      European Journal of Inorganic Chemistry 2006・9

      Pages: 1765-1770

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Topological Variation between Hexa- and Trithiacalix[6]arene-Copper(II) complexes : from Sphere to Wheel by Reducing the Number of the Sulfur Bridges2006

    • Author(s)
      N.Kon
    • Journal Title

      Chemistry Letters 35・4

      Pages: 430-431

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Supramolecular assembly based on π-π stacking and π-cation interactions between thiacalix[6]arene and DMF2006

    • Author(s)
      F.Hamada
    • Journal Title

      Tetrahedron Letters 47・31

      Pages: 5591-5593

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Conformation-Controlled Luminescent Properties of Lanthanide Clusters Containing p-tert-Butylsulfonylcalix[4]arene2006

    • Author(s)
      T.Kajiwara
    • Journal Title

      Inorganic Chemistry 45・13

      Pages: 4880-4882

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Dodeca-Lanthanide Wheel Supported by p-tert-Butylsulfonylcalix[4]arene2006

    • Author(s)
      T.Kajiwara
    • Journal Title

      Chemistry-An Asian Journal 1・3

      Pages: 349-351

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Synthesis and Crystal Structure of p-tert-ButyIthiacalix[8]arene : A New Member of Thiacalixarenes2005

    • Author(s)
      Y.Kondo
    • Journal Title

      J. Incl. Phenom. Macrocycl. Chem. 52・1

      Pages: 45-49

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] A microchip capillary electrophoretic reactor a new methodology for direct measurement of dissociation kinetics of metal complexes2005

    • Author(s)
      T.Takahashi
    • Journal Title

      The Analyst 130・10

      Pages: 1337-1339

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Sulfinylcalix[4]arene-impregnated Amberlite XAD-7 resin for the separation of niobium(V) from tantalum(V)2005

    • Author(s)
      H.Matsumiya
    • Journal Title

      J. Chromatogr. A 1090・10

      Pages: 197-200

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Synthesis and Crystal Structure of p-tert-Butylthiacalix[8]arene : A New Member of Thiacalixarenes2005

    • Author(s)
      Y.Kondo
    • Journal Title

      J.Incl.Phenom.Macrocycl.Chem. 52(1)

      Pages: 45-49

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] A microchip capillary electrophoretic reactor : a new methodology for direct measurement of dissociation kinetics of metal complexes2005

    • Author(s)
      T.Takahashi
    • Journal Title

      The Analyst 130(10)

      Pages: 1337-1339

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Sulfinylcalix[4]arene-impregnated Amberlite XAD-7 resin for the separation of niobium(V) from tantalum(V)2005

    • Author(s)
      H.Matsumiya
    • Journal Title

      J.Chromatogr.A 1090(10)

      Pages: 197-200

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Synthesis and Crystal Structure of p-tert-Butylthiacalix[8]arene : A New Member of Thiacalixarenes2005

    • Author(s)
      Y.Kondo
    • Journal Title

      J.Incl.Phenom.Macrocycl.Chem. 52・1

      Pages: 45-49

    • Related Report
      2005 Annual Research Report
  • [Journal Article] A microchip capillary electrophoretic reactor : a new methodology for direct measurement of dissociation kinetics of metal complexes2005

    • Author(s)
      T.Takahashi
    • Journal Title

      The Analyst 130・10

      Pages: 1337-1339

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Sulfinylcalix[4]arene-impregnated Amberlite XAD-7 resin for the separation of niobium(V) from tantalum(V)2005

    • Author(s)
      H.Matsumiya
    • Journal Title

      J.Chromatogr.A 1090・10

      Pages: 197-200

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Tuning of the Cavity of Water-soluble Thiacalix[4]arene for the Control of Inclusion Ability toward Water-miscible Organic Molecules2004

    • Author(s)
      N.Kon
    • Journal Title

      Collect. Czech. Chem. Commun. 69・5

      Pages: 1080-1096

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Preconcentration of copper, cadmium, and lead with a thiacalix[4]arenetetrasulfonate loaded Sephadex A-25 anion-exchanger for graphite-furnace atomic absorption Spectrometry2004

    • Author(s)
      H.Matsumiya
    • Journal Title

      Anal. Bioanal. Chem. 379・5-6

      Pages: 867-871

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] A p-tert-Butyldithiacalix[4]arene-Copper(II) Complex Having Double-Cone Shape of Unique Heteroditopic Inclusion Behavior2004

    • Author(s)
      N.Kon
    • Journal Title

      Chem. Lett. 33・8

      Pages: 1046-1047

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Tuning of the Cavity of Water-soluble Thiacalix[4]arene for the Control of Inclusion Ability toward Water-miscible Organic Molecules2004

    • Author(s)
      N.Kon
    • Journal Title

      Collect.Czech.Chem.Commun. 69(5)

      Pages: 1080-1096

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Preconcentration of copper, cadmium, and lead with a thiacalix[4]arenetetrasulfonate loaded Sephadex A-25 anion-exchanger for graphite-furnace atomic absorption Spectrometry2004

    • Author(s)
      H.Matsumiya
    • Journal Title

      Anal.Bioanal.Chem. 379(5-6)

      Pages: 867-871

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] A p-tert-Butyldithiacalix[4]arene-Copper(II) Complex Having Double-Cone Shape of Unique Heteroditopic Inclusion Behavior2004

    • Author(s)
      N.Kon
    • Journal Title

      Chem.Lett. 33(8)

      Pages: 1046-1047

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Tuning of the Cavity of Water-soluble Thiacalix[4]arene for the Control of Inclusion Ability toward Water-miscible Organic Molecules2004

    • Author(s)
      N.Kon
    • Journal Title

      Collect.Czech.Chem.Commun. 69・5

      Pages: 1080-1096

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Preconcentration of copper, cadmium, and lead with a thiacalix[4]arenetetrasulfonate loaded Sephadex A-25 anion-exchanger for graphite-furnace atomic absorption Spectrometry2004

    • Author(s)
      H.Matsumiya
    • Journal Title

      Anal.Bioanal.Chem. 379・5-6

      Pages: 867-871

    • Related Report
      2004 Annual Research Report
  • [Journal Article] A p-tert-Butyldithiacalix[4]arene-Copper(II) Complex Having Double-Cone Shape of Unique Heteroditopic Inclusion Behavior2004

    • Author(s)
      N.Kon
    • Journal Title

      Chem.Lett. 33・8

      Pages: 1046-1047

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Octa-Lanthanide Wheels Supported by p-tert-Butylsulfonylcalix[4]arene2004

    • Author(s)
      T.Kajiwara
    • Journal Title

      Angew.Chem.Int.Ed. 43・14

      Pages: 1832-1835

    • Related Report
      2004 Annual Research Report

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Published: 2004-04-01   Modified: 2016-04-21  

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