Design and Preparation of Organic Molecular Crystals as Storage Materials of Clean Energy Gas

• Project/Area Number: 23550052
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Research Field: Organic chemistry
• Research Institution: Kyoto University
• Principal Investigator: TSUE Hirohito 京都大学, 人間・環境学研究科(研究院), 教授 (30271711)
• Co-Investigator(Renkei-kenkyūsha): 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): 2011-04-28 – 2015-03-31
• Project Status: Completed (Fiscal Year 2014)
• Budget Amount: ¥6,110,000 (Direct Cost: ¥4,700,000、Indirect Cost: ¥1,410,000); Fiscal Year 2014: ¥650,000 (Direct Cost: ¥500,000、Indirect Cost: ¥150,000); Fiscal Year 2013: ¥650,000 (Direct Cost: ¥500,000、Indirect Cost: ¥150,000); Fiscal Year 2012: ¥650,000 (Direct Cost: ¥500,000、Indirect Cost: ¥150,000); Fiscal Year 2011: ¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000)
• Keywords: 有機結晶 / 結晶構造 / 気体吸着 / 気体吸蔵

Outline of Final Research Achievements

Investigated were the preparation and gas adsorption behavior of the organic molecular crystals of azacalixarenes and dipeptides in order to explore their possibility to store methane, a clean energy gas, into the organic crystals composed of light elements. As an eventual outcome, the organic molecular crystals of azacalixarenes were found to exhibit the uptake of methane. Gas adsorption states were successfully visualized at an atomic level by means of X-ray crystallography.

