Stabilization of Radical Initiators within a Metal-linked Molecular Capsule

• Project/Area Number: 26620041
• Research Category: Grant-in-Aid for Challenging Exploratory Research
• Allocation Type: Multi-year Fund
• Research Field: Inorganic chemistry
• Research Institution: Tokyo Institute of Technology
• Principal Investigator: Yoshizawa Michito 東京工業大学, 資源化学研究所, 准教授 (70372399)
• Project Period (FY): 2014-04-01 – 2016-03-31
• Project Status: Completed (Fiscal Year 2015)
• Budget Amount: ¥3,900,000 (Direct Cost: ¥3,000,000、Indirect Cost: ¥900,000); Fiscal Year 2015: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000); Fiscal Year 2014: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000)
• Keywords: 分子カプセル / 金属 / 芳香環 / 重合開始剤 / ポリマー

Outline of Final Research Achievements

AIBN and its derivatives are useful reagents for polymer and organic syntheses that generate radical species on stimuli by light or heat. These radical initiators are unstable so that they should be kept in the dark at low temperature to avoid photochemical and thermal decomposition. In this work, we demonstrated the quantitative encapsulation of the radical initiators by a metal-linked molecular capsule in aqueous solutions. We also revealed the remarkable stability of the initiators toward light and heat in the cavity shielded by the polyaromatic capsule shell. The stabilized initiators could be utilized for the radical polymerization of olefins on spontaneous release of the initiators from the capsule.

