Construction and regulation of the reactivity of metalloenzyme models containing hydrophobic micro-space

• Project/Area Number: 26410072
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Research Field: Inorganic chemistry
• Research Institution: Osaka University
• Principal Investigator: OKAMURA Taka-aki 大阪大学, 理学研究科, 准教授 (90252569)
• Project Period (FY): 2014-04-01 – 2017-03-31
• Project Status: Completed (Fiscal Year 2016)
• Budget Amount: ¥5,070,000 (Direct Cost: ¥3,900,000、Indirect Cost: ¥1,170,000); Fiscal Year 2016: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000); Fiscal Year 2015: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000); Fiscal Year 2014: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000)
• Keywords: 生物無機化学 / 酵素 / モデル / 疎水空間 / 水素結合 / 鉄－硫黄クラスター / モリブデン / マグネシウム / ニトロゲナーゼ

Outline of Final Research Achievements

Model complexes of metalloproteins containing “hydrophobic micro-space” were synthesized and their properties were investigated. Molybdenum- and tungsten-enzyme models showed enhancement of the oxygen-atom-transfer reaction of trimethylamine N-oxide or dimethyl sulfoxide by efficient uptake of the substrate into the active site in hydrophobic environment．Modeling of the hydrophobic microenvironment of water-soluble molybdenum enzyme in an aqueous micellar solution was successfully achieved. Unexpected reaction promoted by hydrogen bond in nonpolar solvents was observed. The regulation the hydrolytic activity of magnesium-containing phosphatase models by switching the mode of NH…O hydrogen bond was accomplished in nonpolar solvents. The combination of the hydrophobic space and NH…S hydrogen bonds also regulated the electronic structure of [4Fe4S] cluster in a ferredoxin model.

