Synthetic materials commonly used in the packaging industry generate a considerable amount of waste each year. Chitosan is a promising feedstock for the production of functional biomaterials. From a biological point of view, chitosan is very attractive for food packaging. The purposes of this study were to evaluate the antibacterial activity of a set of chitosan-metal oxide films and different chitosan-modified graphene (oxide) films against two foodborne pathogens: Campylobacter jejuni ATCC 33560 and Listeria monocytogenes 19115. Moreover, we wanted to check whether the incorporation of antimicrobial constituents such as TiO2, ZnO, Fe2O3, Ag, and graphene oxide (GO) into the polymer matrices can improve the antibacterial properties of these nanocomposite films. Finally, this research helps elucidate the interactions of these materials with eukaryotic cells. All chitosan-metal oxide films and chitosan-modified graphene (oxide) films displayed improved antibacterial (C. jejuni ATCC 33560 and L. monocytogenes 19115) properties compared to native chitosan films. The CS-ZnO films had excellent antibacterial activity towards L. monocytogenes (90% growth inhibition). Moreover, graphene-based chitosan films caused high inhibition of both tested strains. Chitosan films with graphene (GO, GOP, GOP-HMDS, rGO, GO-HMDS, rGOP), titanium dioxide (CS-TiO2 20:1a, CS-TiO2 20:1b, CS-TiO2 2:1, CS-TiO2 1:1a, CS-TiO2 1:1b) and zinc oxide (CS-ZnO 20:1a, CS-ZnO 20:1b) may be considered as a safe, non-cytotoxic packaging materials in the future.
Graphene oxide (GO) has recently captured tremendous attention, but only few functionalized graphene derivatives were used as fillers, and insightful studies dealing with the thermal, mechanical, and biological effects of graphene surface functionalization are currently missing in the literature. Herein, reduced graphene oxide (rGO), phosphorylated graphene oxide (PGO), and trimethylsilylated graphene oxide (SiMe3GO) were prepared by the post-modification of GO. The electrostatic interactions of these fillers with chitosan afforded colloidal solutions that provide, after water evaporation, transparent and flexible chitosan-modified graphene films. All reinforced chitosan–graphene films displayed improved mechanical, thermal, and antibacterial (S. aureus, E. coli) properties compared to native chitosan films. Hemolysis, intracellular catalase activity, and hemoglobin oxidation were also observed for these materials. This study shows that graphene functionalization provides a handle for tuning the properties of graphene-reinforced nanocomposite films and customizing their functionalities.
Five different functional phosphorus motifs were trivially installed within graphene oxide (GO) sheets to provide water-dispersible and thermally-stable phosphorus graphene oxide materials (PGO). The presence of exogenous phosphorus heteroatoms on the surface of the tiny carbon sheets was harnessed for the anchoring and growth of metal oxide clusters, exemplified herein by titanium dioxide, and for the chelation and stabilization of small gold nanoparticles. Unexpectedly, both GO and PGO promoted crystallization in a low-temperature liquid-phase medium without thermal annealing treatment. However, the fingerprint of the surface chemistry is illustrated through the formation of different species; while discrete anatase nanoparticles were selectively formed on the surface of GO sheets, a biphasic mixture of anatase and rutile was grown on PGO. The latter provides a more stable material owing to the robustness of the interfacial P–O–Ti bridges. Strong coordination to gold nanoparticles was also observed for PGO due to the presence of PO(OH)2 fragments, compared to the weakly coordinating oxygenated functions in GO. Lastly, the possible delamination of PGO sheets associated with their improved thermal stability renders them promising nanosized fillers for carbohydrate-based bioplastics.
Pyrolysis of filmogenic natural polymers gives rise to the formation of films of few-layers defective, undoped, and doped graphenes with low electrical conductivity (3000 to 5000 Ω/sq). For the sake of valorization of biomass wastes, it would be of interest to decrease the density of structural defects in order to increase the conductivity of the resulting few-layers graphene samples. In the present study, analytical and spectroscopic evidence is provided showing that by performing the pyrolysis at the optimal temperature (1100 °C), under a low percentage of H2, a significant decrease in the density of defects related to the presence of residual oxygen can be achieved. This improvement in the quality of the resulting few-layers defective graphene is reflected in a decrease by a factor of about 3 or 5 for alginic acid and chitosan, respectively, of the electrical resistance. Under optimal conditions, few-layers defective graphene films with a resistance of 1000 Ω /sq were achieved. The electrode made of high-quality graphene prepared at 1100 °C under Ar/H2 achieved a H2 production of 3.62 µmol with a positive applied bias of 1.1 V under LED illumination for 16 h.
Adsorption of Pd(NH3)42+ in preformed chitosan–graphene oxide (CS-GO) beads and their subsequent reduction with NaBH4 afford well-dispersed, high dispersion (~21%) of uniformly sized Pd nanoparticles (~1.7 nm). The resulting Pd/CS-GO exhibits interesting catalytic activity for hydrogen generation by ammonium formate decomposition. The optimal GO proportion of 7 wt% allows reaching, at 60 °C, a turnover frequency above 2200 h−1—being outstanding among the highest values reported for this process to date. Interestingly, no formation of CO or CH4 was detected. The catalyst did not leach, although it underwent gradual deactivation, probably caused by the increase in the Pd average size that became over 3 nm after three uses. Our results are relevant in the context of efficient on-board hydrogen generation from liquid organic hydrogen carriers in transportation.