Influence of Grafting Density and the Ionic Environment on the Structure of Zwitterionic Brushes

Witte, Judith; Koutsioubas, Alexandros; Micciulla, Samantha; Stingaciu, Laura Roxana; Paulin, Mariano Andrés; Dahl, Margarethe; Fettkenhauer, Christian; Lahann, Joerg; Holderer, Olaf; Wellert, Stefan

doi:10.1021/acsapm.4c02879

Title: Influence of Grafting Density and the Ionic Environment on the Structure of Zwitterionic Brushes

Journal Article · Fri May 09 00:00:00 UTC 2025 · ACS Applied Polymer Materials

DOI: https://doi.org/10.1021/acsapm.4c02879 · OSTI ID:2573112

^[1];

^[2]; Micciulla, Samantha ^[3];

^[4]; Paulin, Mariano Andrés ^[5];

^[1]; Fettkenhauer, Christian ^[6]; Lahann, Joerg ^[7];

^[2];

^[1]

Technical Univ. of Berlin (Germany)
Juelich Centre for Neutron Science (JCNS) at Heinz Maier-Leibnitz Zentrum (MLZ), Forschungszentrum Juelich GmbH, Garching (Germany)
Centre National de la Recherche Scientifique (CNRS) (France); Inst. Laue-Langevin (ILL), Grenoble (France)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Helmholtz-Zentrum Berlin (HZB), (Germany). German Research Centre for Materials and Energy; National Atomic Energy Commission (CNEA), Rio Negro (Argentina)
Anton Paar Germany (Germany)
Karlsruhe Inst. of Technology (KIT) (Germany)

Zwitterionic polymer brushes possess a high potential for applications as surface coatings, e.g., in antifouling applications. Their complex association behavior due to the coexistence of oppositely charged groups on the same monomeric unit allows for a broad variation of polarity, hydrophilicity, and the antipolyelectrolyte effect with the variation of the surrounding environment. In this study, planar polysulfobetaine brushes were investigated with neutron reflectometry (NR) and neutron spin–echo spectroscopy under grazing incidence (GINSES) to explore the brush structure and its inner dynamics perpendicular to the substrate. In particular, the effects of the substrate–initiator system and ionic strength on the structure were investigated with neutron reflectometry and a swelling by a factor of 3–5 was found in the presence of aqueous NaCl and MgCl₂ solutions compared to the dry state. During the data analysis, the applicability of a model-free evaluation was also demonstrated for the investigated polysulfobetaine brushes. Furthermore, it was found with GINSES that in contrast to neutral brushes, these polysulfobetaine brushes do not show the typical concentration fluctuations in the nanosecond time range when partially swollen with salt-free water.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 2573112

Journal Information:: ACS Applied Polymer Materials, Journal Name: ACS Applied Polymer Materials Journal Issue: 10 Vol. 7; ISSN 2637-6105

Publisher:: ACS PublicationsCopyright Statement

Country of Publication:: United States

Language:: English

References (51)

