光刺激応答性有機－無機ハイブリッド材料の創出

• Project Area: Creation of Element-Block Polymer Materials
• Project/Area Number: 25102521
• Research Category: Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: Kyoto University
• Principal Investigator: 田中 一生 京都大学, 工学(系)研究科(研究院), 講師 (90435660)
• Project Period (FY): 2013-04-01 – 2015-03-31
• Project Status: Completed (Fiscal Year 2014)
• Budget Amount: ¥7,020,000 (Direct Cost: ¥5,400,000、Indirect Cost: ¥1,620,000); Fiscal Year 2014: ¥3,510,000 (Direct Cost: ¥2,700,000、Indirect Cost: ¥810,000); Fiscal Year 2013: ¥3,510,000 (Direct Cost: ¥2,700,000、Indirect Cost: ¥810,000)
• Keywords: かご型シルセスキオキサン / ハイブリッド / 光応答

Outline of Annual Research Achievements

シリカ化合物の中で、かご型シルセスキオキサン(POSS)は (RSiO1.5)8で表され、T8と呼ばれる一辺が0.3ナノメートルのシリカの立方体構造を中心に、各頂点に有機官能基を持つ物質の総称である。剛直な立方体核から放射線状に側鎖が配置されており、ネットワークポリマーやデンドリマーなど、多分岐型高分子材料構築のビルディングブロックとして有用である。また、官能基Rに修飾を加えることで多種多様な機能の付与が可能である。これらの修飾により、溶媒や他の媒質中において高い分散性を付与することが可能であることから、POSSを分子フィラーとした複合材料の作成が容易となる。以上の利点から、POSSは様々な機能性材料構築に応用が図られている。特に、これまでの研究では剛直性を利用して高分子の耐熱性向上や機械的特性付与に用いられてきた。また、極性基であるシラノール基を持たないため、低誘電材料や表面の疎水化などへの応用も進んでいる。本研究では、POSSを元素ブロックとして高分子材料に組み込むことで高機能材料の創出を目指した。具体的には、まずPOSSをフィラーとして用い、プラスチックの屈折率制御を行った。特に、POSSは樹脂の耐熱性向上に効果が高いことから、高屈折率化と樹脂の機械的特性を両立するための分子フィラーの設計に関する研究を進めた。次に、POSSフィラーによるイオン液体の高性能化を行った。まず、オクタカルボキシPOSSをフィラーとして種々の塩中に添加し、物性変化を調べた。その結果、オクタカルボキシPOSS添加により、汎用イオン液体の融点の低下がみられた。一方、POSSを含まない側鎖のみの化合物では、融点の低下はみられなかった。この結果は、オクタカルボキシPOSS添加により、定義上イオン液体と呼べない塩でも液体化できたことを示している。

