Chirality amplification through unique crystallization - supersaturated solution, melt and crystal co grinding

• Project/Area Number: 24350064
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Partial Multi-year Fund
• Section: 一般
• Research Field: Functional materials chemistry
• Research Institution: Tokyo University of Science
• Principal Investigator: KURODA REIKO 東京理科大学, 総合研究機構, 教授 (90186552)
• Project Period (FY): 2012-04-01 – 2015-03-31
• Project Status: Completed (Fiscal Year 2014)
• Budget Amount: ¥18,330,000 (Direct Cost: ¥14,100,000、Indirect Cost: ¥4,230,000); Fiscal Year 2014: ¥5,460,000 (Direct Cost: ¥4,200,000、Indirect Cost: ¥1,260,000); Fiscal Year 2013: ¥6,240,000 (Direct Cost: ¥4,800,000、Indirect Cost: ¥1,440,000); Fiscal Year 2012: ¥6,630,000 (Direct Cost: ¥5,100,000、Indirect Cost: ¥1,530,000)
• Keywords: キラリティー / 結晶工学 / 結晶成長 / 超分子結晶 / 結晶多形 / 超分子

Outline of Final Research Achievements

100% chirality amplification was achieved by crystallization of super-cooled melt of 2-(4-chlorophenylthio)-3-methyl-2-cyclohexen-1-one) (p-Cl) which always produces achiral crystals from conventional crystallization, using one chiral crystal of its methyl analogue as a seed. Chiral crystals thus induced however go back to the achiral form by facile thermal or mechanical stimuli. The reason underneath was studied with DSC and DFT calculation. Photocyclization reaction of the chiral crystals of p-Cl exhibited enantio-selectivity at its early stage.

Research Products

• [Journal Article] Tunability of guest release properties and crystal structures in a supramolecular benzothiophene heterocyclic host complex (2015)
  • Author(s): T. Wakabayashi, S. Kitamura, H. Tabata, R. Kuroda and Y. Imai
  • Journal Title: CrystEngComm Volume: 17 Issue: 16 Pages: 3064-3069
  • DOI: 10.1039/c4ce02496f
  • Peer Reviewed / Open Access
• [Journal Article] Characteristic solid-state color properties and crystal structures of 2-methyl-3-chlorophenylthio-1,4-naphthalenedione, (2014)
  • Author(s): E. Yotsumoto, T. Inoue, T. Wakabayashi, T. Amako, N. Tajima, R. Kuroda and Y. Imai
  • Journal Title: J. Mol. Str. Volume: 1056/1057 Pages: 189-193
  • Peer Reviewed / Open Access
• [Journal Article] Polymorphism of supramolecular charge-transfer complex composed of 10,10’-dihydroxy-9,9’-biphenanthryl and p-benzoquinone. (2014)
  • Author(s): N. Iwase, Y. Shigeno, T. Wakabayashi, T. Sato, N. Tajima, R. Kuroda and Y. Imai
  • Journal Title: Mole. Cryst. Liq. Cryst. Volume: 592 Issue: 1 Pages: 209-217
  • DOI: 10.1080/15421406.2013.841558
  • Peer Reviewed / Open Access
• [Journal Article] Preparation and Guest Release Properties of Supramolecular 3-Chlorobenzo[b]- thiophene Heterocyclic Host Complex (2014)
  • Author(s): T. Wakabayashi, T. Amako, R. Kuroda and Y. Imai
  • Journal Title: Cryst Growth Des. Volume: 14 Issue: 1 Pages: 32-37
  • DOI: 10.1021/cg401012n
  • Peer Reviewed / Open Access
• [Journal Article] Chiral optical properties of phenyloxazoline derivatives that appear only in the solid state (2014)
  • Author(s): M. Hirayama, Y. Kobayashi, Y. Tanaka, T. Sato, T. Harada, N. Tajima, R. Kuroda, M. Fujiki, Y. Imai
  • Journal Title: Eur. J. Org. Chem Volume: 2014 Issue: 4 Pages: 719-724
  • DOI: 10.1002/ejoc.201301379
  • Peer Reviewed / Open Access
• [Journal Article] Chirality as a crossroad of Chemistry, Physics and Biology (2014)
  • Author(s): R. Kuroda
  • Journal Title: Symmetry Volume: 25 Pages: 91-96
  • Peer Reviewed / Open Access
• [Journal Article] Heteroleptic Ru(II) complexes containing aroyl hydrazone and 2,2’-bipyridyl: Synthesis, X-ray crystal structures, electrochemical and DFT studies (2014)
