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Biological and Environmental Phenomena at the Interface
Antifouling Properties of a Self-Assembling Glutamic Acid-Lysine Zwitterionic Polymer Surface Coating Christopher Ziemba, Maria Khavkin, Dimitris Priftis, Handan Acar, Jun Mao, Maya Benami, Moshe Gottlieb, Matthew V. Tirrell, Yair Kaufman, and Moshe Herzberg Langmuir, Just Accepted Manuscript • DOI: 10.1021/acs.langmuir.8b00181 • Publication Date (Web): 11 Apr 2018 Downloaded from http://pubs.acs.org on April 12, 2018
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Langmuir
Antifouling Properties of a Self-Assembling Glutamic Acid-Lysine Zwitterionic Polymer Surface Coating Christopher Ziemba1,2,3, Maria Khavkin1, Dimitris Priftis4, Handan Acar4, Jun Mao4, Maya Benami1, Moshe Gottlieb6, Matthew Tirrell4,5, Yair Kaufman1*, Moshe Herzberg1* 1
The Jacob Blaustein Institutes for Desert Research, Zuckerberg Institute for Water
Research, The Albert Katz International School of Desert Studies, Ben Gurion University of the Negev, Sede Boqer Campus, Midreshet Ben-Gurion, 84990 Israel 2
Current address: Eawag, Swiss Federal Institute of Aquatic Science and Technology,
Überlandstrasse 133, CH-8600 Dübendorf, Switzerland 3
Current address: Institute of Environmental Engineering, ETH Zürich, CH-8093, Zürich,
Switzerland 4
Institute for Molecular Engineering, University of Chicago, Chicago, Illinois 60637, United
States 5
Materials Science Division, Argonne National Laboratory, Argonne, Illinois 60439, United
States 6
Department of Chemical Engineering, Ben Gurion University of the Negev, Beer-Sheva
84105 Israel
Corresponding Authors *E-mail:
[email protected],
[email protected] KEYWORDS: biofouling, extracellular polymeric substances, polymer brush, quartz crystal microbalance with dissipation, atomic force microscopy
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ABSTRACT There is a need for the development of antifouling materials to resist adsorption of biomacromolecules. Here we describe the preparation of a novel zwitterionic block co-polymer with the potential to prevent or delay the formation of microbial biofilms. The block copolymer comprised of a zwitterionic (hydrophilic) section of alternating glutamic acid (negatively-charged) and lysine (positively-charged) units and a hydrophobic polystyrene section. Cryo-TEM and dynamic-light-scattering (DLS) results showed that on average, the block co-polymer self-assembled into 7 nm diameter micelles in aqueous solutions (0 to 100 mM NaCl, pH 6). Quartz crystal microbalance with dissipation monitoring (QCM-D), atomic force microscopy (AFM), and contact angle measurements demonstrated that the block copolymer self-assembled into a brush-like monolayer on polystyrene surfaces. The brush-like monolayer produced from a 100 mg/L block co-polymer solution exhibited an average distance, d, of approximately 4 - 8 nm between each block co-polymer molecule (center to center). Once the brush-like monolayer self-assembled, it reduced EPS adsorption onto the polystyrene surface by ~70% (mass), reduced the rate of bacterial attachment by >80%, and inhibited the development of thick biofilms. QCM-D results revealed that the EPS molecules penetrate between the chains of the brush and adsorb onto the polystyrene surface. Additionally, AFM analyses showed that the brush-like monolayer prevents the adhesion of large (>d) hydrophilic colloids onto the surface via hydration repulsion; however, molecules or colloids small enough to fit between the brush polymers (
