DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Enrichment and Distribution of Pb2+ Ions in Zwitterionic Poly(cysteine methacrylate) Brushes at the Solid–Liquid Interface

Abstract

Cysteine-based polyzwitterionic brushes have been prepared via a two-step route. First, poly(allyl methacrylate) (PAMA) brushes have been grown from the surface of silicon substrates using surface-initiated atom transfer radical polymerization. The obtained PAMA brushes with free pendant vinyl groups were further modified via radical thiol-ene addition reaction to attach L-cysteine moieties. Surface zeta potential investigations on pH-responsiveness of these poly(cysteine methacrylate) (PCysMA) brushes confirm their zwitterionic character at intermediate pH range, while at pH values either below pH 3.50 or above pH 8.59, they exhibit polyelectrolyte character. Under acid (pH < 3.50) or base (pH > 8.59) conditions, they possess either cationic or anionic character, respectively. In the zwitterionic region, these PCysMA brushes show positive surface $$\zeta$$ potential in the presence of Pb(CH3COO)2 solutions of various concentrations. The results are in line with microscopic investigations using anomalous X-ray reflectivity (AXRR) carried out along the absorption edge of Pb2+ ions. When the photon energies were varied around the absorption L3 edge of lead (13037 eV), the Pb2+ concentration normal to the silicon substrates, as a function of depth inside PCysMA brushes, could be revealed at the nanoscale. Both zeta potential and AXRR measurements confirm the enrichment of Pb2+ ions inside PCysMA brushes, indicating the potential of PCysMA to be used as a water purification material.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [2];  [2];  [2];  [3]; ORCiD logo [2]; ORCiD logo [1];  [1]; ORCiD logo [1]
  1. Argonne National Lab. (ANL), Argonne, IL (United States); Univ. of Chicago, IL (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States)
  3. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Advanced Materials for Energy-Water Systems (AMEWS); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Contributing Org.:
Energy Frontier Research Center (EFRC)
OSTI Identifier:
1595945
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Langmuir
Additional Journal Information:
Journal Volume: 35; Journal Issue: 52; 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

He, Qiming, Qiao, Yijun, Mandia, David J., Gan, Shenglong, Zhang, Huiru, Zhou, Hua, Elam, Jeffrey W., Darling, Seth B., Tirrell, Matthew V., and Chen, Wei. Enrichment and Distribution of Pb2+ Ions in Zwitterionic Poly(cysteine methacrylate) Brushes at the Solid–Liquid Interface. United States: N. p., 2019. Web. doi:10.1021/acs.langmuir.9b02770.
He, Qiming, Qiao, Yijun, Mandia, David J., Gan, Shenglong, Zhang, Huiru, Zhou, Hua, Elam, Jeffrey W., Darling, Seth B., Tirrell, Matthew V., & Chen, Wei. Enrichment and Distribution of Pb2+ Ions in Zwitterionic Poly(cysteine methacrylate) Brushes at the Solid–Liquid Interface. United States. https://doi.org/10.1021/acs.langmuir.9b02770
He, Qiming, Qiao, Yijun, Mandia, David J., Gan, Shenglong, Zhang, Huiru, Zhou, Hua, Elam, Jeffrey W., Darling, Seth B., Tirrell, Matthew V., and Chen, Wei. Mon . "Enrichment and Distribution of Pb2+ Ions in Zwitterionic Poly(cysteine methacrylate) Brushes at the Solid–Liquid Interface". United States. https://doi.org/10.1021/acs.langmuir.9b02770. https://www.osti.gov/servlets/purl/1595945.
@article{osti_1595945,
title = {Enrichment and Distribution of Pb2+ Ions in Zwitterionic Poly(cysteine methacrylate) Brushes at the Solid–Liquid Interface},
author = {He, Qiming and Qiao, Yijun and Mandia, David J. and Gan, Shenglong and Zhang, Huiru and Zhou, Hua and Elam, Jeffrey W. and Darling, Seth B. and Tirrell, Matthew V. and Chen, Wei},
abstractNote = {Cysteine-based polyzwitterionic brushes have been prepared via a two-step route. First, poly(allyl methacrylate) (PAMA) brushes have been grown from the surface of silicon substrates using surface-initiated atom transfer radical polymerization. The obtained PAMA brushes with free pendant vinyl groups were further modified via radical thiol-ene addition reaction to attach L-cysteine moieties. Surface zeta potential investigations on pH-responsiveness of these poly(cysteine methacrylate) (PCysMA) brushes confirm their zwitterionic character at intermediate pH range, while at pH values either below pH 3.50 or above pH 8.59, they exhibit polyelectrolyte character. Under acid (pH < 3.50) or base (pH > 8.59) conditions, they possess either cationic or anionic character, respectively. In the zwitterionic region, these PCysMA brushes show positive surface $\zeta$ potential in the presence of Pb(CH3COO)2 solutions of various concentrations. The results are in line with microscopic investigations using anomalous X-ray reflectivity (AXRR) carried out along the absorption edge of Pb2+ ions. When the photon energies were varied around the absorption L3 edge of lead (13037 eV), the Pb2+ concentration normal to the silicon substrates, as a function of depth inside PCysMA brushes, could be revealed at the nanoscale. Both zeta potential and AXRR measurements confirm the enrichment of Pb2+ ions inside PCysMA brushes, indicating the potential of PCysMA to be used as a water purification material.},
doi = {10.1021/acs.langmuir.9b02770},
journal = {Langmuir},
number = 52,
volume = 35,
place = {United States},
year = {2019},
month = {12}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 1 work
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Removal of heavy metal ions from aqueous system by ion-exchange and biosorption methods
journal, December 2018

