Anti-protein and anti-bacterial behavior of amphiphilic silicones.

Silicones with improved water-driven surface hydrophilicity and anti-biofouling behavior were achieved when bulk-modified with poly(ethylene oxide) (PEO) -silane amphiphiles of varying siloxane tether length: α-(EtO)3Si-(CH2)2-oligodimethylsiloxane m -block-poly(ethylene oxide)8-OCH3 (m = 0, 4, 13, 17, 24, and 30). A PEO8-silane [α-(EtO)3Si-(CH2)3-PEO8-OCH3] served as a conventional PEO-silane control. To examine anti-biofouling behavior in the absence versus presence of water-driven surface restructuring, the amphiphiles and control were surface-grafted onto silicon wafers and used to bulk-modify a medical-grade silicone, respectively. While the surface-grafted PEO-control exhibited superior protein resistance, it failed to appreciably restructure to the surface-water interface of bulk-modified silicone and thus led to poor protein resistance. In contrast, the PEO-silane amphiphiles, while less protein-resistant when surface-grafted onto silicon wafers, rapidly and substantially restructured in bulk-modified silicone, exhibiting superior hydrophilicity and protein resistance. A reduction of biofilm for several strains of bacteria and a fungus was observed for silicones modified with PEO-silane amphiphiles. Longer siloxane tethers maintained surface restructuring and protein resistance while displaying the added benefit of increased transparency.

Antifouling silicones based on surface-modifying additive amphiphiles.

Surface modifying additives (SMAs), which may be readily blended into silicones to improve anti-fouling behavior, must have excellent surface migration potential and must not leach into the aqueous environment. In this work, we evaluated the efficacy of a series of poly(ethylene oxide) (PEO)-based SMA amphiphiles which varied in terms of crosslinkability, siloxane tether length (m) and diblock versus triblock architectures. Specifically, crosslinkable, diblock PEO-silane amphiphiles with two oligodimethylsiloxane (ODMS) tether lengths [(EtO)3Si-(CH2)3-ODMS m -PEO8, m = 13 and 30] were compared to analogous non-crosslinkable, diblock (H-Si-ODMS m -PEO8) and triblock (PEO8-ODMS m -PEO8) SMAs. Prior to water conditioning, while all modified silicone coatings exhibited a high degree of water-driven surface restructuring, that prepared with the non-crosslinkable diblock SMA (m = 13) was the most hydrophilic. After conditioning, all modified silicone coatings were similarly hydrophilic and remained highly protein resistant, with the exception of PEO8-ODMS 30 -PEO8. Notably, despite twice the PEO content, triblock SMAs were not superior to diblock SMAs. For diblock SMAs, it was shown that water uptake and leaching were also similar whether or not the SMA was crosslinkable.

Protein resistance efficacy of PEO-silane amphiphiles: Dependence on PEO-segment length and concentration.

UNLABELLED: In contrast to modification with conventional PEO-silanes (i.e. no siloxane tether), silicones with dramatically enhanced protein resistance have been previously achieved via bulk-modification with poly(ethylene oxide) (PEO)-silane amphiphiles α-(EtO)3Si(CH2)2-oligodimethylsiloxane13-block-PEOn-OCH3 when n=8 and 16 but not when n=3. In this work, their efficacy was evaluated in terms of optimal PEO-segment length and minimum concentration required in silicone. For each PEO-silane amphiphile (n=3, 8, and 16), five concentrations (5, 10, 25, 50, and 100µmol per 1g silicone) were evaluated. Efficacy was quantified in terms of the modified silicones' abilities to undergo rapid, water-driven surface restructuring to form hydrophilic surfaces as well as resistance to fibrinogen adsorption. Only n=8 and 16 were effective, with a lower minimum concentration in silicone required for n=8 (10µmol per 1g silicone) versus n=16 (25µmol per 1g silicone). STATEMENT OF SIGNIFICANCE: Silicone is commonly used for implantable medical devices, but its hydrophobic surface promotes protein adsorption which leads to thrombosis and infection. Typical methods to incorporate poly(ethylene oxide) (PEO) into silicones have not been effective due to the poor migration of PEO to the surface-biological interface. In this work, PEO-silane amphiphiles - comprised of a siloxane tether (m=13) and variable PEO segment lengths (n=3, 8, 16) - were blended into silicone to improve its protein resistance. The efficacy of the amphiphiles was determined to be dependent on PEO length. With the intermediate PEO length (n=8), water-driven surface restructuring and resulting protein resistance was achieved with a concentration of only 1.7wt%.

Direct observation of the nanocomplex surface reorganization of antifouling silicones containing a highly mobile PEO-silane amphiphile.

While nanocomplexity derived from surface reorganization in aqueous biofouling environments is known to give rise to antifouling behavior, quantification of this process is limited. In this work, the surface of an antifouling polymer matrix - a silicone modified with a highly mobile PEO-silane amphiphile - was characterized while undergoing dynamic surface reorganization in aqueous solution via off-resonance tapping mode atomic force microscopy (AFM) and while monitoring surface changes at a rate >25 µm2 min-1. Utilizing multimodal analysis during incubation in aqueous solution and surface force spectroscopic mapping before and after incubation, we directly observed the nanoscopically complex surface of the matrix and its five distinct stages of surface reorganization. Pre- and post-incubation nanomechanical mapping revealed a marked increase in Young's modulus and surface area, as well as increased adhesion and dissipative properties for the post-incubated surface. The observed topographic and viscoelastic changes are explained in terms of surface-air and surface-water interactions. These findings are compared to the bulk matrix reordering observed by immersion dynamic mechanical analysis (DMA) and enhanced protein resistance with increased submersion times as determined by confocal microscopy.