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Design and Synthesis of Nitrogen-bridged Calixarene-type Macrocycles with Extended pi-System, and Their Application as Molecular Recognition Materials

Research Project

Project/Area Number 19550037
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Organic chemistry
Research InstitutionKyoto University

Principal Investigator

TSUE Hirohito  Kyoto University, 環境学研究科, 准教授 (30271711)

Co-Investigator(Kenkyū-buntansha) TAMURA Rui  京都大学, 大学院・人間・環境学研究科, 教授 (60207256)
TAKAHASHI Hiroki  京都大学, 大学院・人間・環境学研究科, 助教 (00321779)
Project Period (FY) 2007 – 2009
Project Status Completed (Fiscal Year 2009)
Budget Amount *help
¥4,030,000 (Direct Cost: ¥3,100,000、Indirect Cost: ¥930,000)
Fiscal Year 2009: ¥910,000 (Direct Cost: ¥700,000、Indirect Cost: ¥210,000)
Fiscal Year 2008: ¥650,000 (Direct Cost: ¥500,000、Indirect Cost: ¥150,000)
Fiscal Year 2007: ¥2,470,000 (Direct Cost: ¥1,900,000、Indirect Cost: ¥570,000)
Keywordsアザカリックスアレーン / 合成 / 分子認識 / 分子不斉 / 酸化挙動 / 分子構造 / 結晶構造 / 気体吸蔵 / 酸化拳動 / ESR
Research Abstract

Investigated were the synthesis and molecular recognition property of novel calixarene-type macrocycles, in which aromatic rings were linked via nitrogen atoms with intrinsic nature that flexibly changes their electronic configurations. As an eventual outcome, it was demonstrated that the present molecular system selectively recognized potassium ion in solution and carbon dioxide in the solid state. Molecular chirality and oxidation behavior of the present system were also revealed.

Report

(4 results)
  • 2009 Annual Research Report   Final Research Report ( PDF )
  • 2008 Annual Research Report
  • 2007 Annual Research Report
  • Research Products

    (57 results)

All 2010 2009 2008 2007 Other

All Journal Article (19 results) (of which Peer Reviewed: 15 results) Presentation (28 results) Book (5 results) Remarks (4 results) Patent(Industrial Property Rights) (1 results)

  • [Journal Article] アザカリックスアレーンの化学2009

    • Author(s)
      津江広人, 石橋孝一, 田村類
    • Journal Title

      有機合成化学協会誌 67

      Pages: 898-908

    • NAID

      10025400198

    • Related Report
      2009 Annual Research Report 2009 Final Research Report
    • Peer Reviewed
  • [Journal Article] Inherent Chirality2009

    • Author(s)
      津江広人
    • Journal Title

      有機合成化学協会誌 67

      Pages: 958-958

    • Related Report
      2009 Annual Research Report 2009 Final Research Report
  • [Journal Article] Azacalix[4]arene Tetramethyl Ether with Inherent Chirality Generated by Substitution on the Nitrogen Bridges2009

    • Author(s)
      K. Ishibashi, H. Tsue, H. Takahashi, R. Tamura
    • Journal Title

      Tetrahedron: Asymmetry 20

      Pages: 375-380

    • Related Report
      2009 Final Research Report
    • Peer Reviewed
  • [Journal Article] 二酸化炭素の特性から眺める環境-気体吸蔵材料の開発を通して-2009

    • Author(s)
      津江広人
    • Journal Title

      人環フォーラム 24

      Pages: 44-47

    • Related Report
      2009 Final Research Report
  • [Journal Article] Azacalix[4]arene Tetramethyl Ether with Inherent Chirality Generated by Substitution on the Nitrogen Bridges2009

    • Author(s)
      H.Tsue, H.Takahashi, R.Tamura
    • Journal Title

      Tetrahedron : Asymmetry 20

      Pages: 375-380

    • Related Report
      2009 Annual Research Report
    • Peer Reviewed
  • [Journal Article] 二酸化炭素の特性から眺める環境 -気体吸蔵材料の開発を通して-2009