  • Author(s): B.Ghosh, S. Naskar, S. Naskar, A. Espinosa. J. Yau, T. C. Mak, R. Sekiya, R. Kuroda, S. K. Chattopadhyay
  • Journal Title: Polyhedron Volume: 72 Pages: 115-121
  • DOI: 10.1016/j.poly.2014.01.031
  • Peer Reviewed / Open Access
• [Journal Article] Synthesis, Characterization, X-ray Crystal Structure, DFT Calculations, and Catalytic Properties of a Dioxidovanadium(V) Complex Derived from Oxamohydrazide and Pyridoxal: A Model Complex of Vanadate-Dependent Bromoperoxidase (2014)
  • Author(s): C. Das, P. Adak, S. Mondal, R. Sekiya, R. Kuroda, S. I. Gorelsky, and S. K. Chattopadhyay
  • Journal Title: Inorg. Chem. Volume: 53 Issue: 21 Pages: 11426-11437
  • DOI: 10.1021/ic501216d
  • Peer Reviewed / Open Access
• [Journal Article] Multiple optical properties of naphthoquinone pigment: 2-methyl-3-(hydroxyl- phenylthio)-1,4-naphthalenedione (2014)
  • Author(s): H. Akiyama, T. Inoue, N. Tajima, R. Kuroda and Y. Imai
  • Journal Title: Organic & Biomolecular Chemistry Volume: 12 Issue: 40 Pages: 7965-7970
  • DOI: 10.1039/c4ob01058b
  • Peer Reviewed / Open Access
• [Journal Article] Molecular recognition of a large bisphenol A derivative,α,α'-bis(4-hydroxyphenyl)-1,4-diisopropylbenzene, using p-benzoquinone derivatives (2014)
  • Author(s): N. Iwase, Y. Shigeno, T. Wakabayashi, T. Sato, N. Tajima, R. Kuroda and Y. Imai, CrystEngComm, 16, 159-163 (2014)
  • Journal Title: CrystEngComm Volume: 16 Issue: 2 Pages: 159-163
  • DOI: 10.1039/c3ce41432a
  • Peer Reviewed
• [Journal Article] Control of variable composition structures by fluorine substituent in supramolecular organic fluorophore composed of 2-naphthalenecarboxylic acid (2013)
  • Author(s): Y. Tanaka, T. Harada, R. Kuroda and Y. Imai,
  • Journal Title: CrystEngComm Volume: 15 Issue: 23 Pages: 4624-4630
  • DOI: 10.1039/c2ce26795k
  • Peer Reviewed
• [Journal Article] Control of variable composition structures by fluorine substituent in supramolecular organic fluorophore composed of 2-naphthalenecarboxylic acid (2013)
  • Author(s): J. Yoshida, S. Nishikiori, R. Kuroda and H. Yuge
  • Journal Title: CrystEngComm. Volume: 15 Issue: 10 Pages: 3451-3457
  • DOI: 10.1002/chem.201203728
  • Peer Reviewed
• [Journal Article] Control of Solid-state Circularly Polarized Luminescence of Binaphthyl Organic Fluorophores through Environmental Changes (2013)
  • Author(s): Takaya Kimoto, Tomoyuki Amako, Nobuo Tajima, Reiko Kuroda, Michiya Fujiki, Yoshitane Imai
  • Journal Title: Asian Journal of Organic Chemistry Volume: 2 Issue: 5 Pages: 2836-2841
  • DOI: 10.1002/ajoc.201300034
  • Peer Reviewed
• [Journal Article] Preparation of a Spontaneously Resolved Chiral Fluorescent System Containing 4-(2-Arylethynyl)benzoic Acid (2013)
  • Author(s): N. Taniguchi, R. Shimomaki, T. Amako, T. Sato, H. Tokutome, N. Tajima, R. Kuroda, M. Fujiki, and Y. Imai
  • Journal Title: Asian J. Org. Chem. Volume: 2 Issue: 8 Pages: 681-687
  • DOI: 10.1002/ajoc.201300084
  • Peer Reviewed
• [Journal Article] Chiral anthracene fluorescence system using achiral 1-naphthylmethylamine. (2013)
  • Author(s): Y. Kobayashi, Y. Tanaka, T. Sato, M. Fujiki, R. Kuroda and Y. Imai
  • Journal Title: CrystEngComm Volume: 15 Issue: 31 Pages: 6259-6263
  • DOI: 10.1039/c3ce40765a
  • Peer Reviewed
• [Journal Article] Nonclassical tunability of solid-state CD and CPL properties of chiral 2-naphthale necarboxylic acid/amine supramolecular organic fluorophore (2012)
  • Author(s): Nishiguchi, N.; Kinuta, T.; Sato, T.; Nakano, Y.; Tokutome, H.; Tajima, N.; Fujiki, M.; Kuroda, R.; Matsubara, Y.; Imai, Y.
