Conformational and configurational features of acidic polysaccharides and their interactions with calcium ions:: a molecular modeling investigation

Modeling simulations have been performed on the four regular glycuronans: alpha-D-(1 --> 4) polygalacturonic, alpha-L-(1 --> 4) polyguluronic, beta-D-(1 --> 4) polymannuronic, and beta-D-(1 --> 4) polyglucuronic acids. The goal of this study was to characterize the similarities and differences in conformational and configurational behavior as well as in calcium binding in order to progress in the understanding of the physicochemical properties of the parent polysaccharides of industrial interest, namely pectin, alginate and glucuronan. This required the evaluation of the accessible conformational space for the disaccharide subunits of the four homopolymers, using the flexible residue protocol of the MM3 molecular mechanics procedure. The results were used to access the configurational statistics of representative polysaccharide chains, as well as for the determination of the regular polysaccharide helices and their conformational transitions. The surfaces of all regular helices likely to occur for each polyuronide were explored for cation binding using the GRID procedure. Both alpha-D-(1 --> 4) polygalacturonate and alpha-L-(1 --> 4) polyguluronate chains exhibit a high specificity for calcium binding, and have well-defined chelation sites. In contrast, beta-D-(1 --> 4) polymannuronate and beta-D-(1 --> 4) polyglucuronate chains do not display any stereospecificity for calcium binding. The results gathered from molecular modeling lead to a clear understanding of the different structural features that are displayed by the four ionic polymers. (C) 1999 Elsevier Science Ltd. All rights reserved.