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Anti-Biofouling Properties of Comblike Block Copolymers with Amphiphilic Side Chains

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Department of Materials Science and Engineering, Cornell University, Ithaca, New York 14853, Department of Materials and Department of Chemical Engineering, University of California at Santa Barbara, Santa Barbara, California 93106, School of Biosciences, The University of Birmingham, Edgbaston, Birmingham B15 5TT, U.K., and National Institute of Standards and Technology, Gaithersburg, Maryland 20899
Cite this: Langmuir 2006, 22, 11, 5075–5086
Publication Date (Web):April 21, 2006
https://doi.org/10.1021/la052978l
Copyright © 2006 American Chemical Society
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    Abstract

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    Surfaces of novel block copolymers with amphiphilic side chains were studied for their ability to influence the adhesion of marine organisms. The surface-active polymer, obtained by grafting fluorinated molecules with hydrophobic and hydrophilic blocks to a block copolymer precursor, showed interesting bioadhesion properties. Two different algal species, one of which adhered strongly to hydrophobic surfaces, and the other, to hydrophilic surfaces, showed notably weak adhesion to the amphiphilic surfaces. Both organisms are known to secrete adhesive macromolecules, with apparently different wetting characteristics, to attach to underwater surfaces. The ability of the amphiphilic surface to undergo an environment-dependent transformation in surface chemistry when in contact with the extracellular polymeric substances is a possible reason for its antifouling nature. Near-edge X-ray absorption fine structure spectroscopy (NEXAFS) was used, in a new approach based on angle-resolved X-ray photoelectron spectroscopy (XPS), to determine the variation in chemical composition within the top few nanometers of the surface and also to study the surface segregation of the amphiphilic block. A mathematical model to extract depth-profile information from the normalized NEXAFS partial electron yield is developed.

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    †

     Cornell University.

    ‡

     Department of Materials, University of California at Santa Barbara.

    ‖

     The University of Birmingham.

    *

     To whom correspondence should be addressed. E-mail:  cober@ ccmr.cornell.edu. Tel:  607-255-8417. Fax:  607-255-2365.

    §

     Department of Chemical Engineering, University of California at Santa Barbara.

    ⊥

     National Institute of Standards and Technology.

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    Gel permeation chromatography, IR and NMR spectra of the block copolymer with amphiphilic side chains and its precursors, MALDI-TOF spectrum of the ethoxylated fluoroalkyl surfactant, roughness profile of surfaces used for biofouling assays, images of Ulva biofilms on the test surfaces before and after exposure to water shear stress. This material is available free of charge via the Internet at http://pubs.acs.org.

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