Molecular Engineering of Polyhydroxyalkanoate-Based Hydrated Networks with Tunable Mechanical and Transport Properties

Molecular Engineering of Polyhydroxyalkanoate-Based Hydrated Networks with Tunable Mechanical and Transport Properties

Abstrakt

Polyhydroxyalkanoates (PHAs) are bio-based, biodegradable and biocompatible polyesters. Their use in soft, water-containing systems is highly relevant for biomedical interfaces, regenerative materials, and drug delivery systems. However, their intrinsic hydrophobicity and semicrystalline morphology limit their performance under hydrated conditions. In this contribution, we present a molecular-level strategy for transforming PHAs into highly porous hydrated architectures with controllable viscoelastic, degradation, and transport properties. By tailoring processing pathways and supramolecular organisation, stable hydrated PHA-based structures were obtained despite the polymer’s inherent hydrophobic character. Physicochemical characterization revealed that modulation of crystallinity, molecular weight and chain mobility enables precise adjustment of mechanical stiffness, elasticity and hydrolytic stability. These effects arise from changes in effective network connectivity and semicrystalline morphology. Swelling behaviour and diffusion kinetics reveal a well-defined structure–transport correlation determined by network topology and polymer–water interactions. Importantly, the resulting materials combine the sustainability and biodegradability of microbial polyesters with the functional characteristics typically associated with soft hydrated systems. Such PHA-based porous networks support the development of sustainable biointerfaces and controlled-release systems. This work demonstrates how controlled manipulation of molecular architecture and semicrystalline morphology can convert conventional biopolyesters into advanced hydrated materials with programmable performance [1–4]. Acknowledgements Acknowledgements This study was funded by the project GA 25–15806S of the Czech Science Foundation (GACR). References [1] V. Kundrat, N. Cernekova, A. Kovalcik, V. Enev, I. Marova, Materials, 2019, 12, 1924. [2] A. Kovalcik, L. Sangroniz, M. Kalina, K. Skopalova, P. Humpolicek, M. Omastova, N. Mundigler, A. J. Muller, Int. J. Biol. Macromol., 2020, 161, 364–376. [3] A. Kovalcik, S. Obruca, M. Kalina, M. Machovsky, V. Enev, M. Jakesova, M. Sobkova, I. Marova, Materials, 2020, 13, 2992. [4] A. Kovalcik, N. Cernekova, F. Fauzi, R. K. Bose, Z. Spitalsky, Z. Kadlecova, L. Vojtova, Z. Vichova, P. Humpolicek, P. Bober, Colloids Surf. B Biointerfaces, 2026, 261, 115417

Polyhydroxyalkanoates (PHAs) are bio-based, biodegradable and biocompatible polyesters. Their use in soft, water-containing systems is highly relevant for biomedical interfaces, regenerative materials, and drug delivery systems. However, their intrinsic hydrophobicity and semicrystalline morphology limit their performance under hydrated conditions. In this contribution, we present a molecular-level strategy for transforming PHAs into highly porous hydrated architectures with controllable viscoelastic, degradation, and transport properties. By tailoring processing pathways and supramolecular organisation, stable hydrated PHA-based structures were obtained despite the polymer’s inherent hydrophobic character. Physicochemical characterization revealed that modulation of crystallinity, molecular weight and chain mobility enables precise adjustment of mechanical stiffness, elasticity and hydrolytic stability. These effects arise from changes in effective network connectivity and semicrystalline morphology. Swelling behaviour and diffusion kinetics reveal a well-defined structure–transport correlation determined by network topology and polymer–water interactions. Importantly, the resulting materials combine the sustainability and biodegradability of microbial polyesters with the functional characteristics typically associated with soft hydrated systems. Such PHA-based porous networks support the development of sustainable biointerfaces and controlled-release systems. This work demonstrates how controlled manipulation of molecular architecture and semicrystalline morphology can convert conventional biopolyesters into advanced hydrated materials with programmable performance [1–4]. Acknowledgements Acknowledgements This study was funded by the project GA 25–15806S of the Czech Science Foundation (GACR). References [1] V. Kundrat, N. Cernekova, A. Kovalcik, V. Enev, I. Marova, Materials, 2019, 12, 1924. [2] A. Kovalcik, L. Sangroniz, M. Kalina, K. Skopalova, P. Humpolicek, M. Omastova, N. Mundigler, A. J. Muller, Int. J. Biol. Macromol., 2020, 161, 364–376. [3] A. Kovalcik, S. Obruca, M. Kalina, M. Machovsky, V. Enev, M. Jakesova, M. Sobkova, I. Marova, Materials, 2020, 13, 2992. [4] A. Kovalcik, N. Cernekova, F. Fauzi, R. K. Bose, Z. Spitalsky, Z. Kadlecova, L. Vojtova, Z. Vichova, P. Humpolicek, P. Bober, Colloids Surf. B Biointerfaces, 2026, 261, 115417

Polyhydroxyalkanoates; Scaffolds; Properties

Polyhydroxyalkanoates; Scaffolds; Properties

KOVALČÍK, A.; TALAŠ ČERNEKOVÁ, N.; FAUZI, F.; BOSE, R.; BOBER, P.

10.05.2026

Stratingh Institute for Chemistry, University of Groningen

Groningen, Netherlands

GroMoChem 2026, Groningen Molecular Chemistry Symposium 10-13 May 2026

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https://gromochem.web.rug.nl/index.php