Aldehyde-conjugated chitosan-graphene oxide glucodynamers: Ternary cooperative assembly and controlled chemical release

Jamal Chabbi; Abdelhafid Aqil; Nadia Katir; Bénédicte Vertruyen; Christine Jerôme; Mohamed Lahcini; Abdelkrim El Kadib

doi:10.1016/j.carbpol.2019.115634

Aldehyde-conjugated chitosan-graphene oxide glucodynamers: Ternary cooperative assembly and controlled chemical release

Carbohydr Polym. 2020 Feb 15:230:115634. doi: 10.1016/j.carbpol.2019.115634. Epub 2019 Nov 21.

Authors

Jamal Chabbi¹, Abdelhafid Aqil², Nadia Katir³, Bénédicte Vertruyen², Christine Jerôme², Mohamed Lahcini⁴, Abdelkrim El Kadib⁵

Affiliations

¹ Euromed Research Center. Engineering Division, Euro-Med University of Fes (UEMF), Route de Meknes, Rond-point de Bensouda. 30070 Fès, Morocco; Centre for Education and Research on Macromolecules, CESAM Research Unit, Chemistry Department, University of Liege, Sart-Tilman B6a, Allée de la Chimie 4000 Liège, Belgium; Laboratory of Organometallic and Macromolecular Chemistry-Composites Materials, Faculty of Sciences and Technologies, Cadi Ayyad University, Avenue Abdelkrim Elkhattabi, B.P. 549, 40000 Marrakech, Morocco.
² Centre for Education and Research on Macromolecules, CESAM Research Unit, Chemistry Department, University of Liege, Sart-Tilman B6a, Allée de la Chimie 4000 Liège, Belgium.
³ Euromed Research Center. Engineering Division, Euro-Med University of Fes (UEMF), Route de Meknes, Rond-point de Bensouda. 30070 Fès, Morocco.
⁴ Laboratory of Organometallic and Macromolecular Chemistry-Composites Materials, Faculty of Sciences and Technologies, Cadi Ayyad University, Avenue Abdelkrim Elkhattabi, B.P. 549, 40000 Marrakech, Morocco; Mohammed VI Polytechnic University, Lot 660, Hay Moulay Rachid, 43150 Ben Guerir, Morocco.
⁵ Euromed Research Center. Engineering Division, Euro-Med University of Fes (UEMF), Route de Meknes, Rond-point de Bensouda. 30070 Fès, Morocco. Electronic address: a.elkadib@ueuromed.org.

PMID: 31887867
DOI: 10.1016/j.carbpol.2019.115634

Abstract

Simultaneous condensation of aromatic aldehydes (Ar_xCHO; x = 1-4) on chitosan biopolymer (CS) affords, after water-evaporation, structurally-conjugated aryl-functionalized CS-Ar_x-f films. Similarly, cooperative assembly of two-dimensional nanometric graphene oxide (GO), aromatic aldehyde and chitosan provides transparent, flexible and crack-free aldehyde-functionalized, ternary-reinforced CS-Ar_x-GO-f nanocomposite films. Homogenous films were obtained using ortho-hydroxybenzaldehyde Ar₁ while the para-hydroxybenzaldehyde Ar₄ was prone to packing inside. Textural and mechanical properties were investigated and expectedly, significant improvement was found for CS-Ar₁-GO-f because of the great dispersion of the aromatic and the presence of the filler. The sensitivity of unsaturated CN imine bond to hydrolysis was explored for triggering controlled release of aromatics from the as-prepared films. All of them were found to induce a time-dependent aromatic release. It has been moreover observed that the release was significantly delayed in CS-Ar_x-GO-f compared to CS-Ar_x-f, a fact attributed to the interplay of the ring with the basal and edges of graphene oxide, through π-π stacking and additional hydrogen bonding interactions. This finding shows that beyond the conventional wisdom using fillers for improving thermal and mechanical properties, the tiny carbon sheets can act as a regulator for aldehyde release, thereby providing a way for more controlled chemical delivery from confined nanocomposites.

Keywords: Aldehyde-functionalization; Chemical release; Chitosan; Graphene oxide; Nanostructured films.