Finally, the reducing end of each HA-g-R glycopolymer was modified to allow its anchorage at a surface. Oxime ligation of HA-g-R and alkoxyamine-(ethylene glycol)4biotin, using aniline as a nucleophilic catalyst at pH 7, provided (HA-g-Le x )-B, (HA-g-Gb3)-B, (HA-g-Lac L )-B and (HA-g-Lac H )-B (Figure ). The same procedure was also performed on underivatized HA (Mw = 40-50 kDa) to synthesize HA-biotin (HA-B) as a non-interacting building block for the construction of glycocalyx models (Figure ). In addition, a peptide with a hexa-histidine sequence and a terminal alkoxyamine (7) was made by solid phase peptide synthesis, and attached to the reducing end of HA-g-Gb3 by oxime ligation, giving (HA-g-Gb3)-H6 (Figure ). Successful terminal modification of the mucin-like glycopolymers was confirmed by crystal microbalance with dissipation monitoring (QCM-D) during construction of the glycocalyx models on surfaces presenting either streptavidin (for biotin capture) or Ni 2+ -nitrilo triacetic acid (NTA) moieties (for histidine capture; vide infra). the mucin-like structures synthesized, with their physical properties. Degree of substitution (DS) with R per HA disaccharide was determined by 1 H-NMR; weight average molecular mass (Mw), number average molecular mass (Mn) and dispersity (Đ = Mw/Mn) were determined by SEC-MALS; see Methods for details.