Hydration and Restructuring of Polar Polymer Interfaces: Implications in Antifouling and Responsive Materials

Blake, Marea J.; Kim, Seonghan; Yang, Zhefei; Meyer III, Harry M.; Retterer, Scott T.; Carrillo, Jan-Michael Y.; Doughty, Benjamin

doi:10.1021/acsami.5c13716

Hydration and Restructuring of Polar Polymer Interfaces: Implications in Antifouling and Responsive Materials

Journal Article · Thu Oct 30 00:00:00 EDT 2025 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.5c13716· OSTI ID:3009447

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Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS)

Manipulating polymer interfaces is crucial for understanding how structure influences function in applications spanning biofouling prevention to energy storage. Moreover, observing how polymers adapt their microscopic structure to changes in their local environment can reveal essential properties that govern their performance in such applications, providing key insights into how to design more effective interfaces. Here, in this study, a series of “grafting-from” polymer brushes with side chains varying in charge, are probed by sum frequency generation (SFG) and modeled using all-atom molecular dynamics (MD) simulations to elucidate how chemical makeup and charge mediate interfacial restructuring in dry versus hydrated states. Results show that charge, in progressing from nonpolar to cationic to zwitterionic, results in dramatic changes in interfacial structure and overall hydration. While net neutral systems, regardless of bulk phase polarity, show minimal interfacial water structuring, the cationic species exhibits strong bulk water signals from the surface potential. Meanwhile, the polymer brushes themselves restructure in water differently independent of charge, impacting the functional groups that are presented to the aqueous phase. Nonpolar and cationic species for instance undergo a change in alkyl group orientations to accommodate hydrating water molecules, whereas the zwitterionic polymer becomes completely disordered in water. Overall, the structure-based behavior trends presented herein have implications in antifouling applications and responsive material interfaces.

View Accepted Manuscript (DOE)

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:: 3009447

Journal Information:: ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 47 Vol. 17; ISSN 1944-8244; ISSN 1944-8252

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (68)