Research Products

• [Journal Article] Highly Efficient Chiral Resolution of DL-Arginine by Cocrystal Formation Followed by Recrystallization under Preferential-Enrichment Conditions (2014)
  • Author(s): S. Iwama, K. Kuyama, Y. Mori, K. Manoj, R. G. Gonnade, K. Suzuki, C. E. Hughes, P. A. Williams, K. D. M. Harris, S. Veesler, H. Takahashi, H. Tsue, and R. Tamura
  • Journal Title: Chem. Eur. J. Volume: 20 Issue: 33 Pages: 10343-10350
  • DOI: 10.1002/chem.201402446
  • Peer Reviewed
• [Journal Article] Selective Adsorption of Mercury(II) Ion by p-tert-Butylcalix[4]thiacrown-5 at a Solid-Liquid Interface (2014)
  • Author(s): T. Takimoto, H. Tsue, R. Tamura, and H. Sasaki
  • Journal Title: Heterocycles Volume: 90 Issue: 2 Pages: 842-846
  • DOI: 10.3987/com-14-s(k)70
  • Peer Reviewed
• [Journal Article] Crystal enginnering of homochiral molecular organization of naproxen in cocrystals and their thermal phase transformation studies (2014)
  • Author(s): K. Manoj, R. Tamura, H. Takahashi, and H. Tsue
  • Journal Title: CrystEngComm Volume: 16 Issue: 26 Pages: 5811-5819
  • DOI: 10.1039/c3ce42415d
  • Peer Reviewed
• [Journal Article] Synthesis of p-tert-butylcalix[4]thiacrowns exhibiting sulfur number-dependent complexation with mercury(II) ion (2014)
  • Author(s): T. Takimoto, H. Tsue, H. Takahashi, R. Tamura, and H. Sasaki
  • Journal Title: Heterocycles Volume: 88 Issue: 2 Pages: 911-917
  • DOI: 10.3987/com-13-s(s)61
  • Peer Reviewed
• [Journal Article] Solid-Gas Sorption Behavior of a New Polymorph of Azacalix[5]arene Pentamethyl Ether as Controlled by Crystal Architecture (2013)
  • Author(s): Hirohito Tsue, Kohei Ono, Satoshi Tokita, Hiroki Takahashi, Rrui Tamura
  • Journal Title: CrystEngComm Volume: 15 Issue: 8 Pages: 1536-1544
  • DOI: 10.1039/c2ce26339d
  • Peer Reviewed
• [Journal Article] Nonporous but yet Gas-Sorbing Molecular Crystals Formed by Macrocyclic Compounds with Nitrogen-Bridges (2013)
  • Author(s): 津江広人
  • Journal Title: Nihon Kessho Gakkaishi Volume: 55 Issue: 1 Pages: 37-41
  • DOI: 10.5940/jcrsj.55.37
  • NAID: 10031156004
  • ISSN: 0369-4585, 1884-5576
  • Peer Reviewed
• [Journal Article] Synthesis of p-Chloroazacalix[5]arene Pentamethyl Ether: Ring Size-Dependent Desorption of N-Benzyl Groups (2012)
  • Author(s): Hirohito Tsue
  • Journal Title: Heterocycles Volume: 86 Issue: 1 Pages: 159-164
  • DOI: 10.3987/com-12-s(n)48
  • Peer Reviewed
• [Journal Article] Occurrence of Spontaneous Resolution of Ketoprofen with a Racemic Crystal Structure by Simple Crystallization under Nonequilibrium Preferential Enrichment Conditions (2012)
  • Author(s): Rajesh G.Gonnade
  • Journal Title: Chemical Communications Volume: 48 Issue: 22 Pages: 2791-2793
  • DOI: 10.1039/c2cc18132k
  • Peer Reviewed
• [Journal Article] Crystallographic analysis of CO2 sorption state in seemingly nonporous molecular crystal of azacalix[4]arene tetramethyl ether exhibiting highly selective CO2 uptake (2012)
  • Author(s): Hirohito Tsue, Hiroki Takahashi, Koichi Ishibashi, Rikako Inoue, Shun Shimizu, Daisuke Takahashi and Rui Tamura
  • Journal Title: CrystEngComm Volume: 14 Issue: 3 Pages: 1021-1026
  • DOI: 10.1039/c1ce06126g
  • Peer Reviewed
• [Presentation] DL-フェニルアラニルグリシン保護体の合成、結晶構造、および気体吸着挙動 (2015)
  • Author(s): 浅井悠志・Kochunnoonny Manoj・高橋弘樹・田村 類・津江広人
  • Organizer: 日本化学会第95春季年会
  • Place of Presentation: 日本大学（船橋市）
  • Year and Date: 2015-03-26
• [Presentation] 配位不飽和なマグネシウムポルフィリンの結晶構造と気体吸着特性 (2015)
  • Author(s): 桶谷龍成・高橋弘樹・田村 類・津江広人
  • Organizer: 日本化学会第95春季年会
