ACS Publications. Most Trusted. Most Cited. Most Read
My Activity

Figure 1Loading Img

Role of Steric Interactions on the Ionic Permeation Inside Charged Microgels: Theory and Simulations

View Author Information
Departamento de Física Aplicada, Facultad de Ciencias, Universidad de Granada, Campus Fuentenueva S/N, 18071 Granada, Spain
Departamento de Física, Escuela Politécnica Superior de Linares, Universidad de Jaén, 23700 Linares, Jaén, Spain
*(A.M.-J.) E-mail: [email protected]
Cite this: Macromolecules 2015, 48, 13, 4645–4656
Publication Date (Web):June 18, 2015
Copyright © 2015 American Chemical Society

    Article Views





    Other access options


    Abstract Image

    In this work, we study the effect of the steric excluded-volume interactions between counterions and thermoresponsive ionic heterogeneous microgel particles. With this aim, we perform Monte Carlo simulations to calculate the microgel effective net charge and the conunterion distribution function inside and around the microgel for different degrees of swelling. These results are compared to the ones obtained solving the Ornstein–Zernike integral equations within the HNC approximation. For this purpose, the equilibrium polymer mass and charge distribution inside the microgel resulting from simulations are used as the input for the integral equations. Two different models are considered to quantify the microgel-ion steric interaction. The model that considers polymer fibers formed by spheres demonstrates to be a very reliable way to predict counterion permeation in such microgels. Finally, integral equations are solved ignoring the steric interaction as well, in order to determine to what extent this effect is playing a significant role. The comparison between both predictions allows us to conclude that the microgel-ion steric repulsion has relevant effects on the counterion permeation if the polymer volume fraction of the microgel is high enough, and that the integral equation theory is a powerful tool to quantitatively predict the local density profiles of ions inside and around the microgel, even in situations where the internal microgel charge and mass density are nonhomogeneous.

    Read this article

    To access this article, please review the available access options below.

    Get instant access

    Purchase Access

    Read this article for 48 hours. Check out below using your ACS ID or as a guest.


    Access through Your Institution

    You may have access to this article through your institution.

    Your institution does not have access to this content. You can change your affiliated institution below.

    Cited By

    This article is cited by 31 publications.

