title: Amphiphilic triblock copolymers with PEGylated hydrocarbon structures as environmentally friendly marine antifouling and fouling-release coatings.
abstract: The ideal marine antifouling (AF)/fouling-release (FR) coating should be non-toxic, while effectively either resisting the attachment of marine organisms (AF) or significantly reducing their strength of attachment (FR). Many recent studies have shown that amphiphilic polymeric materials provide a promising solution to producing such coatings due to their surface dual functionality. In this work, poly(ethylene glycol) (PEG) of different molecular weights (Mw = 350, 550) was coupled to a saturated difunctional alkyl alcohol to generate amphiphilic surfactants (PEG-hydrocarbon-OH). The resulting macromolecules were then used as side chains to covalently modify a pre-synthesized PS8 K-b-P(E/B)25 K-b-PI10 K (SEBI or K3) triblock copolymer, and the final polymers were applied to glass substrata through an established multilayer surface coating technique to prepare fouling resistant coatings. The coated surfaces were characterized with AFM, XPS and NEXAFS, and evaluated in laboratory assays with two important fouling algae, Ulva linza (a green macroalga) and Navicula incerta, a biofilm-forming diatom. The results suggest that these polymer-coated surfaces undergo surface reconstruction upon changing the contact medium (polymer/air vs polymer/water), due to the preferential interfacial aggregation of the PEG segment on the surface in water. The amphiphilic polymer-coated surfaces showed promising results as both AF and FR coatings. The sample with longer PEG chain lengths (Mw = 550 g mol(-1)) exhibited excellent properties against both algae, highlighting the importance of the chemical structures on ultimate biological performance. Besides reporting synthesis and characterization of this new type of amphiphilic surface material, this work also provides insight into the nature of PEG/hydrocarbon amphiphilic coatings, and this understanding may help in the design of future generations of fluorine-free, environmentally friendly AF/FR polymeric coatings.
authors.affiliation: a Department of Chemistry and Chemical Biology , Cornell University , Ithaca , New York 14853 , USA.
authors.forename: Zhaoli
authors.initials: Z
authors.lastname: Zhou
authors.forename: David R
authors.initials: DR
authors.lastname: Calabrese
authors.forename: Warren
authors.initials: W
authors.lastname: Taylor
authors.forename: John A
authors.initials: JA
authors.lastname: Finlay
authors.forename: Maureen E
authors.initials: ME
authors.lastname: Callow
authors.forename: James A
authors.initials: JA
authors.lastname: Callow
authors.forename: Daniel
authors.initials: D
authors.lastname: Fischer
authors.forename: Edward J
authors.initials: EJ
authors.lastname: Kramer
authors.forename: Christopher K
authors.initials: CK
authors.lastname: Ober
mesh_terms: D059001:Aquatic Organisms / Q000187:drug effects*; D018441:Biofilms / Q000187:drug effects / Q000254:growth & development; D057219:Biofouling / Q000517:prevention & control*; D002448:Cell Adhesion / Q000187:drug effects; D017377:Diatoms / Q000502:physiology; D011092:Polyethylene Glycols / Q000737:chemistry*; D011108:Polymers / Q000737:chemistry; D012623:Seawater; D013499:Surface Properties; D013501:Surface-Active Agents / Q000737:chemistry / Q000494:pharmacology*; D044445:Ulva / Q000502:physiology; D014872:Water Movements
chemical_list: D011108:Polymers; D013501:Surface-Active Agents; D011092:Polyethylene Glycols
keywords: alga; amphiphilic polymer; hydrocarbon/PEG surfactants; marine antifouling/fouling release coatings; surface structure