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; 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

阐明碳氢化物与金属离子之间的相互作用在生物有机化学中至关重要，因为许多糖代谢酶和某些糖结合蛋白具有多种二价金属离子，例如mg^<2+>，mn^<2+>，mn^<2+>，co^<2+>，co^<2+>，co^<2+>，Zn^<2> <2> <2>，和Ca^<2^<2^<2^<2^<2^<2>>^2>^<2>>^2^<2>>^2^<2+ In some cases, carboxylate-bridged divalent dimetal centers, a ubiquitous motif in many hydrolytic metalloenzymes, also play important roles via interactions with carbonhydrates.Reactions of MCl_2-nH_2O with N,N'-bis (D-glucopyranosyl)-1, 4, 7-triazacyclononane (D-Glc)_2-tacn),它是由D-葡萄糖和1、4、7-三氮唑烷烷（TACN）原位形成的，它提供了一系列单核二价金属复合物，带有两个β-D-d-葡萄糖基部分，[m {（d-glc）_2-tacn} cl] cl（m = zn（14），ni（13），ni（12），ni（12），ni（12），ni（12）。通过分析和光谱测量和X射线晶体学表征复合物11-14的表征，具有扭曲的八面体M（II）中心，由五型辅助N-糖苷配体绑扎，…更多（B-D-D-葡萄糖吡喃糖基）2-TACN和一个氯化物。每个D-葡萄糖部分通过B-N-糖苷键与TACN束缚在金属中心，并通过C-2羟基进行协调，从而产生λ-木che五元的樱桃环。 11（M = Zn）与[Zn（XDK）（H_2O）]]（21）或[Cu（XDK）（Py）_2]（22）（H_2XDK = M- Xylylenediamine bis（Kemp's triacid imide））产生了homo-and homo-and horotrimetallicecteres的形式， [Zn_2m'{（D-GLC）_2-TACN} _2（XDK）] Cl_2（m'= Zn（31），Cu（32））。 12（M = Cu）与复合物21或22的相似反应提供了[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，复合物31和34具有Zn^<ii> _3或Cu^<ii> Zn^<ii> Cu^<ii> Cu^<ii> Trimetallic Centers，由两个Xdk和两个D-d-葡萄糖基丙烷基固定的羧酸盐基团桥接。 M ... m'分离为3.418（3）-3.462（3）Å（31）和3.414（1）-3.460（1）Å（34）和M ... M'…M角度为155.18（8）°（31）°（31）和161.56（34）°（34）。末端金属离子通过TACN的三个氮原子，C-2羟基的两个氧原子和XDK配体的羧酸氧原子的两个氧原子，由TACN的三个氮原子，两个氧原子和XDK配体的羧酸氧原子配合。中央金属离子位于扭曲的八面体环境中，该环境由（D-GLC）_2-TACN配体的四个氧原子与XDK的两个氧气原子和两个羧酸氧原子相连。用C-1 N-糖苷氨基和C-3羟基坐标到每个金属中心。复合物31-34是金属复合物的第一个例子，其中D-葡萄糖单元充当桥接配体。这些结构可能是木糖或葡萄糖异构酶的非常有用的底物结合模型，该模型通过使用由谷氨酸住宅桥接的二价二脂中心来促进d-葡萄糖<-> d-d-fructose异构化。较少的