HA was chosen as the polymer backbone because the physical properties of films of plain HA polysaccharides grafted to a surface have been studied extensively. HA is very soluble under physiological conditions, and its negative charge and large persistence length (4 nm) facilitate the formation of relatively thick films at comparatively low grafting densities. HA has an alternating sequence of -linked N-acetylglucosamine (GlcNAc) and glucuronic acid (GlcA) residues, the latter of which can be used for derivatization of the polymer with pendant amide groups while controlling the degree of substitution (DS). Introduction of an alkyne through amide bonds on HA has been described, and allows coppercatalyzed azide alkyne cycloaddition (CuAAC) chemistry to incorporate desired pendant groups. Furthermore, the introduction of azides into oligosaccharides is also wellknown. Moreover, the hemiacetal group at the reducing terminus of HA allows chemical modification at a single position by oxime ligation to attach an anchor (e.g., biotin) for grafting the structures to a surface. Lewis x (Le x ) and Gb3 trisaccharides, and lactose (Lac) disaccharides, were chosen as glycan moieties for synthesis of well-defined mucin-like glycopolymers. Le x and Gb3 were selected for their affinity to CTB and STxB, respectively, and lactose (Lac) as a convenient control. The first step was synthesis of the oligosaccharides with a pendant azide group (Figure ).