Research Progress Status

26年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

26年度が最終年度であるため、記入しない。

Research Products

• [Journal Article] Adamantane Ionic Liquids (2014)
  • Author(s): Tanaka, K.; Hiraoka, T.; Ishiguro, F.; Jeon, J.-H.; Chujo, Y.
  • Journal Title: RSC Adv. Volume: 4 Issue: 53 Pages: 28107-28110
  • DOI: 10.1039/c4ra02575j
  • NAID: 120005661548
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Synthesis of Sulfonic Acid-Containing POSS and Its Filler Effects for Enhancing Thermal Stabilities and Lowering Melting Temperatures of Ionic Liquids (2014)
  • Author(s): Jeon, J.-H.; Tanaka, K.; Chujo, Y.
  • Journal Title: J. Mater. Chem. A Volume: 2 Issue: 3 Pages: 624-630
  • DOI: 10.1039/c3ta14039c
  • Peer Reviewed
• [Journal Article] Transformation of Sulfur to Organic–inorganic Hybrids Employed by Networks and Their Application for the Modulation of Refractive Indices (2014)
  • Author(s): Tanaka, K.; Yamane, H.; Mitamura, K.; Watase, S.; Matsukawa, K.; Chujo, Y.
  • Journal Title: Journal of Polymer Science Part A: Polymer Chemistry Volume: 52 Issue: 18 Pages: 2588-2595
  • DOI: 10.1002/pola.27274
  • NAID: 120005661550
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Light-Driven Artificial Enzymes for Selective Oxidation of Guanosine Triphosphate Using Water-Soluble POSS Network Polymers (2014)
  • Author(s): Jeon, J.-H.; Tanaka, K.; Chujo, Y.
  • Journal Title: Org. Biomol. Chem. Volume: 12 Issue: 33 Pages: 6500-6506
  • DOI: 10.1039/c4ob01115e
  • NAID: 120005661551
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] л-Conjugated Polymers Composed of BODIPY or Aza-BODIPY Derivatives Exhibiting High Electron Mobility and Low Threshold Voltage in Electron-Only Devices (2014)
  • Author(s): Yoshii, R. ; Yamane, H. ; Nagai, A. ; Tanaka, K. ; Taka, H. ; Kita, H. ; Chujo, Y.
  • Journal Title: Macromolecules Volume: (印刷中)(Early View) Issue: 7 Pages: 2316-2323
  • DOI: 10.1021/ma5002047
  • Peer Reviewed
• [Journal Article] Conjugated Polymers Based on Tautomeric Units : Regulation of Main-Chain Conjugation and Expression of Aggregation Induced Emission Property via Boron-Complexation (2014)
  • Author(s): Yoshii, R. ; Tanaka, K. ; Chujo, Y.
  • Journal Title: Macromolecules Volume: (印刷中)(Early View) Issue: 7 Pages: 2268-2278
  • DOI: 10.1021/ma500082e
  • Peer Reviewed
• [Journal Article] Production of Three Radical Cations from a Single Photon Using a Photo Acid Generator (2014)
  • Author(s): Tanaka, K.; Ohashi, W.; Okada, H.; Chujo, Y.
  • Journal Title: Tetrahedron Lett. Volume: 55 Issue: 9 Pages: 1635-1659
  • DOI: 10.1016/j.tetlet.2014.01.092
  • Peer Reviewed
• [Journal Article] Enhancement of Dye Dispersibility in Silica Hybrids through Local Heating Induced by the Imidazolium Group under Microwave Irradiation (2014)
  • Author(s): Kajiwara, Y.; Tanaka, K.; Chujo, Y.
  • Journal Title: Polym. J. Volume: 46 Issue: 3 Pages: 195-199
  • DOI: 10.1038/pj.2013.81
  • Peer Reviewed
• [Journal Article] Preparation of Flexible Conductive Films Based on Polymer Composites with Tetrathiafulvalene Nanowires (2013)
  • Author(s): Tanaka, K.; Matsumoto, T.; Nakamura, K.; Kawabe, S.; Chujo, Y.
  • Journal Title: Synth. Met. Volume: 180 Pages: 49-53
  • DOI: 10.1016/j.synthmet.2013.07.030
  • Peer Reviewed
• [Journal Article] Efficient Simultaneous Emission from RGB-Emitting Organoboron Dyes Incorporated into Organic-Inorganic Hybrids and Preparation of White Light-Emitting Materials (2013)
  • Author(s): Kajiwara, Y.; Nagai, A.; Tanaka, K.; Chujo, Y.
