Ion Specificity Influences on the Structure of Zwitterionic Brushes
Abstract
Zwitterionic brushes have a wide range of applications, including use as lubricating surfaces and antifouling membranes. In this study, densely end-tethered poly(cysteine methacrylate) (PCysMA) brushes were synthesized using surface initiated activators regenerated by electron transfer atom transfer radical polymerization (SI-ARGET-ATRP). The structure of the PCysMA brushes was investigated using ellipsometry, X-ray reflectivity (XRR), attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), and atomic force microscopy (AFM). The results of these characterization techniques were used to study the effect of SO42-, Cl-, NO3-, Br-, and SCN- anions, divalent Ca2+ and Ba2+ cations, and trivalent Y3+ cations on the structure of the PCysMA brushes. The results showed that the PCysMA brushes in solution exhibit an antipolyelectrolyte effect to a certain degree, which inversely follows the Hofmeister series of anions. The introduction of divalent cations Ca2+ and Ba2+ had a modest impact on the dimensions of the PCysMA brushes, indicating that chelating interactions between the cations and zwitterion units work against the "antipolyelectrolyte" effect. The complexation was even stronger in the presence of trivalent Y3+ cations, which caused the PCysMA brushes to shrink. These findings highlight the importance of ion specificity to the structure of zwitterionic brushes in aqueous solutions.
- Authors:
-
[1];
[2];
[1]
- Materials Science Division and Center for Molecular Engineering, Argonne National Laboratory, Lemont, Illinois 60439, United States, Pritzker School of Molecular Engineering, University of Chicago, 5640 S Ellis Ave, Chicago, Illinois 60637, United States
- Materials Science Division and Center for Molecular Engineering, Argonne National Laboratory, Lemont, Illinois 60439, United States
- Pritzker School of Molecular Engineering, University of Chicago, 5640 S Ellis Ave, Chicago, Illinois 60637, United States
- Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, United States
- Publication Date:
- Research Org.:
- Univ. of Chicago, IL (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE)
- OSTI Identifier:
- 1958644
- Alternate Identifier(s):
- OSTI ID: 1961336; OSTI ID: 2339567
- Grant/Contract Number:
- SC0022231; AC02-06CH11357
- Resource Type:
- Published Article
- Journal Name:
- Macromolecules
- Additional Journal Information:
- Journal Name: Macromolecules Journal Volume: 56 Journal Issue: 5; Journal ID: ISSN 0024-9297
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Anions; Cations; Ions; Salts; Solution chemistry
Citation Formats
He, Qiming, Qiao, Yijun, Medina Jimenez, Carlos, Hackler, Ryan, Martinson, Alex B. F., Chen, Wei, and Tirrell, Matthew V. Ion Specificity Influences on the Structure of Zwitterionic Brushes. United States: N. p., 2023.
Web. doi:10.1021/acs.macromol.2c02029.
He, Qiming, Qiao, Yijun, Medina Jimenez, Carlos, Hackler, Ryan, Martinson, Alex B. F., Chen, Wei, & Tirrell, Matthew V. Ion Specificity Influences on the Structure of Zwitterionic Brushes. United States. https://doi.org/10.1021/acs.macromol.2c02029
He, Qiming, Qiao, Yijun, Medina Jimenez, Carlos, Hackler, Ryan, Martinson, Alex B. F., Chen, Wei, and Tirrell, Matthew V. Fri .
"Ion Specificity Influences on the Structure of Zwitterionic Brushes". United States. https://doi.org/10.1021/acs.macromol.2c02029.
@article{osti_1958644,
title = {Ion Specificity Influences on the Structure of Zwitterionic Brushes},
author = {He, Qiming and Qiao, Yijun and Medina Jimenez, Carlos and Hackler, Ryan and Martinson, Alex B. F. and Chen, Wei and Tirrell, Matthew V.},
abstractNote = {Zwitterionic brushes have a wide range of applications, including use as lubricating surfaces and antifouling membranes. In this study, densely end-tethered poly(cysteine methacrylate) (PCysMA) brushes were synthesized using surface initiated activators regenerated by electron transfer atom transfer radical polymerization (SI-ARGET-ATRP). The structure of the PCysMA brushes was investigated using ellipsometry, X-ray reflectivity (XRR), attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), and atomic force microscopy (AFM). The results of these characterization techniques were used to study the effect of SO42-, Cl-, NO3-, Br-, and SCN- anions, divalent Ca2+ and Ba2+ cations, and trivalent Y3+ cations on the structure of the PCysMA brushes. The results showed that the PCysMA brushes in solution exhibit an antipolyelectrolyte effect to a certain degree, which inversely follows the Hofmeister series of anions. The introduction of divalent cations Ca2+ and Ba2+ had a modest impact on the dimensions of the PCysMA brushes, indicating that chelating interactions between the cations and zwitterion units work against the "antipolyelectrolyte" effect. The complexation was even stronger in the presence of trivalent Y3+ cations, which caused the PCysMA brushes to shrink. These findings highlight the importance of ion specificity to the structure of zwitterionic brushes in aqueous solutions.},
doi = {10.1021/acs.macromol.2c02029},
journal = {Macromolecules},
number = 5,
volume = 56,
place = {United States},
year = {Fri Feb 24 00:00:00 EST 2023},
month = {Fri Feb 24 00:00:00 EST 2023}
}
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