computational study of enzymatic reaction and metal active species

• Project/Area Number: 25410071
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Research Field: Inorganic chemistry
• Research Institution: Kyushu University
• Principal Investigator: SHIOTA YOSHIHITO 九州大学, 先導物質化学研究所, 准教授 (70335991)
• Project Period (FY): 2013-04-01 – 2016-03-31
• Project Status: Completed (Fiscal Year 2015)
• Budget Amount: ¥5,330,000 (Direct Cost: ¥4,100,000、Indirect Cost: ¥1,230,000); Fiscal Year 2015: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000); Fiscal Year 2014: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000); Fiscal Year 2013: ¥1,820,000 (Direct Cost: ¥1,400,000、Indirect Cost: ¥420,000)
• Keywords: 触媒 / 量子化学計算 / 遷移状態 / 理論計算 / 量子化学 / 反応機構解析 / インド / 中国 / 金属錯体 / 酸素活性化 / 電子状態

Outline of Final Research Achievements

In general physical insight based on the best experimental method is not enough. Thus, we performed theoretical calculations to help better understanding of catalytic systems. In our research we discuss the catalytic mechanism for enzymatic reactions from a theoretical viewpoint. Our computational study suggests the metallic active sight of enzymatic reactions has a interesting electronic structure to activate inert substrates. We determine possible reaction pathway that involves transition states and intermediate.

Research Products

• [Journal Article] Computational Study of Cyclobutane-1,3-diylidene Dicarbenes: Ground-State Spin Multiplicity and New Strategy Toward the Synthesis of Bicyclo[1.1.0]but-1(3)-enes (2016)
  • Author(s): Fujita, Y.; Abe, M.; Shiota, Y.; Suzuki, T.; Yoshizawa, K
  • Journal Title: Bull. Chem. Soc. Jpn Volume: 89
  • NAID: 130005253040
  • Peer Reviewed
• [Journal Article] Formation and High Reactivity of the anti-Dioxo Form of High- Spin m-Oxodioxodiiron(IV) as the Active Species That Cleaves Strong C (2016)
  • Author(s): Masahito Kodera,* Shin Ishiga, Tomokazu Tsuji, Katsutoshi Sakurai, Yutaka Hitomi, Yoshihito Shiota, P. K. Sajith, Kazunari Yoshizawa, Kaoru Mieda, and Takashi Ogura
  • Journal Title: Chemistry A European Journal Volume: 17 Issue: 17 Pages: 1-14
  • DOI: 10.1002/chem.201600048
  • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] Possible Peroxo State of the Dicopper Site of Particulate Methane Monooxygenase from Combined Quantum Mechanics and Molecular Mechanics Calculations (2016)
  • Author(s): Itoyama, S.; Doitomi, K.; Kamachi, T.; Shiota, Y.; Yoshizawa, K.
  • Journal Title: Inorg. Chem Volume: 55 Pages: 2771-2775
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Synthesis and Structure of a Water-soluble μ-η1:η1-N2 Dinuclear RuII Complex with a Polyamine Ligand (2016)
  • Author(s): K. Yoshimoto, T. Yatabe, T. Matsumoto, A. Robertson, H. Nakai, H. Tanaka, T. Kamachi, Y. Shiota, K. Yoshizawa, K. Asazawa, H. Tanaka, Seiji Ogo
  • Journal Title: Chemistry Letters Volume: 45 Issue: 2 Pages: 149-151
  • DOI: 10.1246/cl.151004
  • NAID: 130005124715
  • Peer Reviewed / Open Access
• [Journal Article] A New Family of Anionic FeIII Spin Crossover Complexes Featuring a Weak-field N2O4 Coordination Octahedron (2016)
  • Author(s): Kazuyuki Takahashi, Kiko Kawamukai, Mitsunibu Okai, Tomoyuki Mochida, Takahiro Sakurai, Hitoshi Ohta, Takashi Yamamoto, Yasuaki Einaga, Yoshihito Shiota, Kazunari Yoshizawa
  • Journal Title: Chem. Eur. J. Volume: 22 Issue: 4 Pages: 1253-1257
  • DOI: 10.1002/chem.201504883
  • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] Homogeneous Photocatalytic Water Oxidation with a Dinuclear CoIII-Pyridylmethyl amine Complex (2016)
  • Author(s): T. Ishizuka, A. Watanabe, H. Kotani, D. Hong, K. Satonaka, T. Wada, Y. Shiota, K. Yoshizawa, K. Ohara, K. Yamaguchi, S. Kato, S. Fukuzumi, T. Kojima
  • Journal Title: Inorganic Chemistry Volume: 55 Issue: 3 Pages: 1154-1164
  • DOI: 10.1021/acs.inorgchem.5b02336
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Heterometallic FeIII/K coordination polymer with a wide thermal hysteretic spin transition around room temperature (2016)
  • Author(s): Kang, S.; Shiota, Y.; Kariyazaki, A.; Kanegawa, S.; Yoshizawa, K.; Sato, O.
