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| 糖及糖醇与金属离子配合物的结构研究进展 |
| Recent Progress in the Structures of Metal-Saccharide/Alditol complexes |
| 投稿时间：2026-03-11 修订日期：2026-04-29 |
| DOI： |
| 中文关键词: 糖 糖醇 配位方式 金属离子 晶体结构 |
| 英文关键词:Saccharide, Alditol, Coordination mode, Metal ions, Crystal structure |
| 基金项目:国家重点研发计划(2017YFA0701001),国家自然科学基金项目（12275011, 21001009, 51373003, 117350022）北京大学仪器创制与关键技术研发基金 (7101500246/001, 7101500253/011) 、与中科院化学所合作的材料项目104、核物理与核技术国家重点实验室开放课题(NPT2020KFY14) |
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| 中文摘要: |
| 糖/糖醇是含有多个羟基的有机化合物，因而其具有与金属离子发生络合配位作用的能力。这种络合配位作用在生物识别、药物输运、生物质能源及生物质化工上具有重要意义。本文综述了近年来糖/糖醇与金属离子配合物的单晶X射线衍射研究进展，讨论了七类糖/糖醇配合物的晶体结构。这些配合物的一个显著特征是结构多样性，表现在糖/糖醇的配位模式、金属离子的配位数、金属离子与糖/糖醇分子的摩尔比、羟基脱质子行为，以及第二配体的数量和种类的变化上。造成这一现象的主要原因是糖/糖醇的多个羟基在配合物当中参与直接配位、脱质子后配位、形成氢键，且会相互切换。同时，在某些稀土-糖醇配合物中意外发现，羟基同时与两个稀土离子配位形成μ2桥，该羟基在两个稀土离子的强极化作用下被活化，即使在酸性环境下也能发生脱质子反应。这种羟基脱质子反应具有区域选择性、手性选择性特征。糖/糖醇-金属离子配合物的结构多样性表明：对其研究存在诸多值得探索的方向。对这些配合物结构、功能关系的深入认识，在药物输运和肿瘤的靶向治疗等方面发挥重大功用；且为开发高性能催化剂，促进生物质资源的高效利用提供新思路。 |
| 英文摘要: |
| Saccharides/alditols are organic compounds containing multiple hydroxyl groups, so they have the ability to coordinate with metal ions. This coordination is of great significance in biological recognition, drug transport, biomass energy conversion, and biomass chemical industry. Recently, many crystal structures of metal-saccharide/alditol complexes have been reported. In this review, the crystal structures of the metal complexes related to seven alditol and saccharide ligands, including erythritol, galactitol, myo-inositol, ribose, arabinose, lactose, and glycerol, are discussed. A distinctive feature of these complexes is their structural diversity. The diversity is manifested in the coordination modes of saccharides/alditols, the coordination number of metal ions, the molar ratio between metal ions and saccharide/alditol, and the variety of secondary ligands. In the complexes, the hydroxyl groups play a triple role: 1) coordinate to metal ions directly; 2) take part in the formation of a ?2-bridge and induce a deprotonation reaction; 3) take part in the formation of hydrogen bonds. The OH groups of saccharides/alditol molecules may switch among the three roles in different complexes. To a large extent, the above behavior of OH groups accounts for the structural diversity of these complexes. In the research, we observed unexpected deprotonation on OH groups in lanthanide/alditol complexes. In those complexes, an OH group of an alditol is coordinated with two rare earth ions simultaneously so that a μ2 bridge is formed. Under the strong polarization of the two lanthanide ions, the chemically inert OH group is activated. Subsequently, deprotonation occurs on the OH group despite the fact that the pKa of the OH group is around 14 while the pH value of the solution where the complex was formed is around 3. Further research demonstrated that the deprotonation promoted by μ2 bridges has regioselectivity and chiral selectivity characteristics. The structural diversity of metal ion-saccharide/alditol complexes indicates that there are many directions worth exploring in their research. The in-depth understanding of the structure and functional relationship of these complexes plays a significant role in drug delivery and targeted therapy of tumors. The research on metal ion/alditol/saccharides complexes may bring about new chances in the development of high-performance catalysts and the efficient utilization of biomass resources. |
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