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Title: Antifouling Properties of a Self-Assembling Glutamic Acid-Lysine Zwitterionic Polymer Surface Coating

Abstract

There is a necessity for the development of antifouling materials to resist adsorption of biomacromolecules. Here we describe the preparation of a novel zwitterionic block copolymer with the potential to prevent or delay the formation of microbial biofilms. The block copolymer comprised 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 copolymer 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 copolymer solution exhibited an average distance, d, of approximately 4-8 nm between each block copolymer molecule (center to center). Once the brush-like monolayer self-assembled, it reduced EPS adsorption onto the polystyrene surface by similar to 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, AFMmore » analyses showed that the brush-like monolayer prevents the adhesion of large (>d) hydrophilic colloids onto the surface via hydration repulsion; yet, molecules or colloids small enough to fit between the brush polymers (« less

Authors:
 [1];  [1];  [2];  [2]; ORCiD logo [2];  [1];  [1];  [3];  [1]; ORCiD logo [1]
  1. Ben-Gurion University of the Negev (BGU), Beersheba (Israel)
  2. Univ. of Chicago, IL (United States)
  3. Univ. of Chicago, IL (United States); Argonne National Lab. (ANL), Lemont, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
Ben-Gurion University of the Negev (BGU), Beersheba (Israel)
OSTI Identifier:
1514874
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Langmuir
Additional Journal Information:
Journal Volume: 35; Journal Issue: 5; Journal ID: ISSN 0743-7463
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Ziemba, Christopher, Khavkin, Maria, Priftis, Dimitris, Acar, Handan, Mao, Jun, Benami, Maya, Gottlieb, Moshe, Tirrell, Matthew, Kaufman, Yair, and Herzberg, Moshe. Antifouling Properties of a Self-Assembling Glutamic Acid-Lysine Zwitterionic Polymer Surface Coating. United States: N. p., 2018. Web. doi:10.1021/acs.langmuir.8b00181.
Ziemba, Christopher, Khavkin, Maria, Priftis, Dimitris, Acar, Handan, Mao, Jun, Benami, Maya, Gottlieb, Moshe, Tirrell, Matthew, Kaufman, Yair, & Herzberg, Moshe. Antifouling Properties of a Self-Assembling Glutamic Acid-Lysine Zwitterionic Polymer Surface Coating. United States. https://doi.org/10.1021/acs.langmuir.8b00181
Ziemba, Christopher, Khavkin, Maria, Priftis, Dimitris, Acar, Handan, Mao, Jun, Benami, Maya, Gottlieb, Moshe, Tirrell, Matthew, Kaufman, Yair, and Herzberg, Moshe. Wed . "Antifouling Properties of a Self-Assembling Glutamic Acid-Lysine Zwitterionic Polymer Surface Coating". United States. https://doi.org/10.1021/acs.langmuir.8b00181. https://www.osti.gov/servlets/purl/1514874.
@article{osti_1514874,
title = {Antifouling Properties of a Self-Assembling Glutamic Acid-Lysine Zwitterionic Polymer Surface Coating},
author = {Ziemba, Christopher and Khavkin, Maria and Priftis, Dimitris and Acar, Handan and Mao, Jun and Benami, Maya and Gottlieb, Moshe and Tirrell, Matthew and Kaufman, Yair and Herzberg, Moshe},
abstractNote = {There is a necessity for the development of antifouling materials to resist adsorption of biomacromolecules. Here we describe the preparation of a novel zwitterionic block copolymer with the potential to prevent or delay the formation of microbial biofilms. The block copolymer comprised 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 copolymer 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 copolymer solution exhibited an average distance, d, of approximately 4-8 nm between each block copolymer molecule (center to center). Once the brush-like monolayer self-assembled, it reduced EPS adsorption onto the polystyrene surface by similar to 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; yet, molecules or colloids small enough to fit between the brush polymers (},
doi = {10.1021/acs.langmuir.8b00181},
journal = {Langmuir},
number = 5,
volume = 35,
place = {United States},
year = {Wed Apr 11 00:00:00 EDT 2018},
month = {Wed Apr 11 00:00:00 EDT 2018}
}

Journal Article:
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Cited by: 14 works
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Figures / Tables:

Figure 1 Figure 1: Molecular schematic of the combination of hydrophobic polystyrene (2) to the hydrophilic peptide polymer (1) to form the zwitterionic peptide-polystyrene block copolymer (3).