    1. Manuel Quesada-Pérez, José-Alberto Maroto-Centeno, María del Mar Ramos-Tejada, Alberto Martín-Molina. Coarse-Grained Simulations of Solute Diffusion in Crosslinked Flexible Hydrogels. Macromolecules 2022, 55 (5) , 1495-1504.
    2. Arturo Moncho-Jordá, Ana B. Jódar-Reyes, Matej Kanduč, Alicia Germán-Bellod, Juan M. López-Romero, Rafael Contreras-Cáceres, Francisco Sarabia, Miguel García-Castro, Héctor A. Pérez-Ramírez, Gerardo Odriozola. Scaling Laws in the Diffusive Release of Neutral Cargo from Hollow Hydrogel Nanoparticles: Paclitaxel-Loaded Poly(4-vinylpyridine). ACS Nano 2020, 14 (11) , 15227-15240.
    3. María del Mar Ramos-Tejada, Manuel Quesada-Pérez. Coarse-Grained Simulations of Nanogel Composites: Electrostatic and Steric Effects. Macromolecules 2019, 52 (6) , 2223-2230.
    4. Thiago Colla, Priti S. Mohanty, Sofi Nöjd, Erik Bialik, Aaron Riede, Peter Schurtenberger, Christos N. Likos. Self-Assembly of Ionic Microgels Driven by an Alternating Electric Field: Theory, Simulations, and Experiments. ACS Nano 2018, 12 (5) , 4321-4337.
    5. Shuaidi Zhang, Ren Geryak, Jeffrey Geldmeier, Sunghan Kim, and Vladimir V. Tsukruk . Synthesis, Assembly, and Applications of Hybrid Nanostructures for Biosensing. Chemical Reviews 2017, 117 (20) , 12942-13038.
    6. Won Kyu Kim, Arturo Moncho-Jordá, Rafael Roa, Matej Kanduč, and Joachim Dzubiella . Cosolute Partitioning in Polymer Networks: Effects of Flexibility and Volume Transitions. Macromolecules 2017, 50 (16) , 6227-6237.
    7. Andrey A. Rudov, Arjan P. H. Gelissen, Gudrun Lotze, Andreas Schmid, Thomas Eckert, Andrij Pich, Walter Richtering, and Igor I. Potemkin . Intramicrogel Complexation of Oppositely Charged Compartments As a Route to Quasi-Hollow Structures. Macromolecules 2017, 50 (11) , 4435-4445.
    8. Mehmet Can, Nurettin Sahiner. A facile one-pot synthesis of microgels and nanogels of laminarin for biomedical applications. Journal of Colloid and Interface Science 2021, 588 , 40-49.
    9. Won Kyu Kim, Richard Chudoba, Sebastian Milster, Rafael Roa, Matej Kanduč, Joachim Dzubiella. Tuning the selective permeability of polydisperse polymer networks. Soft Matter 2020, 16 (35) , 8144-8154.
    10. Elena F. Silkina, Taras Y. Molotilin, Salim R. Maduar, Olga I. Vinogradova. Ionic equilibria and swelling of soft permeable particles in electrolyte solutions. Soft Matter 2020, 16 (4) , 929-938.
    11. A. Moncho-Jordá, M. Quesada-Pérez. Crossover of the effective charge in ionic thermoresponsive hydrogel particles. Physical Review E 2019, 100 (5)
    12. Alberto Martín-Molina, Manuel Quesada-Pérez. A review of coarse-grained simulations of nanogel and microgel particles. Journal of Molecular Liquids 2019, 280 , 374-381.
    13. Sebastian Milster, Richard Chudoba, Matej Kanduč, Joachim Dzubiella. Cross-linker effect on solute adsorption in swollen thermoresponsive polymer networks. Physical Chemistry Chemical Physics 2019, 21 (12) , 6588-6599.
    14. Won Kyu Kim, Matej Kanduč, Rafael Roa, Joachim Dzubiella. Tuning the Permeability of Dense Membranes by Shaping Nanoscale Potentials. Physical Review Letters 2019, 122 (10)
    15. Richard Chudoba, Jan Heyda, Joachim Dzubiella. Tuning the collapse transition of weakly charged polymers by ion-specific screening and adsorption. Soft Matter 2018, 14 (47) , 9631-9642.
    16. Oleg Rud, Oleg Borisov, Peter Košovan. Thermodynamic model for a reversible desalination cycle using weak polyelectrolyte hydrogels. Desalination 2018, 442 , 32-43.
    17. David Sean, Jonas Landsgesell, Christian Holm. Computer Simulations of Static and Dynamical Properties of Weak Polyelectrolyte Nanogels in Salty Solutions. Gels 2018, 4 (1) , 2.
    18. Luis Pérez-Mas, Alberto Martín-Molina, Manuel Quesada-Pérez, Arturo Moncho-Jordá. Maximizing the absorption of small cosolutes inside neutral hydrogels: steric exclusion versus hydrophobic adhesion. Physical Chemistry Chemical Physics 2018, 20 (4) , 2814-2825.
    19. Tyler J. Weyer, Alan R. Denton. Concentration-dependent swelling and structure of ionic microgels: simulation and theory of a coarse-grained model. Soft Matter 2018, 14 (22) , 4530-4540.
    20. Irene Adroher-Benítez, Arturo Moncho-Jordá, Gerardo Odriozola. Conformation change of an isotactic poly ( N -isopropylacrylamide) membrane: Molecular dynamics. The Journal of Chemical Physics 2017, 146 (19)
    21. David Julian McClements. Designing biopolymer microgels to encapsulate, protect and deliver bioactive components: Physicochemical aspects. Advances in Colloid and Interface Science 2017, 240 , 31-59.
    22. Irene Adroher-Benítez, Alberto Martín-Molina, Silvia Ahualli, Manuel Quesada-Pérez, Gerardo Odriozola, Arturo Moncho-Jordá. Competition between excluded-volume and electrostatic interactions for nanogel swelling: effects of the counterion valence and nanogel charge. Physical Chemistry Chemical Physics 2017, 19 (9) , 6838-6848.
    23. J. Maldonado-Valderrama, T. del Castillo-Santaella, I. Adroher-Benítez, A. Moncho-Jordá, A. Martín-Molina. Thermoresponsive microgels at the air–water interface: the impact of the swelling state on interfacial conformation. Soft Matter 2017, 13 (1) , 230-238.
    24. Oleg Rud, Tobias Richter, Oleg Borisov, Christian Holm, Peter Košovan. A self-consistent mean-field model for polyelectrolyte gels. Soft Matter 2017, 13 (18) , 3264-3274.
    25. Irene Adroher-Benítez, Silvia Ahualli, Delfi Bastos-González, José Ramos, Jacqueline Forcada, Arturo Moncho-Jordá. The effect of electrosteric interactions on the effective charge of thermoresponsive ionic microgels: Theory and experiments. Journal of Polymer Science Part B: Polymer Physics 2016, 54 (20) , 2038-2049.
    26. M. Braibanti, C. Haro-Pérez, M. Quesada-Pérez, L. F. Rojas-Ochoa, V. Trappe. Impact of volume transition on the net charge of poly- N -isopropyl acrylamide microgels. Physical Review E 2016, 94 (3)
    27. Ángel V. Delgado, Félix Carrique, Rafael Roa, Emilio Ruiz-Reina. Recent developments in electrokinetics of salt-free concentrated suspensions. Current Opinion in Colloid & Interface Science 2016, 24 , 32-43.
    28. L. G. Rizzi, Y. Levin. Influence of network topology on the swelling of polyelectrolyte nanogels. The Journal of Chemical Physics 2016, 144 (11)
    29. A.D. Drozdov, C.-G. Sanporean, J. deClaville Christiansen. Modeling the effect of ionic strength on swelling of pH-sensitive macro- and nanogels. Materials Today Communications 2016, 6 , 92-101.
    30. Arturo Moncho-Jordá, Joachim Dzubiella. Swelling of ionic microgel particles in the presence of excluded-volume interactions: a density functional approach. Physical Chemistry Chemical Physics 2016, 18 (7) , 5372-5385.
    31. Matthew Urich, Alan R. Denton. Swelling, structure, and phase stability of compressible microgels. Soft Matter 2016, 12 (44) , 9086-9094.

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    You’ve supercharged your research process with ACS and Mendeley!

    STEP 1:
    Click to create an ACS ID

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Your Mendeley pairing has expired. Please reconnect