  • Journal Title: Chem. Eur. J. Volume: 22 Issue: 2 Pages: 532-538
  • DOI: 10.1002/chem.201503392
  • Peer Reviewed
• [Journal Article] Persistent four-coordinate iron-centered radical stabilized by π-donation (2016)
  • Author(s): Yusuke Sunada, Shintaro Ishida, Fumiya Hirakawa, Yoshihito Shiota, Kazunari Yoshizawa, Shinji Kanegawa, Osamu Sato, Hideo
  • Journal Title: Chem. Sci. Volume: 7 Issue: 1 Pages: 191-198
  • DOI: 10.1039/c5sc02601f
  • Peer Reviewed / Open Access
• [Journal Article] Assembling an alkyl rotor to access abrupt and reversible crystalline deformation of a cobalt(II) complex (2015)
  • Author(s): S.-Q. Su, T. Kamachi, Z.-S. Yao, Y.-G. Huang, Y. Shiota, K. Yoshizawa, N. Azuma, Y. Miyazaki, M. Nakano, G. Maruta, S. Takeda, S. Kang, S. Kanegawa, O. Sato
  • Journal Title: Nature Communications Volume: 6 Issue: 1 Pages: 8810-8810
  • DOI: 10.1038/ncomms9810
  • Peer Reviewed / Open Access
• [Journal Article] Redox Noninnocent Behavior of Tris(2-pyridylmethyl)amine Bound to a Lewis Acidic Rh(III) Ion Induced by C-H Deprotonation (2015)
  • Author(s): H. Kotani, T. Sugiyama, T. Ishizuka, Y. Shiota, K. Yoshizawa, T. Kojima
  • Journal Title: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY Volume: 137 Issue: 35 Pages: 11222-11225
  • DOI: 10.1021/jacs.5b06237
  • Peer Reviewed / Open Access
• [Journal Article] cis-1,2-Aminohydroxylation of Alkenes Involving a Catalytic Cycle of Osmium(III) and Osmium(V) Centers: Os(V)(O)(NHTs) Active Oxidant with a Macrocyclic Tetradentate Ligand (2015)
  • Author(s): Hideki Sugimoto, Akine Mikami, Kenichiro Kai, P. K. Sajith, Yoshihito Shiota, Kazunari Yoshizawa, Kaori Asano, Takeyuki Suzuki, and Shinobu Itoh
  • Journal Title: Inorg. Chem. Volume: 54 Issue: 14 Pages: 7073-7082
  • DOI: 10.1021/acs.inorgchem.5b01083
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Proton-Assisted Mechanism of NO Reduction on a Dinuclear Ruthenium Complex (2015)
  • Author(s): T. Suzuki, H. Tanaka, Y. Shiota, P. K. Sajith, Y. Arikawa, and K. Yoshizawa
  • Journal Title: Inorg. Chem. Volume: 54 Issue: 15 Pages: 7181-7191
  • DOI: 10.1021/acs.inorgchem.5b00394
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Mechanistic Study of Methanol Oxidation by RuIV-oxo complexes (2015)
  • Author(s): Y. Shiota, S. Takahashi, S. Ohzu, T. Ishizuka, T. Kojima, K. Yoshizawa
  • Journal Title: Journal of Porphyrins and Phthalocyanines Volume: 19 Issue: 01-03 Pages: 417-427
  • DOI: 10.1142/s1088424615500285
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Controlling the redox properties of a pyrroloquinolinequinone (PQQ) derivative in a ruthenium(II) coordination sphere (2015)
  • Author(s): Hiroumi Mitome, Tomoya Ishizuka, Yoshihito Shiota, Kazunari Yoshizawa, Takahiko Kojima
  • Journal Title: Dalton Transactions Volume: 44 Issue: 7 Pages: 3151-3158
  • DOI: 10.1039/c4dt03358b