  • Journal Title: J. Mater. Chem. Volume: 1 Issue: 29 Pages: 4437-4444
  • DOI: 10.1039/c3tc30276h
  • Peer Reviewed
• [Journal Article] Synthesis of Dibenzo[b,f]silepins with a Benzoquinolyl Ligand (2013)
  • Author(s): Tokoro, Y.; Tanaka, K.; Chujo, Y.
  • Journal Title: Org. Lett. Volume: 15 Issue: 10 Pages: 2366-2369
  • DOI: 10.1021/ol400730n
  • Peer Reviewed
• [Journal Article] Rational Design of POSS Fillers for Simultaneous Improvements of Thermomechanical Properties and Lowering Refractive Indices of Polymer Films (2013)
  • Author(s): Jeon, J.-H.; Tanaka, K.; Chujo, Y.
  • Journal Title: J. Polym. Sci. Part A: Polym. Chem. Volume: 51 Issue: 17 Pages: 3583-3589
  • DOI: 10.1002/pola.26757
  • Peer Reviewed
• [Journal Article] Facile Modulation of Optical Properties of Diketonate-Containing Polymers by Regulating Complexation Ratios with Boron (2013)
  • Author(s): Tanaka, K.; Tamashima, K.; Nagai, A.; Okawa, T.; Chujo, Y.
  • Journal Title: Macromolecules Volume: 46 Issue: 8 Pages: 2969-2975
  • DOI: 10.1021/ma400368e
  • Peer Reviewed
• [Journal Article] Rapid Heat Generation under Microwave Irradiation by Imidazolium-Presenting Silica Nanoparticles (2013)
  • Author(s): Okada, H.; Kajiwara, Y.; Tanaka, K.; Chujo, Y.
  • Journal Title: Colloids Surf., A Volume: 428 Pages: 65-69
  • DOI: 10.1016/j.colsurfa.2013.03.048
  • Peer Reviewed
• [Journal Article] Hypoxic Conditions-Selective Upconversion via Triplet-Triplet Annihilation Based on POSS-Core Dendrimer Complexes (2013)
  • Author(s): Tanaka, K.; Okada, H.; Jeon, J.-H.; Inafuku, K.; Ohashi, W.; Chujo, Y.
  • Journal Title: Bioorg. Med. Chem. Volume: 21 Issue: 10 Pages: 2678-2681
  • DOI: 10.1016/j.bmc.2013.03.029
  • Peer Reviewed
• [Journal Article] Effective Light-Harvesting Antennae Based on BODIPY-Tethered Cardo Polyfluorenes via Rapid Energy Transferring and Low Concentration Quenching (2013)
  • Author(s): Yeo, H.; Tanaka, K.; Chujo, Y.
  • Journal Title: Macromolecules Volume: 46 Issue: 7 Pages: 2599-2605
  • DOI: 10.1021/ma400015d
  • Peer Reviewed
• [Journal Article] Synthesis and Optical Properties of Stable Gallafluorene Derivatives: Investigation of Their Emission via Triplet States (2013)
  • Author(s): Matsumoto, T.; Tanaka, K.; Chujo, Y.
  • Journal Title: J. Am. Chem. Soc. Volume: 135 Issue: 11 Pages: 4211-4214
  • DOI: 10.1021/ja400287y
  • Peer Reviewed
• [Journal Article] Synthesis and tuning of optical properties of conjugated polymers involving benzo [h] quinoline-based neutral pentacoordinate organosilicon complexes in the main (2013)
  • Author(s): 所雄一郎、呂鉉旭、田中一生、中條善樹
  • Journal Title: Polymer Chemistry Volume: (印刷中) Issue: 20 Pages: 5237-5242
  • DOI: 10.1039/c3py00215b
  • Peer Reviewed
• [Journal Article] Efficient Light Absorbers Based on Thiophene-Fused Boron Dipyrromethene (BODIPY) Dyes (2013)
  • Author(s): Tanaka, K.; Yamane, H.; Yoshii, R.; Chujo, Y.
  • Journal Title: Bioorg. Med. Chem. Volume: 21 Issue: 10 Pages: 2715-2719
  • DOI: 10.1016/j.bmc.2013.03.050
  • Peer Reviewed
• [Journal Article] High Emission Boron Ketoiminates as A New Class of Aggregation-Induced Emission Enhancement Fluorophores (2013)
  • Author(s): R. Yoshii, A. Nagai, K. Tanaka, Y. Chujo
  • Journal Title: Cheaistry - A European Journal Volume: 19 Issue: 14 Pages: 4506-4512
  • DOI: 10.1002/chem.201203703
  • Peer Reviewed
• [Journal Article] Highly NIR Emissive Di (iso) indomethene BODIPY-Based Polyfluorene : Drastic Change from Deep-Red to NIR Emission via Quantitative Polymer Reaction (2013)
