Metal ion coordination of macromolecular bioligands: formation of zinc(II) complex of hyaluronic acid

The coordination of zinc(II) ion to hyaluronate (Hya), a natural copolymer, in aqueous solution at pH 6 was investigated by potentiometric and circular dichroism (CD) spectroscopic methods, and by monitoring the changes in macroscopic properties by high-precision measurements. The zinc(II)-selective...

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Published in:Carbohydrate research Vol. 332; no. 2; pp. 197 - 207
Main Authors: Burger, Kálmán, Illés, János, Gyurcsik, Béla, Gazdag, Mária, Forrai, Erika, Dékány, Imre, Mihályfi, Katalin
Format: Journal Article
Language:English
Published: Netherlands Elsevier Ltd 18-05-2001
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Summary:The coordination of zinc(II) ion to hyaluronate (Hya), a natural copolymer, in aqueous solution at pH 6 was investigated by potentiometric and circular dichroism (CD) spectroscopic methods, and by monitoring the changes in macroscopic properties by high-precision measurements. The zinc(II)-selective electrode, and CD measurements proved the binding of zinc(II) by Hya. A number of Hya fragments ( M r∼3.3×10 3–1.4×10 6) were studied to estimate the contributions of the polyelectrolyte effect, the solvation and host–guest interactions to the extra stabilization of the macromolecular zinc(II) complexes as compared with the monomeric unit. The zinc(II) ion activity increase reflected a stability decrease for the fragments with M r<4×10 4. This molecular weight differs from that where cleavage of the Hya skeleton starts (∼5×10 5, according to the size-exclusion gel, and anion-exchange chromatographic behavior of the Hya fragments) and from that where the polyelectrolyte effect stops (∼6×10 3). The excess volumes and Bingham shear yield values of the solutions revealed the transformation of the coherent random coil structure stabilized by intermolecular association in the NaHya to an intramolecular association producing the globular structure of the ZnHya molecule, with a smaller but more strongly bound solvate water sheet. The binding of Zn(II) by Hya and the rearrangement of the polymer chain, i.e., a size decrease because of the globular structure of the ZnHya molecule, as a consequence of the complex formation was proved.
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ISSN:0008-6215
1873-426X
DOI:10.1016/S0008-6215(01)00065-9