    • Author(s)
      津江広人
    • Journal Title

      人環フォーラム 24

      Pages: 44-47

    • Related Report
      2008 Annual Research Report
  • [Journal Article] Azacalix[7]arene Heptamethyl Ether: Preparation, Nanochannel Crystal Structure, and Selective Adsorption of Carbon Dioxide2008

    • Author(s)
      H. Tsue, K. Matsui, K. Ishibashi, H. Takahashi, S. Tokita, K. Ono, R. Tamura
    • Journal Title

      J. Org. Chem. 73

      Pages: 7748-7755

    • Related Report
      2009 Final Research Report
    • Peer Reviewed
  • [Journal Article] Azacalix[6]arene Hexamethyl Ether: Synthesis, Structure, and Selective Uptake of Carbon Dioxide in the Solid State2008

    • Author(s)
      H. Tsue, K. Ishibashi, S. Tokita, H. Takahashi, K. Matsui, R. Tamura
    • Journal Title

      Chem. Eur. J. 14

      Pages: 6125-6134

    • Related Report
      2009 Final Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis, Molecular Structure, and Oxidation Behavior of Exhaustively Methylated Azacalix[6]arene2008

    • Author(s)
      K. Ishibashi, H. Tsue, H. Takahashi, S. Tokita, K. Matsui, R. Tamura
    • Journal Title

      Heterocycles 76

      Pages: 541-550

    • NAID

      40016208591

    • Related Report
      2009 Final Research Report
    • Peer Reviewed
  • [Journal Article] Azacalix[4]arene Cation Radicals: Spin-Delocalised Doublet and Triplet-Ground States Observed in the Macrocyclic m-Phenylene System Connected with Nitrogen Atoms2008

    • Author(s)
      K. Ishibashi, H. Tsue, N. Sakai, S. Tokita, K. Matsui, J. Yamauchi, R. Tamura
    • Journal Title

      Chem. Commun.

      Pages: 2812-2814

    • Related Report
      2009 Final Research Report
    • Peer Reviewed
  • [Journal Article] Azacalix[6]arene Hexamethyl Ether : Synthesis, Structure, and Selective Uptake of Carbon Dioxide in the Solid2008

    • Author(s)
      H. Tsue, K. Ishibashi, S. Tokita, H. Takahashi, K. Matsui, R. Tamura
    • Journal Title

      Chemistry : A European Journal 14

      Pages: 6125-6134

    • Related Report
      2008 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Azacalix[4]arene Cation Radicals : Spin-Delocalised Doublet and Triplet-Ground States Observed in the Macrocyclic m-Phenylene System Connected with Nitrogen Atoms2008

    • Author(s)
      K. Ishibashi, H. Tsue, N. Sakai, S. Tokita, K. Matsui, J. Yamauchi, R. Tamura
    • Journal Title

      Chemical Communications

      Pages: 2812-2814

    • Related Report
      2008 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Azacalix[7]arene Heptamethyl Ether : Preparation, Nanochannel Crystal Structure, and Selective Adsorption2008

    • Author(s)
      H. Tsue, K. Matsui, K. Ishibashi, H. Takahashi, S. Tokita, K. Ono, R. Tamura
    • Journal Title

      The Journal of Organic Chemistry 19

      Pages: 7748-7755

    • Related Report
      2008 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Azacalix[4]arene Cation Radicals: Spin-Delocalised Doublet and Triplet-Ground States Observed in the Macrocyclic m-Phenylene System Connected with Nitrogen Atoms2008

    • Author(s)
      K. Ishibashi, H. Tsue, N. Sakai, S. Tokita, K. Matsui, J. Yamauchi, R. Tamura
    • Journal Title

      Chemical Communications (印刷中)

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] 粉末x線回折データを用いる有機化合物の結晶構造解析2007

    • Author(s)
      津江広人, 堀口雅弘, 田村類, 藤井孝太郎, 植草秀裕
    • Journal Title

      有機合成化学協会誌 65

      Pages: 1203-1212

    • NAID

      10020007114

    • Related Report
      2009 Final Research Report
    • Peer Reviewed
  • [Journal Article] 粉末X線回折2007

    • Author(s)
      津江広人
    • Journal Title

      有機合成化学協会誌 65

      Pages: 1227-1227

    • Related Report
      2009 Final Research Report
  • [Journal Article] Frozen 1, 3-Alternate Conformation of Exhaustively Methylated Azacalix[4]arene in Solution: Successful Immobilization by Small but yet Sufficiently Bulky O-Methyl Group2007

