Internal Composition versus the Mechanical Properties of Polyelectrolyte Multilayer Films: The Influence of Chemical Cross-Linking

Boudou, Thomas;Crouzier, Thomas;Auzely-Velty, Rachel;Glinel, Karine;Picart, Catherine
(2009) Langmuir : the A C S journal of surfaces and colloids — Vol. 25, n° 24, p. 13809-13819 (2009)

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Authors
  • Boudou, ThomasGrenoble Institute of Technology and LMGP
    Author
  • Crouzier, ThomasUniversité de Montpellier 2 et 1
    Author
  • Auzely-Velty, RachelCERMAV-CNRS and Université Joseph Fourier
    Author
  • Glinel, Karineorcid-logoUCL; Laboratoire Polymères, Biopolymères, Surfaces, Université de Rouen − CNRS, Mont-Saint-Aignan, France
    Author
  • Picart, CatherineUniversité de Rouen
    Author
Abstract
Different types of polyelectrolyte multilayer Films composed of poly(L-lysine)/hyaluronan (PLL/HA), chitosan/hyaluronan (CHI/HA) and poly(allylamine hydrochloride)poly(L-glutamic acid) (PAH/PGA) have been investigated Cor their internal composition, including water content, ion pairing, and ability to be covalently cross-linked, as well as for their mechanical properties. Film buildup under physiological conditions was monitored by the quartz crystal microbalance with dissipation monitoring (QCM-D) and attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), which allows unambiguous quantification of the different groups present in the polyelectrolytes. (PAH/PGA) films emerged as the most dense films with the lowest hydration (29%) and the highest COO(-) molar density. In addition, PAH is greatly in excess in these films (3 PAH monomers per PGA monomer), The formation of amide bonds during Film cross-linking using the water-soluble carbodiimide EDC was also investigated, All of the films could be cross-linked in a tunable manner, but PAH/PGA exhibited the highest absolute number of amide bonds created, similar to 7 times more than for (PLL/HA) and (CHI/HA) Films. The Young's modulus E of the films measured by AFM nanoindentation was shown to vary over I to 2 orders or magnitude for the different systems. Interestingly, a linear relationship between E and the density of the covalent cross-links created was observed for (PLL/HA) and (CHI/HA) films whereas (PGA/PAH) films exhibited biphasic behavior. The mean distance between covalent cross-links was estimated to be similar to 11 nm for (PLL/HA) and (CHI/HA) films and only similar to 6 nm for (PAH/PGA) Films for the maximum EDC concentration tested (100 mg/mL).
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Citations

Boudou, T., Crouzier, T., Auzely-Velty, R., Glinel, K., & Picart, C. (2009). Internal Composition versus the Mechanical Properties of Polyelectrolyte Multilayer Films: The Influence of Chemical Cross-Linking. Langmuir : the A C S journal of surfaces and colloids, 25(24), 13809-13819. https://doi.org/10.1021/la9018663 (Original work published 2009)