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Glycobiology, 2000, Vol. 10, No. 6 587-594
© 2000 Oxford University Press

Conformational behavior of hyaluronan in relation to its physical properties as probed by molecular modeling

Katia Haxaire, Isabelle Braccini, Michel Milas, Marguerite Rinaudo and Serge Pérez1

Centre de Recherches sur les Macromolécules Végétales, CNRS (associated with Université Joseph Fourier, Grenoble), 38041 Grenoble, France

Hyaluronan (HA) is a linear charged polysaccharide whose structure is made up of repeating disaccharide units. Apparently conflicting reports have been published about the nature of the helical structure of HA in the solid state. Recent developments in the field of molecular modeling of polysaccharides offer new opportunities to reexamine the structural basis underlying the formation and stabilization of ordered structures and their interactions with counterions. The conformational spaces available and the low energy conformations for the disaccharide, trisaccharide, and tetrasaccharide segments of HA were investigated via molecular mechanics calculations using the MM3 force field. First, the results were used to access the configurational statistics of the corresponding polysaccharide. A disordered chain having a persistence length of 75 Å at 25°C is predicted. Then, the exploration of the stable ordered forms of HA led to numerous helical conformations, both left- and right-handed, having comparable energies. Several of these conformations correspond to the experimentally observed ones and illustrate the versatility of the polysaccharide. The double stranded helical forms have also been explored and theoretical structures have been compared to experimentally derived ones.

1 To whom correspondence should be addressed


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