  • Journal Title: Chem.Asian J. Volume: 7 Issue: 2 Pages: 360-366
  • DOI: 10.1002/asia.201100727
  • Peer Reviewed
• [Journal Article] Polymorphic supramolecular organic fluorophore composed of 2-naphthalenecarboxylic acid and benzylamine (2012)
  • Author(s): Y. Kobayashi, et al.
  • Journal Title: CrystEngComm Volume: 14 Pages: 1468-1472
  • Peer Reviewed
• [Journal Article] Preparation of a Supramolecular Heterocyclic Host Complex using Chiral (1R,2S)-2-Amino-1,2-diphenylethanol (2012)
  • Author(s): N. Shiota, et al.
  • Journal Title: J. Mol. Struc. Volume: 1014 Pages: 32-37
  • DOI: 10.1016/j.molstruc.2012.01.027
  • Peer Reviewed
• [Journal Article] Novel Means of Controlling Solid-state CD Property in Supramolecular Organic Fluorophore Comprising 4-[2-(Methylphenyl)ethynyl]benzoic acid by Varying Position of Methyl Substituent (2012)
  • Author(s): N. Nishiguchi, et al.
  • Journal Title: Crystal Growth & Design Volume: 12 Issue: 4 Pages: 1859-1864
  • DOI: 10.1021/cg201496j
  • Peer Reviewed
• [Journal Article] Dependence of Solid-State Optical Properties on Binding Groups in Biphenyl acid/Amine Supramolecular Organic Complexes (2012)
  • Author(s): Takahiro Okuno, Yumeko Sakoda, Takafumi Kinuta, Tomohiro Sato, Hayato Tokutome, Nobuo Tajima, Yoko Nakano, Michiya Fujiki, Reiko Kuroda, Yoshitane Imai
  • Journal Title: CrystEngComm Volume: 14 Issue: 14 Pages: 4819-4825
  • DOI: 10.1039/c2ce25259g
  • Peer Reviewed
• [Journal Article] Solid-state visible molecular recognition system of bisphenol A and its derivatives by solid co-grinding crystallization with benzoquinone (2012)
  • Author(s): N. Iwase, et al.
  • Journal Title: CrystEngComm Volume: 14 Issue: 24 Pages: 8599-8605
  • DOI: 10.1039/c2ce26148k
  • Peer Reviewed
• [Presentation] Formation, transformation of organic crystals and the characterization (2015)
  • Author(s): Reiko Kuroda
  • Organizer: Pacifichem 2015
  • Place of Presentation: Honolulu, Hawaii, USA
  • Year and Date: 2015-12-15 – 2015-12-20
  • Invited
• [Presentation] Chirality Ripening and Crystal to Crystal Conversion (2015)
  • Author(s): Reiko Kuroda,Yuta Hatano, Risa Suzuki and Hideyuki Tabata
  • Organizer: International Conference n the Chemistry of the Organic Solid State (ICCOSS) XXII
  • Place of Presentation: 新潟県新潟市 トキメッセ
  • Year and Date: 2015-07-12 – 2015-07-17
• [Presentation] Engineering the sign of solid-state CD and CPL (2015)
  • Author(s): Reiko Kuroda; Yoshitane Imai; Michiya Fujiki; Nobuo Tajima
  • Organizer: 27th International Symposium on Chirality (ISCD-27)
  • Place of Presentation: Boston, USA
  • Year and Date: 2015-06-28 – 2015-07-01
• [Presentation] Molecular Structure and Chirality (2015)
  • Author(s): Reiko Kuroda
  • Organizer: International School on crystallography: Engineering crystallography: from moleculet to crystal to functional form
  • Place of Presentation: Erice, Italy