    • Author(s)
      H. Tsue, K. Ishibashi, S. Tokita, K. Matsui, H. Takahashi, R. Tamura
    • Journal Title

      Chem. Lett. 36

      Pages: 1374-1375

    • NAID

      10019792572

    • Related Report
      2009 Final Research Report
    • Peer Reviewed
  • [Journal Article] Frozen 1,3-Alternate Conformation of Exhaustively Methylated Azacalix[4]arene in Solution: Successful Immobilization by Small but yet Sufficiently Bulky O-Methyl Group2007

    • Author(s)
      H. Tsue, K. Ishibashi, S. Tokita, K. Matsui, H. Takahashi, R. Tamura
    • Journal Title

      Chemistry Letters 36

      Pages: 1374-1375

    • NAID

      10019792572

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] 紛末X線回折データを用いる有機化合物の結晶構造解析2007

    • Author(s)
      津江広人, 堀口雅弘, 田村 類, 藤井孝太郎, 植草秀裕
    • Journal Title

      有機合成化学協会誌 65

      Pages: 1203-1212

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Presentation] ヒドロキシ基を配したアザカリックス[4]アレーンの合成2010

    • Author(s)
      津江広人, 宮田和志, 石橋孝一, 小野浩平, 田村類
    • Organizer
      日本化学会第90春季年会
    • Place of Presentation
      近畿大学
    • Year and Date
      2010-03-29
    • Related Report
      2009 Annual Research Report 2009 Final Research Report
  • [Presentation] アザカリックス[5]アレーンの結晶構造とSTP条件下での気体吸蔵挙動2010

    • Author(s)
      津江広人, 小野浩平, 時田智, 宮田和志, 高橋弘樹, 田村類
    • Organizer
      日本化学会第90春季年会
    • Place of Presentation
      近畿大学
    • Year and Date
      2010-03-27
    • Related Report
      2009 Annual Research Report 2009 Final Research Report
  • [Presentation] アザカリックス[5]アレーンの合成とSTP条件下での気体吸蔵挙動2009

    • Author(s)
      津江広人, 小野浩平, 時田智, 石橋孝一, 宮田和志, 高橋弘樹, 田村類
    • Organizer
      第20回基礎有機化学連合討論会
    • Place of Presentation
      群馬大学
    • Year and Date
      2009-09-29
    • Related Report
      2009 Annual Research Report 2009 Final Research Report
  • [Presentation] Gas Adsorption Behavior of Azacalixarenes with Nanochannel Crystal Architecture2009

    • Author(s)
      H. Tsue, K. Ishibashi, K. Matsui, S. Tokita, K. Ono, H. Takahashi, R. Tamura
    • Organizer
      10th International Conference on Calixarenes (Calix 2009)
    • Place of Presentation
      Korea University, Seoul, Korea
    • Year and Date
      2009-07-15
    • Related Report
      2009 Final Research Report
  • [Presentation] Gas Adsorption Behavior of Azacalixarenes with Nanochannel Crystal Architecture2009

    • Author(s)
      H.Tsue, K.Ishibashi, K.Matsui, S.Tokita, K.Ono, H.Takahashi, R.Tamura
    • Organizer
      10th International Conference on Calixarenes
    • Place of Presentation
      高麗大学,ソウル,大韓民国
    • Year and Date
      2009-07-15
    • Related Report
      2009 Annual Research Report
  • [Presentation] Azacalixarene with Nanochannel Crystal Architecture as a Selective Carbon Dioxide Reservoir2009

    • Author(s)
      H. Tsue, K. Ishibashi, K. Matsui, S. Tokita, K. Ono, H. Takahashi, R. Tamura
    • Organizer
      4th East Asia Symposium on Functional Dyes and Advanced Materials (EAS-4)
    • Place of Presentation
      International House, Osaka, Japan
    • Year and Date
      2009-06-04
    • Related Report
      2009 Final Research Report
  • [Presentation] Azacalixarene with Nanochannel Crystal Architecture as a Selective Carbon Dioxide Reservoir2009

