title: Protein resistance efficacy of PEO-silane amphiphiles: Dependence on PEO-segment length and concentration.
abstract: 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).
  
  
  
  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%.
authors.affiliation: Department of Biomedical Engineering, Texas A&M University, United States.
authors.forename: Marc A
authors.initials: MA
authors.lastname: Rufin
authors.affiliation: Department of Biomedical Engineering, Texas A&M University, United States.
authors.forename: Mikayla E
authors.initials: ME
authors.lastname: Barry
authors.affiliation: Department of Biomedical Engineering, Texas A&M University, United States.
authors.forename: Paige A
authors.initials: PA
authors.lastname: Adair
authors.affiliation: Department of Biomedical Engineering, Texas A&M University, United States.
authors.forename: Melissa L
authors.initials: ML
authors.lastname: Hawkins
authors.affiliation: Department of Chemistry, Texas A&M University, United States.
authors.forename: Jeffery E
authors.initials: JE
authors.lastname: Raymond
authors.affiliation: Department of Biomedical Engineering, Texas A&M University, United States; Department of Materials Science and Engineering, Texas A&M University, United States. Electronic address: mgrunlan@tamu.edu.
authors.forename: Melissa A
authors.initials: MA
authors.lastname: Grunlan
mesh_terms: D000327:Adsorption; D005340:Fibrinogen / Q000737:chemistry*; D006801:Humans; D011092:Polyethylene Glycols / Q000737:chemistry*; D012821:Silanes / Q000737:chemistry*; D012828:Silicones / Q000737:chemistry; D013499:Surface Properties; D013501:Surface-Active Agents / Q000737:chemistry*; D014867:Water / Q000737:chemistry
chemical_list: D012821:Silanes; D012828:Silicones; D013501:Surface-Active Agents; D014867:Water; D011092:Polyethylene Glycols; D005340:Fibrinogen
keywords: Poly(ethylene oxide); Protein-resistant; Silicone; Surface restructuring; Surface-modifying additive