Fusion and development of multiconfigurational electronic state theory and integral equation theory suitable for quasidegenerate systems in solution

• Project/Area Number: 15K05392
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Research Field: Physical chemistry
• Research Institution: Kyushu University
• Principal Investigator: NAKANO Haruyuki 九州大学, 理学研究院, 教授 (90251363)
• Research Collaborator: YOSHIDA Norio ; WATANABE Yoshihiro
• Project Period (FY): 2015-04-01 – 2019-03-31
• Project Status: Completed (Fiscal Year 2018)
• Budget Amount: ¥4,940,000 (Direct Cost: ¥3,800,000、Indirect Cost: ¥1,140,000); Fiscal Year 2017: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000); Fiscal Year 2016: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000); Fiscal Year 2015: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
• Keywords: 理論化学 / 擬縮退系 / 多配置電子状態理論 / 液体の積分方程式理論 / 相対論的電子状態理論 / シミュレーション手法

Outline of Final Research Achievements

We developed multiconfigurational methods applicable to complicated electronic structures of large molecules and integral-equation-theory based methods for quasidegenerate system in solution phase, and applied them to chemical phenomena in solutions including biological and metal systems: Coordination structure and excitation spectra of Cu(II)-water complexes in aqueous solution; Solvatochromism and preferential solvation of Brooker's merocyanine in water-methanol mixtures; Complex formation of p-carboxybenzeneboronic acid with a monosaccharide; Ion dependence of carbohydrate binding of CBM36; Size-dependent adsorption sites in a Prussian blue nanoparticle, etc.