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Works referenced in this record:

Antifouling Coatings: Recent Developments in the Design of Surfaces That Prevent Fouling by Proteins, Bacteria, and Marine Organisms
journal, September 2010

  • Banerjee, Indrani; Pangule, Ravindra C.; Kane, Ravi S.
  • Advanced Materials, Vol. 23, Issue 6, p. 690-718
  • DOI: 10.1002/adma.201001215

Surface hydration: Principles and applications toward low-fouling/nonfouling biomaterials
journal, October 2010


A Survey of Structure−Property Relationships of Surfaces that Resist the Adsorption of Protein
journal, September 2001

  • Ostuni, Emanuele; Chapman, Robert G.; Holmlin, R. Erik
  • Langmuir, Vol. 17, Issue 18
  • DOI: 10.1021/la010384m

Self-Assembled Monolayers That Resist the Adsorption of Proteins and the Adhesion of Bacterial and Mammalian Cells
journal, October 2001

  • Ostuni, Emanuele; Chapman, Robert G.; Liang, Michael N.
  • Langmuir, Vol. 17, Issue 20
  • DOI: 10.1021/la010552a

Kosmotropes Form the Basis of Protein-Resistant Surfaces
journal, March 2003

  • Kane, Ravi S.; Deschatelets, Pascal; Whitesides, George M.
  • Langmuir, Vol. 19, Issue 6
  • DOI: 10.1021/la020737x

Protein Resistance of Surfaces Prepared by Sorption of End-Thiolated Poly(ethylene glycol) to Gold:  Effect of Surface Chain Density
journal, February 2005

  • Unsworth, Larry D.; Sheardown, Heather; Brash, John L.
  • Langmuir, Vol. 21, Issue 3
  • DOI: 10.1021/la047672d

Controlled Chemical and Structural Properties of Mixed Self-Assembled Monolayers of Alkanethiols on Au(111)
journal, November 2000

  • Chen, Shengfu; Li, Lingyan; Boozer, Christina L.
  • Langmuir, Vol. 16, Issue 24
  • DOI: 10.1021/la000417i

Factors that Determine the Protein Resistance of Oligoether Self-Assembled Monolayers − Internal Hydrophilicity, Terminal Hydrophilicity, and Lateral Packing Density
journal, August 2003

  • Herrwerth, Sascha; Eck, Wolfgang; Reinhardt, Sven
  • Journal of the American Chemical Society, Vol. 125, Issue 31
  • DOI: 10.1021/ja034820y

Strong Repulsive Forces between Protein and Oligo (Ethylene Glycol) Self-Assembled Monolayers: A Molecular Simulation Study
journal, July 2005


In Pursuit of Zero: Polymer Brushes that Resist the Adsorption of Proteins
journal, June 2009

  • Hucknall, Angus; Rangarajan, Srinath; Chilkoti, Ashutosh
  • Advanced Materials, Vol. 21, Issue 23, p. 2441-2446
  • DOI: 10.1002/adma.200900383

Ultra-low fouling peptide surfaces derived from natural amino acids
journal, October 2009


Surface Properties and Reduced Biofouling of Graft-Copolymers That Possess Oppositely Charged Groups
journal, April 2011

  • Herzberg, Moshe; Sweity, Amer; Brami, Matan
  • Biomacromolecules, Vol. 12, Issue 4
  • DOI: 10.1021/bm101470y

Chemical and Physical Factors in Design of Antibiofouling Polymer Coatings
journal, May 2011

  • Eshet, Inbal; Freger, Viatcheslav; Kasher, Roni
  • Biomacromolecules, Vol. 12, Issue 7, p. 2681-2685
  • DOI: 10.1021/bm200476g

Brushes of strong polyelectrolytes in mixed mono- and tri-valent ionic media at fixed total ionic strengths
journal, January 2013