  • Bashir, Arshid; Malik, Lateef Ahmad; Ahad, Sozia
  • Environmental Chemistry Letters, Vol. 17, Issue 2
  • DOI: 10.1007/s10311-018-00828-y

Hybrid flotation—membrane filtration process for the removal of heavy metal ions from wastewater
journal, September 2003


Removal of Cu2+ and Ni2+ from wastewater with a chelating agent and reverse osmosis processes
journal, November 2007


Integration of a membrane bioreactor coupled with reverse osmosis for advanced treatment of municipal wastewater
journal, March 2009


Spherical polyelectrolyte brushes: Comparison between annealed and quenched brushes
journal, October 2001


Interaction of Poly(methacrylic acid) Brushes with Metal Ions:  Swelling Properties
journal, May 2005

  • Konradi, Rupert; Rühe, Jürgen
  • Macromolecules, Vol. 38, Issue 10
  • DOI: 10.1021/ma0486804

Interaction of Poly(methacrylic acid) Brushes with Metal Ions:  An Infrared Investigation
journal, September 2004

  • Konradi, Rupert; Rühe, Jürgen
  • Macromolecules, Vol. 37, Issue 18
  • DOI: 10.1021/ma049126x

Physical Networks of Metal-Ion-Containing Polymer Brushes Show Fully Tunable Swelling, Nanomechanical and Nanotribological Properties
journal, March 2017


Heavy metal ions removal by nano-sized spherical polymer brushes
journal, March 2014

  • Chen, Qing-chuan; Wang, Jie; Chen, Kai-min
  • Chinese Journal of Polymer Science, Vol. 32, Issue 4
  • DOI: 10.1007/s10118-014-1398-9

Mesoporous Films and Polymer Brushes Helping Each Other To Modulate Ionic Transport in Nanoconfined Environments. An Interesting Example of Synergism in Functional Hybrid Assemblies
journal, August 2009

  • Calvo, Alejandra; Yameen, Basit; Williams, Federico J.
  • Journal of the American Chemical Society, Vol. 131, Issue 31
  • DOI: 10.1021/ja9031067

Amino Acid-Based Zwitterionic Poly(serine methacrylate) as an Antifouling Material
journal, December 2012

  • Liu, Qingsheng; Singh, Anuradha; Liu, Lingyun
  • Biomacromolecules, Vol. 14, Issue 1
  • DOI: 10.1021/bm301646y

Zwitterionic Poly(amino acid methacrylate) Brushes
journal, June 2014

  • Alswieleh, Abdullah M.; Cheng, Nan; Canton, Irene
  • Journal of the American Chemical Society, Vol. 136, Issue 26
  • DOI: 10.1021/ja503400r

Study of thiol–ene chemistry on polymer brushes and application to surface patterning and protein adsorption
journal, January 2016