    • Author(s)
      H.Tsue, K.Ishibashi, K.Matsui, S.Tokita, K.Ono, H.Takahashi, R.Tamura
    • Organizer
      4th East Asia Symposium on Functional Dyes and Advanced Materials
    • Place of Presentation
      大阪国際交流センター
    • Year and Date
      2009-06-04
    • Related Report
      2009 Annual Research Report
  • [Presentation] アザカリックス[4]アレーンにおける分子不斉の発現2009

    • Author(s)
      津江広人, 石橋孝一, 高橋弘樹, 田村類
    • Organizer
      モレキュラー・キラリティー2009
    • Place of Presentation
      大阪大学
    • Year and Date
      2009-05-13
    • Related Report
      2009 Annual Research Report 2009 Final Research Report
  • [Presentation] アザカリックス[5]アレーンペンタメチルエーテルの合成と分子構造の解析2009

    • Author(s)
      津江広人, 小野浩平, 石橋孝一, 松井一祐, 高橋弘樹, 田村類
    • Organizer
      日本化学会第89春季年会
    • Place of Presentation
      日本大学
    • Year and Date
      2009-03-29
    • Related Report
      2009 Final Research Report
  • [Presentation] アザカリックス[7]アレーンヘプタメチルエーテルの擬似結晶多形2009

    • Author(s)
      津江広人, 松井一祐, 石橋孝一, 小野浩平, 高橋弘樹, 田村類
    • Organizer
      日本化学会第89春季年会
    • Place of Presentation
      日本大学
    • Year and Date
      2009-03-29
    • Related Report
      2009 Final Research Report
  • [Presentation] アザカリツクス[5]アレーンペンタメチルェーテルの合成と分子構造の解析2009

    • Author(s)
      津江広人, 小野浩平, 石橋孝一, 松井一祐, 高橋弘樹, 田村類
    • Organizer
      第89日本化学会春季年会
    • Place of Presentation
      日本大学
    • Year and Date
      2009-03-29
    • Related Report
      2008 Annual Research Report
  • [Presentation] アザカリツクス[7]アレーンヘプタメチルェーテルの擬似結晶多形2009

    • Author(s)
      津江広人, 松井一祐, 石橋孝一, 小野浩平, 高橋弘樹, 田村類
    • Organizer
      第89日本化学会春季年会
    • Place of Presentation
      日本大学
    • Year and Date
      2009-03-29
    • Related Report
      2008 Annual Research Report
  • [Presentation] 窒素原子を配した大環状かご形化合物の合成と気体吸蔵特性2008

    • Author(s)
      津江広人, 石橋孝一, 時田智, 松井一祐, 小野浩平, 高橋弘樹, 田村類
    • Organizer
      第17回有機結晶シンポジウム
    • Place of Presentation
      大阪大学
    • Year and Date
      2008-11-13
    • Related Report
      2009 Final Research Report 2008 Annual Research Report
  • [Presentation] N-H架橋アザカリックス[7]アレーンの多孔性結晶を用いた二酸化炭素ガスの選択的吸蔵2008

    • Author(s)
      石橋孝一, 津江広人, 松井一祐, 高橋弘樹, 時田智, 小野浩平, 田村類
    • Organizer
      第19回基礎有機化学討論会
    • Place of Presentation
      大阪大学
    • Year and Date
      2008-10-03
    • Related Report
      2009 Final Research Report
  • [Presentation] N-H架橋アザカリックス[7]アレーンの多孔性結晶を用いた二酸化炭素ガスの選択的吸蔵2008

    • Author(s)
      石橋孝一, 津江広人, 松井一祐, 高橋弘樹, 時田智, 小野浩平, 田村
    • Organizer
      第19回基礎有機化学討読会
    • Place of Presentation
      大阪大学
    • Year and Date
      2008-10-03
    • Related Report
      2008 Annual Research Report
  • [Presentation] 窒素原子を配した大環状かご形化合物による二酸化炭素の選択的吸蔵2008