  • Farina, Robert; Laugel, Nicolas; Pincus, Philip
  • Soft Matter, Vol. 9, Issue 44
  • DOI: 10.1039/c3sm51450a

Molecular Understanding and Design of Zwitterionic Materials
journal, November 2014


Zwitterionic Polymers Exhibiting High Resistance to Nonspecific Protein Adsorption from Human Serum and Plasma
journal, May 2008

  • Ladd, Jon; Zhang, Zheng; Chen, Shengfu
  • Biomacromolecules, Vol. 9, Issue 5
  • DOI: 10.1021/bm701301s

Antifouling ultrafiltration membrane composed of polyethersulfone and sulfobetaine copolymer
journal, September 2006


Study on a novel nanofiltration membrane prepared by interfacial polymerization with zwitterionic amine monomers
journal, March 2013


Peptide-Based SAMs that Resist the Adsorption of Proteins
journal, October 2008

  • Chelmowski, Rolf; Köster, Stephan David; Kerstan, Andreas
  • Journal of the American Chemical Society, Vol. 130, Issue 45
  • DOI: 10.1021/ja8065754

Grafting short-chain amino acids onto membrane surfaces to resist protein fouling
journal, January 2011


Sequence, Structure, and Function of Peptide Self-Assembled Monolayers
journal, March 2012

  • Nowinski, Ann K.; Sun, Fang; White, Andrew D.
  • Journal of the American Chemical Society, Vol. 134, Issue 13
  • DOI: 10.1021/ja3006868

Antifouling Gold Surfaces Grafted with Aspartic Acid and Glutamic Acid Based Zwitterionic Polymer Brushes
journal, October 2014

  • Li, Wenchen; Liu, Qingsheng; Liu, Lingyun
  • Langmuir, Vol. 30, Issue 42
  • DOI: 10.1021/la502789v

Cell-Adhesive and Cell-Repulsive Zwitterionic Oligopeptides for Micropatterning and Rapid Electrochemical Detachment of Cells
journal, January 2013

  • Kakegawa, Takahiro; Mochizuki, Naoto; Sadr, Nasser
  • Tissue Engineering Part A, Vol. 19, Issue 1-2
  • DOI: 10.1089/ten.tea.2011.0739

Superior Antifouling Performance of a Zwitterionic Peptide Compared to an Amphiphilic, Non-Ionic Peptide
journal, September 2015

  • Ye, Huijun; Wang, Libing; Huang, Renliang
  • ACS Applied Materials & Interfaces, Vol. 7, Issue 40
  • DOI: 10.1021/acsami.5b06500

Nanoscale engineering of low-fouling surfaces through polydopamine immobilisation of zwitterionic peptides
journal, January 2014


Nature of the N−H···S Hydrogen Bond
journal, October 2009

  • Biswal, Himansu S.; Wategaonkar, Sanjay
  • The Journal of Physical Chemistry A, Vol. 113, Issue 46
  • DOI: 10.1021/jp907658w

O–H···S Hydrogen Bonds Conform to the Acid–Base Formalism
journal, May 2013

  • Bhattacharyya, Surjendu; Bhattacherjee, Aditi; Shirhatti, Pranav R.
  • The Journal of Physical Chemistry A, Vol. 117, Issue 34
  • DOI: 10.1021/jp405414h

The biofilm matrix
journal, August 2010

  • Flemming, Hans-Curt; Wingender, Jost
  • Nature Reviews Microbiology, Vol. 8, Issue 9
  • DOI: 10.1038/nrmicro2415

Solid phase peptide synthesis utilizing 9-fluorenylmethoxycarbonyl amino acids
journal, March 1990


Synthetic lipidation of peptides and amino acids: monolayer structure and properties.
journal, September 1995

  • Berndt, Peter; Fields, Gregg B.; Tirrell, Matthew
  • Journal of the American Chemical Society, Vol. 117, Issue 37
  • DOI: 10.1021/ja00142a019

MALDI-TOF MS Characterization of Carboxyl-End-Capped Polystyrenes Synthesized Using Anionic Polymerization
journal, October 2005