  • Place of Presentation: 日本大学（船橋市）
  • Year and Date: 2015-03-26
• [Presentation] Nonporous but yet CO2-sorbing Molecular Crystals (2014)
  • Author(s): H. Tsue
  • Organizer: Collaborative Conference on Crystal Growth (3CG)
  • Place of Presentation: Holiday Inn Resort Phuket (Thailand)
  • Year and Date: 2014-11-06
  • Invited
• [Presentation] メチオニルアラニン保護体の合成，気体吸着挙動，およびCO2吸着状態の結晶構造解析 (2014)
  • Author(s): 桶谷龍成・森有彌・佐々木皓平・高橋弘樹・田村類・津江広人
  • Organizer: 第23回有機結晶シンポジウム
  • Place of Presentation: 東邦大学（船橋市）
  • Year and Date: 2014-09-16
• [Presentation] Selective CO2 Sorption into Seemingly Nonporous Molecular Crystals of Azacalixarenes (2014)
  • Author(s): H. Tsue, H. Takahashi, R. Inoue, K. Ishibashi, and R. Tamura
  • Organizer: 11th International Workshop on Crystal Growth of Organic Materials (CGOM11)
  • Place of Presentation: 奈良県新公会堂（奈良市）
  • Year and Date: 2014-06-20
  • Invited
• [Presentation] CO2吸蔵状態にあるアザカリックス[4]アレーンの結晶構造解析 (2011)
  • Author(s): 津江広人・高橋弘樹・石橋孝一・井上梨佳子・清水 俊・高橋大輔・田村 類
  • Organizer: 第22回基礎有機化学討論会
  • Place of Presentation: つくば国際会議場（茨城県）
• [Presentation] アザカリックス[4]アレーンの合成，気体吸蔵挙動，およびCO2吸蔵状態の結晶構造解析 (2011)
  • Author(s): 津江広人・高橋弘樹・石橋孝一・井上梨佳子・清水 俊・高橋大輔・田村 類
  • Organizer: 第20回有機結晶シンポジウム
  • Place of Presentation: 富山大学（富山県）
• [Presentation] アザカリックス[4]アレーンの合成，結晶構造，および気体吸蔵特性 (2011)
  • Author(s): 津江広人・高橋弘樹・石橋孝一・井上梨佳子・清水 俊・高橋大輔・田村 類
  • Organizer: 第5回有機π電子系シンポジウム
  • Place of Presentation: ホテルアウィーナ大阪（大阪府）
• [Presentation] Crystallographic analysis of CO2 sorption state in seemingly nonporous molecular crystal of azacalix[4]arene exhibiting highly selective CO2 uptake
  • Author(s): H. Tsue, H. Takahashi, K. Ishibashi, R. Inoue, S. Shimizu, D. Takahashi, and R. Tamura
  • Organizer: Challenges in Organic Materials & Supramolecular Chemistry (ISACS10)
  • Place of Presentation: 京都大学（京都市）
• [Presentation] Solid–gas sorption behavior of nitrogen-bridged calixarene analogues as controlled by crystal architecture
  • Author(s): H. Tsue, K. Ono, S. Tokita, K. Ishibashi, R. Inoue, H. Takahashi, and R. Tamura
  • Organizer: The XXI International Conference on the Chemistry of the Organic Solid State (ICCOSS XXI)
  • Place of Presentation: St. Catherine’s College, Oxford, UK
• [Presentation] 親水性チャネル有するジペプチドの合成と気体吸蔵特性
  • Author(s): 津江広人・佐々木皓平・井上梨佳子・田村類
  • Organizer: 第22回有機結晶シンポジウム
  • Place of Presentation: 北海道大学（北海道）
• [Presentation] 人工甘味料ネオテームの合成とアポホスト結晶の調製
  • Author(s): 津江広人・日笠有利・佐々木皓平・森有彌・高橋弘樹・田村類
  • Organizer: 日本化学会第94春期年会
  • Place of Presentation: 名古屋大学東山キャンパス（名古屋市）
• [Presentation] 疎水性または親水性チャネル有するジペプチドの合成とアポホスト結晶の調製
  • Author(s): 津江広人・佐々木皓平・井上梨佳子・田村類
  • Organizer: 第21回有機結晶シンポジウム
  • Place of Presentation: 東京工業大学すずかけ台キャンパス（神奈川県）
• [Presentation] アザカリックスアレーンの気体吸蔵特性に関する理論的解析
  • Author(s): 津江広人・清水俊・石橋孝一・時田智・松井一裕・小野浩平・高橋弘樹・田村類
  • Organizer: 第21回有機結晶シンポジウム
  • Place of Presentation: 東京工業大学すずかけ台キャンパス（神奈川県）
• [Presentation] 疎水性または親水性チャネル有するジペプチドの合成と気体吸蔵特性
  • Author(s): 津江広人・佐々木皓平・井上梨佳子・田村類
  • Organizer: 日本化学会第93春期年会
  • Place of Presentation: 立命館大学びわこ・くさつキャンパス（滋賀県）
• [Presentation] ジペプチド結晶における気体吸蔵特性の理論的予測
  • Author(s): 津江広人・清水俊・佐々木皓平・田村類
  • Organizer: 日本化学会第93春期年会
  • Place of Presentation: 立命館大学びわこ・くさつキャンパス（滋賀県）
• [Book] Azacalixarene: An Ever-Growing Class in the Calixarene Family (2015)
  • Author(s): H. Tsue and R. Oketani
  • Total Pages: 25
  • Publisher: Springer
• [Remarks] 津江研究室ホームページ
  • URL: http://www.orgmater.h.kyoto-u.ac.jp/tsue/
• [Remarks] 京都大学 大学院人間・環境学研究科 津江研究室
  • URL: http://www.orgmater.h.kyoto-u.ac.jp/tsue/
• [Remarks]
  • URL: http://www.users.iimc.kyoto-u.ac.jp/~z59081/