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
Surface Grafted N‐Oxides have Low‐Fouling and Antibacterial Properties Burmeister, Nils; Zorn, Eilika; Farooq, Aneeq Advanced Materials Interfaces, Vol. 10, Issue 35 https://doi.org/10.1002/admi.202300505	journal	September 2023
Insight into the Origin of the Thermosensitivity of Poly[2‐(dimethylamino)ethyl methacrylate] Liu, Guangming; Wu, Dan; Ma, Chengcheng ChemPhysChem, Vol. 8, Issue 15 https://doi.org/10.1002/cphc.200700464	journal	October 2007
Biomembrane mimetic polymer poly (2‐methacryloyloxyethyl phosphorylcholine‐co‐n‐butyl methacrylate) at the interface of polyurethane surfaces Lee, I.; Kobayashi, K.; Sun, H. Y. Journal of Biomedical Materials Research Part A, Vol. 82A, Issue 2 https://doi.org/10.1002/jbm.a.30951	journal	February 2007
Scalable molecular dynamics with NAMD Phillips, James C.; Braun, Rosemary; Wang, Wei Journal of Computational Chemistry, Vol. 26, Issue 16, p. 1781-1802 https://doi.org/10.1002/jcc.20289	journal	January 2005
CHARMM general force field: A force field for drug-like molecules compatible with the CHARMM all-atom additive biological force fields Vanommeslaeghe, K.; Hatcher, E.; Acharya, C. Journal of Computational Chemistry https://doi.org/10.1002/jcc.21367	journal	January 2009
Molecular level studies of polymer behaviors at the water interface using sum frequency generation vibrational spectroscopy Hankett, Jeanne M.; Liu, Yuwei; Zhang, Xiaoxian Journal of Polymer Science Part B: Polymer Physics, Vol. 51, Issue 5 https://doi.org/10.1002/polb.23221	journal	December 2012
Numerical integration of the cartesian equations of motion of a system with constraints: molecular dynamics of n-alkanes Ryckaert, Jean-Paul; Ciccotti, Giovanni; Berendsen, Herman J. C. Journal of Computational Physics, Vol. 23, Issue 3 https://doi.org/10.1016/0021-9991(77)90098-5	journal	March 1977
Non-biofouling materials prepared by atom transfer radical polymerization grafting of 2-methacryloloxyethyl phosphorylcholine: Separate effects of graft density and chain length on protein repulsion Feng, W.; Brash, J.; Zhu, S. Biomaterials, Vol. 27, Issue 6 https://doi.org/10.1016/j.biomaterials.2005.07.006	journal	February 2006
Hydration and antibiofouling of TMAO-derived zwitterionic polymers surfaces studied with atomistic molecular dynamics simulations Sarker, Pranab; Chen, Grace Tang; Sajib, Md Symon Jahan Colloids and Surfaces A: Physicochemical and Engineering Aspects, Vol. 653 https://doi.org/10.1016/j.colsurfa.2022.129943	journal	November 2022
Surface charge control for zwitterionic polymer brushes: Tailoring surface properties to antifouling applications Guo, Shanshan; Jańczewski, Dominik; Zhu, Xiaoying Journal of Colloid and Interface Science, Vol. 452 https://doi.org/10.1016/j.jcis.2015.04.013	journal	August 2015
Role of the cationic headgroup to conformational changes undergone by shorter alkyl chain surfactant and water molecules at the air-liquid interface Khan, Md. Rubel; Premadasa, Uvinduni I.; Cimatu, Katherine Leslee A. Journal of Colloid and Interface Science, Vol. 568 https://doi.org/10.1016/j.jcis.2020.02.056	journal	May 2020
Surface hydration: Principles and applications toward low-fouling/nonfouling biomaterials Chen, Shenfu; Li, Lingyan; Zhao, Chao Polymer, Vol. 51, Issue 23, p. 5283-5293 https://doi.org/10.1016/j.polymer.2010.08.022	journal	October 2010
Studying Polymer Surfaces and Interfaces with Sum Frequency Generation Vibrational Spectroscopy Lu, Xiaolin; Zhang, Chi; Ulrich, Nathan Analytical Chemistry, Vol. 89, Issue 1 https://doi.org/10.1021/acs.analchem.6b04320	journal	December 2016
Antifouling Properties of Amine-Oxide-Containing Zwitterionic Polymers Luc, Van-Sieu; Lin, Chien-Cheng; Wang, Shao-Yu Biomacromolecules, Vol. 24, Issue 11 https://doi.org/10.1021/acs.biomac.3c00948	journal	October 2023
Surface-Initiated Controlled Radical Polymerization: State-of-the-Art, Opportunities, and Challenges in Surface and Interface Engineering with Polymer Brushes Zoppe, Justin O.; Ataman, Nariye Cavusoglu; Mocny, Piotr Chemical Reviews, Vol. 117, Issue 3 https://doi.org/10.1021/acs.chemrev.6b00314	journal	January 2017
