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

项目成果

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

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

S.Signorella, C.Palopoli, A.Frutos, G.Escandar, T.Tanase, and L.F.Sala: "3-Deoxy-D-erythro-hexos-2-ulose bis (thiosemicarbazone). Studies in Solution and the Solid State"Can.J.Chem.. 77. 1492-1497 (1999)

S.Signorella、C.Palopoli、A.Frutos、G.Escandar、T.Tanase 和 L.F.Sala：“3-Deoxy-D-erythro-hexos-2-ulose bis（缩氨基硫脲）。溶液和固态研究

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

T. Tanase、N. Takeshita 等人：“（μ-氧代或羟基）双（μ-羧基）二钌(III) 与三（1-吡唑基）硼酸酯面封端配体的配合物，通过质子化提供多功能氧化态/去质子耦合”New J.Chem.（法国化学会