Research Products

• [Journal Article] Post-polymerization modification of the side chain in optically active polymers by thiol-ene reaction (2017)
  • Author(s): N. Kanbayashi, S. Miyamoto, Y. Ishido, T. Okamura, and K. Onitsuka
  • Journal Title: Polym. Chem. Volume: 8 Issue: 6 Pages: 985-994
  • DOI: 10.1039/c6py01946c
  • Peer Reviewed
• [Journal Article] Snapshot of Oxidation of Thiolate by Diiodine: Stabilization of Intermediate by NH···S Hydrogen Bonds (2017)
  • Author(s): T. Okamura, T. Kaga, S. Yamashita, R. Furuya, and K. Onitsuka
  • Journal Title: J. Org. Chem. Volume: 82 Issue: 4 Pages: 2187-2192
  • DOI: 10.1021/acs.joc.7b00160
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Enantio- and diastereoselective polymerization: asymmetric allylic alkylation catalyzed by a planar-chiral Cp'Ru complex (2016)
  • Author(s): Kanbayashi, N.; Hosoda, K.; Okamura, T.; Aoshima, S.; Onitsuka, K.
  • Journal Title: Polym. Chem. Volume: 7 Issue: 22 Pages: 3691-3699
  • DOI: 10.1039/c6py00484a
  • Peer Reviewed
• [Journal Article] Unexpected Reaction Promoted by NH+···O=Mo Hydrogen Bonds in Nonpolar Solvents (2016)
  • Author(s): T. Okamura, T. Yamada, Y. Hasenaka, S. Yamashita, and K. Onitsuka
  • Journal Title: Eur. J. Inorg. Chem. Volume: 2016 Issue: 18 Pages: 2952-2961
  • DOI: 10.1002/ejic.201600081
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Comparative studies on the contribution of NH···S hydrogen bonds in tungsten and molybdenum benzenedithiolate complexes (2016)
  • Author(s): T. Okamura, Y. Omi, Y. Hirano, and K. Onitsuka
  • Journal Title: Dalton Trans. Volume: 45 Issue: 39 Pages: 15651-15659
  • DOI: 10.1039/c6dt02250b
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Synthesis, structure and sorption property of metal complexes with mixed multicarboxylate and imidazole-containing ligands (2016)
  • Author(s): L. Luo, P. Wang, Q. Liu, T. Okamura, G.-C. Lv, Y. Lu, and W.-Y. Sun
  • Journal Title: Microporous Mesoporous Mater. Volume: 219 Pages: 199-208
  • DOI: 10.1016/j.micromeso.2015.08.009
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Planar-Chiral Cyclopentadienyl-Ruthenium-Catalyzed Regio- and Enantioselective Asymmetric Allylic Alkylation of Silyl Enolates under Unusually Mild Conditions (2016)
  • Author(s): N. Kanbayashi, A. Yamazawa, K. Takii, T. Okamura, and K. Onitsuka
  • Journal Title: Adv. Synth. Catal. Volume: 358 Issue: 4 Pages: 555-560
  • DOI: 10.1002/adsc.201500970
  • Peer Reviewed
• [Journal Article] Enantio- and diastereoselective asymmetric allylic alkylation catalyzed by a planar-chiral cyclopentadienyl ruthenium complex (2015)
  • Author(s): N. Kanbayashi, K. Hosoda, M. Kato, K. Takii, T. Okamura, and K. Onitsuka
  • Journal Title: Chem. Commun. Volume: 51 Issue: 54 Pages: 10895-10898
  • DOI: 10.1039/c5cc02414e
  • Peer Reviewed
• [Journal Article] Modeling of the hydrophobic microenvironment of water-soluble molybdoenzymes in an aqueous micellar solution (2015)
  • Author(s): Y. Hasenaka, T. Okamura, and K. Onitsuka
  • Journal Title: Dalton Trans. Volume: 44 Issue: 28 Pages: 12618-12622
  • DOI: 10.1039/c5dt01112d
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Significant differences of monooxotungsten(IV) and dioxotungsten(VI) benzenedithiolates containing two intramolecular NH⋯S hydrogen bonds from molybdenum analogues (2015)
  • Author(s): T. Okamura, Y. Omi, M. Fujii, M. Tatsumi, and K. Onitsuka
  • Journal Title: Dalton Trans. Volume: 44 Issue: 41 Pages: 18090-18100
  • DOI: 10.1039/c5dt03278d