Research Products

• [Journal Article] Preparation of highly fluorescent host-guest complexes with tunable color upon encapsulation (2015)
  • Author(s): Masahiro YAMASHINA, Matthew McCullough SARTIN, Yoshihisa SEI, Munetaka AKITA, Satoshi TAKEUCHI, Tahei TAHARA, Michito YOSHIZAWA
  • Journal Title: J. Am. Chem. Soc. Volume: 137 Issue: 29 Pages: 9266-9269
  • DOI: 10.1021/jacs.5b06195
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Well-defined Aqueous Nanoassemblies from Amphiphilic meta-Terphenyls and Their Guest Incorporation (2015)
  • Author(s): Yusuke Okazawa, Kei Kondo, Munetaka Akita, Michito Yoshizawa
  • Journal Title: Chem. Sci. Volume: 6 Issue: 8 Pages: 5059-5062
  • DOI: 10.1039/c5sc01545f
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] A V-Shaped Polyaromatic Amphiphile: Solubilization of Various Nanocarbons in Water and Enhanced Photostability (2015)
  • Author(s): Kei Kondo, Munetaka Akita, Takafumi Nakagawa, Yutaka Matsuo, Michito Yoshizawa
  • Journal Title: Chem. Eur. J. Volume: 21 Issue: 36 Pages: 12741-12746
  • DOI: 10.1002/chem.201501414
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Polyaromatic Molecular Tubes with a Subnanometer Pore and the Guest-Induced Emission Enhancement Behavior (2015)
  • Author(s): Keita Hagiwara, Masafumi Otsuki, Munetaka Akita, Michito Yoshizawa
  • Journal Title: Chem. Commun. Volume: 51 Issue: 52 Pages: 10451-10454
  • DOI: 10.1039/c5cc02931g
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Anisotropic Expansion of an M2L4 Coordination Capsule: Host Capability and Frame Rearrangement (2015)
  • Author(s): Masahiro Yamashina, Tsubasa Yuki, Yoshihisa Sei, Munetaka Akita, Michito Yoshizawa
  • Journal Title: Chem. Eur. J. Volume: 21 Issue: 11 Pages: 4200-4204
  • DOI: 10.1002/chem.201406445
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Polyaromatic Nanocapsules Displaying Aggregation-Induced Enhanced Emissions in Water (2015)
  • Author(s): Y. Okazawa, K. Kondo, M. Akita, M. Yoshizawa
  • Journal Title: Journal of the American Chemical Society Volume: 137 Issue: 1 Pages: 98-101
  • DOI: 10.1021/ja511463k
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] An Aqueous Molecular Tube with Polyaromatic Frameworks Capable of Binding Fluorescent Dyes (2015)
  • Author(s): Keita Hagiwara, Munetaka Akita, Michito Yoshizawa
  • Journal Title: Chemical Science Volume: 6 Issue: 1 Pages: 259-263
  • DOI: 10.1039/c4sc02377c
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] アントラセンを活用した分子集合体の新展開 (2015)
  • Author(s): 近藤 圭・岡澤佑允・吉沢道人
  • Journal Title: 液晶, Volume: 19 Pages: 182-191
  • NAID: 40020640424
• [Journal Article] ラジカル開始剤のカプセル化 ＝耐光性および耐熱性の向上＝ (2015)
  • Author(s): 山科雅裕・吉沢道人
  • Journal Title: 光アライアンス Volume: 6 Pages: 1-4
• [Journal Article] Safe Storage of Radical Initiators within a Polyaromatic Nanocapsule (2014)
  • Author(s): Masahiro Yamashina, Yoshihisa Sei, Munetaka. Akita, Michito Yoshizawa
  • Journal Title: Nature Communications Volume: 5 Issue: 1 Pages: 4662-4662
  • DOI: 10.1038/ncomms5662
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Selective Host-Guest Interactions of a Transformable Coordination Capsule/Tube with Fullerenes (2014)
  • Author(s): N. Kishi, M. Akita, M. Yoshizawa
  • Journal Title: Angewandte Chemie International Edition Volume: 53(印刷中) Issue: 14 Pages: 3604-3607
  • DOI: 10.1002/anie.201311251
  • Peer Reviewed
• [Journal Article] A polyaromatic molecular tube that binds long hydrocarbons with high selectivity (2014)
  • Author(s): Kohei Yazaki, Yoshihisa Sei, Munetaka Akita, Michito Yoshizawa
  • Journal Title: Nature Communications Volume: 5 Issue: 1 Pages: 5179-5179
  • DOI: 10.1038/ncomms6179
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Micellar Polyaromatic Capsules: Enhanced Emissive Properties through Shell-Functionalization (2014)
  • Author(s): K. Kondo, A. Suzuki, M. Akita, M. Yoshizawa
