Non-monotonic swelling of surface grafted hydrogels induced by pH and/or salt concentration

We use a molecular theory to study the thermodynamics of a weak-polyacid hydrogel film that is chemically grafted to a solid surface. We investigate the response of the material to changes in the pH and salt concentration of the buffer solution. Our results show that the pH-triggered swelling of the...

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Autores principales: Longo, Gabriel Sebastián, Olvera de la Cruz, Monica, Szleifer, Igal
Formato: Articulo
Lenguaje:Inglés
Publicado: 2014
Materias:
Acceso en línea:http://sedici.unlp.edu.ar/handle/10915/104750
http://hdl.handle.net/11336/5132
https://aip.scitation.org/doi/10.1063/1.4896562
Aporte de:
id I19-R120-10915-104750
record_format dspace
institution Universidad Nacional de La Plata
institution_str I-19
repository_str R-120
collection SEDICI (UNLP)
language Inglés
topic Ciencias Exactas
Química
gels
electrostatics
polyelectrolytes
free energy
chemical solutions
spellingShingle Ciencias Exactas
Química
gels
electrostatics
polyelectrolytes
free energy
chemical solutions
Longo, Gabriel Sebastián
Olvera de la Cruz, Monica
Szleifer, Igal
Non-monotonic swelling of surface grafted hydrogels induced by pH and/or salt concentration
topic_facet Ciencias Exactas
Química
gels
electrostatics
polyelectrolytes
free energy
chemical solutions
description We use a molecular theory to study the thermodynamics of a weak-polyacid hydrogel film that is chemically grafted to a solid surface. We investigate the response of the material to changes in the pH and salt concentration of the buffer solution. Our results show that the pH-triggered swelling of the hydrogel film has a non-monotonic dependence on the acidity of the bath solution. At most salt concentrations, the thickness of the hydrogel film presents a maximum when the pH of the solution is increased from acidic values. The quantitative details of such swelling behavior, which is not observed when the film is physically deposited on the surface, depend on the molecular architecture of the polymer network. This swelling-deswelling transition is the consequence of the complex interplay between the chemical free energy (acid-base equilibrium), the electrostatic repulsions between charged monomers, which are both modulated by the absorption of ions, and the ability of the polymer network to regulate charge and control its volume (molecular organization). In the absence of such competition, for example, for high salt concentrations, the film swells monotonically with increasing pH. A deswelling-swelling transition is similarly predicted as a function of the salt concentration at intermediate pH values. This reentrant behavior, which is due to the coupling between charge regulation and the two opposing effects triggered by salt concentration (screening electrostatic interactions and charging/discharging the acid groups), is similar to that found in end-grafted weak polyelectrolyte layers. Understanding how to control the response of the material to different stimuli, in terms of its molecular structure and local chemical composition, can help the targeted design of applications with extended functionality. We describe the response of the material to an applied pressure and an electric potential. We present profiles that outline the local chemical composition of the hydrogel, which can be useful information when designing applications that pursue or require the absorption of biomolecules or pH-sensitive molecules within different regions of the film.
format Articulo
Articulo
author Longo, Gabriel Sebastián
Olvera de la Cruz, Monica
Szleifer, Igal
author_facet Longo, Gabriel Sebastián
Olvera de la Cruz, Monica
Szleifer, Igal
author_sort Longo, Gabriel Sebastián
title Non-monotonic swelling of surface grafted hydrogels induced by pH and/or salt concentration
title_short Non-monotonic swelling of surface grafted hydrogels induced by pH and/or salt concentration
title_full Non-monotonic swelling of surface grafted hydrogels induced by pH and/or salt concentration
title_fullStr Non-monotonic swelling of surface grafted hydrogels induced by pH and/or salt concentration
title_full_unstemmed Non-monotonic swelling of surface grafted hydrogels induced by pH and/or salt concentration
title_sort non-monotonic swelling of surface grafted hydrogels induced by ph and/or salt concentration
publishDate 2014
url http://sedici.unlp.edu.ar/handle/10915/104750
http://hdl.handle.net/11336/5132
https://aip.scitation.org/doi/10.1063/1.4896562
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AT szleiferigal nonmonotonicswellingofsurfacegraftedhydrogelsinducedbyphandorsaltconcentration
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