Crystallization-Driven Supramolecular Gelation of Poly(vinyl alcohol) by a Small Catechol Derivative

Catechol-containing molecules have been recognized as versatile building blocks for polymer structures with tailor-made functional properties. While catechol chemistry via metal-ligand coordination, boronate complexation, and oxidation-driven covalent bonds has been well examined in the past, the hy...

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Detalhes bibliográficos
Autores: Bonafe Allende, Juan Cruz, Schmarsow, Ruth Noemí, Matxinandiarena, Eider, García Schejtman, Sergio David, Coronado, Eduardo A., Alvarezigarzabal, Cecilia I., Picchio, Matías Luis, Müller, Alejandro J.
Formato: artículo
Estado:Versión publicada
Fecha de publicación:2022
País:Argentina
Recursos:Consejo Nacional de Investigaciones Científicas y Técnicas
Repositorio:CONICET Digital (CONICET)
Idioma:inglés
OAI Identifier:oai:ri.conicet.gov.ar:11336/212042
Acesso em linha:http://hdl.handle.net/11336/212042
Access Level:acceso abierto
Palavra-chave:catechol
chemistry
hydrogels
crystallization
https://purl.org/becyt/ford/2.5
https://purl.org/becyt/ford/2
Descrição
Resumo:Catechol-containing molecules have been recognized as versatile building blocks for polymer structures with tailor-made functional properties. While catechol chemistry via metal-ligand coordination, boronate complexation, and oxidation-driven covalent bonds has been well examined in the past, the hydrogen bonding ability of these intriguing molecules has been dismissed. In this research, we investigated the gelation of poly(vinyl alcohol) (PVA) triggered by the crystallization of a 3,4-dihydroxy-catechol in water. Strong hydrogen bond interactions between PVA and catechol groups afforded supramolecular hydrogels with near-covalent elastic moduli, yet dynamic, exhibiting reversible gel-to-sol phase transitions around 50-60 °C. We studied the impact of the catechol derivative concentration on the gelation kinetics and physicochemical properties of these dynamic materials. Isothermal experiments revealed that heterogeneous crystallization governs the gelation kinetics. Moreover, because of the quasi-permanent cross-links within the supramolecular polymer network, these hydrogels benefit from ultrastretchability (∼600%) and high toughness (900 kJ·m-3). Our gelation approach is expected to expand the toolbox of catechol chemistry, opening up new avenues in designing dynamic soft materials with facile control over the phase transition, mechanics, and viscoelastic properties.