Bioinspired N-Oxide-Based Zwitterionic Polymer Brushes for Robust Fouling-Resistant Surfaces Feng, Zimou; Feng, Xunda; Lu, Xinglin Environmental Science & Technology, Vol. 57, Issue 18 https://doi.org/10.1021/acs.est.3c00128	journal	April 2023
CHARMM-GUI Nanomaterial Modeler for Modeling and Simulation of Nanomaterial Systems Choi, Yeol Kyo; Kern, Nathan R.; Kim, Seonghan Journal of Chemical Theory and Computation, Vol. 18, Issue 1, p. 479-493 https://doi.org/10.1021/acs.jctc.1c00996	journal	December 2021
Tracking Molecular Transport Across Oil/Aqueous Interfaces: Insight into “Antagonistic” Binding in Solvent Extraction Premadasa, Uvinduni I.; Bocharova, Vera; Lin, Lu The Journal of Physical Chemistry B, Vol. 127, Issue 21 https://doi.org/10.1021/acs.jpcb.3c00386	journal	May 2023
Unveiling the Amphiphilic Nature of TMAO by Vibrational Sum Frequency Generation Spectroscopy Ohto, Tatsuhiko; Backus, Ellen H. G.; Mizukami, Wataru The Journal of Physical Chemistry C, Vol. 120, Issue 31 https://doi.org/10.1021/acs.jpcc.6b04852	journal	July 2016
Role of Ions on the Surface-Bound Water Structure at the Silica/Water Interface: Identifying the Spectral Signature of Stability Rehl, Benjamin; Gibbs, Julianne M. The Journal of Physical Chemistry Letters, Vol. 12, Issue 11 https://doi.org/10.1021/acs.jpclett.0c03565	journal	March 2021
Intermolecular Interactions at the Silica–Liquid Interface Modulate the Fermi Resonance Coupling in Surface Methanol Bui, Thomas T.; Colón, Luis A.; Velarde, Luis The Journal of Physical Chemistry Letters, Vol. 12, Issue 24 https://doi.org/10.1021/acs.jpclett.1c01015	journal	June 2021
The Unexpected Role of Cations in the Self-Assembly of Positively Charged Amphiphiles at Liquid/Liquid Interfaces Lin, Lu; Liu, Zening; Premadasa, Uvinduni I. The Journal of Physical Chemistry Letters, Vol. 13, Issue 46 https://doi.org/10.1021/acs.jpclett.2c02921	journal	November 2022
Multiresponsive Transitions of PDMAEMA Brushes for Tunable Surface Patterning Flemming, Patricia; Janke, Andreas; Simon, Frank Langmuir, Vol. 36, Issue 50 https://doi.org/10.1021/acs.langmuir.0c02711	journal	December 2020
Surface Hydration and Antifouling Activity of Zwitterionic Polymers Chen, Zhan Langmuir, Vol. 38, Issue 15 https://doi.org/10.1021/acs.langmuir.2c00512	journal	April 2022
Effect of Surface Charges in Polymer Coatings on Antifouling Performance in Marine Environments with Sediment Do, Jihwan; Kang, Sung Min Langmuir, Vol. 40, Issue 37 https://doi.org/10.1021/acs.langmuir.4c02304	journal	September 2024
All-Atom Modeling and Simulation of Biopolymer Interface: Dual Role of Antifouling Polymer Brushes Kim, Seonghan; Yang, Zhefei; Jakowski, Jacek Langmuir, Vol. 41, Issue 37 https://doi.org/10.1021/acs.langmuir.5c03882	journal	September 2025
Effect of Salt on Phosphorylcholine-based Zwitterionic Polymer Brushes Zhang, Zhenyu; Moxey, Mark; Alswieleh, Abdullah Langmuir, Vol. 32, Issue 20 https://doi.org/10.1021/acs.langmuir.6b00763	journal	May 2016
Understanding the Oxidative Stability of Antifouling Polymer Brushes Du, Yong; Gao, Jingyao; Chen, Tingting Langmuir, Vol. 33, Issue 29 https://doi.org/10.1021/acs.langmuir.7b01681	journal	July 2017
Effect of Surface Hydration on Antifouling Properties of Mixed Charged Polymers Leng, Chuan; Huang, Hao; Zhang, Kexin Langmuir, Vol. 34, Issue 22 https://doi.org/10.1021/acs.langmuir.8b00768	journal	May 2018
Strong Hydration at the Poly(ethylene glycol) Brush/Albumin Solution Interface Zhang, Kexin; Huang, Hao; Hung, Hsiang-Chieh Langmuir, Vol. 36, Issue 8 https://doi.org/10.1021/acs.langmuir.9b03680	journal	February 2020
Zwitterionization of Tertiary Amines in Nanoporous Block Copolymers: toward Fouling-Resistant Ultrafiltration Membranes Zhang, Chenxu; Zhou, Jiemei; Ye, Xiangyue Macromolecules, Vol. 54, Issue 9 https://doi.org/10.1021/acs.macromol.1c00307	journal	April 2021
Chemical Feedback in the Self-Assembly and Function of Air–Liquid Interfaces: Insight into the Bottlenecks of CO₂ Direct Air Capture Premadasa, Uvinduni I.; Dong, Dengpan; Stamberga, Diana ACS Applied Materials & Interfaces, Vol. 15, Issue 15 https://doi.org/10.1021/acsami.3c00719	journal	March 2023