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] New Synthetic Approach for Optically Active Polymer Bearing Chiral Cyclic Architecture: Combination of Asymmetric Allylic Amidation and Ring-Closing Metathesis Reaction (2015)
  • Author(s): N. Kanbayashi, T. Okamura, and K. Onitsuka
  • Journal Title: Macromolecules Volume: 48 Issue: 23 Pages: 8437-8444
  • DOI: 10.1021/acs.macromol.5b02067
  • Peer Reviewed
• [Journal Article] Efficient uptake of dimethyl sulfoxide by the desoxomolybdenum(IV) dithiolate complex containing bulky hydrophobic groups (2015)
  • Author(s): Y. Hasenaka, T. Okamura, and K. Onitsuka
  • Journal Title: Dalton Trans. Volume: 44 Issue: 13 Pages: 6260-6267
  • DOI: 10.1039/c5dt00075k
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Synthesis and structures of soluble magnesium and zinc carboxylates containing intramolecular NH…O hydrogen bonds in nonpolar solvents (2015)
  • Author(s): T. Okamura, R. Furuya, and K. Onitsuka
  • Journal Title: Dalton Trans. Volume: 44 Issue: 16 Pages: 7512-7523
  • DOI: 10.1039/c5dt00053j
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Behavior of anionic molybdenum(IV, VI) and tungsten(IV, VI) complexes containing bulky hydrophobic dithiolate ligands and intramolecular NH…S hydrogen bonds in nonpolar solvents (2014)
  • Author(s): Y. Hasenaka, T. Okamura, M. Tatsumi, N. Inazumi, and K. Onitsuka
  • Journal Title: Dalton Trans. Volume: 43 Issue: 41 Pages: 15491-15502
  • DOI: 10.1039/c4dt01646g
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Regulation of the Hydrolytic Activity of Mg2+-Dependent Phosphatase Models by Intramolecular NH…O Hydrogen Bonds (2014)
  • Author(s): T. Okamura, R. Furuya, and K. Onitsuka
  • Journal Title: J. Am. Chem. Soc. Volume: 136 Issue: 42 Pages: 14639-14641
  • DOI: 10.1021/ja509006x
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] New Method for Asymmetric Polymerization: Asymmetric Allylic Substitution Catalyzed by a Planar-Chiral Ruthenium Complex (2014)
  • Author(s): N. Kanbayashi, T. Okamura, and K. Onitsuka
  • Journal Title: Macromolecules Volume: 47 Issue: 13 Pages: 4178-4185
  • DOI: 10.1021/ma5008623
  • Peer Reviewed
• [Presentation] 非極性溶媒に可溶な亜硫酸オキシダーゼモデル錯体の合成 (2017)
  • Author(s): 加賀 俊久、岡村 高明、鬼塚 清孝
  • Organizer: 日本化学会第97春季年会
  • Place of Presentation: 慶應義塾大学日吉キャンパス（神奈川県横浜市）
  • Year and Date: 2017-03-16
• [Presentation] かさ高いアシルアミノ基を持つアレーンチオラートが配位した鉄-硫黄クラスターの変換反応 (2016)
  • Author(s): 中森 祐未、岡村 高明・鬼塚 清孝
  • Organizer: 錯体化学会第66回討論会
  • Place of Presentation: 福岡大学七隈キャンパス（福岡市城南区）
  • Year and Date: 2016-09-11
• [Presentation] かさ高いアシルアミノ基を持つアレーンチオラート配位子に覆われた[4Fe-4S]クラスターの溶液構造と反応性 (2016)
  • Author(s): 中森 祐未、岡村 高明、鬼塚 清孝
  • Organizer: 日本化学会第96春季年会
  • Place of Presentation: 同志社大学京田辺キャンパス（京都府・京田辺市）
  • Year and Date: 2016-03-26
• [Presentation] 非常にかさ高いアシルアミノ基を持つアレーンチオラート配位子を用いた[4Fe-4S]クラスターの合成 (2015)
  • Author(s): 中森 祐未、山下 聡史、岡村 高明、鬼塚 清孝
  • Organizer: 錯体化学会第65回討論会
  • Place of Presentation: 奈良女子大学（奈良県・奈良市）
  • Year and Date: 2015-09-22
• [Presentation] 水溶性金属酵素のモデル化を目指した微小疎水空間を有するミセル型モリブデン錯体の合成 (2014)
  • Author(s): 長谷中祐輝、岡村高明、鬼塚清孝
  • Organizer: 第63回高分子討論会
  • Place of Presentation: 長崎大学文教キャンパス（長崎市）
  • Year and Date: 2014-09-25
• [Presentation] 非常に嵩高いアシルミノ基を持つビス(アレーンチオラート)金属錯体の合成と構造 (2014)
  • Author(s): 山下聡史、古屋遼介、岡村高明、鬼塚清孝
  • Organizer: 錯体化学会第64回討論会
  • Place of Presentation: 中央大学後楽園キャンパス（東京都文京区）
  • Year and Date: 2014-09-19
• [Presentation] ミセル中微小疎水空間を有するモリブデン錯体による水溶性金属酵素のモデル化 (2014)
  • Author(s): 長谷中祐輝、岡村高明、鬼塚清孝
  • Organizer: 第63回高分子年次大会
  • Place of Presentation: 名古屋国際会議場（愛知県名古屋市）
  • Year and Date: 2014-05-29
• [Book] Encyclopedia of Polymeric Nanomaterials (2015)
  • Author(s): T. Okamura
  • Total Pages: 2617
  • Publisher: Springer-Verlag, Berlin Heidelberg