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Glass Transition and Water Dynamics in Hyaluronic Acid Hydrogels

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Abstract

Glass transition and water dynamics in hydrated hyaluronic acid (HA) hydrogels crosslinked by divinyl sulfone (DVS) were studied by differential scanning calorimetry (DSC), dielectric relaxation spectroscopy (DRS) and water sorption—desorption (ESI) measurements. A critical water fraction of about h w = 0.17 (g of water per g of hydrated HA) for a change in the hydration properties of the material was estimated. Water crystallization was recorded by DSC during cooling and heating for water fraction values h w ≥ 0.31. The glass transition of the hydrated system was recorded in the water fraction region 0.06 ≤ h w ≤ 0.59. The T g was found to decrease with increasing hydration level, starting from T g = −48 °C down to about T g = −80 °C and then to stabilize there, for the hydration levels where water crystallization occurs, suggesting that the origin of the glass transition is the combined motion of uncrystallized water molecules attached to primary hydration sites and segments of the HA chains. DRS studies revealed two relaxation peaks, associated with the main secondary relaxation process of uncrystallized water molecules (UCW) triggering the mobility of polar groups and the segmental mobility of HA chains (α relaxation). The α relaxation was in good agreement with the results by DSC. A qualitative change in the dynamics of the α relaxation was found for h w = 0.23 and was attributed to a reorganization of water in the material due to structural changes. Finally, the dielectric strength of the relaxation of UCW was found to decrease in the water fraction region of the structural changes, i.e. for h w ~ 0.23.

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Acknowledgments

This research has been co-financed by the European Union (European Social Fund – ESF) and Greek national funds through the Operational Program “Education and Lifelong Learning” of the National Strategic Reference Framework (NSRF) - Research Funding Program: Heracleitus II. Investing in knowledge society through the European Social Fund (A.P. and P.P.) and Research Funding Program: Aristeia (A.K. and P.P.). A.V.L. and M.M.P. acknowledge financial support of projects MAT2011-28791-C03-02 and -03.

The authors would like to acknowledge Sara Poveda Reyes and María Hernández Palacios for the preparation of the HA sheets.

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Authors and Affiliations

  1. Department of Physics, National Technical University of Athens, Zografou Campus, 157 80, Athens, Greece

    Anna Panagopoulou, Apostolos Kyritsis & Polycarpos Pissis

  2. Center for Biomaterials and Tissue Engineering, Universitat Politècnica de València, Camino de Vera s/n, 46022, Valencia, Spain

    Joan Vázquez Molina, Manuel Monleón Pradas, Anna Vallés Lluch & Gloria Gallego Ferrer

  3. CIBER en Bioingeniería, Biomateriales y Nanomedicina (CIBER-BBN), Valencia, Spain

    Manuel Monleón Pradas & Gloria Gallego Ferrer

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  1. Anna Panagopoulou
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  2. Joan Vázquez Molina
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  3. Apostolos Kyritsis
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  4. Manuel Monleón Pradas
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  7. Polycarpos Pissis
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Correspondence to Anna Panagopoulou.

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Panagopoulou, A., Molina, J.V., Kyritsis, A. et al. Glass Transition and Water Dynamics in Hyaluronic Acid Hydrogels. Food Biophysics 8, 192–202 (2013). https://doi.org/10.1007/s11483-013-9295-2

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  • DOI: https://doi.org/10.1007/s11483-013-9295-2

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