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

基本信息

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

项目摘要

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

阐明碳水化合物和金属离子之间的相互作用在生物无机化学中非常重要，因为许多糖代谢酶和一些糖结合蛋白与多种二价金属离子（例如 Mg^2+、Mn^2+）发挥作用、Co^<2+>、Zn^<2+> 和 Ca^<2+> 在某些情况下，羧酸桥联的二价二金属中心是许多物质中普遍存在的基序。 MCl_2-nH_2O 与 N,N'-bis (D-吡喃葡萄糖基)-1, 4, 7-三氮杂环壬烷 (D-Glc)_2-tacn) 反应，形成由 D-葡萄糖和 1, 4, 7-三氮杂环壬烷 (tacn) 原位合成，提供了一系列具有两个 β-D-吡喃葡萄糖基部分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) )) 通过分析和光谱测量以及 X 射线晶体学表征配合物 11-14，其具有通过以下方式连接的扭曲八面体 M(II) 中心。五配位 N-糖苷配体、(b-D-吡喃葡萄糖基) 2-tacn 和氯离子每个 D-葡萄糖部分通过与 tacn 的 b-N-糖苷键连接到金属中心，并通过 C-2 进行额外配位。羟基，产生 11 (M=Zn) 的 λ-gauche 五元螯合环。与 [Zn (XDK)(H_2O)] (21) 或 [Cu(XDK)(py)_2] (22) (H_2XDK=m-苯二甲胺双 (Kemp 氏三酰亚胺)) 生成同质和异质三金属配合物，公式为 [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 的类似反应得到 [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 的两个羧酸酯基团和两个 D-吡喃葡萄糖基残基桥接。M…M' 间隔为 3.418 (3)-。 3.462 (3) Å (31) 和 3.414 (1)-3.460 (1) Å (34) 以及M…M'…M 角度为 155.18 (8) ° (31) 和 161.56 (6)°(34) 末端金属离子通过 (D-Glc)2-tacn 配体通过 tacn 的三个氮原子进行八面体配位。，碳水化合物的C-2羟基的两个氧原子和XDK配体的羧酸根氧原子位于中心金属离子中。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的扭曲八面体环境。C-2 羟基处的去质子化 β-D-吡喃葡萄糖基单元桥接末端和中心具有 C-2 μ-烷氧基和 C-1 N-糖苷氨基和 C-3 羟基的离子配合物 31-34 是金属配合物的第一个例子，其中 D-葡萄糖单元充当桥接配体，这些结构可能是非常有用的木糖或葡萄糖异构酶的底物结合模型，可促进 D-葡萄糖<-。 > 使用谷氨酸残基桥接的二价二金属中心进行 D-果糖异构化。

项目成果

期刊论文数量（106）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

T.Tanase,N.Takeshita, et al: "(μ-Oxo or hydroxo) bis (μ-carboxylato) diruthenium (III) Complexes with Tris (1-byrazolyl) borate Face-capping Ligand, Affording Versatile Oxidation States via a Protonation/deprotonation Couple"New J.Chem.(Chemical Society o

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

DOI：
发表时间：
期刊：
影响因子：
0
作者：
通讯作者：

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）。

DOI：
发表时间：
期刊：
影响因子：
0
作者：
通讯作者：

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