abstract
The precise chemical modification of marine-derived biopolymers provides a unique opportunity for fabricating a toolbox of bioactive (bio)materials with modulated physicochemical and biological properties. Herein, the beta-glucan laminarin was functionalized with phenylboronic acid (PBA) moieties that impart chemical reactivity toward diol-containing polymers via boronate esterification. The modification, which involved a two-pot reaction, was successfully confirmed by nuclear magnetic resonance spectroscopy. The resultant biopolymer readily established boronate ester-crosslinked hydrogels with poly(vinyl alcohol) (PVA) within seconds under physiological conditions. These hydrogels exhibited improved rheological properties, which were easily tunable, and revealed a rapid self-healing behavior upon rupture. Moreover, boronate ester bonds enabled the fabrication of reactive oxygen species-responsive and shear-thinning gels that can be administered in situ and respond to the oxidation state of the surrounding microenvironment. Importantly, due to the catalyst-free and mild-crosslinking conditions, the generated laminarin-PBA/PVA hydrogels did not show toxicity upon direct contact with preosteoblasts for up to 48 h, and thus constitute a promising platform for tissue engineering and drug delivery applications.
keywords
POLYMERS; OXIDATION
subject category
Polymer Science
authors
Amaral, AJR; Gaspar, VM; Mano, JF
our authors
João Mano
Vice Director
Vítor Gaspar
Assistant Professoracknowledgements
This work was supported by the European Research Council (ERC-2014-ADG-669858) and project CICECO-Aveiro Institute of Materials, UIDB/50011/2020 & UIDP/50011/2020, financed by national funds through the Portuguese FCT/MCTES. The NMR spectrometer is part of the National NMR Network (PTNMR) and partially supported by Infrastructure Project N degrees 022161 (co-financed by FEDER through COMPETE 2020, POCI and PORL, and FCT through PIDDAC). This work was also funded by the Programa Operacional Competitividade e InternacionalizacAo (POCI), in the component FEDER, and by national funds (OE) through FCT/MCTES within the scope of the project MARGEL (PTDC/BTM-MAT/31498/2017). VMG acknowledges funding in the form of a Junior Research contract under the scope of project PANGEIA (PTDC/BTM-SAL/30503/2017).