Contribution of Charges in Polyvinyl Alcohol Networks to Marine Antifouling Yang, Wufang; Lin, Peng; Cheng, Daocang ACS Applied Materials & Interfaces, Vol. 9, Issue 21 https://doi.org/10.1021/acsami.7b04079	journal	May 2017
Tuning Surface Functions by Hydrophilic/Hydrophobic Polymer Brushes Liu, Yizhe; Liu, Yubo; Wu, Yang ACS Nano, Vol. 19, Issue 12 https://doi.org/10.1021/acsnano.4c18335	journal	March 2025
Zwitterionic Polymers Exhibiting High Resistance to Nonspecific Protein Adsorption from Human Serum and Plasma Ladd, Jon; Zhang, Zheng; Chen, Shengfu Biomacromolecules, Vol. 9, Issue 5 https://doi.org/10.1021/bm701301s	journal	May 2008
Automation of the CHARMM General Force Field (CGenFF) I: Bond Perception and Atom Typing Vanommeslaeghe, K.; MacKerell, A. D. Journal of Chemical Information and Modeling, Vol. 52, Issue 12 https://doi.org/10.1021/ci300363c	journal	November 2012
Automation of the CHARMM General Force Field (CGenFF) II: Assignment of Bonded Parameters and Partial Atomic Charges Vanommeslaeghe, K.; Raman, E. Prabhu; MacKerell, A. D. Journal of Chemical Information and Modeling, Vol. 52, Issue 12 https://doi.org/10.1021/ci3003649	journal	November 2012
Measuring Polymer Surface Ordering Differences in Air and Water by Sum Frequency Generation Vibrational Spectroscopy Wang, Jie; Paszti, Zoltan; Even, Mark A. Journal of the American Chemical Society, Vol. 124, Issue 24 https://doi.org/10.1021/ja012387r	journal	May 2002
Phase-Sensitive Sum-Frequency Vibrational Spectroscopy and Its Application to Studies of Interfacial Alkyl Chains Ji, Na; Ostroverkhov, Victor; Chen, Chao-Yuan Journal of the American Chemical Society, Vol. 129, Issue 33 https://doi.org/10.1021/ja071989t	journal	August 2007
Zwitterionic Poly(amino acid methacrylate) Brushes Alswieleh, Abdullah M.; Cheng, Nan; Canton, Irene Journal of the American Chemical Society, Vol. 136, Issue 26 https://doi.org/10.1021/ja503400r	journal	June 2014
Strong Surface Hydration and Salt Resistant Mechanism of a New Nonfouling Zwitterionic Polymer Based on Protein Stabilizer TMAO Huang, Hao; Zhang, Chengcheng; Crisci, Ralph Journal of the American Chemical Society, Vol. 143, Issue 40 https://doi.org/10.1021/jacs.1c08280	journal	September 2021
C−H Stretching Vibrations of Methyl, Methylene and Methine Groups at the Vapor/Alcohol ( n = 1−8) Interfaces Lu, Rong; Gan, Wei; Wu, Bao-hua The Journal of Physical Chemistry B, Vol. 109, Issue 29 https://doi.org/10.1021/jp051565q	journal	July 2005
A Sum Frequency Generation Vibrational Study of the Interference Effect in Poly(n-butyl methacrylate) Thin Films Sandwiched between Silica and Water Lu, Xiaolin; Clarke, Matthew L.; Li, Dawei The Journal of Physical Chemistry C, Vol. 115, Issue 28 https://doi.org/10.1021/jp202416z	journal	June 2011
Complex Formation in Aqueous Trimethylamine-N-oxide (TMAO) Solutions Hunger, Johannes; Tielrooij, Klaas-Jan; Buchner, Richard The Journal of Physical Chemistry B, Vol. 116, Issue 16 https://doi.org/10.1021/jp212542q	journal	April 2012
Vibrational Sum Frequency Spectroscopy Studies at Solid/Liquid Interfaces: Influence of the Experimental Geometry in the Spectral Shape and Enhancement Liljeblad, Jonathan F. D.; Tyrode, Eric The Journal of Physical Chemistry C, Vol. 116, Issue 43 https://doi.org/10.1021/jp306838a	journal	October 2012
Double Resolution Model for Studying TMAO/Water Effective Interactions Larini, Luca; Shea, Joan-Emma The Journal of Physical Chemistry B, Vol. 117, Issue 42 https://doi.org/10.1021/jp403635g	journal	July 2013
Superlow Fouling Sulfobetaine and Carboxybetaine Polymers on Glass Slides Zhang, Zheng; Chao, Timothy; Chen, Shengfu Langmuir, Vol. 22, Issue 24 https://doi.org/10.1021/la062175d	journal	November 2006
Silane Layers on Silicon Surfaces: Mechanism of Interaction, Stability, and Influence on Protein Adsorption Aissaoui, Nesrine; Bergaoui, Latifa; Landoulsi, Jessem Langmuir, Vol. 28, Issue 1 https://doi.org/10.1021/la2036778	journal	December 2011
Effect of Dehydration on the Interfacial Water Structure at a Charged Polymer Surface: Negligible χ⁽³⁾ Contribution to Sum Frequency Generation Signal Ye, Shuji; Liu, Guangming; Li, Hongchun Langmuir, Vol. 28, Issue 2 https://doi.org/10.1021/la203690p	journal	January 2012