Ultralow-Fouling, Functionalizable, and Hydrolyzable Zwitterionic Materials and Their Derivatives for Biological Applications Jiang, Shaoyi; Cao, Zhiqiang Advanced Materials, Vol. 22, Issue 9 https://doi.org/10.1002/adma.200901407	journal	November 2009
Kinetics of Water Transfer Between the LCST and UCST Thermoresponsive Blocks in Diblock Copolymer Thin Films Monitored by In Situ Neutron Reflectivity Hu, Neng; Lin, Li; Metwalli, Ezzeldin Advanced Materials Interfaces, Vol. 10, Issue 3 https://doi.org/10.1002/admi.202201913	journal	December 2022
Spacer Effects in Sulfo‐ and Sulfabetaine Polymers on Their Resistance against Proteins and Pathogenic Bacteria Karthäuser, Jana F.; Kopecz, Regina; Schönemann, Eric Advanced Materials Interfaces, Vol. 11, Issue 5 https://doi.org/10.1002/admi.202300873	journal	January 2024
Integrated Antimicrobial and Nonfouling Zwitterionic Polymers Mi, Luo; Jiang, Shaoyi Angewandte Chemie International Edition, Vol. 53, Issue 7 https://doi.org/10.1002/anie.201304060	journal	January 2014
Zwitterionic Polymer Brushes and Core‐Shell Particles Based thereon for Control of Biofouling Kopsch, Fabian; Drechsler, Astrid; Priebs, Martina Macromolecular Chemistry and Physics, Vol. 224, Issue 9 https://doi.org/10.1002/macp.202200454	journal	March 2023
Internal Architecture of Zwitterionic Polymer Brushes Regulates Nonfouling Properties Huang, Chun‐Jen; Li, Yuting; Krause, Jordan B. Macromolecular Rapid Communications, Vol. 33, Issue 11 https://doi.org/10.1002/marc.201100858	journal	February 2012
Atomistic Insights into the Ionic Response and Mechanism of Antifouling Zwitterionic Polymer Brushes Song, Xinzhong; Man, Jia; Zhang, Xiangkuan Small, Vol. 21, Issue 6 https://doi.org/10.1002/smll.202406233	journal	November 2024
Neutron Spin Echo in Polymer Systems, Chapter 1 Richter, Dieter; Monkenbusch, Michael; Arbe, Arantxa Neutron Spin Echo in Polymer Systems https://doi.org/10.1007/b99835	book	January 2005
A grazing incidence neutron spin echo study of near surface dynamics in p(MEO2MA-co-OEGMA) copolymer brushes Wellert, Stefan; Hübner, Jessica; Boyaciyan, Dikran Colloid and Polymer Science, Vol. 296, Issue 12 https://doi.org/10.1007/s00396-018-4421-9	journal	November 2018
Zeta potential measurements of Ta2O5 and SiO2 thin films Bousse, Luc; Mostarshed, Shahriar; Van Der Shoot, Bart Journal of Colloid and Interface Science, Vol. 147, Issue 1 https://doi.org/10.1016/0021-9797(91)90130-Z	journal	November 1991
High-density zwitterionic polymer brushes exhibit robust lubrication properties and high antithrombotic efficacy in blood-contacting medical devices Song, Xinzhong; Man, Jia; Qiu, Yinghua Acta Biomaterialia, Vol. 178 https://doi.org/10.1016/j.actbio.2024.02.032	journal	April 2024
Enhancement of the propagation of human embryonic stem cells by modifications in the gel architecture of PMEDSAH polymer coatings Qian, Xu; Villa-Diaz, Luis G.; Kumar, Ramya Biomaterials, Vol. 35, Issue 36 https://doi.org/10.1016/j.biomaterials.2014.08.015	journal	December 2014
Hydroxide and hydronium ion adsorption — A survey Zimmermann, Ralf; Freudenberg, Uwe; Schweiß, Rüdiger Current Opinion in Colloid & Interface Science, Vol. 15, Issue 3 https://doi.org/10.1016/j.cocis.2010.01.002	journal	June 2010
Resistance of zwitterionic telomers accumulated on metal surfaces against nonspecific adsorption of proteins Kitano, Hiromi; Kawasaki, Akio; Kawasaki, Hideaki Journal of Colloid and Interface Science, Vol. 282, Issue 2 https://doi.org/10.1016/j.jcis.2004.08.157	journal	February 2005
Scattering depth correction of evanescent waves in inelastic neutron scattering using a neutron prism Frielinghaus, H.; Holderer, O.; Lipfert, F. Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 686 https://doi.org/10.1016/j.nima.2012.05.064	journal	September 2012
The spin-echo spectrometer at the Spallation Neutron Source (SNS) Ohl, M.; Monkenbusch, M.; Arend, N. Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 696 https://doi.org/10.1016/j.nima.2012.08.059	journal	December 2012
New tools for grazing incidence neutron scattering experiments open perspectives to study nano-scale tribology mechanisms Frielinghaus, H.; Gvaramia, M.; Mangiapia, G. Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 871 https://doi.org/10.1016/j.nima.2017.07.064	journal	November 2017
