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Preparation of DNA-crosslinked Polyacrylamide Hydrogels
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Tuning smart microgel swelling and responsive behavior through strong and weak polyelectrolyte pair assembly.

Eunice Costa1, Margaret M Lloyd, Caroline Chopko

  • 1REQUIMTE, Departamento de Química, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, Caparica, Portugal.

Langmuir : the ACS Journal of Surfaces and Colloids
|June 9, 2012
PubMed
Summary

Layer-by-layer assembly of polyelectrolytes on smart microgels precisely controls swelling and responsiveness. This method offers a flexible approach to engineer microgel properties for diverse applications.

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Area of Science:

  • Materials Science
  • Polymer Chemistry
  • Nanotechnology

Background:

  • Smart microgels, such as cross-linked poly(N-isopropylacrylamide)-co-(methacrylic acid) [poly(NIPAAm-co-MAA)], exhibit tunable swelling and responsive behavior.
  • Layer-by-layer (LbL) assembly is a versatile technique for fabricating multilayered structures with controlled properties.

Purpose of the Study:

  • To investigate the fine-tuning of microgel swelling and responsive behavior using LbL assembly of polyelectrolyte pairs.
  • To understand how the choice of polyelectrolyte pair and termination layer influences microgel properties.

Main Methods:

  • Synthesis of poly(NIPAAm-co-MAA) microgels using supercritical carbon dioxide.
  • LbL assembly of weak (poly(L-lysine)/poly(L-glutamic acid), poly(allylamine hydrochloride)/poly(acrylic acid)) and strong (poly(diallyldimethylammonium chloride)/poly(sodium styrene sulfonate)) polyelectrolyte pairs.
  • Analysis of swelling and thermoresponsive behavior, including ATR FT-IR studies.

Main Results:

  • Polycation-terminated microgels showed reduced swelling and increased thermoresponsiveness with weak polyelectrolyte pairs, while polyanion-terminated microgels exhibited increased swelling and reduced responsiveness.
  • Strong polyelectrolyte pairs led to less distinct differences between terminated microgels due to ionic cross-linking.
  • Increased ionic strength diminished the observed effects due to charge shielding.
  • ATR FT-IR confirmed correlations between swelling, responsiveness, H-bonding, and charge distribution.

Conclusions:

  • LbL assembly provides a simple and flexible strategy to engineer smart microgels.
  • Microgel properties like size, surface chemistry, charge, and permeability can be precisely controlled by selecting appropriate polyelectrolyte pairs and assembly conditions.
  • This approach enables the development of advanced functional materials for various applications.