Model Complexes for Non-Redox Active Metalloenzymes(Structural and Functional Model Complexes for Non-Redox Active Metalloenzymes Involving Dinuclear Metal Centers)

非氧化还原活性金属酶的模型配合物(涉及双核金属中心的非氧化还原活性金属酶的结构和功能模型配合物)

• 批准号: 09044103
• 负责人: TANASE Tomoaki
• 金额: $ 2.24万
• 依托单位: Nara Women's University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for international Scientific Research
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1998
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09044103/
• 关键词: metalloenzymes; dimetal centers; biomimetic models; carboxylate bridges; carbohydrates; phosphate esters; hydrolysis; isomerization; 核酸

1. Carboxylate-bridged dinuclear metal centers containing non-redox active ions such as Mg^<2+>, Ca^<2+>, Mn^<2+> and Zn^<2+> arc an important bioinorganic motif occurring at the active centers of phosphate ester-processing metalloenzymes. We have systematically studied non-redox active dimetallic complexes by utilizing a biscarboxylate ligand, m-xylylendiamine bis(Kemps triacid imide) (H^2XDK). Zinc-containing homo- and heterodimetallic complexes with diphenylphosphate, [ZnM(XDK){ mu-eta^<12>-(PhO)_2O_2}{eta^1-(PhO_2PO_2}(CH_3OH)_2(H20)]( M = Zn, Co), were prepared in the reactions of [ZnM(XDK)(acac)_2(CH_3OH)_2]with (PhO)_2PO_2H_2. Analogous Mg_2, Mn_2, and Ca_2 complexes. [M_2(XDK){mueta_2-(PhO)_2PO_2){mu_1-(PhO)_2PO_2}(CH_3OH)m(H_2O)n] ( M = Mg, m = 3, n = 1 ; M = Mn, m = n = 2 ; M = Ca, m = 3, n = 1), were obtained. Complexes were characterized by X-ray crystallography, consisting of an asymmetric dimetallic center bridged by XDK and (PhO)_2P0_2, . Variable-temperature ^<3l>p{^1H} … More NMR experiments demonstrated that the terminally coordinated phosphate ester ligand dissociates from the dimetallic center in solution and exchanges with the bridging one. The phosphate ester exchange rate increases in the order Ca^<2+> > Zn^<2+> > Mg^<2+>, providing useful information for understanding phosphate ester-processing metalloenzymes. New dinuclear complexes of Co(II), Cu(I), and Cu(II) were also prepared and their biorelevant reactions were examined.2. Interactions of carbohydrates with metal ions are vital in biological systems. We have studied the synthesis, characterization, and reactivities of various transition metal complexes with sugar ligands. The mononuclear Co(II) complexes with a heptadentate N-glycoside ligand, [Co(II)((L-Rha or D-Man)_3-tren)]^<2+> showed a molecular recognition property for SO^<2-> anton through chiral inversion of the metal center. Peroxo-bridged dinuclear cobalt (III) comp1ex, [((D-Glc, or Mal)_2-tren)Co(mu-02)Co((D-Glc, or Mal)_2-tren)]X3 (X = Cl, Br), were prepared and characterized by X-ray crystallography to consist of two octahedral Co(III) ions bridged by peroxide. The dinuclear structure is further supported by some hydrogen bonds between the sugar moieties. Interestingly, almost reversible dioxygen binding through the mu-peroxo dimer was monitored by electronic absorption spectral changes upon UV irradiation ; Novel Mn(II)Mn(III)Mn(II) trinuclear complexes with mannopyranose-bridging uri'rs were prepared and characterized by X-ray crystallography. Futhermore, many attempts were made to form biomimetic dimetal centers with tacn-anchored sugar moieties. Less

