Simulations Explain the Swelling Behavior of Hydrogels with Alternating Neutral and Weakly Acidic Blocks
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F22%3A10453768" target="_blank" >RIV/00216208:11310/22:10453768 - isvavai.cz</a>
Result on the web
<a href="https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=1394oLfvzT" target="_blank" >https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=1394oLfvzT</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1021/acs.macromol.2c01916" target="_blank" >10.1021/acs.macromol.2c01916</a>
Alternative languages
Result language
angličtina
Original language name
Simulations Explain the Swelling Behavior of Hydrogels with Alternating Neutral and Weakly Acidic Blocks
Original language description
We used computer simulations to study the equilibrium swelling of weak (pH-responsive) polyelectrolyte hydrogels as a function of pH and salt concentration in a supernatant solution. Our simulations were designed to represent recently synthesized gels composed of tetrapoly(acrylic acid) and tetrapoly(ethylene glycol) stars. To model the ionization equilibrium of the weak acid groups and the exchange of small ions with the reservoir, we applied the recently developed grand reaction Monte Carlo method. We showed that the ionization of these gels as a function of the pH significantly deviates from the ideal Henderson-Hasselbalch equation due to two main contributions: (1) electrostatic interactions and (2) Donnan partitioning of small ions. The first contribution dominates in the gels composed of alternating neutral and acidic blocks, contrasting with our previous observations that both contributions are comparably strong in hydrogels composed of homogeneously distributed weak acid groups. We also critically examined the counterion condensation argument, previously invoked to explain why the experimentally observed swelling was lower than predicted by theory. Thus, a detailed analysis of the simulations allowed us to understand which of the above effects dominates in different systems and why, thereby allowing us to identify the correct physical origin of the deviations from ideal swelling. Such an understanding is important not only for correctly interpreting experimental measurements but also for designing polyelectrolyte gels tailored to exhibit specific swelling response to pH and salt concentration.
Czech name
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Czech description
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Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
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OECD FORD branch
10404 - Polymer science
Result continuities
Project
<a href="/en/project/GC21-31978J" target="_blank" >GC21-31978J: Simulations of reaction equilibria in polymer systems - method development and applications</a><br>
Continuities
P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)
Others
Publication year
2022
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Macromolecules
ISSN
0024-9297
e-ISSN
1520-5835
Volume of the periodical
55
Issue of the periodical within the volume
23
Country of publishing house
US - UNITED STATES
Number of pages
10
Pages from-to
10751-10760
UT code for WoS article
000887467600001
EID of the result in the Scopus database
2-s2.0-85142625856