Structural basis for the carbohydrate-specificity of basic winged-bean lectin and its differential affinity for Gal and GalNAc

The crystal structure of the complexes of basic winged-bean lectin with galactose, 2-methoxygalactose, N-acetylgalactos­amine and methyl-α-N-acetylgalactosamine have been determined. Lectin–sugar interactions involve four hydrogen bonds and a stacking interaction in all of the complexes. In addition, an N—­HO hydrogen bond involving the hydroxyl group at C2 exists in the galactose and 2-methoxygalactose complexes. An additional hydrophobic interaction involving the methyl group in the latter leads to the higher affinity of the methyl derivative. In the lectin–N-acetylgalactosamine complex the N—HO hydrogen bond is lost, but a compensatory hydrogen bond is formed involving the O atom of the acetamido group. In addition, the CH₃ moiety of the acetamido group is involved in hydrophobic interactions. Consequently, the 2-methyl and acetamido derivatives of galactose have nearly the same affinity for the lectin. The methyl group α-linked to the galactose takes part in additional hydrophobic interactions. Therefore, methyl-α-N-acetylgalactosamine has a higher affinity than N-acetylgalactos­amine for the lectin. The structures of basic winged-bean lectin–sugar complexes provide a framework for examining the relative affinity of galactose and galactosamine for the lectins that bind to them. The complexes also lead to a structural explanation for the blood-group specificity of basic winged-bean lectin.