Academic Significance and Societal Importance of the Research Achievements

溶液内化学過程を分子論的に取り扱う基本的な手法を与えるとともに，触媒化学，生物化学，生物物理など，工業・医療・創薬等を支える基礎的分野への知見を提供した。

Research Products

• [Journal Article] Synthesis of Redox-switchable 5,15-Dialkyl-10,20-diaryl-5,15-diazaporphyrins and Diversification of their N-Alkyl Groups (2019)
  • Author(s): Mutoh Mai、Sudoh Keisuke、Furukawa Ko、Minoura Mao、Nakano Haruyuki、Matano Yoshihiro
  • Journal Title: Asian Journal of Organic Chemistry Volume: 8 Issue: 3 Pages: 352-355
  • DOI: 10.1002/ajoc.201900085
  • Peer Reviewed
• [Journal Article] Three-Dimensional Reference Interaction Site Model Self-Consistent Field Study on the Coordination Structure and Excitation Spectra of Cu(II)-Water Complexes in Aqueous Solution (2019)
  • Author(s): Yang Chen、Watanabe Yoshihiro、Yoshida Norio、Nakano Haruyuki
  • Journal Title: The Journal of Physical Chemistry A Volume: 未定 Issue: 15 Pages: 3344-3354
  • DOI: 10.1021/acs.jpca.9b01364
  • Peer Reviewed
• [Journal Article] Direct and Regioselective Amination of β-Unsubstituted 5,15-Diazaporphyrins with Amines: A Convenient Route to Near-Infrared-Responsive Diazaporphyrin Sensitizers (2018)
  • Author(s): Omomo, S.; Sugai, T.; Minoura, M.; Nakano, H.; Matano, Y.
  • Journal Title: Angewandte Chemie International Edition Volume: 57 Issue: 14 Pages: 3797-3800
  • DOI: 10.1002/anie.201800471
  • Peer Reviewed
• [Journal Article] Redox Switchable 19π and 18π 5,10,20-Triaryl-5,15-diazaporphyrinoid-Nickel(II) Complexes (2018)
  • Author(s): Keisuke Sudoh, Takuroh Hatakeyama, Ko Furukawa, Haruyuki Nakano, Yoshihiro Matano
  • Journal Title: Journal of Porphyrins and Phthalocyanines Volume: 22 Issue: 07 Pages: 542-551
  • DOI: 10.1142/s1088424618500529
  • Peer Reviewed
• [Journal Article] β-Functionalization of 5,15-Diazaporphyrins with Phosphorus, Oxygen, and Sulfur-Containing Substituents (2018)
  • Author(s): Sugai Takuma、Minoura Mao、Nakano Haruyuki、Matano Yoshihiro
  • Journal Title: Bulletin of the Chemical Society of Japan Volume: 91 Issue: 8 Pages: 1264-1266
  • DOI: 10.1246/bcsj.20180123
  • NAID: 130007434221
  • Peer Reviewed
• [Journal Article] A computational scheme of pKa values based on the three-dimensional reference interaction site model self-consistent field theory coupled with the linear fitting correction scheme (2018)
  • Author(s): Fujiki Ryo、Kasai Yukako、Seno Yuki、Matsui Toru、Shigeta Yasuteru、Yoshida Norio、Nakano Haruyuki
  • Journal Title: Physical Chemistry Chemical Physics Volume: 20 Issue: 43 Pages: 27272-27279
  • DOI: 10.1039/c8cp04354j
  • Peer Reviewed
• [Journal Article] Synthesis and properties of redox-switchable zinc complexes of 10,15,20-triaryl-15-aza-5-oxaporphyrin (2018)
  • Author(s): Sudoh Keisuke、Furukawa Ko、Nakano Haruyuki、Shimizu Soji、Matano Yoshihiro
  • Journal Title: Heteroatom Chemistry Volume: 29 Issue: 5-6
  • DOI: 10.1002/hc.21456
  • Peer Reviewed / Open Access
• [Journal Article] Redox Switchable 19π and 18π 5,10,20-Triaryl-5,15-diazaporphyrinoid-Nickel(II) Complexes (2018)
  • Author(s): Keisuke Sudoh, Takuroh Hatakeyama, Ko Furukawa, Haruyuki Nakano, Yoshihiro Matano
  • Journal Title: J. Porphyr. Phthalocyanines Volume: 印刷中
  • Peer Reviewed
• [Journal Article] Nitrogen-Bridged Metallodiazaporphyrin Dimers: Synergistic Effects of Nitrogen Bridges and meso-Nitrogen Atoms on Structure and Properties (2017)
  • Author(s): Masahiro Kawamata, Takuma Sugai, Mao Minoura, Yasuhisa Maruyama, Ko Furukawa, Cole Holstrom, Victor N. Nemykin, Haruyuki Nakano, and Yoshihiro Matano
  • Journal Title: Chem. Asian J. Volume: 12 Issue: 7 Pages: 816-821
  • DOI: 10.1002/asia.201700204
  • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] Unsymmetrically Substituted D-π-A Type 5,15-Diazaporphyrin Sensitizers: Synthesis and Optical and Photovoltaic Properties (2017)
