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金属硝酸盐与碳水化合物之间的相互作用:半乳糖醇与三价镧系元素和二价碱土金属离子的拓扑配位行为。

Interaction between metal nitrates and carbohydrates: the topology coordination behavior of galactitol with trivalent lanthanide and divalent alkaline earth ions.

作者信息

Su Yunlan, Yang Limin, Xu Yizhuang, Wang Zheming, Weng Shifu, Yan Chunhua, Wang Dujin, Wu Jinguang

机构信息

State Key Laboratory of Rare Earth Material Chemistry and Applications, Department of Chemical Biology, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China.

出版信息

Inorg Chem. 2007 Jul 9;46(14):5508-17. doi: 10.1021/ic061414h. Epub 2007 Jun 9.

Abstract

It has long been known that metal ions and saccharides are involved in many biochemical processes. In this paper, metal nitrates were used as reactants to detect the coordination structures of the hydroxyl groups of galactitol in different environments. Three novel crystal structures and FT-IR spectra of metal nitrate-galactitol complexes of La(NO3)3.C6H14O6.(4)H2O, 2Ca(NO3)2.C6H14O6.H2O, and Sr(NO3)2.C6H14O6 were examined in an effort to clarify the structural factors that control metal ion interactions with saccharides in aqueous and biological systems. The coordination structures of galactitol with alkaline earth and lanthanide nitrates in the solid state were compared using FT-IR, Raman, and X-ray diffraction techniques to extensively discuss the coordination rules of different kinds of metal ions. Results provided a model of the coordination sites found in sugars and showed that the introduction of NO3- made the coordination modes of galactitol more diverse and complex than those of the corresponding chloride complexes. Specifically, new coordination modes of galactitol and complicated topology networks were found in 2Ca(NO3)2.C6H14O6.H2O and Sr(NO3)2.C6H14O6. FT-IR results are consistent with the crystal structures and thus provide the possibility of using the similarity of IR spectra to speculate about unknown structures when the compounds are difficult to prepare as single crystals.

摘要

长期以来,人们一直知道金属离子和糖类参与许多生物化学过程。在本文中,金属硝酸盐被用作反应物,以检测不同环境中半乳糖醇羟基的配位结构。研究了La(NO3)3·C6H14O6·4H2O、2Ca(NO3)2·C6H14O6·H2O和Sr(NO3)2·C6H14O6三种金属硝酸盐-半乳糖醇配合物的新型晶体结构和傅里叶变换红外光谱,以阐明控制金属离子在水性和生物体系中与糖类相互作用的结构因素。利用傅里叶变换红外光谱、拉曼光谱和X射线衍射技术比较了半乳糖醇与碱土金属和镧系硝酸盐在固态下的配位结构,以广泛讨论不同种类金属离子的配位规则。结果提供了一个糖类中配位位点的模型,并表明NO3-的引入使半乳糖醇的配位模式比相应的氯化物配合物更加多样和复杂。具体而言,在2Ca(NO3)2·C6H14O6·H2O和Sr(NO3)2·C6H14O6中发现了半乳糖醇的新配位模式和复杂的拓扑网络。傅里叶变换红外光谱结果与晶体结构一致,因此当化合物难以制备成单晶时,提供了利用红外光谱相似性推测未知结构的可能性。

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