Organometallic and Cluster Chemistry in M+I40etalloenzymes with Reducing Activities

具有还原活性的 M I40 金属酶中的有机金属和簇化学

• 批准号: 18GS0207
• 负责人: TATSUMI Kazuyuki
• 金额: $ 370.66万
• 依托单位: Nagoya University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Creative Scientific Research
• 财政年份: 2006
• 资助国家: 日本
• 起止时间: 2006 至 2010
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-18GS0207/
• 关键词: 金属-硫黄クラスター; ニトロゲナーゼ; ヒドロゲナーゼ; 還元系金属酵素; 金属硫黄クラスター; 小分子活性化; アセチルCoA合成酵素; COデヒドロゲナーゼ; 有機金属化学; 金属酵素

Through the integration of coordination/organometallic chemistry, structural biology, and theoretical chemistry, we have undertaken the chemical study of reductases, the importance of which has been noticed recently in connection with social needs for energy and food. Our accomplishments in this program have exceeded our expectations, and we have achieved significant results that provide clues in understanding the enzymatic function of reductases at the cluster active sites. We have succeeded in synthesizing favourable models of the active-sites of nitrogenase and hydrogenase, and their physicochemical properties have been clarified, enabling us to study the chemistry of these enzymes. From the theoretical analysis of the newly synthesized dinuclear complex that activates dinitrogen, we revealed its reaction mechanism, which also provides us with important information concerning the reaction mechanisms of nitrogenase and hydrogenases. We have also discovered the novel[4Fe-3S] cluster in the structure of an oxygen-tolerant[NiFe] hydrogenase.

通过配位/有机金属化学、结构生物学和理论化学的结合，我们承担了还原酶的化学研究，其重要性最近被注意到与社会对能量和食物的需求有关。我们在这个项目中取得的成就超出了我们的预期，我们已经取得了重要的成果，为理解还原酶在簇活性部位的酶功能提供了线索。我们成功地合成了固氮酶和氢酶活性中心的有利模型，并阐明了它们的物理化学性质，使我们能够研究这些酶的化学。通过对新合成的激活氮素的双核配合物的理论分析，揭示了它的反应机理，也为固氮酶和氢酶的反应机理提供了重要的信息。我们还在耐氧[NiFe]氢酶的结构中发现了新的[4Fe-3S]簇。

项目成果

Dihydrogen activation by sulfido-bridged dinuclear Ru/Ge complexes: insight into the [NiFe] hydrogenase unready state.

• DOI: 10.1039/c0cc03391j
• 发表时间: 2011-01
• 期刊: Chemical communications
• 影响因子: 4.9
• 作者: Tsuyoshi Matsumoto;N. Itakura;Yukiko Nakaya;K. Tatsumi

Dinitrogen Cleavage by a Diniobium Tetrahydride Complex: Formation of a Nitride and Its Conversion to Imide Species

四氢化铌络合物的二氮裂解：氮化物的形成及其向酰亚胺物质的转化

• 发表时间: 2007
• 期刊: Angew. Chem., Int. Ed. 46
• 作者: F. Akagi;T. Matsuo;H. Kawaguchi
• 通讯作者: H. Kawaguchi

Model Chemistry of Acetyl-CoA Synthase and Methyl-CoM Reductase

乙酰辅酶A合酶和甲基辅酶M还原酶的模型化学

• 发表时间: 2010
• 作者: Garcon;F.;Sasaki;T.(7名中6番);Okkenhaug;K.;友納栄一;藤原誠,田中武雄,志水一平,松谷貴臣,日坂真樹,安江常夫,生田孝,田屋昌樹,木村吉秀,高井義造,川崎忠寛,市橋幹雄;Tsuyoshi Matsumoto
• 通讯作者: Tsuyoshi Matsumoto

Thiolate-bridged Dinuclear Fe(CO)_3-Ni, Fe(CO)_2(CN)_2-Ni, and Fe(CO)(CN)_2-Ni" Complexes as Structural Models of the [NiFe] Hydrogenase Active Site

硫醇桥联双核 Fe(CO)_3-Ni、Fe(CO)_2(CN)_2-Ni 和 Fe(CO)(CN)_2-Ni" 配合物作为 [NiFe] 氢化酶活性位点的结构模型

• 发表时间: 2010
• 作者: Kazuyuki Tatsumi;Yasuhiro Ohki;Zilong Li;Soichiro Tanino
• 通讯作者: Soichiro Tanino

Activation of H_2 by S-donor/O-donor-bridged Heterodunuclear Complexes relevant to the Function of [NiFe] Hydrogenase

S-供体/O-供体桥接异双核复合物对 H_2 的激活与 [NiFe] 氢化酶的功能相关

• 发表时间: 2009
• 作者: K. Tatsumi;T. Matsumoto;Y. Ohki
• 通讯作者: Y. Ohki