title: Stability of lead(II) complexes of alginate oligomers.
abstract: The current work reports on the Pb(ll) complexes formed with oligomeric uronic acids (carboxylated saccharide residues) found polymerized in the cell walls and envelopes of algae and bacteria alike. The application of partial acid hydrolysis, size-exclusion chromatography (SEC), 1H NMR, and scanned deposition stripping chronopotentiometry (SSCP) has permitted the determination of stability constants for Pb(II) with both mannuronic (M) and guluronic (G) acid oligomers ranging from the dimer to the pentamer. The determined logarithm of the stability constants range between 4.11 +/- 0.05 and 5.00 +/- 0.04 mol(-1) x dm3 for the eight oligomers studied (pH 6; I = 0.1 mol x dm(-3)). Additional experiments under the same experimental conditions employing galacturonic and glucuronic acid oligomers yielded slightly lower values (2.19 +/- 0.10 to 4.02 +/- 0.07 mol(-1) x dm3) that were expected based on their structure, whereby the monomers which were not included in the alginate oligomer series (unavailable by SEC), yielded the lowest stability constants. This work demonstrates the applicability of the SSCP technique for the determination of stability constants for metal-ligand complexes in which the ligands display relatively low molecular mass. Previous studies on heavy metal interaction with the matrix polysaccharide alginate have largely been restricted to the whole polymer that forms a gel upon binding to network bridging ions such as calcium. The results will be discussed in this context with the emphasis being placed on the relevance of these findings to processes occurring at the biointerface and results from the relevant literature.
authors.affiliation: Laboratory of Physical Chemistry and Colloid Science, Wageningen University, P.O. Box 8038, 6700 EK Wageningen, The Netherlands. ta.davis@umontreal.ca
authors.forename: Thomas A
authors.initials: TA
authors.lastname: Davis
authors.forename: Jose P
authors.initials: JP
authors.lastname: Pinheiro
authors.forename: Hans
authors.initials: H
authors.lastname: Grasdalen
authors.forename: Olav
authors.initials: O
authors.lastname: Smidsrød
authors.forename: Herman P
authors.initials: HP
authors.lastname: van Leeuwen
mesh_terms: D000464:Alginates / Q000737:chemistry*; D002850:Chromatography, Gel; D004563:Electrochemistry; D020723:Glucuronic Acid / Q000737:chemistry; D006603:Hexuronic Acids / Q000737:chemistry; D007854:Lead / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy
chemical_list: D000464:Alginates; D006603:Hexuronic Acids; D007854:Lead; D020723:Glucuronic Acid