  • Ji, Haining; Nonidez, William K.; Advincula, Rigoberto C.
  • Macromolecules, Vol. 38, Issue 24
  • DOI: 10.1021/ma050816q

Mechanisms of Peptide Amphiphile Internalization by SJSA-1 Cells in Vitro
journal, April 2009

  • Missirlis, Dimitris; Khant, Htet; Tirrell, Matthew
  • Biochemistry, Vol. 48, Issue 15
  • DOI: 10.1021/bi802356k

Viscoelastic Properties of Extracellular Polymeric Substances Can Strongly Affect Their Washing Efficiency from Reverse Osmosis Membranes
journal, August 2016

  • Ferrando Chavez, Diana Lila; Nejidat, Ali; Herzberg, Moshe
  • Environmental Science & Technology, Vol. 50, Issue 17
  • DOI: 10.1021/acs.est.6b01458

Extraction of extracellular polymeric substances (EPS) of sludges
journal, May 2002


Verwendung von Schwingquarzen zur W�gung d�nner Schichten und zur Mikrow�gung
journal, April 1959


Wettability of porous surfaces
journal, January 1944

  • Cassie, A. B. D.; Baxter, S.
  • Transactions of the Faraday Society, Vol. 40, p. 546-551
  • DOI: 10.1039/tf9444000546

Simple-to-Apply Wetting Model to Predict Thermodynamically Stable and Metastable Contact Angles on Textured/Rough/Patterned Surfaces
journal, March 2017

  • Kaufman, Yair; Chen, Szu-Ying; Mishra, Himanshu
  • The Journal of Physical Chemistry C, Vol. 121, Issue 10
  • DOI: 10.1021/acs.jpcc.7b00003

Salt-Responsive Zwitterionic Polymer Brushes with Tunable Friction and Antifouling Properties
journal, August 2015


Synthesis, Characterization, and Aqueous Solution Behavior of Electrolyte- and pH-Responsive Carboxybetaine-Containing Cyclocopolymers
journal, December 2003

  • Thomas, David B.; Vasilieva, Yulia A.; Armentrout, R. Scott
  • Macromolecules, Vol. 36, Issue 26
  • DOI: 10.1021/ma0345807

Effects of shear rate on biofouling of reverse osmosis membrane during tertiary wastewater desalination
journal, January 2013


Deposition of extracellular polymeric substances (EPS) and microtopographical changes on membrane surfaces during intermittent filtration conditions
journal, November 2006


Relation between EPS adherence, viscoelastic properties, and MBR operation: Biofouling study with QCM-D
journal, December 2011


Hearing What You Cannot See and Visualizing What You Hear: Interpreting Quartz Crystal Microbalance Data from Solvated Interfaces
journal, December 2011

  • Reviakine, Ilya; Johannsmann, Diethelm; Richter, Ralf P.
  • Analytical Chemistry, Vol. 83, Issue 23
  • DOI: 10.1021/ac201778h

Zeta potential of microfluidic substrates: 1. Theory, experimental techniques, and effects on separations
journal, January 2004


A comparative study of the nature of biopolymers extracted from anaerobic and activated sludges
journal, June 1990


Hydration forces between mica surfaces in electrolyte solutions
journal, July 1982


Dlvo and hydration forces between mica surfaces in Mg2+, Ca2+, Sr2+, and Ba2+ chloride solutions
journal, February 1984


Extracellular polymeric substances (EPS) of microbial aggregates in biological wastewater treatment systems: A review
journal, November 2010


Selective crosslinking or addressing of individual domains within block copolymer nanostructures
journal, July 2016


Works referencing / citing this record:

Povidone-iodine-functionalized fluorinated copolymers with dual-functional antibacterial and antifouling activities
journal, January 2019

  • Borjihan, Qinggele; Yang, Jiebing; Song, Qing
  • Biomaterials Science, Vol. 7, Issue 8
  • DOI: 10.1039/c9bm00583h

Protein-resistant surface based on zwitterion-functionalized nanoparticles for marine antifouling applications
journal, January 2020

  • Sun, Ding; Li, Peiyun; Li, Xiong
  • New Journal of Chemistry, Vol. 44, Issue 5
  • DOI: 10.1039/c9nj04266k

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