Controlled swelling of biomaterial devices for improved antifouling polymer coatings.

Nonspecific interactions between cells and implantable elastomers often leads to failure modes for devices such as catheters, cosmetic and reconstructive implants, and sensors. To reduce these interactions, device surfaces can be coated with hydrophilic polymers, where greater polymer density enhances antifouling properties. Although graft-from coating techniques result in higher density polymer films and lower fouling in controlled settings, simpler graft-to methods show similar results on complex implanted devices, despite limited density. To address the need for improved graft-to methods, we developed Graft then shrink (GtS) where elastomeric materials are temporarily swollen during polymer grafting. Herein, we demonstrate a graft-to based method for poly(oligo(ethylene glycol) methyl ether methacrylate) (pOEGMA) on swollen silicone, GtS, that enhances grafted polymer content and fouling resistance. Total grafted polymer content of pOEGMA on toluene swollen silicone increased over ~ 13 × compared to non-swollen controls, dependent on the degree of silicone swelling. Increases in total grafted polymer within the top 200 µm of the material led to bacterial and mammalian cell adhesion reductions of 75% and 91% respectively, compared to Shrink then Graft (StG) antifouling polymer coated controls. GtS allows for the simple 3D coating of swellable elastomers (e.g., silicone medical devices) with improved antifouling pOEGMA coatings.

Graft-Then-Shrink: Simultaneous Generation of Antifouling Polymeric Interfaces and Localized Surface Plasmon Resonance Biosensors.

Antifouling polymer coatings that are simple to manufacture are crucial for the performance of medical devices such as biosensors. "Grafting-to", a simple technique where presynthesized polymers are immobilized onto surfaces, is commonly employed but suffers from nonideal polymer packing leading to increased biofouling. Herein, we present a material prepared via the grafting-to method with improved antifouling surface properties and intrinsic localized surface plasmon resonance (LSPR) sensor capabilities. A new substrate shrinking fabrication method, Graft-then-Shrink, improved the antifouling properties of polymer-coated Au surfaces by altering graft-to polymer packing while simultaneously generating wrinkled Au structures for LSPR biosensing. Thiol-terminated, antifouling, hydrophilic polymers were grafted to Au-coated prestressed polystyrene (PS) followed by shrinking upon heating above the PS glass transition temperature. Interestingly, the polymer molecular weight and hydration influenced Au wrinkling patterns. Compared to Shrink-then-Graft controls, where polymers are immobilized post shrinking, Graft-then-Shrink increased the polymer content by 76% in defined footprints and improved the antifouling properties as demonstrated by 84 and 72% reduction in macrophage adhesion and protein adsorption, respectively. Wrinkled Au LSPR sensors had sensitivities of ∼200-1000 Δλ/ΔRIU, comparing favorably to commercial LSPR sensors, and detected biotin-avidin and desthiobiotin-avidin complexation in a concentration-dependent manner using a standard plate reader and a 96-well format.