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Formation and Characterization of a Reactive Chromium(V)-Oxo Complex: A Mechanistic Insight into Hydrogen-Atom Transfer Reactions (2015)
  • Author(s): H. Kotani, S. Kaida, T. Ishizuka, M. Sakaguchi, T. Ogura, Y. Shiota, K. Yoshizawa, T. Kojima
  • Journal Title: Chemical Science Volume: 6 Issue: 2 Pages: 945-955
  • DOI: 10.1039/c4sc02285h
  • NAID: 120007130469
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] A Ferromagnetically Coupled Fe42 Cyanide-Bridged Nanocage (2015)
  • Author(s): S. Kang, H. Zheng, T. Liu, K. Hamachi, S. Kanegawa, K. Sugimoto, Y. Shiota, S. Hayami, M. Mito, T. Nakamura, M. Nakano, M. Baker, H. Nojiri, K. Yoshizawa, C. Duan, and O. Sato
  • Journal Title: Nature Communications Volume: 6 Issue: 1 Pages: 5955-5955
  • DOI: 10.1038/ncomms6955
  • Peer Reviewed / Open Access
• [Journal Article] Gas-phase acidity of 1,1-bis(trifluoromethanesulfonyl)propane derivatives and related compounds: Experimental and theoretical studies (2015)
  • Author(s): Zang, M.; Sonoda, T.; Shiota, Y.; Mishima, M.; Yanai, H.; Fujita, M.; Taguchi, T.
  • Journal Title: J. Phys. Org. Chem. Volume: 28 Pages: 181-186
  • Peer Reviewed
• [Journal Article] Hydrogen Atom Abstraction Reactions Independent of C-H Bond Dissociation Energies of Organic Substrates in Water: Significance of Oxidant-Substrate Adduct Formation (2014)
  • Author(s): T. Ishizuka, S. Ohzu, H. Kotani, Y. Shiota, K. Yoshizawa, T. Kojima
  • Journal Title: Chem. Sci. Volume: 5 Issue: 4 Pages: 1429-1436
  • DOI: 10.1039/c3sc53002g
  • Peer Reviewed
• [Journal Article] Roles of Carboxylate Donors in O-O Bond Scission of Peroxodiiron(III) to High-Spin Oxodiiron(IV) with a New Carboxylate-Containing Dinucleating Ligand (2014)
  • Author(s): M. Kodera, T. Tsuji, T. Yasunaga, Y. Kawahara, T. Hirano, Y. Hitomi, T. Nomura, T. Ogura, Y. Kobayashi, Sajith P. K., Y. Shiota, and K. Yoshizawa
  • Journal Title: Chem. Sci. Volume: 5 Issue: 6 Pages: 2282-2292
  • DOI: 10.1039/c3sc51541a
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] 309."Role of Acidic Proton in the Decomposition of NO over Dimeric Cu(I) Active Sites in Cu-ZSM-5 Catalyst: A QM/MM Study (2014)
  • Author(s): Sajith P. K., Y. Shiota, and K. Yoshizawa
  • Journal Title: ACS Catal. Volume: 4 Issue: 6 Pages: 2075-2085
  • DOI: 10.1021/cs500223z
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Binding of Scandium Ions to Metalloporphyrin–Flavin Complexes for Long-Lived Charge Separation (2014)
  • Author(s): T. Kojima, R. Kobayashi, T. Ishizuka, S. Yamakawa, H. Kotani, T. Nakanishi, K. Ohkubo, Y. Shiota, K. Yoshizawa, and S. Fukuzumi
  • Journal Title: Chem. Eur. J. Volume: 20 Issue: 47 Pages: 15518-15532
  • DOI: 10.1002/chem.201403960
  • NAID: 120007136507
