Fully Synthetic, Biomimicking Polysulfates With Tunable Anticoagulant and Endothelial Cell–Selective Bioactivity
Source: PubMed Central Open Access, NCBI / U.S. National Library of Medicine
ABSTRACT We present a versatile method for fabricating glycosaminoglycan (GAG)‐inspired polyelectrolyte brush coatings from fully synthetic sulfated PHEMA block copolymers. Using a bioinert backbone enables evaluation of sulfation effects independently of natural GAGs’ carbohydrate backbone. A degree of sulfation above 70% imparted anticoagulant activity, extending plasma coagulation times beyond 500 s at 0.1 mg mL. Controlled self‐assembly enabled fabrication and photoimmobilization of uniform, nanometer‐thin brushes on polystyrene substrates. The polysulfate brushes exhibited molecular weight‐dependent properties: under serum‐free conditions, endothelial cells (HUVECs) selectively proliferated on longer‐OSO‐BP (65 kDa) compared to shorter‐OSO‐BP (15 kDa) brushes, while smooth muscle cells (SMCs) remained quiescent. Despite comparable VEGF and bFGF surface densities (0.5 ng cm),‐OSO‐BP coatings better preserved VEGF bioactivity, likely due to higher chain flexibility. In co‐culture under serum conditions (5%), HUVEC/SMC ratios remained near unity with persistent colocalization, indicating restrained SMC overgrowth and stabilized vascular co‐culture relevant to preventing neointimal hyperplasia. These findings highlight synthetic polysulfate brush coatings as a platform for studying sulfation‐driven growth factor interactions and vascular cell competition at biomaterial interfaces, promoting reendothelialization in vitro. The system therefore represents a functional mimetic o
Abstract
ABSTRACT We present a versatile method for fabricating glycosaminoglycan (GAG)‐inspired polyelectrolyte brush coatings from fully synthetic sulfated PHEMA block copolymers. Using a bioinert backbone enables evaluation of sulfation effects independently of natural GAGs’ carbohydrate backbone. A degree of sulfation above 70% imparted anticoagulant activity, extending plasma coagulation times beyond 500 s at 0.1 mg mL. Controlled self‐assembly enabled fabrication and photoimmobilization of uniform, nanometer‐thin brushes on polystyrene substrates. The polysulfate brushes exhibited molecular weight‐dependent properties: under serum‐free conditions, endothelial cells (HUVECs) selectively proliferated on longer‐OSO‐BP (65 kDa) compared to shorter‐OSO‐BP (15 kDa) brushes, while smooth muscle cells (SMCs) remained quiescent. Despite comparable VEGF and bFGF surface densities (0.5 ng cm),‐OSO‐BP coatings better preserved VEGF bioactivity, likely due to higher chain flexibility. In co‐culture under serum conditions (5%), HUVEC/SMC ratios remained near unity with persistent colocalization, indicating restrained SMC overgrowth and stabilized vascular co‐culture relevant to preventing neointimal hyperplasia. These findings highlight synthetic polysulfate brush coatings as a platform for studying sulfation‐driven growth factor interactions and vascular cell competition at biomaterial interfaces, promoting reendothelialization in vitro. The system therefore represents a functional mimetic of GAGs, reproducing key electrostatic features while avoiding the structural complexity of native polysaccharides. Sulfated PHEMA‐based polyelectrolyte brushes are introduced as a reductionist platform to probe glycosaminoglycan‐inspired bioactivity. High charge density governs growth factor interactions and is associated with distinct vascular cell responses, enabling balanced endothelial and smooth muscle cell co‐culture. These fully synthetic coatings decouple structural complexity from function, offering tunable and cell‐instructive interfaces for blood‐contacting biomaterials and implant coatings. mabi70201-abs-0001 graphical