  • Author(s): Satoshi Omomo, Yukihiro Tsuji, Kenichi Sugiura, Tomohiro Higashino, Haruyuki Nakano, Hiroshi Imahori, and Yoshihiro Matano
  • Journal Title: ChemPlusChem Volume: 印刷中 Issue: 5 Pages: 695-704
  • DOI: 10.1002/cplu.201700051
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Solvatochromism and Preferential Solvation of Brooker's Merocyanine in Water-Methanol Mixtures (2017)
  • Author(s): Yuichi Tanaka, Yukio Kawashima, Norio Yoshida, Haruyuki Nakano
  • Journal Title: J. Comput. Chem. Volume: 38 Issue: 28 Pages: 2411-2419
  • DOI: 10.1002/jcc.24902
  • Peer Reviewed
• [Journal Article] Syntheses, Properties, and Catalytic Activities of Metal(II) Complexes and Free Bases of Redox-Switchable 20π, 19π, and 18π 5,10,15,20-Tetraaryl-5,15-diazaporphyrinoids (2017)
  • Author(s): Keisuke Sudoh, Takaharu Satoh, Toru Amaya, Ko Furukawa, Mao Minoura, Haruyuki Nakano, Yoshihiro Matano
  • Journal Title: Chem. Eur. J. Volume: 23 Issue: 64 Pages: 16364-16373
  • DOI: 10.1002/chem.201703664
  • Peer Reviewed
• [Journal Article] Theoretical analysis of complex formation of p-carboxybenzeneboronic acid with a monosaccharide (2016)
  • Author(s): Yuki Seno, Norio Yoshida, Haruyuki Nakano
  • Journal Title: J. Mol. Liq. Volume: 印刷中 Pages: 93-98
  • DOI: 10.1016/j.molliq.2015.12.063
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] The ion-dependence of carbohydrate binding of CBM36: MD and 3D-RISM study (2016)
  • Author(s): Shoichi Tanimoto, Masahiro Higashi, Norio Yoshida, Haruyuki Nakano
  • Journal Title: Journal of Physics: Condensed Matter Volume: 28 Issue: 34 Pages: 344005-344005
  • DOI: 10.1088/0953-8984/28/34/344005
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Redox-Switchable 20π-, 19π-, and 18π-Electron 5,10,15,20-Tetraaryl-5,15-diazaporphyrinoid Nickel(II) Complexes (2016)
  • Author(s): Takaharu Satoh, Mao Minoura, Haruyuki Nakano, Ko Furukawa, Yoshihiro Matano
  • Journal Title: Angew. Chem. Int. Ed. Volume: 55 Issue: 6 Pages: 2235-2238
  • DOI: 10.1002/anie.201510734
  • Peer Reviewed
• [Journal Article] Comparison of electronic effects of β-aryl substituents on optical and electrochemical properties of 5,15-diazaporphyrin π-systems (2015)
  • Author(s): Satoshi Omomo, Ko Furukawa, Haruyuki Nakano, Yoshihiro Matano
  • Journal Title: J. Porphyr. Phthalocyanines Volume: 19 Issue: 06 Pages: 775-785
  • DOI: 10.1142/s1088424615500509
  • Peer Reviewed
• [Journal Article] Theoretical analysis of co-solvent effect on the proton transfer reaction of glycine in a water-acetonitrile mixture (2015)
  • Author(s): Yukako Kasai, Norio Yoshida, Haruyuki Nakano
  • Journal Title: J. Chem. Phys. Volume: 142 Issue: 20
  • DOI: 10.1063/1.4921432
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Three-Dimensional Reference Interaction Site Model Self-Consistent Field Analysis of Solvent and Substituent Effects on the Absorption Spectra of Brooker's Merocyanine (2015)
  • Author(s): Yuichi Tanaka, Norio Yoshida, Haruyuki Nakano
  • Journal Title: J. Comput. Chem. Volume: 36 Issue: 22 Pages: 1655-1663
  • DOI: 10.1002/jcc.23980
  • Peer Reviewed / Acknowledgement Compliant
• [Presentation] A Three-Dimensional Reference Interaction Site Model Self-Consistent-Field Study on the Coordination Structure and Excitation Spectra of Cu(II)-Water Complexes in Aqueous Solution (2018)
  • Author(s): Chen Yang, Yoshihiro Watanabe, Norio Yoshida, and Haruyuki Nakano
  • Organizer: ICMARI
  • Int'l Joint Research
• [Presentation] Relativistic two-component theory by quasi-degenerate perturbation theory and its numerical assessment (2018)
  • Author(s): Kodai Kanemaru, Nobuki Inoue, Masahiro Higashi, Yoshihiro Watanabe, Haruyuki Nakano
  • Organizer: ICMARI
  • Int'l Joint Research
• [Presentation] Development of theoretical pKa prediction method (2018)