  • Year and Date: 2015-06-06 – 2015-06-13
  • Invited
• [Presentation] Techniques for Crystal Optical Characterisation: Chiroptical spectroscopy (2015)
  • Author(s): Reiko Kuroda
  • Organizer: International School on crystallography: Engineering crystallography: from moleculet to crystal to functional form
  • Place of Presentation: Erice, Italy
  • Year and Date: 2015-06-06 – 2015-06-13
  • Invited
• [Presentation] 複素環ユニットを有する芳香族カルボン酸/アミン系超分子ホスト錯体の生成と置換基効果 (2015)
  • Author(s): 北村 沙也香・若林 卓志・田端 秀行・黒田 玲子・今井 喜胤
  • Organizer: 日本化学会第95春季年会
  • Place of Presentation: 千葉県船橋市 日本大学理工学部 船橋キャンパス
  • Year and Date: 2015-03-26 – 2015-03-29
• [Presentation] アキラルな拡張π電子系フェナントリルカルボン酸とアキラルなアミン分子を用いた超分子有機発光体の生成挙動 (2015)
  • Author(s): 西川 智貴・谷口 直哉・原田 拓典・黒田 玲子・藤木 道也・今井 喜胤
  • Organizer: 日本化学会第95春季年会
  • Place of Presentation: 千葉県船橋市 日本大学理工学部 船橋キャンパス
  • Year and Date: 2015-03-26 – 2015-03-29
• [Presentation] 複素環ユニットを有するナフトキノン系機能性色素の開発 (2015)
  • Author(s): 左古 章浩・秋山 弘毅・田島 暢夫・黒田 玲子・今井 喜胤
  • Organizer: 日本化学会第95春季年会
  • Place of Presentation: 千葉県船橋市 日本大学理工学部 船橋キャンパス
  • Year and Date: 2015-03-26 – 2015-03-29
• [Presentation] ベンゼンユニット連結型新規グアイアズレン誘導体の開発 (2015)
  • Author(s): 岡崎 守・大久保 凌;・田島 暢夫・黒田 玲子・武隈 真一・今井 喜胤
  • Organizer: 日本化学会第95春季年会
  • Place of Presentation: 千葉県船橋市 日本大学理工学部 船橋キャンパス
  • Year and Date: 2015-03-26 – 2015-03-29
• [Presentation] 右と左からみた生命の世界 (2015)
  • Author(s): 黒田玲子
  • Organizer: 生命の起原および進化学会
  • Place of Presentation: 東京都葛飾区 東京理科大学葛飾キャンパス
  • Year and Date: 2015-03-15
  • Invited
• [Presentation] Chirality in the Solid State (2015)
  • Author(s): R. Kuroda
  • Organizer: The 19th Hiroshima International Symposium on Synchrotron Radiation
  • Place of Presentation: 広島県東広島市、広島大学Faculty Club
  • Year and Date: 2015-03-05 – 2015-03-06
  • Invited
• [Presentation] 結晶のスゴ技―キラリティーの創生・転写・増幅と光反応 (2014)
  • Author(s): 黒田玲子
  • Organizer: 有機結晶部会シンポジウム
  • Place of Presentation: 千葉県船橋市東邦大習志野キャンパス
  • Year and Date: 2014-09-15 – 2014-09-17
  • Invited
• [Presentation] Formation and interconversion of crystals in the solid state (2014)
  • Author(s): Reiko Kuroda, Ryo Sekiya, Yuuta Hatano, Risa Suzuki, Hideyuki Tabata
  • Organizer: 26th International Symposium on Chirality (ISCD 26)
  • Place of Presentation: Prague、Czech Republic
  • Year and Date: 2014-07-27 – 2014-07-30
• [Presentation] Chiral Amlification through Crystallization: Solution, Seeding and Solid Co-grinding Crystallization (2014)
  • Author(s): Reiko Kuroda; Ryo Sekiya, Risa Suzuki, Yuuta Hatano, Hideyuki Tabata
  • Organizer: Congress of ACTS-2014 and CGOM11
  • Place of Presentation: 奈良県奈良市Nara Prefectural New Public Hall
  • Year and Date: 2014-06-17 – 2014-06-20
  • Invited
• [Presentation] Preparation of π-Conjugated Supramolecular Organic Fluorophore with Circularly Polarized Luminescence by Co-grinding Crystallization (2014)
  • Author(s): Naoya Taniguchi, Shota Kamiyoshi, Tomohiro Sato, Hayato Tokutome, Reiko Kuroda, Michiya Fujiki, Yoshitane Ima
