Development of Artificial Sugar-Transformation Systems by Biomimic Multimetallic Centers

通过仿生多金属中心开发人工糖转化系统

• 批准号: 10440194
• 负责人: TANASE Tomoaki
• 金额: $ 6.14万
• 依托单位: Nara Women's University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B).
• 财政年份: 1998
• 资助国家: 日本
• 起止时间: 1998 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-10440194/
• 关键词: Sugar Transformation; Dimetallic Center; Sugar Complex; N-Glycoside; Biscarboxylate Ligand; Zn; Cu; Trinuclear Complex

Elucidation of interactions between carbohydrates and metal ions is of importance in bioinorganic chemistry, since many sugar-metabolizing enzymes and some sugar-binding proteins function with a variety of divalent metal ions such as Mg^<2+>, Mn^<2+>, Co^<2+>, Zn^<2+>, and Ca^<2+>. In some cases, carboxylate-bridged divalent dimetal centers, a ubiquitous motif in many hydrolytic metalloenzymes, also play important roles via interactions with carbohydrates.Reactions of MCl_2-nH_2O with N,N'-bis (D-glucopyranosyl)-1, 4, 7-triazacyclononane (D-Glc)_2-tacn), which was formed from D-glucose and 1, 4, 7-triazacyclononane (tacn) in situ, afforded a series of mononuclear divalent metal complexes with two β-D-glucopyranosyl moieties, [M{(D-Glc)_2-tacn}Cl]Cl (M=Zn (11), Cu (12), Ni (13), Co (14)). Complexes 11-14 were characterized by analytical and spectroscopic measurements and X-ray crystallography to have a distorted octahedral M(II) center ligated by the pentacoordinate N-glycoside ligand, … More (b-D-glucopyranosyl) 2-tacn, and a chloride anion. Each D-glucose moiety is tethered to the metal center through the b-N-glycosidic bond with tacn and additionally coordinated via the C-2 hydroxyl group, resulting in a λ-gauche five-membered chelate ring. Reactions of 11 (M=Zn) with [Zn (XDK)(H_2O)] (21) or [Cu(XDK)(py)_2] (22) (H_2XDK=m-xylylenediamine bis (Kemp's triacid imide)) yielded homo-and heterotrimetallic complexes formulated as [Zn_2M'{(D-Glc)_2-tacn}_2(XDK)] Cl_2 (M'=Zn (31), Cu (32)). The similar reactions of 12 (M=Cu) with complex 21 or 22 afforded [Cu_2M'{(D-Glc)_2-tacn}_2(XDK)]-Cl_22 (M'=Cu (33), Zn (34)). X-ray crystallographic study revealed that complexes 31 and 34 have a Zn^<II>_3 or Cu^<II>Zn^<II>Cu^<II> trimetallic centers bridged by two carboxylate groups of XDK and two D-glucopyranosyl residues. The M…M' separations are 3.418 (3)-3.462 (3) Å (31) and 3.414 (1)-3.460 (1) Å (34) and the M…M'…M angles are 155.18 (8) ° (31) and 161.56 (6)°(34). The terminal metal ions are octahedrally coordinated by the (D-Glc)2-tacn ligand through three nitrogen atoms of tacn, two oxygen atoms of C-2 hydroxyl groups of the carbohydrates, and a carboxylate oxygen atom of XDK ligand. The central metal ions sit in a distorted octahedral environment ligated by four oxygen atoms of the carbohydrate residues in the (D-Glc)_2-tacn ligands and two carboxylate oxygen atoms of XDK.The deprotonated β-D-glucopyranosyl unit at C-2 hydroxyl group bridges the terminal and central ions with the C-2 μ-alkoxo group and with the C-1 N-glycosidic amino and the C-3 hydroxyl groups coordinating to each metal center. Complexes 31-34 are the first examples of metal complexes in which D-glucose units act as bridging ligands. These structures could be very useful substrate binding models of xylose or glucose isomerases, which promote D-glucose <-> D-fructose isomerization by using divalent dimetallic centers bridged by a glutamate residue. Less

