Armoring Vascular Implant by Glycocalyx‐Mimetic Coating with Clustered Morphology and Hydrophilic Lubrication

The endothelial glycocalyx is a natural protective layer for blood vessels. Efficient construction of a reliable glycocalyx‐mimetic coating on a vascular implant possesses great potential but remains a challenge. Herein, a novel glycocalyx‐mimetic coating featuring the clustered morphology and hydrophilic lubrication is developed via the layer‐by‐layer self‐assembly of polyethyleneimine (PEI) and phosphorylcholine‐modified hyaluronic acid (HA‐PC). The zwitterionic PC groups in HA‐PC exhibited an anti‐polyelectrolyte effect to induce the molecular folding and aggregation of HA in solution and enhance its binding capacity to PEI, resulting in an endothelial glycocalyx‐mimetic clustered morphology. Besides, zwitterions, rather than hydrophobic groups, can achieve hydrophilic lubrication properties through spatial synergy with HA while inducing the molecular folding of HA, ultimately constructing a glycocalyx‐mimetic coating. Such a coating can function well as armor to vascular stent, by virtue of excellent anti‐coagulation, anti‐inflammation, and endothelial promotion properties in vivo and in vitro. The findings not only provide new insights into the interactions between PC‐modified polyelectrolytes but also render a promising glycocalyx‐mimetic coating to armor vascular implants.