Thermodynamically Consistent Force Fields for the Assembly of Inorganic, Organic, and Biological Nanostructures: The INTERFACE Force Field Heinz, Hendrik; Lin, Tzu-Jen; Kishore Mishra, Ratan Langmuir, Vol. 29, Issue 6 https://doi.org/10.1021/la3038846	journal	January 2013
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
Second-order spectral lineshapes from charged interfaces Ohno, Paul E.; Wang, Hong-fei; Geiger, Franz M. Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/s41467-017-01088-0	journal	October 2017
Water-mediated interactions between trimethylamine-N-oxide and urea Hunger, Johannes; Ottosson, Niklas; Mazur, Kamila Physical Chemistry Chemical Physics, Vol. 17, Issue 1 https://doi.org/10.1039/C4CP02709D	journal	January 2015
Antibiofouling polymer interfaces: poly(ethylene glycol) and other promising candidates Lowe, Sean; O'Brien-Simpson, Neil M.; Connal, Luke A. Polymer Chemistry, Vol. 6, Issue 2 https://doi.org/10.1039/C4PY01356E	journal	January 2015
A modified TIP3P water potential for simulation with Ewald summation Price, Daniel J.; Brooks, Charles L. The Journal of Chemical Physics, Vol. 121, Issue 20 https://doi.org/10.1063/1.1808117	journal	November 2004
A smooth particle mesh Ewald method Essmann, Ulrich; Perera, Lalith; Berkowitz, Max L. The Journal of Chemical Physics, Vol. 103, Issue 19 https://doi.org/10.1063/1.470117	journal	November 1995
Constant pressure molecular dynamics simulation: The Langevin piston method Feller, Scott E.; Zhang, Yuhong; Pastor, Richard W. The Journal of Chemical Physics, Vol. 103, Issue 11 https://doi.org/10.1063/1.470648	journal	September 1995
A new approach to vibrational sum frequency generation spectroscopy using near infrared pulse shaping Chowdhury, Azhad U.; Watson, Brianna R.; Ma, Ying-Zhong Review of Scientific Instruments, Vol. 90, Issue 3 https://doi.org/10.1063/1.5084971	journal	March 2019
The structure of water–DMF binary mixtures probed by linear and nonlinear vibrational spectroscopy Tomar, Deepak; Rana, Bhawna; Jena, Kailash C. The Journal of Chemical Physics, Vol. 152, Issue 11 https://doi.org/10.1063/1.5141757	journal	March 2020
Sensitivity of sum frequency generation experimental conditions to thin film interference effects Cotton, Daniel E.; Roberts, Sean T. The Journal of Chemical Physics, Vol. 154, Issue 11 https://doi.org/10.1063/5.0039897	journal	March 2021
Sum frequency generation as a proxy for ellipsometry: Not just a phase Dramstad, Thorn A.; Wu, Zhihao; Massari, Aaron M. The Journal of Chemical Physics, Vol. 156, Issue 11 https://doi.org/10.1063/5.0076252	journal	March 2022
Quantitative spectral and orientational analysis in surface sum frequency generation vibrational spectroscopy (SFG-VS) Wang *, Hong-Fei; Gan † ‡, Wei; Lu † ‡ §, Rong International Reviews in Physical Chemistry, Vol. 24, Issue 2 https://doi.org/10.1080/01442350500225894	journal	April 2005
Recent advances of zwitterionic carboxybetaine materials and their derivatives Cao, Bin; Tang, Qiong; Cheng, Gang Journal of Biomaterials Science, Polymer Edition, Vol. 25, Issue 14-15 https://doi.org/10.1080/09205063.2014.927300	journal	June 2014
New Information on Water Interfacial Structure Revealed by Phase-Sensitive Surface Spectroscopy Ostroverkhov, Victor; Waychunas, Glenn A.; Shen, Y. R. Physical Review Letters, Vol. 94, Issue 4 https://doi.org/10.1103/PhysRevLett.94.046102	journal	February 2005
Trimethylamine N -oxide–derived zwitterionic polymers: A new class of ultralow fouling bioinspired materials Li, Bowen; Jain, Priyesh; Ma, Jinrong Science Advances, Vol. 5, Issue 6 https://doi.org/10.1126/sciadv.aaw9562	journal	June 2019
Quantitative Sum-Frequency Generation Vibrational Spectroscopy of Molecular Surfaces and Interfaces: Lineshape, Polarization, and Orientation Wang, Hong-Fei; Velarde, Luis; Gan, Wei Annual Review of Physical Chemistry, Vol. 66, Issue 1 https://doi.org/10.1146/annurev-physchem-040214-121322	journal	April 2015
Flexible approach to vibrational sum-frequency generation using shaped near-infrared light Chowdhury, Azhad U.; Liu, Fangjie; Watson, Brianna R. Optics Letters, Vol. 43, Issue 9 https://doi.org/10.1364/OL.43.002038	journal	January 2018

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