  • Organizer: Congress of ACTS-2014 and CGOM11
  • Place of Presentation: 奈良県奈良市 Nara Prefectural New Public Hall
  • Year and Date: 2014-06-17 – 2014-06-20
• [Presentation] キラル種結晶によるキラル結晶の誘導とその安定性 (2014)
  • Author(s): 黒田玲子、波多野裕太、関谷亮、田端秀行
  • Organizer: モレキュラーキラリティー2014
  • Place of Presentation: 宮城県仙台市 仙台国際センター
  • Year and Date: 2014-06-06 – 2014-06-07
• [Presentation] ピレンユニットを導入した軸不斉ビナフチル化合物の円偏光発光(CPL)特性 (2014)
  • Author(s): 中林和輝 ，尼子智之，田島暢夫，黒田玲子， 藤木道也，今井喜胤
  • Organizer: モレキュラーキラリティー2014
  • Place of Presentation: 宮城県仙台市 仙台国際センター
  • Year and Date: 2014-06-06 – 2014-06-07
• [Presentation] フェニルエチニルベンゼン系光学活性超分子ホスト-ゲスト錯体の創製 (2014)
  • Author(s): 若林卓志・尼子智之・田端秀行・黒田玲子・今井喜胤
  • Organizer: 第12回ホスト・ゲスト化学シンポジウム
  • Place of Presentation: 東京都目黒区東京工業大学大岡山キャンパス
  • Year and Date: 2014-05-31 – 2014-06-01
• [Presentation] ゲスト分子包接特性を有するフェニルエチニルベンゼン系光学活性超分子錯体の創製 (2014)
  • Author(s): 若林卓志・尼子智之・田端秀行・黒田玲子・今井喜胤
  • Organizer: 日本化学会第94回春季年会
  • Place of Presentation: 名古屋
• [Presentation] 円偏光発光(CPL)特性を有するアリールエチニルベンゼン系光学活性超分子有機発光体の創製 (2014)
  • Author(s): 西川智貴・谷口直哉・原田拓典・黒田玲子・藤木道也・今井喜胤
  • Organizer: 日本化学会第94回春季年会
  • Place of Presentation: 名古屋
• [Presentation] 無溶媒結晶化法による円偏光発光(CPL)特性を有する光学活性超分子有機発光体の創製 (2014)
  • Author(s): 谷口直哉・神吉翔太・佐藤友宏・徳留隼人・黒田玲子・藤木道也・今井喜胤
  • Organizer: 日本化学会第94回春季年会
  • Place of Presentation: 名古屋
• [Presentation] Molecules, crystals and living organisms looking through the eyes of chirality (2013)
  • Author(s): R. Kuroda
  • Organizer: Nano Gathering
  • Place of Presentation: Gotenburg, Sweden
  • Invited
• [Presentation] Symmetry and Chirality in Chemistry and Physics (2013)
  • Author(s): R. Kuroda
  • Organizer: Symmetry Festival
  • Place of Presentation: Delft, Hollnad
  • Invited
• [Presentation] Unique solid-state reactions and molecular rearrangements controlled by crystal structures (2013)
  • Author(s): R. Kuroda
  • Organizer: ICOSS XX
  • Place of Presentation: Oxfoed, UK
  • Invited
• [Presentation] 結晶の融解・凝固過程における多形と固相光反応 (2013)
  • Author(s): 黒田玲子・田端秀行・鈴木梨紗
  • Organizer: 有機結晶シンポジウム
  • Place of Presentation: 札幌
• [Presentation] 結晶化におけるキラル増幅 I 溶液からの結晶化 (2012)
  • Author(s): 黒田玲子・関谷亮
  • Organizer: 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(横浜)
  • Year and Date: 2012-11-08
• [Presentation] Left and right handedness in nature - molecules, crystals and snails (2012)
  • Author(s): Reiko Kuroda
  • Organizer: Royal Swedish Academy of Science, Academy Lectures in Chemistry
  • Place of Presentation: Royal Swedish Academy of Science (Stockholm)(招待講演)
  • Year and Date: 2012-10-19
• [Presentation] 固体キラル化学の展開と測定装置の開発 (2012)
  • Author(s): 黒田玲子
  • Organizer: 錯体化学秋の学校
  • Place of Presentation: 氷見温泉(富山)(招待講演)
  • Year and Date: 2012-09-24
• [Presentation] 凝集状態のキラリティー測定に挑む (2012)
  • Author(s): 黒田玲子
  • Organizer: 第30回関西界面科学セミナー
  • Place of Presentation: シーパル須磨(神戸)(招待講演)
  • Year and Date: 2012-07-06