    • Author(s)
      津江広人, 石橋孝一, 時田智, 松井一祐, 高橋弘樹, 田村類
    • Organizer
      第17回環境化学討論会
    • Place of Presentation
      神戸国際会議場
    • Year and Date
      2008-06-11
    • Related Report
      2009 Final Research Report 2008 Annual Research Report
  • [Presentation] アザカリックス[6]アレーン完全メチル化体の分子構造と酸化挙動2008

    • Author(s)
      石橋孝一, 津江広人, 酒井尚子, 時田智, 松井一祐, 高橋弘樹, 山内淳, 田村類
    • Organizer
      第88日本化学会春季年会
    • Place of Presentation
      立教大学
    • Year and Date
      2008-03-30
    • Related Report
      2009 Final Research Report 2007 Annual Research Report
  • [Presentation] アザカリックス[7]アレーンメチルエーテルの合成と分子構造2008

    • Author(s)
      津江広人, 松井一祐, 石橋孝一, 時田智, 高橋弘樹, 田村類
    • Organizer
      第88日本化学会春季年会
    • Place of Presentation
      立教大学
    • Year and Date
      2008-03-29
    • Related Report
      2009 Final Research Report 2007 Annual Research Report
  • [Presentation] アザカリックス[6]アレーン完全メチル化体の合成と酸化挙動2007

    • Author(s)
      石橋孝一, 津江広人, 酒井尚子, 内田幸明, 時田智, 松井一祐, 高橋弘樹, 山内淳, 田村類
    • Organizer
      第37回構造有機化学討論会
    • Place of Presentation
      北海道大学
    • Year and Date
      2007-10-29
    • Related Report
      2009 Final Research Report 2007 Annual Research Report
  • [Presentation] N-H架橋アザカリックス[6]アレーンのナノチャネル結晶と気体吸蔵特性2007

    • Author(s)
      石橋孝一, 津江広人, 時田智, 松井一祐, 高橋弘樹, 田村類
    • Organizer
      第37回構造有機化学討論会
    • Place of Presentation
      北海道大学
    • Year and Date
      2007-10-28
    • Related Report
      2009 Final Research Report 2007 Annual Research Report
  • [Presentation] アザカリックス[n]アレーンにおけるスピン非局在化二重項状態と基底三重項状態2007

    • Author(s)
      石橋孝一, 津江広人, 酒井尚子, 内田幸明, 時田智, 松井一祐, 山内淳, 田村類
    • Organizer
      第1回分子化学討論会
    • Place of Presentation
      東北大学
    • Year and Date
      2007-09-17
    • Related Report
      2009 Final Research Report 2007 Annual Research Report
  • [Presentation] Azacalix[6]arene with N-H Bridges: Preparation and Crystal Structure with Nanochannel Architecture2007

    • Author(s)
      H. Tsue, K. Ishibashi, S. Tokita, K. Matsui, H. Takahashi, R. Tamura
    • Organizer
      9th International Conference on Calixarene Chemistry (Calix 2007)
    • Place of Presentation
      Maryland University, College Park, MD, USA
    • Year and Date
      2007-08-06
    • Related Report
      2009 Final Research Report
  • [Presentation] Spin-Delocalized Doublet and Triplet-Ground States of Azacalix[4]arene Cation Radicals2007

    • Author(s)
      K. Ishibashi, H. Tsue, N. Sakai, Y. Uchida, S. Tokita, K. Matsui, J. Yamauchi, R. Tamura
    • Organizer
      9th International Conference on Calixarene Chemistry (Calix 2007)
    • Place of Presentation
      Maryland University, College Park, MD, USA
    • Year and Date
      2007-08-06
    • Related Report
      2009 Final Research Report
  • [Presentation] Azacalix[6]arene with N-H Bridges: Preparation and Crystal Structure with Nanochannel Architecture2007

    • Author(s)
      H. Tsue, K. Ishibashi, S. Tokita, K. Matsui, H. Takahashi, R. Tamura
    • Organizer
      9th International Conference on Calixarene Chemistry (Calix 2007)
    • Place of Presentation
      米国メリーランド州メリーランド大学
    • Year and Date
      2007-08-06
    • Related Report
      2007 Annual Research Report
  • [Presentation] Spin-Delocalized Doublet and Triplet-Ground States of Azacalix[4]arene Cation Radicals2007

