Enhancing the protein resistance of silicone via surface-restructuring PEO–silane amphiphiles with variable PEO length

Rufin, Marc A.; Gruetzner, J. A.; Hurley, M. J.; Hawkins, Melissa L.; Raymond, E. S.; Raymond, Jeffery E.; Grunlan, Melissa A.

doi:10.1039/c4tb02042a

Cited by 43 publications

(60 citation statements)

References 73 publications

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“…PEO-silane amphiphiles ( m = 13; n = 3, 8, and 16) were prepared and characterized as previously reported using a two-step hydrosilylation procedure [44]. Briefly, α,ω-bis-(SiH)ODMS 13 was reacted with vinyltriethoxysilane in a regioselective reaction using Wilkinson’s catalyst.…”

Section: Methodsmentioning

confidence: 99%

“…These include silicones bulk-crosslinked with conventional PEO-silanes such as triethoxysilylpropyl PEO monomethyl ether [(EtO) 3 Si-(CH 2 ) 3 -PEO n- OCH 3 ] [24,25] and allyl PEO monomethyl ether [CH 2 = CHCH 2 -PEO n -OCH 3 ] [43] as well as silicones surface-grafted with allyl PEO monomethyl ether [27,43]. We recently demonstrated that for silicones bulk-modified with PEO-silanes ( n = 3, 8, and 16), poor surface restructuring of PEO was observed [44]. In this way, the surfaces remained hydrophobic, even after exposure to water, and exhibited high protein adsorption similar to that of unmodified silicone.…”

Section: Introductionmentioning

confidence: 99%

“…We have reported silicones with enhanced protein resistance prepared via bulk-modification with PEO-silane amphiphiles bearing an oligodimethylsiloxane (ODMS) tether [α-(EtO) 3 -(CH 2 ) 3 -ODMS m - block -PEO n -OCH 3 ] [44–47]. Silicones bulk-modified with these PEO-silane amphiphiles were observed to undergo substantial and rapid water-driven surface restructuring to form a PEO-enriched surface (by atomic force microscopy [AFM]) [47] with high resistance to proteins [44–47] and other biofoulers [48].…”

Section: Introductionmentioning

confidence: 99%

“…Silicones bulk-modified with these PEO-silane amphiphiles were observed to undergo substantial and rapid water-driven surface restructuring to form a PEO-enriched surface (by atomic force microscopy [AFM]) [47] with high resistance to proteins [44–47] and other biofoulers [48]. Their ability to function as an effective “surface-modifying additive” (SMA) can be attributed to the ODMS tether’s flexibility [40] as well as similar composition and thus compatibility with the silicone matrix.…”

Section: Introductionmentioning

confidence: 99%

“…More recently, silicones were modified using PEO-silane amphiphiles with a variable PEO-segment length ( m = 13; n = 3, 8, and 16) (Fig. 1) [44]. Water-driven change from a hydrophobic to hydrophilic (i.e.…”

Section: Introductionmentioning

confidence: 99%

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

et al. 2016

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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 100 μmol per 1 g 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 (10 μmol per 1 g silicone) versus n = 16 (25 μmol per 1 g 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 1.7 wt%.

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Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

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

et al. 2016

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Combinatorial Polyacrylamide Hydrogels for Preventing Biofouling on Implantable Biosensors

et al. 2022

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Biofouling on the surface of implanted medical devices and biosensors severely hinders device functionality and drastically shortens device lifetime. Poly(ethylene glycol) and zwitterionic polymers are currently considered “gold‐standard” device coatings to reduce biofouling. To discover novel anti‐biofouling materials, a combinatorial library of polyacrylamide‐based copolymer hydrogels is created, and their ability is screened to prevent fouling from serum and platelet‐rich plasma in a high‐throughput parallel assay. It is found that certain nonintuitive copolymer compositions exhibit superior anti‐biofouling properties over current gold‐standard materials, and machine learning is used to identify key molecular features underpinning their performance. For validation, the surfaces of electrochemical biosensors are coated with hydrogels and their anti‐biofouling performance in vitro and in vivo in rodent models is evaluated. The copolymer hydrogels preserve device function and enable continuous measurements of a small‐molecule drug in vivo better than gold‐standard coatings. The novel methodology described enables the discovery of anti‐biofouling materials that can extend the lifetime of real‐time in vivo sensing devices.

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Thromboresistance of Polyurethanes Modified with PEO‐Silane Amphiphiles

Ngo

Lim

Johnson

et al. 2020

Macromolecular Bioscience

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Surface‐induced thrombosis is problematic in blood‐contacting devices composed of silicones or polyurethanes (PUs). Poly(ethylene oxide)‐silane amphiphiles (PEO‐SA) are previously shown effective as surface modifying additives (SMAs) in silicones for enhanced thromboresistance. This study investigates PEO‐SAs as SMAs in a PU at various concentrations: 5, 10, 25, 50, and 100 µmol g−1 PU. PEO‐SA modified PUs are evaluated for their mechanical properties, water‐driven surface restructuring, and adhesion resistance against a human fibrinogen (HF) solution as well as whole human blood. Stability is assessed by monitoring hydrophilicity, water uptake, and mass loss following air‐ or aqueous‐conditioning. PEO‐SA modified PUs do not demonstrate plasticization, as evidenced by minimal changes in glass transition temperature, modulus, tensile strength, and percent strain at break. These also show a concentration‐dependent increase in hydrophilicity that is sustained following air‐ and aqueous‐conditioning for concentrations ≥25 µmol g−1. Additionally, water uptake and mass loss are minimal at all concentrations. Although protein resistance is not enhanced versus an HF solution, PEO‐SA modified PUs have significantly reduced protein adsorption and platelet adhesion from human blood at concentrations ≥10 µmol g−1. Overall, this study demonstrates the versatility of PEO‐SAs as SMAs in PU, which leads to enhanced and sustained hydrophilicity as well as thromboresistance.

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Enhancing the protein resistance of silicone via surface-restructuring PEO–silane amphiphiles with variable PEO length

Cited by 43 publications

References 73 publications

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

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

Combinatorial Polyacrylamide Hydrogels for Preventing Biofouling on Implantable Biosensors

Thromboresistance of Polyurethanes Modified with PEO‐Silane Amphiphiles

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