  • Author(s): Ryo Fujiki, Yukako Kasai, Yuki Seno, Toru Matsui, Yasuteru Shigeta, Norio Yoshida, Haruyuki Nakano
  • Organizer: ICMARI
  • Int'l Joint Research
• [Presentation] 3D-RISM法における溶媒分子配向を取り込んだ溶媒和自由エネルギー表式の評価 (2018)
  • Author(s): 谷本 勝一, 吉田 紀生, 中野 晴之
  • Organizer: 第12回分子科学討論会2018福岡
• [Presentation] Development of quantitative pKa prediction method based on quantum chemical method and statistical mechanics theory of liquids (2018)
  • Author(s): 藤木涼, 笠井友佳子, 妹尾裕貴, 松井亨, 重田育照, 吉田紀生, 中野晴之
  • Organizer: 凝縮系の理論化学2018
• [Presentation] 擬縮退摂動論に基づいた論2成分法の評価 (2018)
  • Author(s): 金丸恒大、井上頌基、渡邊祥弘、東雅大、中野晴之
  • Organizer: 凝縮系の理論化学2018
• [Presentation] Effect of the distributed partial wave expansion on the solvation free energy in the 3D-RISM theory (2018)
  • Author(s): Shoichi Tanimoto, Norio Yoshida, Haruyuki Nakano
  • Organizer: 255th ACS National Meeting & Exposition
  • Int'l Joint Research
• [Presentation] Development of a theoretical prediction method for pKa (2017)
  • Author(s): Ryo Fujiki, Yukako Kasai, Norio Yoshida, Toru Matsui, Yasuteru Shigeta, Haruyuki Nakano
  • Organizer: 「柔らかな分子系」国際シンポジウム（第5回公開シンポジウム）
  • Int'l Joint Research
• [Presentation] New solvation free energy expression for the three-dimensional reference interaction site model combined with the distributed partial wave expansion correction (2017)
  • Author(s): Shoichi Tanimoto, Norio YOSHIDA, Haruyuki NAKANO
  • Organizer: The 5th Symposium; Studying the Function of Soft Molecular Systems by the Concerted Use of Theory and Experiment
  • Int'l Joint Research
• [Presentation] 擬縮退摂動論に基づく相対論2成分法の定式化 (2017)
  • Author(s): 金丸恒大、井上頌基、渡邊祥弘、東雅大、中野晴之
  • Organizer: 第11回分子科学討論会
• [Presentation] 部分波展開法と3D-RISM法の結合による新たな溶媒和自由エネルギー計算式の提案 (2017)
  • Author(s): 谷本 勝一, 吉田 紀生, 中野 晴之
  • Organizer: 第11回分子科学討論会
• [Presentation] 部分波展開法と3D-RISM法の結合による新たな溶媒和自由エネルギー計算式の提案 (2017)
  • Author(s): Shoichi Tanimoto, Norio Yoshida, Haruyuki Nakano
  • Organizer: 第55回日本生物物理学会年会
• [Presentation] Ca2+依存性糖質結合モジュールの分子認識におけるCa2+の役割 (2016)
  • Author(s): 谷本勝一、東雅大、吉田紀生、中野晴之
  • Organizer: 第6回CSJ化学フェスタ2016
  • Place of Presentation: 東京
  • Year and Date: 2016-11-14
• [Presentation] MD及び3D-RSIM法によるCBM36の糖鎖結合に対する イオン種依存性の研究 (2016)
  • Author(s): 谷本勝一、東雅大、吉田紀生、中野晴之
  • Organizer: 第10回分子科学討論会
  • Place of Presentation: 神戸
  • Year and Date: 2016-09-13
• [Presentation] バイオマス利用に向けた酵素反応解析 (2015)
  • Author(s): 谷本勝一、東雅大、吉田紀生、中野晴之
  • Organizer: 第6回CMSI研究会
  • Place of Presentation: 東京大学本郷キャンパス、東京
  • Year and Date: 2015-12-08
• [Presentation] Role of calcium ion in molecular recognition process of calcium-dependent carbohydrate-binding module (2015)
  • Author(s): Shoichi Tanimoto, Masahiro Higashi, Norio Yoshida, Haruyuki Nakano
  • Organizer: The 4th International Symposium "Dynamical ordering of biomolecular systems for creation of integrated functions
  • Place of Presentation: 西新プラザ、福岡
  • Year and Date: 2015-11-23
  • Int'l Joint Research
• [Presentation] Role of calcium ion in molecular recognition process of calcium-dependent carbohydrate-binding module (2015)
  • Author(s): Norio Yoshida, Shoichi Tanimoto, Masahiro Higashi, Haruyuki Nakano
  • Organizer: 34rd International Conference on Solution Chemistry
  • Place of Presentation: Bohemia Technical University, Prague, Czech
  • Year and Date: 2015-08-31
  • Int'l Joint Research
• [Presentation] Role of calcium ion in molecular recognition process of calcium-dependent carbohydrate-binding module (2015)
  • Author(s): Shoichi Tanimoto, Masahiro Higashi, Norio Yoshida, Haruyuki Nakano
  • Organizer: 45th IUPAC World Chemistry Congress
  • Place of Presentation: BEXCO、釜山、大韓民国
  • Year and Date: 2015-08-10
  • Int'l Joint Research
• [Book] 基礎化学結合論（基幹教育シリーズ化学）第2版 (2015)
  • Author(s): 中野 晴之・原田 賢介・大橋 和彦・寺嵜 亨・関谷 博
  • Total Pages: 92
  • Publisher: 学術図書出版社
• [Remarks] Haruyuki Nakano
  • URL: http://ccl.scc.kyushu-u.ac.jp/~nakano/index_e.html