  • Tan, Khooi Y.; Ramstedt, Madeleine; Colak, Burcu
  • Polymer Chemistry, Vol. 7, Issue 4
  • DOI: 10.1039/C5PY01687H

Polyelectrolyte Brushes Grafted at the Air/Water Interface
journal, December 1997

  • Ahrens, Heiko; Förster, Stephan; Helm, Christiane A.
  • Macromolecules, Vol. 30, Issue 26
  • DOI: 10.1021/ma970949e

Synthesis and swelling behavior of a weak polyacid brush
journal, September 2002

  • Biesalski, M.; Johannsmann, D.; Rühe, J.
  • The Journal of Chemical Physics, Vol. 117, Issue 10
  • DOI: 10.1063/1.1490924

Synthesis of gold nanoparticles inside polyelectrolyte brushes
journal, January 2007

  • Azzaroni, Omar; Brown, Andrew A.; Cheng, Nan
  • Journal of Materials Chemistry, Vol. 17, Issue 32
  • DOI: 10.1039/b704849a

Charged Polymer Brushes: Counterion Incorporation and Scaling Relations
journal, November 1998


Structure of Polyelectrolyte Brushes in the Presence of Multivalent Counterions
journal, July 2016


Diblock copolymers based on allyl methacrylate: Synthesis, characterization, and chemical modification
journal, January 2007

  • París, Rodrigo; de la Fuente, José Luis
  • Journal of Polymer Science Part A: Polymer Chemistry, Vol. 45, Issue 16
  • DOI: 10.1002/pola.22100

The Anionic Polymerization of Allyl Acrylate and of Allyl Methacrylate
journal, March 1966

  • Bywater, S.; Black, P. E.; Wiles, D. Am.
  • Canadian Journal of Chemistry, Vol. 44, Issue 6
  • DOI: 10.1139/v66-097

Bulk atom transfer radical polymerization of allyl methacrylate: Polymerization of Allyl Methacrylate
journal, April 2005

  • París, Rodrigo; de la Fuente, José Luis
  • Journal of Polymer Science Part A: Polymer Chemistry, Vol. 43, Issue 11
  • DOI: 10.1002/pola.20709

50th Anniversary Perspective : Polymer Functionalization
journal, June 2017


Electronic structure of silicon nanowires: A photoemission and x-ray absorption study
journal, March 2000


Spatial Control over Cross-Linking Dictates the pH-Responsive Behavior of Poly(2-( tert -butylamino)ethyl methacrylate) Brushes
journal, January 2014

  • Alswieleh, Abdullah M.; Cheng, Nan; Leggett, Graham J.
  • Langmuir, Vol. 30, Issue 5
  • DOI: 10.1021/la403666y

Dissociation Behavior of Weak Polyelectrolyte Brushes on a Planar Surface
journal, April 2009

  • Dong, Rong; Lindau, Manfred; Ober, Christopher K.
  • Langmuir, Vol. 25, Issue 8
  • DOI: 10.1021/la8039384

Perspective: Interfacial materials at the interface of energy and water
journal, July 2018

  • Darling, Seth B.
  • Journal of Applied Physics, Vol. 124, Issue 3
  • DOI: 10.1063/1.5040110

Counterion Distribution around a Spherical Polyelectrolyte Brush Probed by Anomalous Small-Angle X-ray Scattering
journal, October 2004

  • Dingenouts, N.; Patel, M.; Rosenfeldt, S.
  • Macromolecules, Vol. 37, Issue 21
  • DOI: 10.1021/ma048828j

Counterion Distribution around DNA Probed by Solution X-Ray Scattering
journal, May 2003


Generalized skew-symmetric interfacial probability distribution in reflectivity and small-angle scattering analysis
journal, November 2017


Element Specific Monolayer Depth Profiling
journal, August 2014

  • Macke, Sebastian; Radi, Abdullah; Hamann-Borrero, Jorge E.
  • Advanced Materials, Vol. 26, Issue 38
  • DOI: 10.1002/adma.201402028

Coil-globule type transitions in polymers. 1. Collapse of layers of grafted polymer chains
journal, January 1991

  • Zhulina, E. B.; Borisov, O. V.; Pryamitsyn, V. A.
  • Macromolecules, Vol. 24, Issue 1
  • DOI: 10.1021/ma00001a023