  • Author(s): R. Yoshii, A. Nagai, K. Tanaka, Y. Chujo
  • Journal Title: Journal of Polyimer Science, Part A : Polymer Chemistry Volume: 51 Issue: 8 Pages: 1726-1733
  • DOI: 10.1002/pola.26547
  • Peer Reviewed
• [Journal Article] Synthesis of Highly Transparent Conductive Films with Strong Absorption in Near-Infrared Region Based on Tetrathiafulvalene-Tethered Pendant-Type Polymers (2013)
  • Author(s): Tanaka, K.; Matsumoto, T.; Chujo, Y.
  • Journal Title: Synth. Met. Volume: 163 Issue: 23 Pages: 13-18
  • DOI: 10.1002/pola.23684
  • Peer Reviewed
• [Journal Article] Catch and Release with DNA by Imidazolium-Presenting Iron Oxide Nanoparticles via Anion Exchange (2013)
  • Author(s): Tanaka, K.; Narita, A.; Chujo, Y.
  • Journal Title: Compos. Interface. Volume: 20 Issue: 1 Pages: 27-32
  • DOI: 10.1080/15685543.2013.762891
  • NAID: 120005466677
  • Peer Reviewed
• [Journal Article] Regulation of Dispersion/Aggregation of Phosphonium-Presenting Iron Oxide Nanoparticles by Anion Exchange (2013)
  • Author(s): Tanaka, K.; Narita, A.; Suzuki, K.; Chujo, Y.
  • Journal Title: Compos. Interface. Volume: 20 Issue: 9 Pages: 557-564
  • DOI: 10.1080/15685543.2012.762862
  • Peer Reviewed
• [Journal Article] POSS Fillers for Modulating Thermal Properties of Ionic Liquids (2013)
  • Author(s): Jeon, J.-H.; Tanaka, K.; Chujo, Y.
  • Journal Title: RSC Adv. Volume: 3 Issue: 7 Pages: 2422-2427
  • DOI: 10.1039/c2ra22683a
  • Peer Reviewed
• [Journal Article] Heat-Initiated Detection for Reduced Glutathione with 19F NMR Probes Based on Modified Gold Nanoparticles (2013)
  • Author(s): Kitamura, N.; Tanaka, K.; Chujo, Y.
  • Journal Title: Bioorg. Med. Chem. Lett. Volume: 23 Issue: 1 Pages: 281-286
  • DOI: 10.1016/j.bmcl.2012.10.105
  • Peer Reviewed
• [Presentation] Unique Optical Materials Based on POSS (2014)
  • Author(s): Kazuo Tanaka, Yoshiki Chujo
  • Organizer: Silicon-Containing Polymers and Composites
  • Place of Presentation: San Diego, U.S.A.
  • Year and Date: 2014-12-14
  • Invited
• [Presentation] Modulation of Thermal Properties of Ionic Liquids Based on POSS (2014)
  • Author(s): Kazuo Tanaka, Yoshiki Chujo
  • Organizer: Asian Chemical Conference
  • Place of Presentation: ハノイ、ベトナム
  • Year and Date: 2014-11-07
  • Invited
• [Presentation] Unique Thermal Properties of POSS Ionic Materials (2014)
  • Author(s): Kazuo Tanaka, Yoshiki Chujo
  • Organizer: Asian Chemical Conference
  • Place of Presentation: クアラルンプール、マレーシア
  • Year and Date: 2014-11-03
  • Invited
• [Presentation] Development of POSS-based Functional Materials
  • Author(s): Kazuo Tanaka, Yoshiki Chujo
  • Organizer: KIPS-ESPCI 2013 Meeting
  • Place of Presentation: フランス、パリ
  • Invited
• [Presentation] Design of Advanced Materials Based on POSS
  • Author(s): Kazuo Tanaka, Yoshiki Chujo
  • Organizer: BIT’s 3rd Annual World Congress of Nano Science & Technology-2013
  • Place of Presentation: 中国、西安
  • Invited
• [Presentation] POSSネットワークポリマーを基盤とした光駆動型人工酵素の開発
  • Author(s): 田中一生、ジョン＝ジョンファン、中條善樹
  • Organizer: 第62回高分子討論会
  • Place of Presentation: 金沢大学
  • Invited
• [Presentation] Aggregation-Induced Emission of Organoboron Compounds
  • Author(s): Kazuo Tanaka, Yoshiki Chujo
  • Organizer: The 1st International Symposium on Aggregation-Induced Emission
  • Place of Presentation: 中国、武漢
  • Invited
• [Presentation] ナノマテリアルを基盤とした分子プローブ開発と生体情報の定量化
  • Author(s): 田中一生、中條善樹
  • Organizer: 東京大学化学生命工学専攻講演会
  • Place of Presentation: 東京大学
  • Invited