Bioinspired marine antifouling coatings: Status, prospects, and future Jin, Huichao; Tian, Limei; Bing, Wei Progress in Materials Science, Vol. 124 https://doi.org/10.1016/j.pmatsci.2021.100889	journal	February 2022
Hydration State Variation of Polyzwitterion Brushes through Interplay with Ions Higaki, Yuji; Kobayashi, Motoyasu; Takahara, Atsushi Langmuir, Vol. 36, Issue 31 https://doi.org/10.1021/acs.langmuir.0c01672	journal	July 2020
Molecular Design of Zwitterionic Polymer Interfaces: Searching for the Difference Laschewsky, André; Rosenhahn, Axel Langmuir, Vol. 35, Issue 5 https://doi.org/10.1021/acs.langmuir.8b01789	journal	July 2018
Ion-Specific Hydration States of Zwitterionic Poly(sulfobetaine methacrylate) Brushes in Aqueous Solutions Sakamaki, Tatsunori; Inutsuka, Yoshihiro; Igata, Kosuke Langmuir, Vol. 35, Issue 5 https://doi.org/10.1021/acs.langmuir.8b03104	journal	November 2018
Ion Specificity Influences on the Structure of Zwitterionic Brushes He, Qiming; Qiao, Yijun; Medina Jimenez, Carlos Macromolecules, Vol. 56, Issue 5 https://doi.org/10.1021/acs.macromol.2c02029	journal	February 2023
Effect of Magnesium Salts with Chaotropic Anions on the Swelling Behavior of PNIPMAM Thin Films Reitenbach, Julija; Geiger, Christina; Wang, Peixi Macromolecules, Vol. 56, Issue 2 https://doi.org/10.1021/acs.macromol.2c02282	journal	January 2023
Unveiling the Layered Structure of Sulfobetaine Polymer Brushes through Bimodal Atomic Force Microscopy Mondarte, Evan Angelo Quimada; Shi, Yuchen; Koh, Xue Qi Macromolecules, Vol. 56, Issue 13 https://doi.org/10.1021/acs.macromol.3c00721	journal	June 2023
Aqueous Swelling of Zwitterionic Poly(sulfobetaine methacrylate) Brushes in the Presence of Ionic Surfactants Yang, Zhefei; Zhang, Shouwei; Tarabara, Volodymyr V. Macromolecules, Vol. 51, Issue 3 https://doi.org/10.1021/acs.macromol.7b01830	journal	January 2018
Grazing Incidence Neutron Spin Echo Study of Poly(N-isopropylacrylamide) Brushes Witte, Judith; Krause, Patrick; Kyrey, Tetyana Macromolecules, Vol. 53, Issue 5 https://doi.org/10.1021/acs.macromol.9b01247	journal	February 2020
Fouling Resistance and Release Properties of Poly(sulfobetaine) Brushes with Varying Alkyl Chain Spacer Lengths and Molecular Weights Khakzad, Fahimeh; Dewangan, Narendra K.; Li, Tzu-Han ACS Applied Materials & Interfaces, Vol. 15, Issue 1 https://doi.org/10.1021/acsami.2c16417	journal	December 2022
Looking inside Poly(N-isopropylacrylamide) Microgels: Nanomechanics and Dynamics at Solid–Liquid Interfaces Witte, Judith; Kyrey, Tetyana; Lutzki, Jana ACS Applied Polymer Materials, Vol. 3, Issue 2 https://doi.org/10.1021/acsapm.0c01265	journal	January 2021
Polyzwitterions: From Surface Properties and Bioactivity Profiles to Biomedical Applications Paschke, Stefan; Lienkamp, Karen ACS Applied Polymer Materials, Vol. 2, Issue 2 https://doi.org/10.1021/acsapm.9b00897	journal	December 2019
Self-Assembly, Antipolyelectrolyte Effect, and Nonbiofouling Properties of Polyzwitterions Georgiev, George S.; Kamenska, Elena B.; Vassileva, Elena D. Biomacromolecules, Vol. 7, Issue 4 https://doi.org/10.1021/bm050938q	journal	April 2006
Investigation of the Hydration of Nonfouling Material Poly(sulfobetaine methacrylate) by Low-Field Nuclear Magnetic Resonance Wu, Jiang; Lin, Weifeng; Wang, Zhen Langmuir, Vol. 28, Issue 19 https://doi.org/10.1021/la300394c	journal	May 2012
Zwitteration: Coating Surfaces with Zwitterionic Functionality to Reduce Nonspecific Adsorption Schlenoff, Joseph B. Langmuir, Vol. 30, Issue 32 https://doi.org/10.1021/la500057j	journal	April 2014
Surface Chemistry and Rheology of Polysulfobetaine-Coated Silica Starck, Pierre; Mosse, Wade K. J.; Nicholas, Nathan J. Langmuir, Vol. 23, Issue 14 https://doi.org/10.1021/la700642d	journal	June 2007
Film Thickness Dependence of Protein Adsorption from Blood Serum and Plasma onto Poly(sulfobetaine)-Grafted Surfaces Yang, Wei; Chen, Shengfu; Cheng, Gang Langmuir, Vol. 24, Issue 17 https://doi.org/10.1021/la801487f	journal	September 2008