    • Author(s)
      K. Ishibashi, H. Tsue, N. Sakai, Y. Uchida, S. Tokita, K. Matsui, J. Yamauchi, R. Tamura
    • Organizer
      9th International Conference on Calixarene Chemistry (Calix 2007)
    • Place of Presentation
      米国メリーランド州メリーランド大学
    • Year and Date
      2007-08-06
    • Related Report
      2007 Annual Research Report
  • [Presentation] 親水性[60]フラーレンを固定化した不均一系光増感剤の合成とフェノール性内分泌撹乱物質の可視光光分解2007

    • Author(s)
      津江広人, 菅江清信, 平塚絵美, 山本昌由, 田村 類
    • Organizer
      第16回環境化学討論会
    • Place of Presentation
      北九州国際会議場
    • Year and Date
      2007-06-20
    • Related Report
      2007 Annual Research Report
  • [Presentation] [60]フラーレンの光増感作用を利用したフェノール性内分泌撹乱物質の可視光光分解2007

    • Author(s)
      津江広人, 平塚絵美, 菅江清信, 山本昌由, 田村 類
    • Organizer
      第16回環境化学討論会
    • Place of Presentation
      北九州国際会議場
    • Year and Date
      2007-06-20
    • Related Report
      2007 Annual Research Report
  • [Presentation] アザカリックス[4]アレーンメチルエーテルの酸化挙動の解析2007

    • Author(s)
      石橋孝一, 津江広人, 酒井尚子, 内田幸明, 時田智, 松井一祐, 山内淳, 田村類
    • Organizer
      第11回ESRフォーラム研究会
    • Place of Presentation
      けいはんなプラザ
    • Year and Date
      2007-06-09
    • Related Report
      2009 Final Research Report 2007 Annual Research Report
  • [Book] 基礎環境化学-環境を化学反応から捉えるためのエッセンス-2009

    • Author(s)
      津江広人, 田村類
    • Total Pages
      101
    • Publisher
      サイエンス社
    • Related Report
      2009 Final Research Report
  • [Book] 基礎環境化学 -環境を化学反応から捉えるためのエツセンス-2009

    • Author(s)
      津江広人, 田村類
    • Total Pages
      101
    • Publisher
      サイエンス社
    • Related Report
      2008 Annual Research Report
  • [Book] Heterocyclic Supramolecules I(K. Matsumoto, Ed., Topic in Heterocyclic Chemistry, Vol. 17)2008

    • Author(s)
      H. Tsue, K. Ishibashi, R. Tamura
    • Publisher
      Springer-Verlag
    • Related Report
      2009 Final Research Report
  • [Book] Heterocyclic Supramolecules I2008

    • Author(s)
      H. Tsue, K. Ishibashi, R. Tamura
    • Total Pages
      25
    • Publisher
      Springer-Verlag
    • Related Report
      2008 Annual Research Report
  • [Book] Heterocyclic Supramolecules2008

    • Author(s)
      H. Tsue, K. Ishibashi, R. Tamura
    • Publisher
      Springer-Verlag(印刷中)
    • Related Report
      2007 Annual Research Report
  • [Remarks]

    • URL

      http://www.users.iimc.kyoto-u.ac.jp/~z59081/

    • Related Report
      2009 Final Research Report
  • [Remarks]

    • URL

      http://www.users.iimc.kyoto-u.ac.jp/~z59081/index.html

    • Related Report
      2009 Annual Research Report
  • [Remarks]

    • URL

      http://www.users.kudpc.kyoto-u.ac.jp/~s50195/

    • Related Report
      2008 Annual Research Report
  • [Remarks]

    • URL

      http://www.users.kudpc.kyoto-u.ac.jp/~s50195/

    • Related Report
      2007 Annual Research Report
  • [Patent(Industrial Property Rights)] 新規含窒素大環状化合物及びその用途2009

    • Inventor(s)
      津江広人, 石橋孝一, 時田智, 酒井健一
    • Industrial Property Rights Holder
      津江広人,石橋孝一,時田智,酒井健一
    • Industrial Property Number
      2009-021511
    • Filing Date
      2009-02-05
    • Related Report
      2009 Final Research Report 2008 Annual Research Report

URL: 

Published: 2007-04-01   Modified: 2016-04-21  

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