阐明碳水化合物与金属离子之间的相互作用在生物无机化学中具有重要意义，因为许多糖代谢酶和一些糖结合蛋白与各种二价金属离子如Mg^<2+>, Mn^<2+>, Co^<2+>, Zn^<2+>和Ca^<2+>起作用。在某些情况下，羧酸桥接二价二金属中心，在许多水解金属酶中普遍存在的基序，也通过与碳水化合物的相互作用发挥重要作用。MCl_2-nH_2O与由d -葡萄糖和1,4,7 -三氮杂环壬烷（tacn）原位生成的N，N'-二（d -葡萄糖吡喃基）- 1,4,7 -三氮杂环壬烷（D-Glc）_2-tacn)反应，得到一系列具有两个β- d -葡萄糖吡喃基基团的单核二价金属配合物[M{(D-Glc)_2-tacn}Cl]Cl (M=Zn (11), Cu (12), Ni （13), Co(14)）。配合物11-14通过分析和光谱测量以及x射线晶体学表征为具有一个扭曲的八面体M（II）中心，由五配位n -糖苷配体，…More (b-D-glucopyranosyl) 2-tacn和一个氯阴离子连接。每个d -葡萄糖片段通过与tacn的b- n -糖苷键连接到金属中心，并通过C-2羟基进行配位，形成一个λ-间扭式五元螯合环。11 （M=Zn）与[Zn (XDK)(H_2O)]（21）或[Cu(XDK)(py)_2] (22) （H_2XDK= M -二甲二胺二（Kemp的三酸亚胺））反应生成了均异三金属配合物[Zn_2M'{(D-Glc)_2-tacn}_2(XDK)] Cl_2 （M'=Zn (31), Cu(32))）。12 （M=Cu）与配合物21或22的类似反应产生[Cu_2M'{(D-Glc)_2-tacn}_2(XDK)]-Cl_22 (M'=Cu （33), Zn(34)）。x射线晶体学研究表明，配合物31和34具有Zn^<II>_3或Cu^<II>Zn^<II>Cu^<II>三金属中心，由XDK的两个羧酸基和两个d -葡萄糖酰基残基桥接。M…M‘间距为3.418 (3)-3.462 (3)Å（31）和3.414 (1)-3.460 (1)Å （34）， M…M’…M角分别为155.18(8)°（31）和161.56(6)°（34）。末端金属离子与（D-Glc）2-tacn配体通过tacn的三个氮原子、碳水化合物C-2羟基的两个氧原子和XDK配体的一个羧酸氧原子进行八面配位。中心金属离子位于扭曲的八面体环境中，由（D-Glc）_2-tacn配体中碳水化合物残基的四个氧原子和XDK的两个羧酸氧原子连接。C-2羟基上去质子化的β- d -葡萄糖吡喃基单元与C-2 μ-烷氧基、C-1 n -糖苷氨基和C-3羟基连接末端和中心离子。配合物31-34是d -葡萄糖单元作为桥接配体的金属配合物的第一个例子。这些结构可能是木糖或葡萄糖异构酶非常有用的底物结合模型，它们通过谷氨酸残基桥接的二价双金属中心促进d -葡萄糖<-> d -果糖异构化。少

项目成果

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T. Tanase、N. Takeshita 等人：“（μ-氧代或羟基）双（μ-羧基）二钌 (III) 与 Tris (1-byrazolyl) borate Face-capping 配体的配合物，通过质子化提供多功能氧化态/deprotonation Couple"New J.Chem.(化学会o

S.Signorella,T.Tanase, et al: "3-Deoxy-D-erythro-hexos-2-ulose bis(thiosemicarbazone).Studies in Solution and Solid State"Can.J.Chem.(Chemical Society of Canada). 77. 1492-1497 (1999)

S.Signorella、T.Tanase 等人：“3-脱氧-D-赤式-己糖-2-乌糖双(缩氨基硫脲)。溶液和固态研究”Can.J.Chem.（加拿大化学会）。

T.Tanase, T.Inagaki, Y.Yamada, M.Kato, E.Ota, M.Yamazaki, M.Sato, W.Mori, K.Yamaguchi, et al: "Tetranuclear Iron (III) Complexes with Amino Acids Involving a Planar (μ-Oxo)(μ-hydroxo) bis (μ-alkoxo) bis (μ-carboxylato) tetrairon Core"J.Chem.Soc., Dalton T

T.Tanase、T.Inagaki、Y.Yamada、M.Kato、E.Ota、M.Yamazaki、M.Sato、W.Mori、K.Yamaguchi 等人：“四核铁 (III) 与涉及氨基酸的配合物平面（μ-氧代）（μ-羟基）双（μ-烷氧基）双（μ-羧基）四铁核“J.Chem.Soc.，Dalton T

T.Tanase,T.Onaka, et al: "Peroxo-Bridged Dinuclear Cobalt(III) Complex Containing N-Glycoside Ligands from Tris(2-aminoethyl) amine and D-Glucose or Maltose (α,D-Glucopyranosyl-(I->4)-D-Glucose)"Inorg.Chem.(American Chemical Society). 38. 3150-3159 (1999)

T. Tanase、T. Onaka 等人：“含有来自三（2-氨基乙基）胺和 D-葡萄糖或麦芽糖的 N-糖苷配体的过氧桥双核钴 (III) 复合物（α,D-吡喃葡萄糖基-(I- >4)-D-葡萄糖)“Inorg.Chem.(美国化学会). 38. 3150-3159 (1999)

S.Yano,T.Tanase, et al: "First Synthesis and Characterization of Zinc(II) Complexes Containing N-Glycosides Derived from Ethylenediamine and D-Glucosamine"J.Chem.Soc., Dalton Trans.(Royal Society of Chemistry). 1851-1855 (1999)

S.Yano,T.Tanase 等人：“含有乙二胺和 D-葡萄糖胺衍生的 N-糖苷的锌 (II) 配合物的首次合成和表征”J.Chem.Soc.，Dalton Trans.（英国皇家化学学会）