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的羧酸桥接双核金属中心，如Mg^<2+>, Ca^<2+>, Mn^<2+>和Zn^<2+>，是发生在磷酸酯加工金属酶活性中心的重要生物无机基序。我们系统地研究了非氧化还原活性的双金属配合物，利用双羧酸配体，间二胺二（Kemps三酸亚胺）（H^2XDK）。用[ZnM(XDK)(acac)_2(CH_3OH)_2]与（PhO）_2PO_2H_2反应制备了含锌的同异二金属配合物[ZnM(XDK){mu-eta^<12>-(PhO)_2O_2}{eta^1-(PhO_2PO_2}(CH_3OH)_2(H20)]（M = Zn, Co）。类似的Mg_2， Mn_2和Ca_2配合物。[M_2 (XDK) {mueta_2 -(越南河粉)_2PO_2) {mu_1 -(越南河粉)_2PO_2} (CH_3OH) m (H_2O) n] (m =毫克,m = 3, n = 1; m = Mn, m = n = 2; m = Ca, m = 3, n = 1),。配合物由XDK和（PhO）_2P0_2桥接的不对称双金属中心组成。更多的核磁共振实验表明，末端配位的磷酸酯配体在溶液中与双金属中心解离，与桥接中心交换。磷酸酯交换速率以Ca^<2+> > Zn^<2+> > Mg^<2+>的顺序递增，为了解磷酸酯加工金属酶提供了有用的信息。制备了新的Co（II）、Cu(I)和Cu（II）的双核配合物，并对它们的生物相关反应进行了研究。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。我们研究了各种糖配体过渡金属配合物的合成、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->的分子识别特性。制备了过氧桥接双核钴（III）配合物[((D-Glc，或Mal)_2-tren)Co(mu-02)Co((D-Glc，或Mal)_2-tren)]X3 (X = Cl, Br)，并用X射线晶体学对其进行了表征。双核结构由糖段之间的氢键进一步支持。有趣的是，紫外照射下，电子吸收光谱变化监测了通过多过氧二聚体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，并对其进行了x射线晶体学表征。此外，许多尝试形成仿生二金属中心与碳锚定糖部分。少

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）。