Department of Inorganic and Analytical Chemistry, University of Szeged, Dóm tér 7, H-6720 Szeged, Hungary.
Department of Organic Chemistry, University of Szeged, Dóm tér 8, H-6720 Szeged, Hungary and Materials and Solution Structure Research Group, Institute of Chemistry, University of Szeged, H-6720 Szeged, Hungary.
Dalton Trans. 2017 Jan 24;46(4):1065-1074. doi: 10.1039/c6dt04356a.
The complex formation equilibria between Ca ions and six carbohydrate derivatives related to d-glucose was quantitatively characterized by potentiometry, freezing point depression and polarimetry. Complexation could not be observed for d-glucose, while weak association was deduced for d-sorbitol and d-mannitol. Stronger complexes are formed with d-gluconate and d-heptagluconate due to the presence of the carboxylate group. In addition to the plausible 1 : 1 species, the 1 : 2 species can also be detected at higher ligand to metal ratios. The ML type complex is also formed with d-glucuronate and d-glucarate. The strong association for d-gluconate and d-heptagluconate was attested by freezing point depression measurements. Polarimetric results show that for these two ligands the specific rotation of the complexed and free anions is only slightly different. The stability of the 1 : 1 complexes follows the order: mannitol < sorbitol < glucuronate < heptagluconate ≈ gluconate < glucarate. The formation of the ML type species has been established for polyhydroxy ligands having at least one carboxylate group in addition to the conformational flexibility.
采用电位滴定法、冰点降低法和旋光法定量研究了 Ca 离子与 6 种与 d-葡萄糖有关的碳水化合物衍生物之间的配合物形成平衡。d-葡萄糖不能形成配合物,而 d-山梨糖醇和 d-甘露醇则推断为弱缔合。由于存在羧酸盐基团,d-葡萄糖酸和 d-七葡萄糖酸形成更强的配合物。除了可能的 1:1 物种外,在较高的配体与金属比下也可以检测到 1:2 物种。ML 型配合物也形成于 d-葡萄糖醛酸和 d-葡萄糖酸中。冰点降低测量证明了 d-葡萄糖酸和 d-七葡萄糖酸的强缔合作用。旋光结果表明,对于这两种配体,配合物和游离阴离子的比旋光度仅略有不同。1:1 配合物的稳定性顺序为:甘露醇<山梨糖醇<葡萄糖醛酸<七葡萄糖酸≈葡萄糖酸<葡萄糖酸。除了构象灵活性之外,具有至少一个羧酸盐基团的多羟基配体已被确定形成 ML 型物种。