  • Journal Title: European Journal of Organic Chemistry Volume: 2014 Issue: 33 Pages: 7389-7394
  • DOI: 10.1002/ejoc.201403136
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] A Solvato-Fluorochromic Macrocycle of Multiple Anthracene Fluorophores in Close Proximity (2014)
  • Author(s): Zhiou Li, Yoshihisa Sei, Munetaka Akita, Michito Yoshizawa
  • Journal Title: Chemistry - An Asian Journal Volume: 9 Issue: 4 Pages: 1016-1019
  • DOI: 10.1002/asia.201301648
  • Peer Reviewed
• [Journal Article] Molecular Architectures of Multi-Anthracene Assemblies (2014)
  • Author(s): Michito Yoshizawa, Jeremy. K. Klosterman
  • Journal Title: Chemical Society Reviews Volume: 43 Issue: 6 Pages: 1885-1898
  • DOI: 10.1039/c3cs60315f
  • Peer Reviewed
• [Journal Article] アントラセン環の殻を持つ三次元ナノ構造体の創製 (2014)
  • Author(s): 萩原啓太・吉沢道人
  • Journal Title: 有機合成化学会誌 Volume: 72 Pages: 692-701
  • NAID: 130004548617
  • Peer Reviewed
• [Presentation] アントラセン環を有する金属架橋カプセル：ベンゼン環およびキサンチン環上のメチル基認識 (2015)
  • Author(s): ○松野 匠・山科雅裕・清 悦久・吉沢道人・穐田宗隆
  • Organizer: 第5回CSJ化学フェスタ
  • Place of Presentation: タワーホール船堀（東京都・江戸川区）
  • Year and Date: 2015-10-13
• [Presentation] アントラセン環を有する金属架橋カプセル：キサンチン類のメチル基認識 (2015)
  • Author(s): ○松野 匠・山科雅裕・清 悦久・吉沢道人・穐田宗隆
  • Organizer: 第26回基礎有機化学討論会
  • Place of Presentation: 愛媛大学・松山大学（愛媛県・松山市）
  • Year and Date: 2015-09-24
• [Presentation] アントラセン環を有する金属架橋カプセル：蛍光分子の内包と光物性 (2015)
  • Author(s): ○山科雅裕・Matthew M. Sartin・竹内佐年・田原太平・吉沢道人・穐田宗隆
  • Organizer: 第65回錯体化学討論会
  • Place of Presentation: 奈良女子大学（奈良県・奈良市）
  • Year and Date: 2015-09-21
• [Presentation] Construction of Supramolecular Nanospaces Encircled by Multi-Anthracene Panels (2015)
  • Author(s): 吉沢道人
  • Organizer: International Symposium on Macrocyclic and Supramolecular Chemistry (ISMSC-2015)
  • Place of Presentation: Strasbourg（France）
  • Year and Date: 2015-06-28
  • Int'l Joint Research / Invited
• [Presentation] アントラセン環を有する金属架橋カプセル：カフェインの選択的内包 (2015)
  • Author(s): ○松野 匠・山科雅裕・清 悦久・吉沢道人・穐田宗隆
  • Organizer: 第13回 ホスト・ゲスト化学シンポジウム
  • Place of Presentation: 東北大学 川内北キャンパス（宮城県・仙台市）
  • Year and Date: 2015-06-06
• [Presentation] アントラセン環を有する分子チューブによる長鎖炭化水素の認識 (2014)
  • Author(s): 矢崎晃平、清 悦久、吉沢道人、穐田宗隆
  • Organizer: 第4回CSJ化学フェスタ
  • Place of Presentation: タワーホール船堀(東京都江戸川区）
  • Year and Date: 2014-10-14 – 2014-10-16
• [Presentation] アントラセン環を含む両親媒性分子カプセルを用いた蛍光分子認識 (2014)
  • Author(s): 鈴木 輝、吉沢道人、穐田宗隆
  • Organizer: 第4回CSJ化学フェスタ
  • Place of Presentation: タワーホール船堀(東京都江戸川区）
  • Year and Date: 2014-10-14 – 2014-10-16
• [Presentation] アントラセン環を含む両親媒性テープ状分子を利用した分子カプセルの構築と分子認識 (2014)
  • Author(s): 鈴木 輝、吉沢道人、穐田宗隆
  • Organizer: 第63回高分子討論会
  • Place of Presentation: 長崎大学文教キャンパス(長崎県長崎市）
  • Year and Date: 2014-09-24 – 2014-09-26
• [Presentation] アントラセン環に囲まれた空間を有する分子チューブによる長鎖炭化水素の認識 (2014)
  • Author(s): 矢崎晃平、清 悦久、吉沢道人、穐田宗隆
  • Organizer: 第63回高分子討論会
  • Place of Presentation: 長崎大学文教キャンパス(長崎県長崎市）
  • Year and Date: 2014-09-24 – 2014-09-26
• [Presentation] 多環芳香族ナノ空間：ラジカル開始剤の反応性制御 (2014)
  • Author(s): 吉沢道人、山科雅裕
  • Organizer: 第63回高分子討論会
  • Place of Presentation: 長崎大学文教キャンパス(長崎県長崎市）
  • Year and Date: 2014-09-24 – 2014-09-26
• [Remarks] 穐田・吉沢研究室ホームページ
  • URL: http://www.res.titech.ac.jp/~smart/smartj.html
• [Remarks] 東京工業大学 資源化学研究所 穐田・吉沢研究室ホームページ
  • URL: http://www.res.titech.ac.jp/~smart/smartj.html
• [Patent(Industrial Property Rights)] 分子カプセル、ステロイドの水溶化方法及び水溶化ステロイド (2014)
  • Inventor(s): 吉沢道人、山科雅裕、穐田宗隆
  • Industrial Property Rights Holder: 吉沢道人、山科雅裕、穐田宗隆
  • Industrial Property Rights Type: 特許
  • Industrial Property Number: 2014-088505
  • Filing Date: 2014-04-22
• [Patent(Industrial Property Rights)] フタロシアニン及びポルフィリン等の水溶化剤、水溶化体、及び水溶化方法 (2014)
  • Inventor(s): 吉沢道人、神山美穂、鈴木 輝、穐田宗隆
  • Industrial Property Rights Holder: 吉沢道人、神山美穂、鈴木 輝、穐田宗隆
  • Industrial Property Rights Type: 特許
  • Industrial Property Number: 2014-021941
  • Filing Date: 2014-04-08