Thickness-Dependent Properties of Polyzwitterionic Brushes Cheng, Nan; Brown, Andrew A.; Azzaroni, Omar Macromolecules, Vol. 41, Issue 17 https://doi.org/10.1021/ma800625y	journal	August 2008
Versatile inhibition of marine organism settlement by zwitterionic polymer brushes Higaki, Yuji; Nishida, Jin; Takenaka, Ai Polymer Journal, Vol. 47, Issue 12 https://doi.org/10.1038/pj.2015.77	journal	September 2015
Dynamic surface antifouling: mechanism and systems Xie, Qingyi; Pan, Jiansen; Ma, Chunfeng Soft Matter, Vol. 15, Issue 6 https://doi.org/10.1039/C8SM01853G	journal	January 2019
Advances in polymers for anti-biofouling surfaces Krishnan, Sitaraman; Weinman, Craig J.; Ober, Christopher K. Journal of Materials Chemistry, Vol. 18, Issue 29 https://doi.org/10.1039/b801491d	journal	January 2008
Chain dimensions and surface characterization of superhydrophilic polymer brushes with zwitterion side groups Kobayashi, Motoyasu; Terayama, Yuki; Kikuchi, Moriya Soft Matter, Vol. 9, Issue 21 https://doi.org/10.1039/c3sm27700c	journal	January 2013
Neutron reflectivity study of the swollen structure of polyzwitterion and polyeletrolyte brushes in aqueous solution Kobayashi, Motoyasu; Ishihara, Kazuhiko; Takahara, Atsushi Journal of Biomaterials Science, Polymer Edition, Vol. 25, Issue 14-15 https://doi.org/10.1080/09205063.2014.952992	journal	September 2014
Characterization of swollen structure of high-density polyelectrolyte brushes in salt solution by neutron reflectivity Kobayashi, Motoyasu; Terayama, Yuki; Hino, Masahiro Journal of Physics: Conference Series, Vol. 184 https://doi.org/10.1088/1742-6596/184/1/012010	journal	August 2009
Anti-polyelectrolyte and polyelectrolyte effects on conformations of polyzwitterionic chains in dilute aqueous solutions Liu, Zening; Keum, Jong K.; Li, Tianyu PNAS Nexus, Vol. 2, Issue 7 https://doi.org/10.1093/pnasnexus/pgad204	journal	June 2023
Model-independent determination of the surface scattering-length-density profile from specular reflectivity data Pedersen, J. S. Journal of Applied Crystallography, Vol. 25, Issue 2 https://doi.org/10.1107/S0021889891010907	journal	April 1992
Model-independent recovery of interfacial structure from multi-contrast neutron reflectivity data Koutsioubas, Alexandros Journal of Applied Crystallography, Vol. 52, Issue 3 https://doi.org/10.1107/S1600576719003534	journal	April 2019
anaklasis: a compact software package for model-based analysis of specular neutron and X-ray reflectometry data sets Koutsioubas, Alexandros Journal of Applied Crystallography, Vol. 54, Issue 6 https://doi.org/10.1107/S1600576721009262	journal	October 2021
Multivalent counterions diminish the lubricity of polyelectrolyte brushes Yu, J.; Jackson, N. E.; Xu, X. Science, Vol. 360, Issue 6396 https://doi.org/10.1126/science.aar5877	journal	June 2018
FIGARO: The new horizontal neutron reflectometer at the ILL Campbell, R. A.; Wacklin, H. P.; Sutton, I. The European Physical Journal Plus, Vol. 126, Issue 11 https://doi.org/10.1140/epjp/i2011-11107-8	journal	November 2011
Electrokinetic Properties of TiO2 Nanotubular Surfaces Lorenzetti, Martina; Gongadze, Ekaterina; Kulkarni, Mukta Nanoscale Research Letters, Vol. 11, Issue 1 https://doi.org/10.1186/s11671-016-1594-3	journal	August 2016
A Parabolic Density Profile for Grafted Polymers Milner, S. T.; Witten, T. A.; Cates, M. E. Europhysics Letters (EPL), Vol. 5, Issue 5 https://doi.org/10.1209/0295-5075/5/5/006	journal	March 1988
V6: The Reflectometer at BER II Trapp, Marcus Journal of large-scale research facilities JLSRF, Vol. 3 https://doi.org/10.17815/jlsrf-3-154	journal	May 2017
In vitro biocompatibility analysis of protein-resistant amphiphilic polysulfobetaines as coatings for surgical implants in contact with complex body fluids Karthäuser, Jana F.; Gruhn, Dierk; Martínez Guajardo, Alejandro Frontiers in Bioengineering and Biotechnology, Vol. 12 https://doi.org/10.3389/fbioe.2024.1403654	journal	July 2024

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36 MATERIALS SCIENCE
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Title: Influence of Grafting Density and the Ionic Environment on the Structure of Zwitterionic Brushes

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