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铁(III)与透明质酸的水相和固相配合物。电位滴定和红外光谱研究。

Aqueous and solid complexes of iron(III) with hyaluronic acid. Potentiometric titrations and infrared spectroscopy studies.

作者信息

Mercê Ana Lucia Ramalho, Marques Carrera Luiz Carlos, Santos Romanholi Lilian Kelly, Lobo Recio María Angeles

机构信息

Departamento de Química, Universidade Federal do Paraná, CP 19081, Centro Politécnico, Curitiba, 81531-990, Brazil.

出版信息

J Inorg Biochem. 2002 Apr 28;89(3-4):212-8. doi: 10.1016/s0162-0134(01)00422-6.

Abstract

The coordination of iron(III) ion to hyaluronic acid (Hyal) in aqueous solutions and solid state was accomplished by potentiometric titrations and infrared spectroscopy. The potentiometric titration studies provided the binding constants for the complexes found in the systems and the speciation of these species according to the variation of pH values. The complexes found presented a complexing ability through both the chelating moieties of Hyal (via the N-glucosamine and D-glucoronic acid), showing no special preference for either one while in solid state, but when in aqueous solution the complexation via the N-glucosamine moiety was the preferred, forming two complexed species, ML and ML(2) (log K(ML)=8.2 and log K(ML2)=7.9). The presence of a mu-oxo complex via the D-glucoronic acid was also detected in both aqueous (log K=6.7) and solid states via the N-glucosamine and D-glucoronic acid simultaneously linked to two Hyal chains. A structure for this latter complex was suggested. The results indicated that these complexes could be used in eliminating the excess iron(III) in living organisms.

摘要

通过电位滴定法和红外光谱法研究了水溶液和固态下铁(III)离子与透明质酸(Hyal)的配位情况。电位滴定研究给出了体系中形成的配合物的结合常数以及这些物种随pH值变化的形态。所发现的配合物通过透明质酸的螯合部分(经由N-葡萄糖胺和D-葡萄糖醛酸)展现出络合能力,在固态时对两者均无特别偏好,但在水溶液中,经由N-葡萄糖胺部分的络合作用更受青睐,形成两种络合物种,ML和ML₂(log K(ML)=8.2,log K(ML₂)=7.9)。通过同时连接到两条透明质酸链上的N-葡萄糖胺和D-葡萄糖醛酸,在水溶液(log K=6.7)和固态中均检测到经由D-葡萄糖醛酸形成的μ-氧代配合物。并提出了后一种配合物的结构。结果表明,这些配合物可用于清除生物体内过量的铁(III)。

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