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Molecular Motor-driven Abrupt Anisotropic Shape Change in a Single Crystal of a Ni Complex (2014)
  • Author(s): Z.-S. Yao, M. Mito, T. Kamachi, Y. Shiota, K. Yoshizawa, N. Azuma, Y. Miyazaki, K. Takahashi, K. Zhang, T. Nakanishi, S. Kang, S. Kanegawa, O. Sato
  • Journal Title: Nature Chem. Volume: 6 Issue: 12 Pages: 1079-1083
  • DOI: 10.1038/nchem.2092
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Tetranuclear Ruthenium(II) Complex with a Dinucleating Ligand Forming Multi-Mixed-Valence States (2014)
  • Author(s): S. Ohzu, T. Ishizuka, H. Kotani, Y. Shiota, K. Yoshizawa, T. Kojima
  • Journal Title: Inorganic Chemistry Volume: 53 Issue: 24 Pages: 12677-12679
  • DOI: 10.1021/ic502422u
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Light-induced Spin-crossover Actuated Single-chain Magnet (2013)
  • Author(s): T. Liu, H. Zheng, S. Kang, Y. Shiota, S. Hayami, M. Mito, O. Sato, K. Yoshizawa, S. Kanegawa, and C. Duan
  • Journal Title: Nature Commun. Volume: 4 Issue: 1 Pages: 2826-2826
  • DOI: 10.1038/ncomms3826
  • Peer Reviewed
• [Journal Article] Multi-Step Spin Crossover Accompanied by Symmetry Breaking in an Fe(III) Complex: Crystallographic Evidence and DFT Studies (2013)
  • Author(s): Z.-Y. Li, J.-W. Dai, Y. Shiota, K. Yoshizawa, S. Kanegawa, and O. Sato
  • Journal Title: Chem. Eur. J. Volume: 19 Issue: 39 Pages: 12948-12952
  • DOI: 10.1002/chem.201302272
  • Peer Reviewed
• [Journal Article] Computational Prediction for Singlet- and Triplet-Transition Energies of Charge-Transfer Compounds (2013)
  • Author(s): S. Huang, Q. Zhang, Y. Shiota, T. Nakagawa, H. Kuwabara, K. Yoshizawa, and C. Adachi
  • Journal Title: J. Chem. Theor. Comp. Volume: 9 Issue: 9 Pages: 3872-3877
  • DOI: 10.1021/ct400415r
  • Peer Reviewed
• [Journal Article] Role of Tyrosine Residue in Methane Activation at the Dicopper Site of pMMO: A DFT Study (2013)
  • Author(s): Y. Shiota, G. Juhasz, K. Yoshizawa
  • Journal Title: Inorg. Chem. Volume: 52 Issue: 14 Pages: 7907-7917
  • DOI: 10.1021/ic400417d
  • Peer Reviewed
• [Journal Article] Multiply-Fused Porphyrins－Effects of Extended π-Conjugation on the Optical and Electrochemical Properties (2013)
  • Author(s): T. Ishizuka, Y. Saegusa, Y. Shiota, K. Ohtake, K. Yoshizawa, and T. Kojima
  • Journal Title: Chem. Commun. Volume: 49 Issue: 53 Pages: 5939-5941
  • DOI: 10.1039/c3cc42831a
  • NAID: 120007136573
  • Peer Reviewed
• [Journal Article] Complete Photochromic Structural Change of Ruthenium(II)-Diimine Complexes Based on the Control of the Excited States by Metallation (2013)
  • Author(s): T. Sawaki, T. Ishizuka, M. Kawano, Y. Shiota, K. Yoshizawa, and T. Kojima
  • Journal Title: Chem. Eur. J. Volume: 19 Issue: 27 Pages: 8978-8990
  • DOI: 10.1002/chem.201300437
  • Peer Reviewed
• [Journal Article] Heteronuclear RuIIAgI Complexes Having a Pyrroloquinolinequinone (PQQ) Derivative as a Bridging Ligand (2013)