1.含有非氧化还原活性离子（例如Mg^<2+>、Ca^<2+>、Mn^<2+>和Zn^<2+>）的羧酸桥双核金属中心是存在于磷酸酯加工金属酶活性中心的重要生物无机基序。我们利用双羧酸盐配体间二甲苯二胺双(肯普斯三酰亚胺) (H^2XDK) 系统地研究了非氧化还原活性双金属配合物。通过以下反应制备了含锌同二金属和异二金属与磷酸二苯酯的配合物，[ZnM(XDK){ mu-eta^<12>-(PhO)_2O_2}{eta^1-(PhO_2PO_2}(CH_3OH)_2(H2O)](M = Zn, Co) [ZnM(XDK)(acac)_2(CH_3OH)_2]与(PhO)_2PO_2H_2。类似的 Mg_2、Mn_2 和 Ca_2 配合物。 获得[M_2(XDK){mueta_2-(PhO)_2PO_2){mu_1-(PhO)_2PO_2}(CH_3OH)m(H_2O)n](M = Mg，m = 3，n = 1；M = Mn，m = n = 2；M = Ca，m = 3，n = 1)。通过 X 射线晶体学对配合物进行了表征，该配合物由 XDK 和 (PhO)_2P0_2 桥接的不对称双金属中心组成。变温 ^<3l>p{^1H} … 更多 NMR 实验表明，末端配位的磷酸酯配体在溶液中从双金属中心解离，并与桥联配体交换。磷酸酯交换率按Ca^<2+> > Zn^<2+> > Mg^<2+> 的顺序增加，为理解磷酸酯加工金属酶提供了有用的信息。还制备了新的Co(II)、Cu(I)和Cu(II)双核配合物，并考察了它们的生物相关反应。 2．碳水化合物与金属离子的相互作用在生物系统中至关重要。我们研究了各种过渡金属与糖配体配合物的合成、表征和反应性。具有七齿N-糖苷配体的单核Co(II)配合物[Co(II)((L-Rha或D-Man)_3-tren)]^<2+>通过金属中心的手性反转显示出对SO^<2->安东的分子​​识别特性。制备了过氧桥联双核钴 (III) 复合物 [((D-Glc, 或 Mal)_2-tren)Co(mu-02)Co((D-Glc, 或 Mal)_2-tren)]X3 (X = Cl, Br)，并通过 X 射线晶体学表征，由两个通过过氧化物桥联的八面体 Co(III) 离子组成。双核结构进一步受到糖部分之间的一些氢键的支持。有趣的是，通过紫外线照射时电子吸收光谱的变化监测了通过 mu-peroxo 二聚体的几乎可逆的双氧结合；制备了新型 Mn(II)Mn(III)Mn(II) 三核配合物，并通过 X 射线晶体学对其进行了表征。此外，人们进行了许多尝试以形成具有TACN锚定的糖部分的仿生二金属中心。较少的

项目成果

T.Tanase, T.Onaka, et al: "Peroxo-bridged Dinuclear Cobalt (III) Complexes Containing N-Glycoside Ligands from Tris (2-aminoethyl) amine and D-Glucose and Their Reversible Dioxygen Binding Properties" Chemical Communications (The Royal Society of Chemistr

T.Tanase、T.Onaka 等人：“含有来自三 (2-氨基乙基) 胺和 D-葡萄糖的 N-糖苷配体的过氧桥联双核钴 (III) 配合物及其可逆的双氧结合特性” 化学通讯 (The Royal)

D.D.LeCloux and S.J.Lippard: "Synthesis and Characterization of a Novel Class of Dicopper(I)Bis(carboxylate)-Bridged Complexes" Inorg.Chem.36. 4035-4046 (1997)

D.D.LeCloux 和 S.J.Lippard：“新型二铜（I）双（羧酸盐）桥络合物的合成和表征”Inorg.Chem.36。

T.Tanase, T.Onaka, M.Nakagoshi, I.Kinoshita, K.Shibata, M.Doe.J.Fujii, and S.Yano: "Peroxo-bridged Dinuclear Cobalt(II) Complexes Containing N-Glycoside Ligands from Tris(2-aminoethyl)amine and D-Glucose and Their Reversible Dioxygen Binding Properties" C

T.Tanase、T.Onaka、M.Nakagoshi、I.Kinoshita、K.Shibata、M.Doe.J.Fujii 和 S.Yano：“含有来自 Tris 的 N-糖苷配体的过氧桥双核钴 (II) 配合物

S.Yano,T.Tanase, et al: "Antifungal Nickel(II) Complexes Derived from Amino Sugars against Pathogenic Yeast, Candida Albicans"J.Inorg.Biochem.(Elsevier). 69. 15-23 (1998)

S.Yano，T.Tanase 等人：“源自氨基糖的抗真菌镍 (II) 复合物可对抗致病性酵母、白色念珠菌”J.Inorg.Biochem.（Elsevier）。

D.D.LeCloux, S.J.Lippard: "Synthesis and Characterization of a Novel Class of Dicopper (I) Bis (carboxylate) -Bridge Complexes" Inorganic Chemistry (American Chemical Society). 36. 4035-4046 (1997)

D.D.LeCloux、S.J.Lippard：“新型二铜 (I) 双（羧酸盐）桥配合物的合成和表征”无机化学（美国化学会）。