  • Author(s): H. Mitome, T. Ishizuka, Y. Shiota, K. Yoshizawa,T. Kojima
  • Journal Title: Inorg. Chem. Volume: 52 Issue: 5 Pages: 2274-2276
  • DOI: 10.1021/ic302617b
  • Peer Reviewed
• [Journal Article] Thiophene-Fused Bisdehydro[12]annulene That Undergoes Transannular Alkyne Cycloaddition by Either Light or Heat (2013)
  • Author(s): A. Fukazawa, H. Oshima, Y. Shiota, S. Takahashi, K. Yoshizawa, S. Yamaguchi
  • Journal Title: J. Am. Chem. Soc. Volume: 135 Issue: 5 Pages: 1731-1734
  • DOI: 10.1021/ja3126849
  • Peer Reviewed
• [Journal Article] DFT Study of the Mechanism for Methane Hydroxylation by Solube Methane Monooxygenase (sMMO) : Effects of Oxidation State, Spin State, and Coordinaton Number (2013)
  • Author(s): Huang Shu-Ping, et al
  • Journal Title: Dalton Trans. Volume: 42 Issue: 4 Pages: 1011-1023
  • DOI: 10.1039/c2dt31304a
  • Peer Reviewed
• [Presentation] 塩田淑仁 糸山修平 吉澤一成 (2016)
  • Author(s): 銅二核活性点におけるメタン活性化に関する理論的研究
  • Organizer: 第９６春季年会
  • Place of Presentation: 京都
  • Year and Date: 2016-03-24
• [Presentation] Mechanistic study of methanol oxidation by RuIV–oxo complexes (2015)
  • Author(s): 塩田淑仁 髙橋翔也 小島隆彦 吉澤一成
  • Organizer: pacifichem2015
  • Place of Presentation: ホノルル（米国）
  • Year and Date: 2015-12-15
  • Int'l Joint Research
• [Presentation] Ruオキソ錯体によるメタノール酸化反応に関する理論的研究 (2015)
  • Author(s): 塩田淑仁 髙橋翔也 小島隆彦 吉澤一成
  • Organizer: コンピュータ化学会２０１５秋季年会
  • Place of Presentation: 函館
  • Year and Date: 2015-10-30
• [Presentation] 膜結合型メタンモノオキシゲナーゼのペルオキソ状態に関する理論的考察 (2015)
  • Author(s): 塩田淑仁 糸山修平 土井富一城 蒲池高志 吉澤一成
  • Organizer: 第９回分子科学討論会
  • Place of Presentation: 東京
  • Year and Date: 2015-09-16
• [Presentation] Theoretical Study of Methanol Oxidation by RuIV-oxo Complexes (2015)
  • Author(s): 塩田淑仁 髙橋翔也 小島隆彦 吉澤一成
  • Organizer: The 15th ICQC, 北京
  • Place of Presentation: 北京(中国)
  • Year and Date: 2015-06-08
  • Int'l Joint Research
• [Presentation] Ruオキソ錯体によるメタノール酸化反応に関する理論的研究 (2015)
  • Author(s): 塩田淑仁 髙橋翔也 小島隆彦 吉澤一成
  • Organizer: 理論化学討論会２０１５
  • Place of Presentation: 大阪
  • Year and Date: 2015-05-20
• [Presentation] スピンクロスオーバー錯体におけるポテンシャルエネルギー曲面の 交差に関する理論的研究 (2014)
  • Author(s): 塩田淑仁
  • Organizer: 日本化学会
  • Place of Presentation: 名古屋市
• [Presentation] pMMOによるメタン活性化に関する理論的研究 (2013)
  • Author(s): 塩田淑仁
  • Organizer: 日本コンピュータ化学会
  • Place of Presentation: 福岡市
• [Presentation] スピンクロスオーバー錯体におけるポテンシャルエネルギー曲面の 交差に関する理論的研究 (2013)
  • Author(s): 塩田淑仁
  • Organizer: 分子科学会
  • Place of Presentation: 京都市
• [Book] 錯体化学選書１０ 金属錯体の量子 計算化学 (2014)
  • Author(s): 山口兆 編
  • Total Pages: 529
  • Publisher: 三共出版
• [Remarks] 研究業績
  • URL: http://trout.scc.kyushu-u.ac.jp/yoshizawaJ/pagesJ/publicationsJ.html
• [Remarks] ホームページ
  • URL: http://trout.scc.kyushu-u.ac.jp/yoshizawaJ/shiota.html
• [Remarks] 研究業績
  • URL: http://trout.scc.kyushu-u.ac.jp/yoshizawaJ/pagesJ/publicationsJ.html